Title of Invention

METAL COLLOIDAL PARTICLES AND METAL COLLOID

Abstract The invention discloses a metal colloidal particles capable of forming a metal colloid by dispersing in either or both of an aqueous dispersion medium and a nonaqueous dispersion medium in a proportion ranging from 0.1 to 95 weight % while mixing, comprising metal particles of one or more of metal selected from the group consisting of Au, Ag, Pt, Cu, Pd, Ni, Zn, Ru, Rh and Ir and a protective agent coordination- modified on the surface of the particles, the protective agent having a carbon skeleton containing oxygen and nitrogen in the molecule, and having a structure of being coordination-modified on the surface of the metal particles using an atom or an atomic group of oxygen and nitrogen as an anchor, wherein the protective agent has one, or two or more functional groups selected from the group consisting of alkoxysilyl group, silanol group and hydroxyalkyl group in a molecular structure.
Full Text TECHNICAL FIELD
The present invention relates to a metal colloid which
is excellent in long-term stability of a colloidal solution
and is suited for thin-filming, and its use. Furthermore,
the present invention relates to a metal colloid which can
easily form a metal specular glossy area on various base
materials,and its use. Particularly, the present invention
relates to metal colloidal particles and a metal colloid,
which can easily form a metal glossy area showing various
gold-based color tones on various base materials, and the use
of the metal colloid.
This application claims priority from Japanese Patent
Application No. 2004-187872 filed on June 25, 2004, Japanese
Patent Application No. 2004-235261 filed on August 12, 2004
and Japanese Patent Application No. 2004-284027 filed on
September 29, 2004, the disclosure of which is incorporated
by reference herein.
BACKGROUND ART
Since a metal colloid shows a color peculiar to the
particle size and the kind of metal, a measuring tip for


optical analysis which utilizes the metal colloid as an
optical filter is known (see, for example, Japanese
Unexamined Patent Application, First Publication No. Hei 10-
160737) . The metal colloid used in this measuring tip is
obtained by previously preparing a metal colloidal dispersion
and mixing the colloidal dispersion with a silane coupling
agent, thereby to introduce an amino group as a functional
group into the surface of the colloid. However, when the
metal colloid is formed and then the surface protective agent
is introduced into the surface of the colloid, the protective
agent may not be sufficiently introduced because of the
deposit which has already been present on the metal surface
of the colloid. Since the metal colloid is synthesized in an
aqueous system, the surface protective agent is influenced by
hydrolysis and thus stability of the colloid deteriorates.
Furthermore, the amino group to be introduced into the amino
group is used as a functional group for a protein or enzyme,
and therefore the amino group is located outside and the
siloxane bond of the protective agent is located on the
surface of the colloid. Therefore, according to surface
properties of colloidal particles, adhesion between the
protective agent and the colloidal particles may become
insufficient and thus the metal colloidal film is unstable.
In addition, as a metal colloid used as a conductive
ink or a material of a conductive coat, a highly conductive


aqueous metal colloidal solution containing an organic
component is known (see, for example, Japanese Unexamined
Patent Application, First Publication No. 2001-325831).
However, this metal colloid is also produced by the aqueous
reaction and is obtained by mixing with the organic component
after forming a metal colloid and therefore have the same
problems described above.
Also it has hitherto been known to use a metal colloid
as a colorant of a coating composition or glass. For example,
it is known that a metal colloid is prepared by reducing a
metal compound in the presence of a high-molecular weight
pigment dispersant (see, for example, Japanese Unexamined
Patent Application, First Publication No. Hei 11-80647).
However, this method also includes a major specific example
wherein a metal colloid is formed by the aqueous reaction and
therefore have the same problems described above.
Furthermore, a coexisting polymer protective colloid is a
pigment dispersant and is not obtained by bonding a
protective agent comprising a silane coupling agent with the
surface of colloidal particles.
Furthermore, there is known a method of mixing
chlorauric acid with a protective polymer to form a gold
colloid, the method using a protective polymer having an
amino group in the end or side chain portion opposite the
surface of metal particles (see, for example, Japanese


Unexamined Patent Application, First Publication No. 2000-
160210). This method is intended to produce a gold colloid
without using a reducing agent such as sodium borohydride
which is commonly used, and the reductive action of a
protective polymer is utilized. However, in this case, since
the protective agent is a polymer, the resulting colloid
contains a lot of organic chains and is insufficient in heat
resistance.
A gold ink, which has hitherto been sold and used as a
gold powder, has been obtained by treating the surface of a
flat shaped brass powder (copper-zinc alloy powder) with a
saturated fatty acid having 16 to 22 carbon atoms and used
for lithographic printing. However, a lithographic printing
ink has high viscosity and is not suited for use as an ink
having low viscosity which is used for gravure printing.
Therefore, there is disclosed a gold powder for gold ink
which is prepared by coating 100 parts by weight of a flaky
brass metal powder having an average particle size of 10 urn
or less with 0.1 to 2 parts by weight of a saturated fatty
acid having 14 to 22 carbon atoms and 0.1 to 2 parts by
weight of a fatty acid amide having 14 to 22 carbon atoms
while mixing (see, for example, Japanese Unexamined Patent
Application, First Publication No. 2001-19872) as measure
which can attain the same specular gloss as that in case of
gravure printing in the lithographic printing and also can


exert the same effect as that of a smooth paper in case of
using a paper having no smooth surface. In Japanese
Unexamined Patent Application, First Publication No. 2001-
19872, when using, as a printing ink, a gold ink obtained by
mixing a gold powder having an average particle size of 10 µm
or less prepared by a mechanical crushing method with a
predetermined amount of the saturated fatty acid and the
fatty acid amide, a metal specular glossy film is obtained.
Also, a method of preparing a metal colloid with a
silica film by a heat treatment using an amino group-
containing alkoxysilane is known (see, for example, Extended
Abstracts of 66th Fall Meeting of the Chemical Society of
Japan, pp.322 and Proc SPIE Sol-gel Optics III, Vol. 2288,
pp.130-139).
However, the amino group-containing silane used in this
method is used so as to promote the production of a colloid
from chlorauric acid as a raw material, and is not used as
the protective agent. According to this method, since
colloidalization is conducted by a heat treatment, properties
of the colloid produced vary depending on the temperature and
stable permeation and absorption performances. Moreover,
hydrolysis of a sol-gel solution is promoted by an acid
containing in a raw material in an alkoxide, and thus
lifetime of the solution tends to be shortened and
furthermore the solution is unstable.


DISCLOSURE OF THE INVENTION
Furthermore, it is known that a gold colloid obtained
by protecting nano-sized gold particles with a protective
agent having a low molecular weight shows gold metal gloss
after drying at room temperature. Examples of the protective
agent used in this case include fatty acids such as citric
acid having 1 to 8 carbon atoms, adipic acid, malic acid,
acetic acid, propionic acid, butyric acid, valeric acid and
caproic acid; and amines such as monomethylamine,
dimethylamine, trimethylamine, monoethylamine, diethylamine,
triethylamine, monopropylamine, isopropylamine,
monobutylamine, secondary butylamine, tertiary butylamine,
monopentylamine and monohexylamine. However, in case of the
gold colloid obtained by using the protective agent, the
upper limit of the concentration of metal contained in the
colloidal solution is about 5% by weight. When the
concentration is more than the upper limit, there arise
problems that aggregation or gelation occurs and the
concentration can not be increased because of poor stability.
For example, in order to exhibit golden gloss by coating and
air-drying a metal colloid made of gold as metal, it is
necessary that the gold content is at least 20% by weight
based on a fibrous base material such as paper. When the
concentration of the metal colloid protected with a low-


molecular weight protective agent is increased in disregard
of stability, the coated surface shows metal gloss but is far
from golden gloss and also the coat is easily peeled off
because of poor adhesion.
When a polymer binder is added to the metal colloid so
as to solve this problem, nano-sized metal particles cause
plasmon color development (SPR: Surface Plasma) due to
surface plasma resonance and show are a red or reddish violet
color, and thus no golden gloss is exhibited.
Heretofore, there has never been obtained a metal
colloid which exhibit gold color tones such as pink gold and
green gold, based on gold used in jewelries.
The present inventors have been investigated about
stability with time so as to enhance additional value of the
metal colloid. As a result of intensive study, they have
found to provide a metal colloid having excellent stability
with time by using a protective agent containing at least one
of sulfur and oxygen, or using a protective agent containing
nitrogen. Whereby, any influence is not exerted on metal
gloss of a coat formed by coating a metal colloidal coating
material.
First object of the present invention is to solve the
above problems in a conventional metal colloid and the method
of preparing the same and to provide a conventional colloid
which is excellent in long-term stability of a colloidal


solution and is suited for thin-filming, and its use.
Second object of the present invention is to provide
metal colloid which can easily form a metal specular glossy
area on various base materials, and its use.
Third object of the present invention is to provide a
metal colloidal particles and a metal colloid, which can
easily form a metal glossy area showing various color tones,
and the use of the metal colloid.
Fourth object of the present invention is to provide a
metal colloid-containing coat formed article, a transfer
sheet and a base material with a conductive film, wherein a
coat having a metal specular glossy area and excellent heat
resistance is formed.
Five object of the present invention is to provide a
metal colloid-containing coat formed article, a transfer
sheet and a base material with a conductive film, wherein a
coat showing various color tones is formed.
Sixth object of the present invention is to provide a
base material with a conductive film, comprising a low-
resistance conductive film
Seventh object of the present invention is to provide a
pen, a brush-pencil, a cartridge for pen, a disposable ampul,
a stamp pad and a seal impression, which are excellent in
quality-retaining property.
Eighth object of the present invention is to provide a


drawn material having color tone and metal gloss peculiar to
metal.
The first aspect of the present invention provides
metal colloidal particles capable of forming a metal colloid
by dispersing in either or both of an aqueous dispersion
medium and a nonaqueous dispersion medium in a predetermined
proportion while mixing, comprising metal particles and a
protective agent coordination-modified on the surface of the
particles, the protective agent having a carbon skeleton
containing either or both of sulfur and oxygen in the
molecule, and having a structure of being coordination-
modified on the surface of the metal particles using an atom
or an atomic group of either or both of sulfur and oxygen as
an anchor, wherein the protective agent has one, or two or
more functional groups selected from the group consisting of
alkoxysilyl group, silanol group and hydroxyalkyl group in a
molecular structure.
Since the protective agent is firmly bonded to the
surface of metal particles using an atom or an atomic group
of either or both of sulfur and oxygen as an anchor, high
stability is attained. The alkoxysilyl group, the silanol
group and the hydroxyalkyl group contained in the molecular
structure of the protective agent have high reactivity and
chemically bonded to all base materials. Metal particles are
spontaneously self-organized and cause closest packing, and


are condensed with a reactive functional group. Therefore,
it is considered that a coat obtained by coating or spraying
the metal colloid made of the metal colloidal particles
according to the first aspect has high strength and is
converted into an organic-inorganic hybrid bulk between
particles.
The second aspect of the present invention provides the
metal colloidal particles of the invention according to the
first aspect, wherein the protective agent further contains
nitrogen and has a structure of being coordination-modified
on the surface of metal particles using nitrogen or an atomic
group including nitrogen as an anchor.
The third aspect of the present invention provides the
metal colloidal particles of the invention according to the
first aspect, wherein oxygen contained in the protective
agent is derived from at least one selected from the group
consisting of carbonyl group, carboxyl group, aldehyde group,
amide group and sulfonyl group.
The fourth aspect of the present invention provides the
metal colloidal particles of the invention according to any
one of the first to third aspects, wherein either or both of
the alkoxysilyl group and the hydroxyalkyl group contained in
the protective agent are chelete-coordinated by a chelating
agent.
The fifth aspect of the present invention provides the


metal colloidal particles of the invention according to the
first aspect, wherein the metal particles constituting the
metal colloidal particles are one or two or more metal
particles made of metal selected from the group consisting of
Au, Ag, Pt, Cu, Pd, Ni, Zn, Ru, Rh and Ir.
The sixth aspect of the present invention provides the
metal colloidal particles of the invention according to the
fifth aspect, wherein the metal particles constituting the
metal colloidal particles are made of Au and have an average
particle size within a range from 1 to 60 nm.
The seventh aspect of the present invention provides
the metal colloidal particles of the invention according to
any one of the first to sixth aspects, wherein a coat formed
by coating, spraying, printing, ejecting or transferring a
metal colloid, which is obtained by dispersing metal
colloidal particles containing Au colloidal particles as a
main component and also containing 0.1 to 10% metal particles
having an average particle size of 1 to 10 nm, in addition to
the Au colloidal particles, in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a pink gold color tone.
The eighth aspect of the present invention provides the
metal colloidal particles of the invention according to any
one of the first to sixth aspects, which are either or both
of metal colloidal particles containing Au colloidal


particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, and metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag and Cu as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 40% and the content of Ag in impurities is from 40
to 60% by weight based on 100% by weight of impurities, a
coat formed by coating, spraying, printing, ejecting or
transferring a metal colloid, which is obtained by dispersing
the metal colloidal particles in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a yellow gold color tone.
The ninth aspect of the present invention provides the
metal colloidal particles of the invention according to any
one of the first to sixth aspects, which are either or both
of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, and metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag and Cu as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 40% and the content of Ag in impurities is 65% by
weight or more based on 100% by weight of impurities, a coat


formed by coating, spraying, printing, ejecting or
transferring a metal colloid, which is obtained by dispersing
the metal colloidal particles in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a green gold color tone.
The tenth aspect of the present invention provides the
metal colloidal particles of the invention according to any
one of the first to sixth aspects, which are either or both
of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, and metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag and Cu as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 40% and the content of Ag in impurities is 30% by
weight or less based on 100% by weight of impurities, a coat
formed by coating, spraying, printing, ejecting or
transferring a metal colloid, which is obtained by dispersing
the metal colloidal particles in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a red gold color tone.
The eleventh aspect of the present invention provides
the metal colloidal particles of the invention according to
any one of the first to sixth aspects, which are either or


both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles, Cu particles and Pd particles as impurities, in
addition to Au particles, and metal colloidal particles
containing metal particles made of an alloy containing Au as
a main component and also containing Ag, Cu and Pd as
impurities, wherein when the content of impurities in the
metal colloidal particles is from 5 to 40% and the content of
Ag in impurities is 30% by weight or less based on 100% by
weight of impurities, a coat formed by coating, spraying,
printing, ejecting or transferring a metal colloid, which is
obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a pink gold color tone.
The twelfth aspect of the present invention provides
the metal colloidal particles of the invention according to
any one of the first to sixth aspects, which are either or
both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Pd
particles as impurities, in addition to Au particles, and
metal colloidal particles containing metal particles made of
an alloy containing Au as a main component and also
containing Pd as impurities, wherein when the content of
impurities in the metal colloidal particles is from 5 to 40%,
a coat formed by coating, spraying, printing, ejecting or


transferring a metal colloid, which is obtained by dispersing
the metal colloidal particles in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a white gold color tone.
The thirteenth aspect of the present invention provides
a metal colloid which is characterized in that the metal
colloidal particles of any one of any one of the first to
twelfth embodiments are dispersed in either or both of an
aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing.
The fourteenth aspect of the present invention provides
a metal colloid which is characterized in that the metal
colloidal particles of any one of the first to twelfth
embodiments are mixed with a sol-gel solution in a
predetermined proportion.
The fourteenth aspect of the present invention provides
the metal colloid of the invention according to the
fourteenth aspect, wherein the sol-gel solution is a solution
capable of forming at least one compound selected from the
group consisting of silica, titania, zirconia, alumina,
tantalum oxide and niobium oxide.
The sixteenth aspect of the present invention provides
a metal colloidal thin film which is characterized in that
the metal colloidal particles of any one of the first to
twelfth embodiments are dispersed in either or both of an


aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing to form a metal
colloid and a film is formed by using the metal colloid.
The seventeenth aspect of the present invention
provides a metal colloid-containing coat formed article which
is formed by coating, spraying, printing, ejecting or
transferring the metal colloid of any one of the thirteenth
to fifteenth embodiments on the surface of a base material,
and removing the dispersion medium from the metal colloid.
The eighteenth aspect of the present invention provides
a metal colloid-containing coat formed article, wherein the
base material is jewelry and the jewelry is made of a noble
metal clay.
The nineteenth aspect of the present invention provides
the metal colloid-containing coat formed article of the
invention according the seventeenth or eighteenth aspect,
further comprising one, two or more kinds selected from the
group consisting of metal powder, metal foil, fine metal
particles, brightener, lame agent, cut pieces of colored
paper, natural gems and artificial gems.
The twentieth aspect of the present invention provides
the metal colloid-containing coat formed article of the
according to the nineteenth aspect, wherein the metal used in
the metal powder, metal foil or fine metal particles is Au.
The twenty-first aspect of the present invention


provides a transfer sheet comprising a metal colloid-
containing coat formed by coating, spraying, printing,
ejecting or transferring the metal colloid of any one of the
thirteenth to fifteenth aspects on a transfer substrate
wherein either of both of the surface and the back surface
are subjected to a release treatment, and removing the
dispersion medium from the metal colloid.
The twenty-second aspect of the present invention
provides the transfer sheet of the invention according to the
twenty-first aspect, wherein the metal colloid-containing
coat contains one, two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems.
The twenty-third aspect of the present invention
provides the transfer sheet of the invention according to the
twenty-second aspect, wherein the metal used in the metal
powder, metal foil or fine metal particles is Au.
The twenty-third aspect of the present invention
provides a metal colloid-containing coat formed article
comprising a transfer film transferred from the transfer
sheet of any one of the twenty-first to twenty-third aspects.
The twenty-fifth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the twenty-fourth aspect, further


comprising one, or two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems.
The twenty-sixth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the twenty-fifth aspect, wherein
the metal used in the metal powder, metal foil or fine metal
particles is Au.
The twenty-seventh aspect of the present invention
provides a base material with a conductive film, having
resistivity of 1 × 10-3 Ω.cm or less, which is obtained by
coating, spraying, printing, ejecting or transferring the
metal colloid of any one of the thirteenth to fifteenth
aspects on a base material, and maintaining the base material
with the metal colloid in a predetermined atmosphere at a
temperature of 15 to 450°C for 1 to 60 minutes.
The twenty-eighth aspect of the present invention
provides a pen, a brush-pencil, a cartridge for pen and a
disposable ampul, each being filled with the metal colloid of
any one of the thirteenth to fiftheenth aspects as an ink.
The twenty-ninth aspect of the present invention
provides a drawn material which is drawn by an ink jet
printer using the metal colloid of any one of the thirteenth
to fiftheenth aspects as an ink.


The thirteenth aspect of the present invention provides
a metal colloidal particles capable of forming a metal
colloid by dispersing in either or both of an aqueous
dispersion medium and a nonaqueous dispersion medium in a
predetermined proportion while mixing, comprising metal
particles and a protective agent coordination-modified on the
surface of the particles, the protective agent having a
carbon skeleton containing nitrogen in the molecule, and
having a structure of being coordination-modified on the
surface of the metal particles using nitrogen or an atomic
group including nitrogen as an anchor, wherein the protective
agent has one, or two or more functional groups selected from
the group consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure, and the metal
particles contain an Au component as a main component and
also contain one, or two or more metal components other than
the Au component as an accessory component.
Since the protective agent is firmly bonded to the
surface of metal particles using an atom or an atomic group
of either or both of sulfur and oxygen as an anchor, high
stability is attained. The alkoxysilyl group, the silanol
group and the hydroxyalkyl group contained in the molecular
structure of the protective agent have high reactivity and
chemically bonded to all base materials. Metal particles are
spontaneously self-organized and cause closest packing, and


are condensed with a reactive functional group. Therefore,
it is considered that a coat obtained by coating or spraying
the metal colloid made of the metal colloidal particles
according the thirtieth aspect has high strength and is
converted into an organic-inorganic hybrid bulk between
particles.
When the metal particles constituting the metal
colloidal particles are composed of an Au component as a main
component and one, or two or more metal components other than
the Au component as an accessory component, a coat formed by
using a metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows metal color with color
tone which is different from that peculiar to an Au simple
substance. By changing the kind or content of metal
constituting the accessory component, it is possible to
exhibit various gold-based color tones.
The thirty-first aspect of the present invention
provides the metal colloidal particles of the invention
according to the thirtieth aspect, wherein the accessory
component constituting the metal particles contains at least
an Ag component and a Cu component, and the content of the
accessory component in the metal particles is from 5 to 40%
by weight and the content of the Ag component in the
accessory component is from 40 to 60% by weight.
In the thirty-first aspect, a coat formed by using a


metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows yellow gold color tone.
The thirty-second aspect of the present invention
provides the metal colloidal particles of the invention
according to the thirtieth aspect, wherein the accessory
component constituting the metal particles contains at least
Ag particles and Cu particles, and the content of the
accessory component in the metal particles is from 5 to 40%
by weight and the content of Ag component in the accessory
component is 65% by weight or more.
In the thirty-second aspect, a coat formed by using a
metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows green gold color tone.
The thirty-third aspect of the present invention
provides the metal colloidal particles of the invention
according to the thirtieth aspect, wherein the accessory
component constituting the metal particles contains at least
Ag particles and Cu particles, and the content of the
accessory component in the metal particles is from 5 to 40%
by weight and the content of Ag component in the accessory
component is 30% by weight or less.
In the thirty-third aspect, a coat formed by using a
metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows red gold color tone.
The thirty-fourth aspect of the present invention


provides the metal colloidal particles of the invention
according to the thirtieth aspect, wherein the accessory
component constituting metal particles contains at least Ag
particles, Cu particles and Pd particles, and the content of
the accessory component in the metal particles is from 5 to
40% by weight and the content of the Ag component in the
accessory component is 30% by weight or less.
In the thirty-fourth aspect, a coat formed by using a
metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows pink gold color tone.
The thirty-fifth aspect of the present invention
provides the metal colloidal particles of the invention
according to the thirtieth aspect, wherein the accessory
component constituting the metal particles contains at least
Pd particles, and the content of the accessory component in
the metal particles is from 5 to 40% by weight.
In the thirty-fifth aspect, a coat formed by using a
metal colloid obtained by dispersing metal colloidal
particles in a dispersion medium shows white gold color tone.
The thirty-sixth aspect of the present invention
provides the metal colloidal particles of the according to
any one of the thirtieth to thirty-fifth aspect, wherein, by
mixing an alkoxysilane having an amino group with a metal
compound in a nonaqueous medium and reducing the metal
compound in the presence of a reducing agent, a protective


agent made of the alkoxysilane is linked to the surface of
metal particles using a nitrogen atomic group as an anchor.
The thirty-seventh aspect of the present invention
provides the metal colloidal particles of the according to
any one of the thirtieth to thirty-sixth aspect, wherein the
atomic group including nitrogen is at least one selected from
the group consisting of amino group, amide atomic group and
imide atomic group.
The thirty-eighth aspect of the present invention
provides the metal colloidal particles of the invention
according to any one of the thirtieth to thirty-seventh
aspects, wherein either of both of the alkoxysilyl group and
the hydroxyalkyl group contained in a protective agent is
chelete-coordinated by a chelating agent.
The thirty-ninth aspect of the present invention
provides a metal colloid which is characterized in that the
metal colloidal particles of any one of the thirtieth to
thirty-eighth are dispersed in either or both of an aqueous
dispersion medium and a nonaqueous dispersion medium in a
predetermined proportion.
In the thirty-ninth aspect, metal colloidal particles,
when the protective agent is firmly bonded to the surface of
metal particles using a nitrogen atom or an atomic group as
an anchor, a colloidal solution is extremely stable and a
high concentration metal colloid can be obtained. Also less


viscosity change and color tone change occur. Furthermore, a
thin film having large film strength can be formed.
The fortieth aspect of the present invention provides a
metal colloidal thin film which is formed by using the metal
colloid of the thirty-ninth aspect.
In the fortieth aspect, the metal colloid-containing
coat formed by using the metal colloid of the present
invention shows various gold-based color tones.
The forty-first aspect of the present invention
provides a metal colloid-containing coat formed article which
is formed by coating, spraying, printing, ejecting or
transferring the metal colloid of the thirty-ninth aspect on
the surface of a base material, and removing the dispersion
medium from the metal colloid.
In the forty-first aspect, the metal colloid-containing
coat formed by coating the metal colloid of the present
invention on the surface of the base material and removing
the dispersion medium shows various gold-based color tones.
The forty-second aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the forty-first aspect, further
comprising one, two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems.


In the forty-second aspect, decorativeness is enhanced
by containing the metal powder in or the surface of the coat.
The forty-third aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the forty-second aspect, wherein
he metal used in the metal powder, metal foil or fine metal
particles is Au.
In the forty-third aspect, when Au is used as metal
used in the metal powder, metal foil or fine metal particles,
high sensuousness is obtained.
The forty-fourth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the forty-third aspect, wherein
the jewelry is jewelry made of noble metal clay.
The forty-fifth aspect of the present invention
provides a transfer sheet comprising a metal colloid-
containing coat formed by coating, spraying, printing,
ejecting or transferring the metal colloid of the thirty-
ninth aspect on a transfer substrate wherein either of both
of the surface and the back surface are subjected to a
release treatment, and removing the dispersion medium from
the metal colloid.
In the forty-fifth aspect, the transfer sheet with a
metal colloid-containing coat, which is formed by using the
metal colloid of the present invention, can form a transfer


film which shows various gold-based color tones.
The forty-sixth aspect of the present invention
provides the transfer sheet of the invention according to the
forty-fifth aspect, wherein the metal colloid-containing coat
contains one, two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems.
In the forty-sixth aspect, decorativeness is enhanced
by containing the metal powder in the coat.
The forty-seventh aspect of the present invention
provides the transfer sheet of the invention according to the
forty-sixth aspect, wherein the metal used in the metal
powder, metal foil or fine metal particles is Au.
In the forty-seventh aspect, when Au is used as metal
used in the metal powder, metal foil or fine metal particles,
high sensuousness is obtained.
The forty-eighth aspect of the present invention
provides a metal colloid-containing coat formed article
comprising a transfer film transferred from the transfer
sheet of the forty-sixth or forty-seventh aspect.
In the forty-eighth aspect, the metal colloid-
containing coat formed article comprising the transfer film
transferred from the transfer sheet on the surface shows
various gold-based color tones.


The forty-ninth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the forty-eighth aspect, wherein
the base material to be transferred is jewelry and the
jewelry is jewelry made of a noble metal clay.
The fifty aspect of the present invention provides a
pen, a brush-pencil, a cartridge for pen and a disposable
ampul, each being filled with the metal colloid of the
thirty-ninth aspect as an ink.
The fifty-first aspect of the present invention
provides a metal colloid-containing coat formed article
wherein a metal colloid-containing coat with optional
patterns is formed by drawing through an ink jet printer
using the metal colloid of the thirty-ninth aspect as an ink.
The fifty-second aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the fifty-first aspect, further
comprising one, or two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, and lame agent, cut pieces of colored paper,
natural gems and artificial gems.
The fifty-third aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the fifty-first aspect, wherein
the metal used in the metal powder, metal foil or fine metal


particles is Au.
The fifty-fourth aspect of the present invention
provides a metal colloid-containing coat formed article
wherein metal colloidal particles comprise metal particles
and a protective agent coordination-modified on the surface
of the particles, the protective agent having a carbon
skeleton containing nitrogen in the molecule, and having a
structure of being coordination-modified on the surface of
metal particles using nitrogen or an atomic group including
nitrogen as an anchor, and the protective agent contains one,
or two or more functional groups selected from the group
consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure, the metal
colloid-containing coat formed article being formed by
coating, spraying, printing, ejecting or transferring a metal
colloid which is obtained by dispersing in either or both of
an aqueous dispersion medium and a nonaqueous dispersion
medium in a predetermined proportion while mixing, on the
surface of a base material, and removing the dispersion
medium from the metal colloid.
The fifty-fifth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the fifty-fourth aspect, wherein
the base material is jewelry and the jewelry is made of a
noble metal clay.


The fifty-sixth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the fifty-fourth or fifty-fifth
aspect, further comprising one, two or more kinds selected
from the group consisting of metal powder, metal foil, fine
metal particles, brightener, lame agent, cut pieces of
colored paper, natural gems and artificial gems.
The fifty-seventh aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the fifty-sixth aspect, wherein
the metal used in the metal powder, metal foil or fine metal
particles is Au.
The fifty-eighth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to any one of fifty-fourth to fifty-
seventh aspects, wherein the metal particles constituting the
metal colloidal particles are made of Au and have an average
particle size within a range from 1 to 60 nm.
The fifty-ninth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to any one of fifty-fourth to fifty-
eighth aspects, wherein a coat formed by coating, spraying,
printing, ejecting or transferring a metal colloid, which is
obtained by dispersing metal colloidal particles containing
Au colloidal particles as a main component and also


containing 0.1 to 10% metal particles having an average
particle size of 1 to 10 nm, in addition to the Au colloidal
particles, in a dispersion medium, and removing the
dispersion medium from the metal colloid, shows a pink gold
color tone.
The sixtieth aspect of the present invention provides a
transfer sheet wherein metal colloidal particles comprise
metal particles and a protective agent coordination-modified
on the surface of the particles, the protective agent having
a carbon skeleton containing nitrogen in the molecule, and
having a structure of being coordination-modified on the
surface of metal particles using nitrogen or an atomic group
including nitrogen as an anchor, and the protective agent
contains one, or two or more functional groups selected from
the group consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure, the metal
colloid-containing coat formed article having a metal
colloid-containing coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid which is obtained by
dispersing in either or both of an aqueous dispersion medium
and a nonaqueous dispersion medium in a predetermined
proportion while mixing, on a transfer substrate wherein
either of both of the surface and the back surface are
subjected to a release treatment, and removing the dispersion
medium from the metal colloid.


The sixty-first aspect of the present invention
provides the transfer sheet of the invention according to the
sixtieth, wherein the metal colloid-containing coat contains
one, or two or more kinds selected from the group consisting
of metal powder, metal foil, fine metal particles, brightener,
lame agent, cut pieces of colored paper, natural gems and
artificial gems.
The sixty-second aspect of the present invention
provides the transfer sheet of the invention according to the
sixty-first aspect, wherein the metal used in the metal
powder, metal foil or fine metal particles is Au.
The sixty-third aspect of the present invention
provides the transfer sheet of the invention according to any
one of the sixtieth to sixty-second aspects, wherein the
metal particles constituting the metal colloidal particles
are made of Au and have an average particle size within a
range from 1 to 60 nm.
The sixty-fourth aspect of the present invention
provides the transfer sheet of the invention according to any
one of the sixtieth to sixty-third aspects, wherein a coat
formed by coating, spraying, printing, ejecting or
transferring a metal colloid, which is obtained by dispersing
metal colloidal particles containing Au colloidal particles
as a main component and also containing 0.1 to 10% metal
particles having an average particle size of 1 to 10 nm, in


addition to the Au colloidal particles, in a dispersion
medium, and removing the dispersion medium from the metal
colloid, shows a pink gold color tone.
The sixty-fifth aspect of the present invention
provides a metal colloid-containing coat formed article
comprising a transfer film transferred from the transfer
sheet of any one of the sixtieth to six fourth aspects.
The sixty-sixth aspect of the present invention
provides an invention according to the sixty-fifth aspect,
wherein the base material is jewelry and the jewelry is made
of a noble metal clay.
The sixty-seventh aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the sixty-fifth or sixty-sixth
aspect, further comprising one, two or more kinds selected
from the group consisting of metal powder, metal foil, fine
metal particles, brightener, lame agent, cut pieces of
colored paper, natural gems and artificial gems.
The sixty-eighth aspect of the present invention
provides the metal colloid-containing coat formed article of
the invention according to the sixty-seventh aspect, wherein
the metal used in the metal powder, metal foil or fine metal
particles is Au.
The sixty-ninth aspect of the present invention
provides a base material with a conductive film, having


resistivity of 1 × 103 Ω.cm or less wherein metal colloidal
particles comprise metal particles and a protective agent
coordination-modified on the surface of the particles, the
protective agent having a carbon skeleton containing nitrogen
in the molecule, and having a structure of being
coordination-modified on the surface of metal particles using
nitrogen or an atomic group including nitrogen as an anchor,
and he protective agent contains one, or two or more
functional groups selected from the group consisting of
alkoxysilyl group, silanol group and hydroxyalkyl group in a
molecular structure, the base material with a conductive film
being obtained by coating, spraying, printing, ejecting or
transferring a metal colloid which is obtained by dispersing
in either or both of an aqueous dispersion medium and a
nonaqueous dispersion medium in a predetermined proportion
while mixing, on a base material, and maintaining the base
material with the metal colloid in a predetermined atmosphere
at a temperature of 15 to 450°C for 1 to 60 minutes.
The seventieth aspect of the present invention provides
the base material with a conductive film of the invention
according to the sixty-fifth to sixty-sixth aspect, wherein
the metal particles constituting the metal colloidal
particles are made of Au and have an average particle size
within a range from 1 to 60 nm.
The seventy-first aspect of the present invention


provides the base material with a conductive film of the
invention according to the sixty-ninth or seventieth aspect,
wherein a coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained
by dispersing metal colloidal particles containing Au
colloidal particles as a main component and also containing
0.1 to 10% metal particles having an average particle size of
1 to 10 nm, in addition to the Au colloidal particles, in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a pink gold color tone.
The seventy-second aspect of the present invention
provides a pen, a brush-pencil, a cartridge for pen and a
disposable ampul wherein metal colloidal particles comprise
metal particles and a protective agent coordination-modified
on the surface of the particles, the protective agent having
a carbon skeleton containing nitrogen in the molecule, and
having a structure of being coordination-modified on the
surface of metal particles using nitrogen or an atomic group
including nitrogen as an anchor, and the protective agent
contains one, or two or more functional groups selected from
the group consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure, the pen, the
brush-pencil, the cartridge for pen and the disposable ampul
being filled with a metal colloid as an ink obtained by
dispersing in either or both of an aqueous dispersion medium


and a nonaqueous dispersion medium in a predetermined
proportion while mixing.
The seventy-third aspect of the present invention
provides the pen, the brush-pencil, the cartridge for pen and
the disposable ampul of the invention according to the
seventy-second aspect, wherein the metal particles
constituting the metal colloidal particles are made of Au and
have an average particle size within a range from 1 to 60 nm.
The seventy-fourth aspect of the present invention
provides the pen, the brush-pencil, the cartridge for pen and
the disposable ampul of the invention according to the sixty-
second or sixty-third aspect, wherein a coat formed by
coating, spraying, printing, ejecting or transferring a metal
colloid, which is obtained by dispersing metal colloidal
particles containing Au colloidal particles as a main
component and also containing 0.1 to 10% metal particles
having an average particle size of 1 to 10 nm, in addition to
the Au colloidal particles, in a dispersion medium, and
removing the dispersion medium from the metal colloid, shows
a pink gold color tone.
The seventy-fifth aspect of the present invention
provides a stamp pad and a seal impression pad wherein metal
colloidal particles comprise metal particles and a protective
agent coordination-modified on the surface of the particles,
the protective agent having a carbon skeleton containing


nitrogen in the molecule, and having a structure of being
coordination-modified on the surface of metal particles using
nitrogen or an atomic group including nitrogen as an anchor,
and the protective agent contains one, or two or more
functional groups selected from the group consisting of
alkoxysilyl group, silanol group and hydroxyalkyl group in a
molecular structure, the stamp pad and the seal impression
pad being impregnated with a metal colloid as an ink obtained
by dispersing in either or both of an aqueous dispersion
medium and a nonaqueous dispersion medium in a predetermined
proportion while mixing.
The seventy-sixth aspect of the present invention
provides a drawn material which is drawn by using an ink with
which the stamp pad or seal impression pad of the seventy-
fifth aspect is impregnated.
The seventy-seventh aspect of the present invention
provides a drawn material wherein metal colloidal particles
comprise metal particles and a protective agent coordination-
modified on the surface of the particles, the protective
agent having a carbon skeleton containing nitrogen in the
molecule, and having a structure of being coordination-
modified on the surface of metal particles using nitrogen or
an atomic group including nitrogen as an anchor, and the
protective agent contains one, or two or more functional
groups selected from the group consisting of alkoxysilyl


group, silanol group and hydroxyalkyl group in a molecular
structure, the drawn material being drawn by an ink jet
printer using, as an ink, a metal colloid obtained by
dispersing in either or both of an aqueous dispersion medium
and a nonaqueous dispersion medium in a predetermined
proportion while mixing.
The seventy-eighth aspect of the present invention
provides the drawn material of the invention according to the
seventy-seventh aspect, wherein the metal particles
constituting the metal colloidal particles are made of Au and
have an average particle size within a range from 1 to 60 ran.
The seventy-ninth aspect of the present invention
provides the drawn material of the invention according to the
seventy-seventh or seventy-eighth aspect, wherein a coat
formed by coating, spraying, printing, ejecting or
transferring a metal colloid, which is obtained by dispersing
metal colloidal particles containing Au colloidal particles
as a main component and also containing 0.1 to 10% metal
particles having an average particle size of 1 to 10 nm, in
addition to the Au colloidal particles, in a dispersion
medium, and removing the dispersion medium from the metal
colloid, shows a pink gold color tone.
EFFECTS OF THE INVENTION
The metal colloidal particles of the present invention


are characterized by metal colloidal particles capable of
forming a metal colloid by dispersing in either or both of an
aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing, comprising metal
particles and a protective agent coordination-modified on the
surface of the particles, the protective agent having a
carbon skeleton containing either or both of sulfur and
oxygen in the molecule, and having a structure of being
coordination-modified on the surface of metal particles using
an atom or an atomic group of either or both of sulfur and
oxygen as an anchor, wherein the protective agent contains
one, or two or more functional groups selected from the group
consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure. The metal
colloid of the present invention is characterized in that the
metal colloidal particles are dispersed in either or both of
an aqueous dispersion medium and a nonaqueous dispersion
medium in a predetermined proportion while mixing, or the
metal colloidal particles of the present invention are mixed
with a sol-gel solution in a predetermined proportion. Since
the protective agent is firmly bonded to the surface of metal
particles using an atom or an atomic group of either or both
of sulfur and oxygen as an anchor, and is preferably firmly
bonded to the surface of metal particles even in case of
using a nitrogen atom or an atomic group as an anchor, a


colloidal solution is extremely stable and a high
concentration metal colloid can be obtained. Also less
viscosity change and color tone change occur. Furthermore, a
thin film having large film strength can be formed.
Therefore, the thin film using the metal colloid of the
present invention is suited for used as optical materials
such as color filter and display panel. Also it is possible
to obtain a transfer sheet and a low-resistance base material
with a conductive film, each being made of the metal colloid
of the present invention. Furthermore, the metal colloidal
particles of the present invention is suited for use as a pen,
a brush-pencil, a cartridge for pen and a disposable ampul,
each containing the metal colloid of the present invention as
an ink; a stamp pad and a seal impression pad, each being
impregnated with the metal colloid of the present invention
as an ink; and an ink jet printer using the metal colloid of
the present invention as an ink.
In the metal colloidal particles of the present
invention, since the protective agent constituting the metal
colloidal particles is firmly bonded to the surface of metal
particles using a nitrogen atom or an atomic group as an
anchor, high stability is attained. The alkoxysilyl group,
the silanol group and the hydroxyalkyl group contained in the
molecular structure of the protective agent have high
reactivity and chemically bonded to all base materials.


Metal particles are spontaneously self-organized and cause
closest packing, and are condensed with a reactive functional
group. Therefore, it is considered that a coat obtained by
coating or spraying the metal colloid made of the metal
colloidal particles of the present invention has high
strength and is converted into an organic-inorganic hybrid
bulk between particles. When the metal particles
constituting the metal colloidal particles are composed of an
Au component as a main component and one, or two or more
metal components other than the Au component as an accessory
component, a coat, which is formed by coating, spraying,
printing, ejecting or transferring a metal colloid obtained
by dispersing the metal colloidal particles in a dispersion
medium, and removing the dispersion medium from the metal
colloid, shows metal color with color tone which is different
from that peculiar to an Au simple substance. By changing
the kind or content of metal constituting the accessory
component, it is possible to exhibit various gold-based color
tones.
The metal colloid of the present invention is
characterized in that the metal colloidal particles of the
present invention are dispersed in either or both of an
aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing. Since the
protective agent constituting the metal colloidal particles


is firmly bonded to the surface of metal particles using a
nitrogen atom or an atomic group as an anchor, a colloidal
solution is extremely stable and a high concentration metal
colloid can be obtained. Also less viscosity change and
color tone change occur. Furthermore, a thin film having
large film strength can be formed. Furthermore, the transfer
sheet comprising a metal colloid-containing coat formed using
the metal colloid of the present invention can form a
transfer film which shows various gold-based color tones.
Furthermore, it is suited for use as a pen, a brush-pencil, a
cartridge for pen and a disposable ampul, each containing the
metal colloid of the present invention as an ink; a stamp pad
and a seal impression pad, each being impregnated with the
metal colloid of the present invention as an ink; and an ink
jet printer using the metal colloid of the present invention
as an ink.
The metal colloid-containing coat formed article and
the transfer sheet of the present invention have a metal
specular glossy area with various color tones and also have a
metal colloid-containing coat wherein a coat having excellent
heat resistance is formed.
The base material with a conductive film of the present
invention has a metal specular glossy area with various color
tones and has excellent heat resistance, and also enable the
formation of a low-resistance conductive film.


Furthermore, the pen, the brush-pencil, the cartridge
for pen, the disposable ampul, the stamp pad and the seal
impression pad of the present invention are excellent in
quality-retaining property of the metal colloid filled or
impregnated. The drawn material obtained by using them has
color tone and metal gloss peculiar to metal.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic view showing metal colloidal
particles of the present invention.
Fig. 2 is a photograph wherein metal colloidal
particles of the present invention obtained in Synthesis
Example 1 are placed in a storage container.
Fig. 3 is a transmission electron micrograph of metal
colloidal particles of the present invention obtained in
Synthesis Example 1.
Fig. 4 is a graph showing viscosity change of metal
colloids of Example 1 and Comparative Example 1 in
Comparative Evaluation 1.
Fig. 5 is a graph showing permeability immediately
after the preparation of a metal colloid of Example 3.
Fig. 6 is a graph showing permeability after use under
thermal loading for 400 hours after the preparation of a
metal colloid of Example 3.
Fig. 7 is a photograph showing a Japanese paper wherein


characters are written on the surface using a metal colloid
of Example 4.
Fig. 8 is a photograph showing a glass cup wherein
patterns are drawn on the surface using a metal colloid of
Example 6.
Fig. 9 is a photograph of a coffee cup made of
porcelain wherein characters are written on the surface using
a metal colloid of Example 6.
Fig. 10 A is a photograph showing a plastic model, the
surface of which is coated with a metal colloid of Example 7.
Fig. 10 B is a photograph showing a picture frame, the
frame portion of which is coated with a metal colloid of
Example 7.
Fig. 11 A is a photograph showing a ring made of a
silver clay, the surface of which is coated with a metal
colloid of Example 8
Fig. 11 B is a photograph showing an earring, the
surface of which is coated with a metal colloid of Example 8.
Fig. 11 C is a photograph showing a broach, the surface
of which is coated with a metal colloid of Example 8.
Fig. 12 is a photograph showing a method of coating a
metal colloid using a writing brush for manicure of Example 9.
Fig. 13 is a photograph showing finger nails wherein a
metal colloid-containing coat is formed on the surface using
the coating method of Fig. 12.


Fig. 14 is a photograph showing a method of spraying a
metal colloid using an airbrush for manicure of Example 10.
Fig. 15 is a photograph showing finger nails wherein a
metal colloid-containing coat is formed on the surface using
the spraying method of Fig. 14.
Fig. 16 is a photograph showing artificial nails of
Example 15 wherein a metal colloid-containing coat showing a
pink gold color tone on the surface is formed.
Fig. 17 A is a photograph showing artificial nails of
Example 16 wherein a metal colloid-containing coat showing a
yellow gold color tone on the surface is formed.
Fig. 17 B is a photograph showing artificial nails of
Example 17 wherein a metal colloid-containing coat showing a
green gold color tone on the surface is formed.
Fig. 17 C is a photograph showing artificial nails of
Example 18 wherein a metal colloid-containing coat showing a
red gold color tone on the surface is formed.
Fig. 17D is a photograph showing artificial nails of
Example 19 wherein a metal colloid-containing coat showing a
pink gold color tone on the surface is formed.
Fig. 17E is a photograph showing artificial nails of
Example 20 wherein a metal colloid-containing coat showing a
white gold color tone on the surface is formed.
Fig. 18 A is a photograph showing artificial nails of
Example 22 wherein a metal colloid-containing coat and


natural gems of pearl and diamond are formed in combination
on the surface.
Fig. 18 B is a photograph showing artificial nails of
Example 23 wherein a metal colloid-containing coat, a gold
foil powder and natural gems of diamond and pink sapphire are
formed in combination on the surface.
Fig. 19 is a sectional view showing a transfer sheet
Example of 24.
Fig. 20 A is a sectional view showing a cartridge for
pen which is filled with a metal colloid of Example 38 as an
ink.
Fig. 20 B is a sectional view showing a pen connected
with a cartridge for pen of Example 38.
Fig. 21 is a sectional view showing a disposable ampul
of Example 39.
Fig. 22 is a photograph showing a stamp pad and a seal
impression pad which are made by impregnating with a metal
colloid of Example 40.
Fig. 23 is a photograph showing a skippet provided with
patterns using the stamp pad of Fig. 22.
Fig. 24 is a graph showing a paper provided with
patterns using the seal impression pad of Fig. 22.
Fig. 25 is a photograph showing leather wallet, a
business card and a greeting card wherein a picture is drawn
by an ink jet printer apparatus using a metal colloid of


Example 41 as an ink.
Fig. 26 A is a photograph showing a memorial card
wherein characters are written on the surface using a metal
colloid.
Fig. 26 B is a photograph of a doll, the surface of
which is coated with a metal colloid.
Fig. 27 A is a photograph of a ring, the surface of
which is coated with a metal colloid.
Fig. 27 B is a photograph showing a pierced earring,
the surface of which is coated with a metal colloid.
Fig. 27 C is a photograph showing a watch, the surface
of which is coated with a metal colloid.
Fig. 28 is a photograph showing finger nails wherein
metal colloid-containing coat is formed on the surface by the
coating method of Fig. 12.
Fig. 29 is a photograph showing finger nails wherein a
metal colloid-containing coat is formed by the spraying
method of Fig. 14.
Fig. 30 is a photograph showing artificial nails of
Example 77 wherein a metal colloid-containing coat, a lame
agent and natural gems of diamond and pink sapphire are
formed in combination on the surface.
Fig. 31 is a photograph showing artificial nails of
Example 78 wherein a metal colloid-containing coat and
natural gems of ruby, diamond and sapphire are formed in

combination on the surface.
Fig. 32 A is a photograph showing a stamp pad and seal
impression pad which are made by impregnating with a metal
colloid of Example 94.
Fig. 32 B is a photograph showing a memorial card
provided with patterns using seal impression pad of Fig* 32 A.
Fig. 33 A is a photograph showing s greeting card
wherein a metal colloid-containing coat is formed by drawing
a picture using an ink jet printer apparatus of Example 95.
Fig. 33 B is a photograph showing a mortuary tablet
wherein metal colloid-containing coat is formed by drawing a
picture using an ink jet printer apparatus of Example 95.
[Brief Description of the Reference Numerals]
1: Transfer sheet
2: Base material
3: Transfer layer
4: Surface protective layer
5: Metal colloid-containing coat layer
6: Adhesive layer
10: Cartridge for pen
11: Tubular body
12: Metal colloid
13: Lid portion
14: Plug
20: Pen

21: Upper shaft barrel
22: Lower shaft barrel
23: Connection portion
24: Core portion
26: Tip
30: Dispensable ampul
31: Tubular body
32: Lid portion
33: Cut portion
34: Metal colloid
BEST MODE FOR CARRYING OUT THE INVENTION
The first best mode for carrying out the present
invention will now be described.
The metal colloidal particles of the present invention
are characterized by metal colloidal particles capable of
forming a metal colloid by dispersing in either or both of an
aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing, comprising metal
particles and a protective agent coordination-modified on the
surface of the particles, the protective agent having a
carbon skeleton containing either or both of sulfur and
oxygen in the molecule, and having a structure of being
coordination-modified on the surface of metal particles using
an atom or an atomic group of either or both of sulfur and


oxygen as an anchor, wherein the protective agent contains
one, or two or more functional groups selected from the group
consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure. Since the
protective agent is firmly bonded to the surface of metal
particles using an atom or an atomic group of either or both
of sulfur and oxygen as an anchor, high stability is attained.
The alkoxysilyl group, the silanol group and the hydroxyalkyl
group contained in the molecular structure of the protective
agent have high reactivity and chemically bonded to all base
materials. Metal particles are spontaneously self-organized
and cause closest packing, and are condensed with a reactive
functional group. Therefore, it is considered that a coat
obtained by coating or spraying the metal colloid made of the
metal colloidal particles of the present invention has high
strength and is converted into an organic-inorganic hybrid
bulk between particles.
As shown in Fig. 1, since one end of the protective
agent is bonded to the surface of metal particles (Au
particles in Fig. 1) using a protective agent coordination-
modified site represented by X as an anchor, the protective
agent is firmly bonded to the surface of metal particles and
thus a metal colloidal solution having good stability is
obtained. Since the protective agent end site represented by
R located at the other end of the protective agent


constitutes the outermost surface of the colloid and this
protective agent end site is provided with a functional group
with high reactivity, adhesion with the base material is
excellent. The fact that the protective agent is bonded to
the surface of metal particles using the protective agent
coordination-modified site represented by X can be confirmed
by analytical means, for example, NMR, GPC, TG-DTA, FT-IR,
XPS, TOF-SIMS, Small Angle X-ray Scattering (SAXS), visible
ultraviolet spectroscopy, Surface Enhanced Raman Scattering
(SERS) or X-ray Absorption Fine Structure (XAFS). Using the
above analytical means, it is possible to confirm by what
element or atomic group the protective agent is anchored.
In the metal colloidal particles of the present
invention, it is preferred that the protective agent further
contains nitrogen and has a structure of being coordination-
modified on the surface of metal particles using nitrogen or
an atomic group including nitrogen as an anchor.
Consequently, a coordination-modifying force increases and
the number of points at witch the protective agent is
coordinated increases, and thus stability with time of the
metal colloid is extremely improved.
Oxygen contained in the protective agent is derived
from at least one selected from the group consisting of
carbonyl group, carboxyl group, aldehyde group, amide group
and sulfonyl group. The atomic group including nitrogen in


the protective agent include at least one selected from the
group consisting of amino group, amide atomic group and imide
atomic group.
The method of producing metal colloidal particles of
the present invention is not limited. The method may be a
method by which the above bonded structure to metal colloidal
particles is obtained. An example of a specific method is as
follows. In a nonaqueous system, an alkoxysilane having a
thiol group is mixed with a metal compound and the metal
compound is reduced in the presence of a reducing agent to
obtain metal colloidal particles wherein the protective agent
comprising the alkoxysilane is bonded to the surface of metal
particles using the alkoxysilane having a thiol group as an
anchor.
Metal colloidal particles are produced by the reductive
reaction of the nonaqueous system in the presence of the
alkoxysilane having a thiol group. The nonaqueous system
means that metal reduction of the metal compound is conducted
in an organic solution of a thio group-containing
alkoxysilane or an alcohol without conducting metal reduction
in an aqueous solution of the metal compound. In the method
of bonding the thio group-containing alkoxysilane after
producing metal colloidal particles by the reductive reaction
in the aqueous solution like a conventional method, since the
alkoxysilane is exposed in water, the substitution reaction


may not proceed by the influence of the hydrolysis. If the
substitution reaction proceeds, stability is impaired by the
following hydrolysis and thus it is difficult to obtain metal
colloidal particles of the present invention.
Metal colloidal particles wherein either or both of an
alkoxysilyl group and a hydroxyalkyl group are chelete-
coordinated by using a chelating agent such as (3 diketon have
the effect of delaying the hydrolysis reaction and stability
is enhanced furthermore.
The alkoxysilane preferably has one or two amino groups
and also has an organic chain (-CH2-)n wherein n is 1 to 3.
When the alkoxysilane has three or more amino groups, the
organic chain is lengthened. As a result, not only color
stability deteriorates after firing, but also it becomes
difficult to synthesize and it is expensive. When n of the
organic chain is 3 or more, the organic chain is lengthened
and stability deteriorates.
Specific examples of the alkoxysilane having an amino
group used in the present invention include γ-
aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-
β (aminoethyl) γ-aminopropyltrimethoxysilane and N-
β (aminoethyl) γ-aminopropyltriethoxysilane. A molar ratio of
amount of these protective agents (amino group-containing
alkoxysilane) to the amount of metal may be from 2 to 40.


Examples of the metal of metal particles include one,
or two or more kinds selected from the group consisting of Au,
Ag, Pt, Cu, Pd, Ni, Zn, Ru, Rh and Ir. As the metal compound
used to produce these metal particles, for example, there can
be used metal salts such as chlorauric acid, gold potassium
cyanide, silver chloride, silver nitride, silver sulfide,
silver cyanide, chloroplatinic acid, tetrachlorohexaamine
platinum, palladium nitrate, palladium chloride, chloroiridic
acid, iridium chloride, ruthenium chloride, ruthenium nitrate,
rhodium chloride, rhodium nitrate, nickel sulfate, nickel
chloride, copper acetate and zinc chloride.
As the reducing agent, for example, there can be used
sodium borohydride, trimethylamineborane, dimethylamineborane,
tertiary butylamineborane, secondary amine, tertiary
aminehypophosphite, glycerin, alcohol, hydrogen peroxide,
hydrazine, hydrazine sulfate, aqueous formaldehyde solution,
tartrate, glucose, sodium N-N-diethylglycine, sodium sulfite,
sulfurous acid gas and ferrous sulfate.
The average particle size of metal particles
constituting metal colloidal particles is within a range from
1 to 100 nm, and preferably from 1 to 80 nm. When the metal
particles constituting metal colloidal particles contain Au
as a main component, the average particle size of Au
particles is preferably within a range from 1 to 60 nm. The
metal colloidal particles are granular particles having a


spherical, multiangular or ameboid shape.
In the metal colloidal particles of the present
invention, since the protective agent is bonded to the
surface of metal particles using an atom or an atomic group
of either or both of sulfur and oxygen as an anchor, the
metal colloidal solution is stable. For example, as shown in
Examples described hereinafter, the viscosity within 80 days
is from 25 to 30 cP and viscosity change (viscosity with time
within 80 days/initial viscosity) is 1.5 or less (1.25 to
1.50 in Examples) relative to the initial viscosity of 20 cP.
Furthermore, according to the present invention, a high
concentration metal colloid can be obtained. The
concentration of the metal colloid obtained by a conventional
method is approximately 1% by weight or less. In the present
invention, a metal colloid having a concentration of 10% by
weight or more can be obtained. Moreover, in such a high
concentration metal colloid, the colloidal solution is stable
and, as described above, viscosity change is small. For
example, in case of a metal colloid of gold, the gold
concentration is stable within a range from 0.1 to 95% by
weight and an organic solvent or water can be used as a
dispersion medium. The concentration of gold in the metal
colloid is more preferably within a range from 10 to 60% by
weight.
The metal colloid of the present invention and the thin


film obtained from the metal colloid have excellent heat
resistance. Specifically, change of color tone is 2% or less
even when maintained at a heating base temperature, for
example, from about 300 to 400°C for 400 hours, and color
tone scarcely changes. In Examples described hereinafter,
the metal colloid as a binder was added to a silica sol and a
film was formed on a glass substrate by spin coating, and
then permeability was measured at 300°C. As a result, change
was scarcely recognized.
The metal colloidal particles of the present invention
having a particle size of 0.1 to 60 nm are excellent in
stability. When the particle size is more than 60 nm, there
arises a phenomenon wherein sedimentation naturally occurs
due to dead weight. When the particle size is less than 0.1
nm, the color developing effect is lowered.
When the metal particles contain Au particles as a main
component, the metal colloidal particles of the present
invention show glossy color tone peculiar to Au particles. A
coat formed by coating or spraying a metal colloid, which is
obtained by dispersing metal colloidal particles containing
Au colloidal particles as a main component and also
containing 0.1 to 10% metal particles having an average
particle size of 1 to 10 nm, in addition to the Au colloidal
particles, in a dispersion medium, and removing the
dispersion medium from the metal colloid, shows a pink gold


color tone.
In the metal colloidal particles which are either or
both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, and metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag and Cu as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 40% and the content of Ag in impurities is from 40
to 60% by weight based on 100% by weight of impurities, a
coat formed by coating or spraying a metal colloid, which is
obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a yellow gold color tone.
Although the metal colloidal particles show yellow gold
color tone, metal colloidal particles, which contain Au as a
main component and also contain metal particles made of an
alloy containing Ag and Cu as impurities, can also the same
yellow gold color tone. By using metal colloidal particles
obtained by mixing metal colloidal particles containing Au
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, with metal colloidal particles containing metal
particles made of the above alloy, the same yellow gold color

tone can be shown.
The above color tone can be identified by CIE 197 6
L*a*b* color space (light source for measurement C: color
temperature: 6774K). In case of yellow gold color tone of
the present invention, psychometric lightness value L* in CIE
1976 L*a*b* color space is from 25 to 99, chromaticness
indices value a* and value b* are from +0.1 to +10 and from
+20 to +60, respectively. CIE 1976 L*a*b* color space refers
to color space defined by Commission Internationale de
l'Eclairage (CIE) on 1976 so that a fixed distance in the
color system has the difference, which is perceptually
equirate, within any color range by converting CIE XYZ color
system. Sychometric lightness value L*, chromaticness
indices value a* and value b* are determined by the
rectangular coordinate system in the CIE 197 6 L*a*b* color
space and are represented by the following equations (1) to
(3) :

where X/X0, Y/Y0, and Z/Z0 > 0.008856, X, Y and Z each
represents tristimulus value of the object color, and X0, Y0,
and Z0 each represents a tristimulus value of a light source
for lighting the object color and Y0 is standardized to 100.
In the metal colloidal particles which are either or


both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, or metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag and Cu as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 4 0% and the content of Ag in impurities is 65% by
weight or more based on 100% by weight of impurities, a coat
formed by coating or spraying a metal colloid, which is
obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the coated or sprayed
dispersion medium from the metal colloid, shows a green gold
color tone. In the green gold color tone of the present
invention, the psychometric lightness value L* in the CIE
1976 L*a*b* color space is from 25 to 99, and chromaticness
indices value a* and value b* are from -0.1 to -40 and from
+0.1 to +60, respectively.
In the metal colloidal particles which are either or
both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles and Cu particles as impurities, in addition to Au
particles, or metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Ag or Cu as impurities, wherein when the


content of impurities in the metal colloidal particles is
from 5 to 40% and the content of Ag in impurities is 30% by
weight or less based on 100% by weight of impurities, a coat
formed by coating or spraying a metal colloid, which is
obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the coated or sprayed
dispersion medium from the metal colloid, shows a red gold
color tone. In the red gold color tone of the present
invention, the psychometric lightness value L* in the CIE
1976 L*a*b* color space is from 25 to 99, and chromaticness
indices value a* and value b* are from +25 to +50 and from
+0.1 to +60, respectively.
In the metal colloidal particles which are either or
both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Ag
particles, Cu particles and Pd particles as impurities, in
addition to Au particles, or metal colloidal particles
containing metal particles made of an alloy containing Au as
a main component and also cntaining Ag, Cu and Pd as
impurities, wherein when the content of impurities in the
metal colloidal particles is from 5 to 40% and the Ag content
is 30% by weight or less based on 100% by weight of
impurities, a coat formed by coating or spraying a metal
colloid, which is obtained by dispersing the metal colloidal
particles in a dispersion medium, and removing the coated or


sprayed dispersion medium from the metal colloid, shows a
pink gold color tone. In the pink gold color tone of the
present invention, the psychometric lightness value L* in the
CIE 1976 L*a*b* color space is from 25 to 99, and
chromaticness indices value a* and value b* are from +10 to
+25 and from +0.1 to +60, respectively.
In the metal colloidal particles which are either or
both of metal colloidal particles containing Au colloidal
particles as a main component and also containing Pd
particles as impurities, in addition to Au particles, or
metal colloidal particles containing metal particles made of
an alloy containing Au as a main component and also
containing Pd as impurities, wherein when the content of
impurities in the metal colloidal particles is from 5 to 40%,
a coat formed by coating or spraying a metal colloid, which
is obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the coated or sprayed
dispersion medium from the metal colloid, shows a white gold
color tone. In the white gold color tone of the present
invention, the psychometric lightness value L* in the CIE
1976 L*a*b* color space is from 25 to 99, and chromaticness
indices value a* and value b* are from +0.1 to +10 and from
+0.1 to +20, respectively.
The metal colloid of the present invention is
characterized in that the above metal colloidal particles of


the present invention are dispersed in an aqueous or
nonaqueous solvent in a predetermined proportion while mixing,
or the metal colloidal particles of the present invention are
mixed with a sol-gel solution in a predetermined proportion.
The solvent may be aqueous or nonaqueous and the mixing
proportion can also be optionally adjusted. As the sol-gel
solution, for example, there can be used a solution for
forming at least one compound selected from the group
consisting of silica, titania, zirconia, alumina, tantalum
oxide and niobium oxide. By using these binders, the metal
can be uniformly dispersed in the binder and desired
characteristics can be effectively utilized. For example, in
the gold colloid, a red color filter utilizing absorption at
approximately 510 run can be realized by uniform dispersion.
When the binder has heat resistance, the effect is further
enhanced.
The metal colloid thin film of the present invention
can be formed using the metal colloid, but the method of
forming a film is not specifically limited. For example, the
thin film may be formed by coating, spraying, printing,
ejecting or transferring a solution, which is prepared by
dispersing the metal colloidal particles in an organic
solvent, or a solution prepared by mixing with a sol-gel
solution, on the surface of a base material, followed by
drying, or coating, spraying, printing, ejecting or


transferring the solution, followed by drying and further
firing. A metal colloid-containing coat formed article can
be obtained by coating, spraying, printing, ejecting or
transferring the metal colloid of the present invention on a
base material and removing the dispersion medium from the
metal colloid. Examples of the base material include
materials selected from the group consisting of glass,
plastic, metal, lumber, ceramic including tile, cement,
concrete, stone, fiber, paper and leather. Specific examples
of the base material include materials selected from the
group consisting of artificial nail, natural hair, artificial
hair, jewelries, plastic model, small bag for amulet case and
skippet, card for business card, memorial card, invitation
card and greeting card, colored paper, doll, deity and
Buddhist image, mortuary tablet, clothes, woven fabric and
picture frame. Deity and Buddhist image as used herein
refers to an image relating to any religion existing in the
world and is not limited to denomination of the religion.
When the base material is jewelry, this jewelry may be made
of a noble metal clay.
It is preferred that the metal colloid-containing coat
formed article of the present invention further contains one,
or two or more kinds selected from the group consisting of
metal powder, metal foil, fine metal particles, brightener,
lame agent, cut pieces of colored paper, natural gems and


artificial gems. When the coat contains the above metal
powder, decorativeness is enhanced. High sensuousness is
obtained by using Au as metal used in the metal powder, metal
foil or fine metal particles.
A transparent material comprising the metal colloid of
the present inventional thin film on the surface of the base
material may be used. For example, the metal colloid of the
present invention can be used as a metal pigment which is
used in applications such as calligraphy, ceramic art, glass
blowing, religion and family's Buddhist altar. Also the
metal colloid may be used after filling water based and oil
based ball-point pens with the metal colloid as an ink. The
metal colloid can also be used as a pen ink solution for
penwriting brush, fountain pen or marker, and a brush-pencil
and a cartridge for pen and disposable ampul. Particularly
in a pen filled with the metal colloid as the ink, it is not
necessary to transfer the ink to a container and it is very
advantageous to easily draw characters or patterns of the
metal colloid. The disposable ampul refers to a disposal
container made of a synthetic resin wherein a metal colloid
is sealed by filling a metal colloid and thermally bond-
contacting the upper of the container, sealing of the metal
colloid can be easily broken by rotating the lid portion in
the lateral direction and can be used as an ink comprising
the metal colloid after transferring to any container. When


a small amount of the metal colloid is stored using the
disposable ampul, since sealing of a required amount of the
metal colloid may be broken in case of using, expensive metal
colloid hardly deteriorates. Therefore, it is very effective.
The type and form of the pen, the cartridge for pen and the
disposable ampul are not limited. The metal colloid can also
be used as an ink for printing on a paper or a film. The
metal colloid can also be used as cosmetic decoration such as
nail art. Furthermore, it can also be used as a coating
material for forming a wiring material. Examples of the
printing method, include, but are not limited to lithographic
printing, gravure printing, offset printing, carton printing,
metal printing, form printing, duplex printing, over printing,
ink jet printing, screen printing, slit coating method,
dispenser method, spin coating method, spraying method,
dipping method and airbrushing method.
Since the thin film made of the metal colloid has color
tone and high transparency according to colloidal particles,
a transparent material with this thin film formed thereon can
be used as a color filter and a plasma display panel (PDP).
It can also be used as a transfer sheet with a metal
colloid-containing coat, which is formed by coating, spraying,
printing, ejecting or transferring the metal colloid of the
present invention on a transfer substrate wherein either or
both of the surface and the back surface are subjected to a


release treatment, and removing the dispersion medium from
the metal colloid. The transfer sheet of the present
invention preferably contains or two or more kinds selected
from the group consisting of metal powder, metal foil, fine
metal particles, brightener, lame agent, cut pieces of
colored paper, natural gems and artificial gems in the metal
colloid-containing coat. Decorativeness is enhanced by-
containing the metal powder in the coat. High sensuousness
is obtained by using Au as metal used in the metal powder,
metal foil or fine metal particles.
By transferring the metal colloid-containing coat of
the transfer sheet of the present invention to the surface of
the base material, a metal colloid-containing coat formed
article with a transfer film formed on the surface can be
obtained. Examples of the base material to which the coat is
transferred include materials selected from the group
consisting of glass, plastic, metal, lumber, ceramic
including tile, cement, concrete, stone, fiber, paper and
leather. Specific examples of the base material include
materials selected from the group consisting of artificial
nail, natural hair, artificial hair, jewelries, plastic model,
small bag for amulet case and skippet, card for business card
and memorial card, colored paper, doll, deity and Buddhist
image, mortuary tablet, clothes, woven fabric and picture
frame. Deity and Buddhist image as used herein refers to an


image relating to any religion existing in the world and is
not limited to denomination of the religion. When the base
material is jewelry, this jewelry may be made of a noble
metal clay. It is preferred that the base material to which
the coat is transferred further contains one, or two or more
kinds selected from the group consisting of metal powder,
metal foil, fine metal particles, brightener, lame agent, cut
pieces of colored paper, natural gems and artificial gems.
When the base material contains the above metal powder,
decorativeness is enhanced. High sensuousness is obtained by
using Au as metal used in the metal powder, metal foil or
fine metal particles.
Furthermore, a base material with a low-resistance
conductive film having resistivity of 1 × 10-3 Ω.cm or less
can be obtained by coating, spraying, printing, ejecting or
transferring the metal colloid of the present invention on a
base material and maintaining the base material with the
metal colloid in a predetermined atmosphere at a temperature
of 15 to 450°C for 1 to 60 minutes. Regarding the conditions
for forming a conductive film, it is preferred to maintain at
a temperature within a range from 15 to 350°C for 30 to 60
minutes. When the retention time is less than 30 minutes at
the temperature within the above range, desired conductivity
may not be exhibited because of insufficient decomposition or
elimination of the solvent or the protective agent. Even


when the retention time exceeds 60 minutes, resistivity of
the resulting conductive film does not change remarkably,
excess retention time is not preferred in view of
productivity and cost. When the temperature is within a
range from 350 to 450°C, it is preferable to maintain for 1
to 60 minutes. When the retention time is less than one
minute at the temperature within the above range, desired
conductivity may not be exhibited because of insufficient
decomposition or elimination of the solvent or the protective
agent, or insufficient sintering. Even when the retention
time exceeds 60 minutes, resistivity of the resulting
conductive film does not change remarkably, excess retention
time is not preferred in view of productivity and cost.
Also it is possible to produce a stamp pad and a seal
impression pad, impregnated with the metal colloid of the
present invention as an ink. Furthermore, it can also be
used as a drawn material drawn by using an ink with which the
stamp pad or seal impression pad is impregnated, or a drawn
material drawn by an ink jet printer using the metal colloid
of the present invention as an ink.
The second best mode for carrying out the present
invention will now be described.
The metal colloidal particles of the present invention
are characterized by metal colloidal particles capable of
forming a metal colloid by dispersing in either or both of an


aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing, comprising metal
particles and a protective agent coordination-modified on the
surface of the particles, the protective agent having a
carbon skeleton containing nitrogen in the molecule, and
having a structure of being coordination-modified on the
surface of metal particles using nitrogen or an atomic group
including nitrogen as an anchor, wherein the protective agent
contains one, or two or more functional groups selected from
the group consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure, and the metal
particles contain an Au component as a main component and
also contain one, or two or more metal components other than
the Au component as an accessory component.
Since the protective agent constituting metal colloidal
particles in the metal colloid, which constitutes the coat,
has a carbon skeleton containing nitrogen in the molecule,
and having a structure of being firmly coordination-modified
on the surface of metal particles using nitrogen or an atomic
group including nitrogen as an anchor, the metal colloid
obtained by the metal colloidal particles in a dispersion
medium shows extremely high stability. As a result, a high
concentration metal colloid can be obtained and also less
viscosity change and color tone change occur. The
alkoxysilyl group, the silanol group and the hydroxyalkyl


group contained in the molecular structure of the protective
agent have high reactivity and chemically bonded to all base
materials. Metal particles are spontaneously self-organized
and cause closest packing, and are condensed with a reactive
functional group. Therefore, it is considered that a metal
colloid-containing coat made of the metal colloid having
these characteristics of the present invention is converted
into an organic-inorganic hybrid bulk between particles, and
therefore has comparatively high film strength as compared
with a metal colloid-containing coat formed by using a metal
colloid comprising a nonreactive protective agent or a metal
colloid comprising a protective agent having low reactivity.
Since the protective agent is firmly bonded to the
surface of metal particles by bonding one end of the
protective agent is bonded to the surface of metal particles
using a protective agent coordination-modified site as an
anchor, metal colloid having good stability is obtained.
Since the protective agent end site located at the other end
of the protective agent constitutes the outermost surface of
the colloid and this protective agent end site is provided
with one, or two or more functional groups with high
reactivity selected from the group consisting of alkoxysilyl
group, silanol group and hydroxyalkyl group, adhesion with
the base material is excellent. The fact that the protective
agent is bonded to the surface of metal particles using the


protective agent coordination-modified site can be confirmed
by analytical means, for example, NMR, GPC, TG-DTA, FT-IR,
XPS, TOF-SIMS, SAXS, visible ultraviolet spectroscopy, SERS
or XAFS. Using the above analytical means, it is possible to
confirm by what element or atomic group the protective agent
is anchored.
In metal colloidal particles of the present invention,
when metal particles contain an Au component as a main
component and also contains one, or two or more metal
components different from the Au component as an accessory
component, a coat formed by using a metal colloid prepared by
dispersing the metal colloidal particles in a dispersion
medium shows metal color which is different from that
peculiar to an Au simple substance. By changing the kind or
proportion of the metal constituting the accessory component,
various gold-based color tones can be exhibited. In the
metal colloidal particles showing various gold-based color
tones, (1) metal particles may be made of an alloy containing
Au as a main component and also containing Ag and Cu as an
accessory component, or metal particles may be made of (2) a
mixture obtained by mixing Au particles as a main component
with Ag particles and Cu particles as an accessory component,
in addition to Au particles, or (3) metal particles may be
made by appropriately using (1) and (2) in combination.
In the metal colloidal particles of the present


invention, it is preferred that the accessory component
constituting metal particles contains at least both Ag
particles and Cu particles and the content of the accessory
component in metal particles is from 5 to 40% by weight, and
the content of Ag component in the accessory component is
from 40 to 60% by weight. A coat formed by using a metal
colloid obtained by dispersing the resulting metal colloidal
particles in a dispersion medium shows a yellow gold color
tone.
The above color tone can be identified by CIE 1976
L*a b* color space (light source for measurement C: color
temperature: 6774K). In case of the yellow gold color tone
shown with the above constitution, psychometric lightness
value L* in CIE 1976 L*a*b* color space is from 25 to 99,
chromaticness indices value a* and value b* are from +0.1 to
+10 and from +20 to +60, respectively.
In the metal colloidal particles of the present
invention, it is preferred that the accessory component
constituting metal particles contains at least both a Ag
particles and Cu particles and the content of the accessory
component in metal particles is from 5 to 4 0% by weight, and
the content of Ag component in the accessory component is 65%
by weight or more. A coat formed by using a metal colloid
obtained by dispersing the resulting metal colloidal
particles in a dispersion medium shows a green gold color


tone. In case of the green gold color tone shown with the
above constitution, psychometric lightness value L* in CIE
1976 L*a*b* color space is from 25 to 99, chromaticness
indices value a* and value b* are from -0.1 to -40 and from
+0.1 to +60, respectively.
In the metal colloidal particles of the present
invention, it is preferred that the accessory component
constituting metal particles contains at least both Ag
particles and Cu particles and the content of the accessory
component in metal particles is from 5 to 40% by weight, and
the content of Ag component in the accessory component is 30%
by weight or less. A coat formed by using a metal colloid
obtained by dispersing the resulting metal colloidal
particles in a dispersion medium shows a red gold color tone.
In case of the green gold color tone shown with the above
constitution, psychometric lightness value L* in CIE 1976
L*a*b* color space is from 25 to 99, chromaticness indices
value a* and value b* are from +25 to +50 and from +0.1 to
+60, respectively.
In the metal colloidal particles of the present
invention, it is preferred that the accessory component
constituting metal particles contains at least Ag particles,
Cu particles and Pd particles and the content of the
accessory component in metal particles is from 5 to 40% by
weight, and the content of Ag component in the accessory


component is 30% by weight or less. A coat formed by using a
metal colloid obtained by dispersing the resulting metal
colloidal particles in a dispersion medium shows a pink gold
color tone. In case of the pink gold color tone shown with
the above constitution, psychometric lightness value L* in
CIE 1976 L*a*b* color space is from 25 to 99, chromaticness
indices value a* and value b* are from +10 to +25 and from
+0.1 to +60, respectively.
In the metal colloidal particles of the present
invention, it is preferred that the accessory component
constituting metal particles contains at least Pd particles
and the content of the accessory component in metal particles
is from 5 to 40% by weight. A coat formed by using a metal
colloid obtained by dispersing the resulting metal colloidal
particles in a dispersion medium shows a white gold color
tone. In case of the pink gold color tone shown with the
above constitution, psychometric lightness value L* in CIE
1976 L*a*b* color space is from 25 to 99, chromaticness
indices value a* and value b* are from +0.1 to +10 and from
+0.1 to +20, respectively.
The method of producing metal colloidal particles of
the present invention is not limited. The method may be a
method by which the above bonded structure to metal colloidal
particles is obtained. An example of a specific method is as
follows. In a nonaqueous system, an alkoxysilane having an


amino group is mixed with a metal compound and the metal
compound is reduced in the presence of a reducing agent to
obtain metal colloidal particles wherein the protective agent
comprising the alkoxysilane is bonded to the surface of metal
particles using a nitrogen atomic group of the alkoxysilane
as an anchor. The nonaqueous system means that metal
reduction of the metal compound is conducted in an organic
solution of an amino group-containing alkoxysilane or an
alcohol without conducting metal reduction in an aqueous
solution of the metal compound. In the method of bonding the
amino group-containing alkoxysilane after producing metal
colloidal particles by the reductive reaction in the aqueous
solution like a conventional method, since the alkoxysilane
is exposed in water, the substitution reaction may not
proceed by the influence of the hydrolysis. If the
substitution reaction proceeds, stability is impaired by the
following hydrolysis and thus it is difficult to obtain metal
colloidal particles of the present invention. The atomic
group including nitrogen in the protective agent constituting
the metal colloidal particles of the present invention
includes at least one selected from the group consisting of
amino group, amide atomic group and imide atomic group.
Metal colloidal particles wherein an alkoxysilyl group
is chelete-coordinated by using a chelating agent such as (3
diketon have the effect of delaying the hydrolysis reaction


and stability is enhanced furthermore. The alkoxysilane
preferably has one or two amino groups and also has an
organic chain (-CH2-)n wherein n is 1 to 3. When the
alkoxysilane has three or more amino groups, the organic
chain is lengthened. As a result, not only color stability
deteriorates after firing, but also it becomes difficult to
synthesize and it is expensive. When n of the organic chain
is 3 or more, the organic chain is lengthened and stability
deteriorates. Specific examples of the alkoxysilane having
an amino group used in the present invention include y-
aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-
β (aminoethyl) γ-aminopropyltrimethoxysilane and N-
β (aminoethyl) γ-aminopropyltriethoxysilane. A molar ratio of
amount of these protective agents (amino group-containing
alkoxysilane) to the amount of metal may be from 2 to 40.
Examples of the metal of metal particles include one,
or two or more kinds selected from the group consisting of Au
as a main component, and Ag, Pt, Cu, Pd, Ni, Zn, Ru, Rh and
Ir as an accessory component. As the metal compound used to
produce these metal particles, for example, there can be used
metal salts such as chlorauric acid, gold potassium cyanide,
silver chloride, silver nitride, silver sulfide, silver
cyanide, chloroplatinic acid, tetrachlorohexaamine platinum,
palladium nitrate, palladium chloride, chloroiridic acid,


iridium chloride, ruthenium chloride, ruthenium nitrate,
rhodium chloride, rhodium nitrate, nickel sulfate, nickel
chloride, copper acetate and zinc chloride. As the reducing
agent, for example, there can be used sodium borohydride,
trimethylamineborane, dimethylamineborane, tertiary
butylamineborane, secondary amine, 2-methylaminoethanol,
diethamolamine, tertiary amine, diethylmethylamine, 2-
dimethylaminoethanol, methyldiethanolamine, tertiary
aminehypophosphite, glycerin, alcohol, hydrogen peroxide,
hydrazine, hydrazine sulfate, aqueous formaldehyde solution,
tartrate, glucose, sodium N-N-diethylglycine, sodium sulfite,
sulfurous acid gas and ferrous sulfate.
The average particle size of metal particles is within
a range from 1 to 100 nm, and preferably from 1 to 80 nm.
The average particle size of metal particles is particularly
preferably within a range from 1 to 60 nm. The metal
colloidal particles of the present invention are granular
particles having a spherical, multiangular or ameboid shape.
The metal particles having an average particle size of 0.1 to
60 nm are excellent in stability. When the particle size is
more than 60 nm, there arises a phenomenon wherein
sedimentation naturally occurs due to dead weight. When the
particle size is less than 0.1 nm, the color developing
effect is lowered.
The metal colloid of the present invention is


characterized in that the above metal colloidal particles of
the present invention are dispersed in either or both of an
aqueous dispersion medium and a nonaqueous dispersion medium
in a predetermined proportion while mixing. The solvent may
be aqueous or nonaqueous and the mixing proportion can also
be optionally adjusted. In the metal colloid of the present
invention, since the protective agent constituting metal
colloidal particles is firmly bonded to the surface of metal
particles using a nitrogen atom or an atomic group as an
anchor, a colloidal solution is extremely stable and a high
concentration metal colloid can be obtained. The
concentration of the metal colloid obtained by a conventional
method is approximately 1% by weight or less. In the present
invention, a metal colloid having a concentration of 10% by
weight or more can be obtained. Moreover, in such a high
concentration metal colloid, the colloidal solution is stable
and less viscosity occurs, as described above. Furthermore,
a thin film having larger film strength can be formed.
The metal colloid thin film of the present invention
can be formed by using the above metal colloid, but the film
forming method is not specifically limited. For example, a
thin film may be formed by coating a metal colloidal solution
prepared by dispersing the metal colloidal particles in an
organic solvent on the surface of a base material, followed
by drying, or coating the solution, followed by drying and


further firing. A metal colloid-containing coat showing
various gold-based color tones can be obtained by coating the
metal colloid of the present invention on the surface of the
base material.
It is preferred that he metal colloid-containing coat
formed article formed by coating the metal colloid of the
present invention on the surface of the base material and
removing the dispersion medium from the metal colloid further
contains one, or two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems. Decorativeness is enhanced by
containing the metal powder in or the surface of the coat.
When Au is used as metal used in the metal powder, metal foil
or fine metal particles, high sensuousness is obtained.
Examples of the method of coating the metal colloid on the
surface of the base material include, but are not limited to,
lithographic printing, gravure printing, offset printing,
carton printing, metal printing, form printing, duplex
printing, over printing, ink jet printing, screen printing,
slit coating method, dispenser method, spin coating method,
spraying method, dipping method and airbrushing method, and
all conventionally known methods can be used.
Examples of the base material used in the metal
colloid-containing coat formed article of the present


invention include materials such as glass, plastic, metal,
lumber, ceramic including tile, cement, concrete, stone,
fiber, paper and leather. Specific examples of the base
material include materials such as artificial nail, natural
hair, artificial hair, jewelries, plastic model, small bag
for amulet case and skippet, card fro business car, memorial
card, invitation card and greeting card, colored paper, doll,
deity and Buddhist image, mortuary tablet, clothes, woven
fabric and picture frame. Deity and Buddhist image as used
herein refers to an image relating to any religion existing
in the world and is not limited to denomination of the
religion. When the base material is jewelry, this jewelry
may be made of a noble metal clay.
The transfer sheet of the present invention will now be
described.
The transfer sheet of the present invention is
characterized by comprising a metal colloid-containing coat
formed by coating, spraying, printing, ejecting or
transferring the metal colloid of the present invention on a
transfer substrate wherein either of both of the surface and
the back surface are subjected to a release treatment, and
removing the dispersion medium from the metal colloid.
Examples of the method of coating the metal colloid on the
surface of the transfer substrate include, but are not
limited to, lithographic printing, gravure printing, offset


printing, carton printing, metal printing, form printing,
duplex printing, over printing, ink jet printing, screen
printing, slit coating method, dispenser method, spin coating
method, spraying method, dipping method and airbrushing
method, and all conventionally known methods can be used. By
further comprising a surface protective layer made of an
acrylic resin between the transfer substrate and the metal
colloid-containing coat, the surface protective layer is
formed on the surface of the transfer film in case of
transferring. By further comprising an adhesive layer made
of a hot melt type resin on the surface of the metal colloid-
containing coat, adhesion between the transfer film and the
surface of the base material is improved in case of
transferring. In the transfer sheet of the present invention,
one, or two or more kinds selected from the group consisting
of metal powder, metal foil, fine metal particles, brightener,
lame agent, cut pieces of colored paper, natural gems and
artificial gems used in the metal colloid-containing coat
formed article of the present invention are preferably
contained in the metal colloid-containing coat.
Decorativeness is enhanced by containing the metal powder in
the coat. High sensuousness is obtained by using Au as metal
used in the metal powder, metal foil or fine metal particles
A metal colloid-containing coat formed article with a
transfer film formed on the surface can be obtained by


transferring the metal colloid-containing coat of the
transfer sheet of the present invention on the surface of the
base material. Examples of the base material on which the
coated is transferred include materials selected from the
group of materials consisting of glass, plastic, metal,
lumber, ceramic including tile, cement, concrete, stone,
fiber, paper and leather. Specific examples of the base
material include materials selected from the group consisting
of artificial nail, natural hair, artificial hair, jewelries,
plastic model, small bag for amulet case and skippet, card
for business card and memorial card, colored paper, doll,
deity and Buddhist image, mortuary tablet, clothes, woven
fabric and picture frame. Deity and Buddhist image as used
herein refers to an image relating to any religion existing
in the world and is not limited to denomination of the
religion. When the base material is jewelry, this jewelry
may be made of a noble metal clay. It is preferred that the
base material on which the coat is transferred further
contains one, or two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems. Decorativeness is enhanced by
containing the above metal powder in the base material. High
sensuousness is obtained by using Au as metal used in the
metal powder, metal foil or fine metal particles.


The pen, the brush-pencil, the cartridge for pen and
the disposable ampul of the present invention will now be
described.
The pen, the brush-pencil, the cartridge for pen and
the disposable ampul of the present invention is a pen, a
brush-pencil, a cartridge for pen and a disposable ampul,
which are characterized by being filled with the above metal
colloid of the present invention. In the metal colloidal
particles in the metal colloid used in the present invention,
since the protective agent is bonded to the surface of metal
particles using nitrogen or an atomic group including
nitrogen as an anchor, the metal colloidal solution is stable
and viscosity change to the initial viscosity is low, a pen,
a brush-pencil, a cartridge for pen and a disposable ampul,
which are excellent in quality-retaining property can be
obtained. With the constitution of the metal particles
constituting the metal colloid filled in the pen, characters
and patterns showing various gold-based color tones can be
drawn. The pen filled with the metal colloid as an ink is
very advantageous to easily draw characters and patterns made
of the metal colloid because the ink is easily transferred to
a container. It is possible to use as a water based ball-
point pen, an oil based ball-point pen and a brush-pencil.
The type and form of the pen are not limited.
An example of a cartridge for pen filled with the metal


colloid of the present invention as an ink, and a pen
connected with the cartridge for pen will now be described.
As shown in Fig. 20 A, there was prepared a cartridge
10 for pen which is composed of a tubular body 11 having a
closed lower portion, a lid portion 13 which is joined with
the upper portion of the tubular body 11 and is provided with
a spherical continuous hole at center, and a spherical plug
14 having a diameter, which is smaller than the shape of the
continuous hole and is enough to prevent from falling off
from the continuous hole, inserted into the continuous hole
of the lid portion 13, the tubular body 11 being filled with
the metal colloidal 12 of the present invention. The tubular
body 11 and the lid portion 13 are preferably made of a
synthetic resin, and the spherical plug 14 is preferably made
of metal. In the cartridge 10 for pen, when the spherical
plug 14 inserted loosely is pushed up into the cartridge in
the state where the lid portion 13 faces downward or
obliquely downward, a gap is formed between the lid portion
13 and the spherical plug 14 and the metal colloid is
discharged from the gap due to gravity.
As shown in Fig. 20 B, a pen 20 comprising the
cartridge 10 for pen incorporated thereinto is composed of a
cylindrical upper shaft barrel 21, a cylindrical lower shaft
barrel 22, the upper end of which can be connected to the
lower end of the upper shaft barrel 21, and a tip 26 which is


connected to the other end of the lower shaft barrel 22. The
inner wall of the lower shaft barrel 22 is provided with a
convex portion 23a which inserts the cartridge 10 for pen and
contacts with the lid portion 13, thereby to push up the
spherical plug 14 into the cartridge 10 for pen. In the
connection portion 23, there is provided a core portion 24
capable of being impregnated with the dilute metal colloidal
solution discharging from the cartridge 10 due to gravity
while protruding the other end of the lower shaft barrel 22
when the cartridge 10 for pen is connected to the connection
portion 23 and the spherical plug 14 is pushed up by the
connection portion 23. The tip 2 6 connected to the other end
of the lower shaft barrel 22 serves to eject the metal
colloid, with which the core portion 24 is impregnated, from
the tip. The upper shaft barrel 21, the cylindrical lower
shaft barrel 22 and the connection portion 23 are preferably
made of a synthetic resin. The core portion 24 is preferably
made of a synthetic resin having a structure wherein pores
capable of being impregnated with the metal colloid are
formed.
The cartridge 10 for pen was connected to the pen 20 by
contacting the lid portion 13 of the cartridge with the
connection portion 23 and pushing the connection portion 23
and the plug 14 into the cartridge 10 for pen. In that case,
the metal colloidal 12 filled into the cartridge 10 is


discharged from the gap between the lid portion 13 and the
spherical plug 14 and thus the core portion 24 is impregnated
with the dilute metal colloidal solution, which is supplied
to the tip 26 through the core portion 24. The pen
comprising the cartridge 10 for pen connected thereto is easy
to draw and was capable of drawing smoothly. This pen is
very advantageous to write desired characters and to draw
predetermined patterns on the desired base material, and the
characters and patterns drawn by the pen showed metal color
with various gold-based color tones and metal gloss and were
excellent in brightness. The type and form of the cartridge
for pen are not limited.
The disposable ampul refers to a disposal container
made of a synthetic resin wherein a metal colloid is sealed
by filling a metal colloid and thermally bond-contacting the
upper of the container, sealing of the metal colloid can be
easily broken by rotating the lid portion in the lateral
direction and can be used as an ink comprising the metal
colloid after transferring to any container. When a small
amount of the metal colloid is stored using the disposable
ampul, since sealing of a required amount of the metal
colloid may be broken in case of using, expensive metal
colloid hardly deteriorates.
An example of the disposable ampul will now be
described.


As shown in Fig. 21, a disposable ampul 30 is composed
of a tubular body 31 having a closed lower portion, a cut
portion 33 joined with the upper portion of the tubular body
31, and a lid portion 32. The cut portion 33 is provided
with a smaller width than that of the tubular body 31 and the
lid portion 32 so that it can be cut by a hand operation.
The tubular body 31, the lid portion 32 and the cut portion
33 are preferably made of a synthetic resin. The disposable
ampul 30 has a structure that a metal colloid 34 is sealed by
thermal contact bonding of the cut portion 33 and the lid
portion 32 after filling the tubular body 31 with a metal
colloid 34.
In the disposable ampul 30 thus obtained, the lid
portion 32 can be easily cut from the cut portion 33 through
the lever rule by laterally rotating the lid portion 32 and
the cut surface is communicated with the inside of the
tubular body 31. The metal colloid filled in the tubular
body 31 can be used after taking out from the communicated
portion. The type and form of the disposable ampul are not
limited.
The stamp pad and the seal impression pad of the
present invention will now be described.
The stamp pad and the seal impression pad of the
present invention are a stamp pad and a seal impression pad,
impregnated with the metal colloid of the present invention


as an ink. It is possible to use as the stamp pad and the
seal impression pad by sufficiently impregnating with the
metal colloid adjusted to a predetermined concentration. The
patterns made of the metal colloid formed by using the stamp
pad and the seal impression pad of the present invention show
gold-based color tone and metal gloss by the constitution of
the metal particles constituting the metal colloid.
Furthermore, it can also be used as a drawn material wherein
optional patterns are drawn by using an ink with which the
stamp pad or seal impression pad are impregnated.
Furthermore, the metal colloid-containing coat formed
article using the ink jet printer of the present invention
will be described.
The metal colloid-containing coat formed article using
the ink jet printer of the present invention is a metal
colloid-containing coat formed article which is characterized
by drawing through an ink jet printer using the metal colloid
of the present invention as an ink. The metal colloid-
containing coat formed article drawn by an ink jet printer
using the metal colloid of the present invention as an ink
show gold-based color tone and metal gloss by the
constitution of the metal particles constituting the metal
colloid. Specifically, first, a paper wherein patterns are
written on the surface by a commercially available black ink
using a seal impression and a stamp, a colored paper wherein


characters and patterns are drawn on the surface using a
black pen, and a colored paper wherein a hand print and a
foot print are formed using a black ink are prepared. Using
an image scanner, the surface of the paper and that of the
colored paper are scanned and the resulting image data are
inputted into a computer. By an ink jet printer using the
metal colloid of the present invention as an ink, image data
are printed on the paper and the colored paper based on the
inputted image data. Characters and patterns printed on the
paper and the colored paper using the metal colloid of the
present invention show the same shape as that of black
colored characters and patterns drawn and also show metal
gloss and color tone peculiar to metal and are excellent in
brightness.
In this embodiment, using the image scanner, the
surface of the paper and that of the colored paper were
scanned and the resulting image data were inputted into a
computer and then printed using the ink jet printer. Using
the image scanner, not only base papers such as paper and
colored paper, but also a photograph of these base papers,
and a print and a publication in which these patterns and
characters are described may be scanned and the resulting
image data may be inputted into a computer and directly
printed using an ink jet printer to obtain a metal colloid-
containing coat formed article.


The third best mode for carrying out the present
invention will now be described.
The metal colloid-containing coat formed article of the
present invention is characterized in that it is formed by
coating, spraying, printing, ejecting or transferring a metal
colloid on the surface of a base material and removing the
dispersion medium from the metal colloid. The metal colloid
used in the present invention is formed by dispersing metal
colloidal particles in either or both of an aqueous
dispersion medium or a nonaqueous dispersion medium in a
predetermined proportion. The metal colloidal particles of
the present invention comprise metal particles and a
protective agent coordination-modified on the surface of the
particles. The protective agent has a carbon skeleton
containing nitrogen in the molecule, and has a structure of
being coordination-modified on the surface of metal particles
using nitrogen or an atomic group including nitrogen as an
anchor. Furthermore, the protective agent contains one, or
two or more functional groups selected from the group
consisting of alkoxysilyl group, silanol group and
hydroxyalkyl group in a molecular structure.
Since the protective agent constituting metal colloidal
particles in the metal colloid, which constitutes the coat,
has a carbon skeleton containing nitrogen in the molecule,
and having a structure of being firmly coordination-modified

on the surface of metal particles using nitrogen or an atomic
group including nitrogen as an anchor, the metal colloid
obtained by the metal colloidal particles in a dispersion
medium shows extremely high stability. As a result, a high
concentration metal colloid can be obtained and also less
viscosity change and color tone change occur. The
alkoxysilyl group, the silanol group and the hydroxyalkyl
group contained in the molecular structure of the protective
agent have high reactivity and chemically bonded to all base
materials. Metal particles are spontaneously self-organized
and cause closest packing, and are condensed with a reactive
functional group. Therefore, it is considered that a metal
colloid-containing coat made of the metal colloid having
these characteristics of the present invention is converted
into an organic-inorganic hybrid bulk between particles, and
therefore has comparatively high film strength as compared
with a metal colloid-containing coat formed by using a metal
colloid comprising a nonreactive protective agent or a metal
colloid comprising a protective agent having low reactivity.
Since the protective agent is firmly bonded to the
surface of metal particles by bonding one end of the
protective agent is bonded to the surface of metal particles
using a protective agent coordination-modified site as an
anchor, metal colloid having good stability is obtained.
Since the protective agent end site located at the other end


of the protective agent constitutes the outermost surface of
the colloid and this protective agent end site is provided
with one, or two or more functional groups with high
reactivity selected from the group consisting of alkoxysilyl
group, silanol group and hydroxyalkyl group, adhesion with
the base material is excellent. The fact that the protective
agent is bonded to the surface of metal particles using the
protective agent coordination-modified site can be confirmed
by analytical means, for example, NMR, GPC, TG-DTA, FT-IR,
XPS, TOF-SIMS, SAXS, visible ultraviolet spectroscopy, SERS
or XAFS. Using the above analytical means, it is possible to
confirm by what element or atomic group the protective agent
is anchored.
Examples of base material used in the metal colloid-
containing coat formed article of the present invention
include metarials such as glass, plastic, metal, lumber,
ceramic including tile, cement, concrete, stone, fiber, paper
and leather. Specific examples of the base material include
artificial nail, natural hair, artificial hair, jewelries,
plastic model, small bag such as amulet case and skippet,
card such as business card, memorial card, invitation card
and greeting card, colored paper, doll, deity and Buddhist
image, mortuary tablet, clothes, woven fabric and picture
frame. Deity and Buddhist image as used herein refers to an
image relating to any religion existing in the world and is


not limited to denomination of the religion. When the base
material is jewelry, this jewelry may be made of a noble
metal clay.
It is preferred that the metal colloid-containing coat
formed article of the present invention further contains one,
or two or more kinds selected from the group consisting of
metal powder, metal foil, fine metal particles, brightener,
lame agent, cut pieces of colored paper, natural gems and
artificial gems. Decorativeness is enhanced by containing
the metal powder in or on the surface of the coat. High
sensuousness is obtained by using Au as metal used in the
metal powder, metal foil or fine metal particles. Examples
of the method of coating the metal colloid on the surface of
the base material include, but are not limited to,
lithographic printing, gravure printing, carton printing,
metal printing, form printing, duplex printing, over printing,
ink jet printing, screen printing, slit coating method,
dispenser method, spin coating method, spraying method,
dipping method and airbrushing method, and all conventionally
known methods can be used.
The atomic group including nitrogen in the protective
agent constituting the metal colloidal particles of the
present invention includes at least one selected from the
group consisting of amino group, amide atomic group and imide
atomic group. The method of producing metal colloidal


particles of the present invention is not limited. The
method may be a method by which the above bonded structure to
metal colloidal particles is obtained. An example of a
specific method is as follows. In a nonaqueous system, an
alkoxysilane having an amino group is mixed with a metal
compound and the metal compound is reduced in the presence of
a reducing agent to obtain metal colloidal particles wherein
the protective agent comprising the alkoxysilane is bonded to
the surface of metal particles using a nitrogen atomic group
of the alkoxysilane as an anchor. The nonaqueous system
means that metal reduction of the metal compound is conducted
in an organic solution of an amino group-containing
alkoxysilane or an alcohol without conducting metal reduction
in an aqueous solution of the metal compound. In the method
of bonding the amino group-containing alkoxysilane after
producing metal colloidal particles by the reductive reaction
in the aqueous solution like a conventional method, since the
alkoxysilane is exposed in water, the substitution reaction
may not proceed by the influence of the hydrolysis. If the
substitution reaction proceeds, stability is impaired by the
following hydrolysis and thus it is difficult to obtain metal
colloidal particles of the present invention.
Metal colloidal particles wherein an alkoxysilyl group
is chelete-coordinated by using a chelating agent such as (3
diketon have the effect of delaying the hydrolysis reaction


and stability is enhanced furthermore. The alkoxysilane
preferably has one or two amino groups and also has an
organic chain (-CH2-)n wherein n is 1 to 3. When the
alkoxysilane has three or more amino groups, the organic
chain is lengthened. As a result, not only color stability
deteriorates after firing, but also it becomes difficult to
synthesize and it is expensive. When n of the organic chain
is 3 or more, the organic chain is lengthened and stability
deteriorates. Specific examples of the alkoxysilane having
an amino group used in the present invention include γ-
aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-
β(aminoethyl) γ-aminopropyltrimethoxysilane and N-
β(aminoethyl)γ******-aminopropyltriethoxysilane. A molar ratio of
amount of these protective agents (amino group-containing
alkoxysilane) to the amount of metal may be from 2 to 40.
Examples of the metal of metal particles constituting
metal colloidal particles include one, or two or more kinds
selected from the group consisting of Au, Ag, Pt, Cu, Pd, Ni,
Zn, Ru, Rh and Ir. As the metal compound used to produce
these metal particles, there can be used metal salts such as
chlorauric acid, gold potassium dicyanide, silver chloride,
silver nitride, silver sulfide, silver cyanide,
chloroplatinic acid, tetrachlorohexaamine platinum, palladium
nitrate, palladium chloride, chloroiridic acid, iridium


chloride, ruthenium chloride, ruthenium nitrate, rhodium
chloride, rhodium nitrate, nickel sulfate, nickel chloride,
copper acetate and zinc chloride. As the reducing agent, for
example, there can be used sodium borohydride,
trimethylamineborane, dimethylamineborane, tertiary
butylamineborane, secondary amine, tertiary
aminehypophosphite, glycerin, alcohol, hydrogen peroxide,
hydrazine, hydrazine sulfate, aqueous formaldehyde solution,
tartrate, glucose, sodium N-N-diethylglycine, sodium sulfite,
sulfurous acid gas and ferrous sulfate.
The average particle size of the metal particles
constituting metal colloidal particles is within a range from
1 to 100 nm, and preferably from 1 to 80 nm. When the metal
particles constituting metal colloidal particles contain Au
as a main component, the average particle size of Au
particles is preferably within a range from 1 to 60 nm. The
metal colloidal particles are granular particles having a
spherical, multiangular or ameboid shape. The metal
colloidal particles having an average particle size of 0.1 to
60 nm are excellent in stability. When the particle size is
more than 60 nm, there arises a phenomenon wherein
sedimentation naturally occurs due to dead weight. When the
particle size is less than 0.1 nm, the color developing
effect is lowered.
According to the present invention, a high


concentration metal colloid can be obtained- The
concentration of the metal colloid obtained by a conventional
method is approximately 1% by weight or less. In the present
invention, a metal colloid having a concentration of 10% by
weight or more can be obtained. Moreover, in such a high
concentration metal colloid, the colloidal solution is stable
and, as described above, viscosity change is small. For
example, in case of a metal colloid of gold wherein the metal
colloidal particles contain Au, the Au concentration is
stable within a range from 0.1 to 95% by weight and an
organic solvent or water can be used as a dispersion medium.
The concentration of Au in the metal colloid is more
preferably within a range from 10 to 60% by weight. The
metal colloid of the present invention and the thin film
obtained from the metal colloid have excellent heat
resistance. Specifically, change of color tone is 2% or less
even when maintained at a heating base temperature, for
example, from about 300 to 400°C for 400 hours, and color
tone scarcely changes.
When the metal particles as a component of the metal
colloid constituting a film contain Au particles as a main
component, the metal colloidal particles of the present
invention show glossy color tone peculiar to Au particles. A
coat formed by formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained


by dispersing metal colloidal particles containing Au
colloidal particles as a main component and also containing
0.1 to 10% metal particles having an average particle size of
1 to 10 nm, in addition to the Au colloidal particles, in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a pink gold color tone.
The above color tone can be identified by CIE 197 6
L*a*b* color space (light source for measurement C: color
temperature: 6774K). In case of the pink gold color tone of
the present invention, psychometric lightness value L* in CIE
1976 L*a*b* color space is from 25 to 99, chromaticness
indices value a* and value b* are from +10 to +25 and from
+0.1 to +60, respectively.
The transfer sheet of the present invention will now be
described.
The transfer sheet of the present invention is
characterized by having a metal colloid-containing coat
formed by coating, spraying, printing, ejecting or
transferring a metal colloid used in the above metal colloid-
containing coat formed article on a transfer substrate
wherein either of both of the surface and the back surface
are subjected to a release treatment, and removing the
dispersion medium from the metal colloid. Examples of the
method of coating the metal colloid on the surface of the
transfer substrate include, but are not limited to,


lithographic printing, gravure printing, offset printing,
carton printing, metal printing, form printing, duplex
printing, over printing, ink jet printing, screen printing,
slit coating method, dispenser method, spin coating method,
spraying method, dipping method and airbrushing method, and
all conventionally known methods can be used. By further
comprising a surface protective layer made of an acrylic
resin between the transfer substrate and the metal colloid-
containing coat, the surface protective layer is formed on
the surface of the transfer film in case of transferring. By
further comprising an adhesive layer made of a hot melt type
resin on the surface of the metal colloid-containing coat,
adhesion between the transfer film and the surface of the
base material is improved in case of transferring. In the
transfer sheet of the present invention, one, or two or more
kinds selected from the group consisting of metal powder,
metal foil, fine metal particles, brightener, lame agent, cut
pieces of colored paper, natural gems and artificial gems
used in the metal colloid-containing coat formed article of
the present invention are preferably contained in the metal
colloid-containing coat. Decorativeness is enhanced by
containing the metal powder in the coat. High sensuousness
is obtained by using Au as metal used in the metal powder,
metal foil or fine metal particles
A metal colloid-containing coat formed article with a


transfer film formed on the surface can be obtained by
transferring the metal colloid-containing coat of the
transfer sheet of the present invention on the surface of the
base material. Examples of the base material on which the
coated is transferred include materials selected from the
group of materials consisting of glass, plastic, metal,
lumber, ceramic including tile, cement, concrete, stone,
fiber, paper and leather. Specific examples of the base
material include materials selected from the group consisting
of artificial nail, natural hair, artificial hair, jewelries,
plastic model, small bag for amulet case and skippet, card
for business card and memorial card, colored paper, doll,
deity and Buddhist image, mortuary tablet, clothes, woven
fabric and picture frame. Deity and Buddhist image as used
herein refers to an image relating to any religion existing
in the world and is not limited to denomination of the
religion. When the base material is jewelry, this jewelry
may be made of a noble metal clay. It is preferred that the
base material on which the coat is transferred further
contains one, or two or more kinds selected from the group
consisting of metal powder, metal foil, fine metal particles,
brightener, lame agent, cut pieces of colored paper, natural
gems and artificial gems. Decorativeness is enhanced by
containing the above metal powder in the base material. High
sensuousness is obtained by using Au as metal used in the


metal powder, metal foil or fine metal particles
The base material with a conductive film of the present
invention will now be described.
The base material with a conductive film of the present
invention is obtained by coating, spraying, printing,
ejecting or transferring a metal colloid used in the metal
colloid-containing coat formed article of the present
invention on a base material and maintaining the base
material with the metal colloid in a predetermined atmosphere
at a temperature of 15 to 450°C for 1 to 60 minutes. The
resulting conductive film is a low-resistance conductive film
having resistivity of 1 × 10-3 Ω.cm or less. The material of
the base material used in the base material with a conductive
film of the present invention is not specifically limited.
According to the method of forming the base material with a
conductive film, first, the metal colloid is coated on the
base material by coating, spraying, printing, ejecting or
transferring using a method such as lithographic printing,
gravure printing, offset printing, carton printing, metal
printing, form printing, duplex printing, over printing, ink
jet printing, screen printing, slit coating method, dispenser
method, spin coating method, spraying method, dipping method
or airbrushing method. Then, the base material with the
metal colloid is maintained in a predetermined atmosphere at
a temperature within a range from 15 to 450°C for 1 to 60


minutes. The solvent contained in the metal colloid is
removed by subjecting to the heat treatment to obtain a
conductive film having low resistance. The base material
with a conductive film of the present invention can be used
as a wiring material. Regarding the conditions for forming a
conductive film, it is preferred to maintain at a temperature
within a range from 15 to 350°C for 30 to 60 minutes. When
the retention time is less than 30 minutes at the temperature
within the above range, desired conductivity may not be
exhibited because of insufficient decomposition or
elimination of the solvent or the protective agent. Even
when the retention time exceeds 60 minutes, resistivity of
the resulting conductive film does not change remarkably,
excess retention time is not preferred in view of
productivity and cost. When the temperature is within a
range from 350 to 450°C, it is preferable to maintain for 1
to 60 minutes. When the retention time is less than one
minute at the temperature within the above range, desired
conductivity may not be exhibited because of insufficient
decomposition or elimination of the solvent or the protective
agent, or insufficient sintering. Even when the retention
time exceeds 60 minutes, resistivity of the resulting
conductive film does not change remarkably, excess retention
time is not preferred in view of productivity and cost.
The pen, the brush-pencil, the cartridge for pen and


the disposable ampul of the present invention will now be
described.
The pen, the brush-pencil, the cartridge for pen and
the disposable ampul of the present invention is a pen, a
brush-pencil, a cartridge for pen and a disposable ampul,
which are characterized by being filled with the above metal
colloid of the present invention. In the metal colloidal
particles in the metal colloid used in the present invention,
since the protective agent is bonded to the surface of metal
particles using nitrogen or an atomic group including
nitrogen as an anchor, the metal colloidal solution is stable
and viscosity change to the initial viscosity is low, a pen,
a brush-pencil, a cartridge for pen and a disposable ampul,
which are excellent in quality-retaining property can be
obtained. The pen filled with the metal colloid as an ink is
very advantageous to easily draw characters and patterns made
of the metal colloid because the ink is easily transferred to
a container. It is possible to use as a water based ball-
point pen, an oil based ball-point pen and a brush-pencil.
The type and form of the pen are not limited.
An example of a cartridge for pen filled with the metal
colloid of the present invention as an ink, and a pen
connected with the cartridge for pen will now be described.
As shown in Fig. 20 A, a cartridge 10 for pen is
composed of a tubular body 11 having a closed lower portion,


a lid portion 13 which is joined with the upper portion of
the tubular body 11 and is provided with a spherical
continuous hole at center, and a spherical plug 14 inserted
loosely into the continuous hole of the lid portion 13, the
tubular body 11 being filled with the metal colloidal 12 of
the present invention. The tubular body 11 and the lid
portion 13 are preferably made of a synthetic resin, and the
spherical plug 14 is preferably made of metal. In the
cartridge 10 for pen, when the spherical plug 14 inserted
loosely is pushed up into the cartridge in the state where
the lid portion 13 faces downward or obliquely downward, a
gap is formed between the lid portion 13 and the spherical
plug 14 and the metal colloid is discharged from the gap due
to gravity.
As shown in Fig. 20 B, a pen 20 comprising the
cartridge 10 for pen incorporated thereinto is composed of a
cylindrical upper shaft barrel 21, a cylindrical lower shaft
barrel 22, the upper end of which can be connected to the
lower end of the upper shaft barrel 21, and a tip 26 which is
connected to the other end of the lower shaft barrel 22. The
inner wall of the lower shaft barrel 22 is provided with a
connecting portion 23 which inserts the cartridge 10 for pen
and contacts with the lid portion 13, thereby to push up the
spherical plug 14 into the cartridge 10 for pen. In the
connection portion 23, there is provided a core portion 24


capable of being impregnated with the dilute metal colloidal
solution discharging from the cartridge 10 due to gravity
while protruding the other end of the lower shaft barrel 22
when the cartridge 10 for pen is connected to the connection
portion 23 and the spherical plug 14 is pushed up by the
connection portion 23. The tip 26 connected to the other end
of the lower shaft barrel 22 serves to eject the metal
colloid, with which the core portion 24 is impregnated, from
the tip. The upper shaft barrel 21, the cylindrical lower
shaft barrel 22 and the connection portion 23 are preferably
made of a synthetic resin. The core portion 24 is preferably
made of a synthetic resin having a structure wherein pores
capable of being impregnated with the metal colloid are
formed.
The cartridge 10 for pen was connected to the pen 20 by
contacting the lid portion 13 of the cartridge with the
connection portion 23 and pushing the connection portion 23
and the plug 14 into the cartridge 10 for pen. In that case,
the metal colloidal 12 filled into the cartridge 10 is
discharged from the gap between the lid portion 13 and the
spherical plug 14 and thus the core portion 24 is impregnated
with the dilute metal colloidal solution, which is supplied
to the tip 26 through the core portion 24. The pen
comprising the cartridge 10 for pen connected thereto is easy
to draw and was capable of drawing smoothly. This pen thus


obtained is very advantageous to write desired characters and
to draw predetermined patterns on the desired base material,
and the characters and patterns drawn by the pen showed metal
color with various gold-based color tones and metal gloss and
were excellent in brightness. The type and form of the
cartridge for pen are not limited.
The disposable ampul refers to a disposal container
made of a synthetic resin wherein a metal colloid is sealed
by filling a metal colloid and thermally bond-contacting the
upper of the container, sealing of the metal colloid can be
easily broken by rotating the lid portion in the lateral
direction and can be used as an ink comprising the metal
colloid after transferring to any container. When a small
amount of the metal colloid is stored using the disposable
ampul, since sealing of a required amount of the metal
colloid may be broken in case of using, expensive metal
colloid hardly deteriorates.
An example of the disposable ampul will now be
described.
As shown in Fig. 21, a disposable ampul 30 is composed
of a tubular body 31 having a closed lower portion, a cut
portion 33 joined with the upper portion of the tubular body
31, and a lid portion 32. The cut portion 33 is provided
with a smaller width than that of the tubular body 31 and the
lid portion 32 so that it can be cut by a hand operation.


The tubular body 31, the lid portion 32 and the cut portion
33 are preferably made of a synthetic resin. The disposable
ampul 30 has a structure that a metal colloid 34 is sealed by
thermal contact bonding of the cut portion 33 and the lid
portion 32 after filling the tubular body 31 with a metal
colloid 34.
In the disposable ampul 30 thus obtained, the lid
portion 32 can be easily cut from the cut portion 33 through
the lever rule by laterally rotating the lid portion 32 and
the cut surface is communicated with the inside of the
tubular body 31. The metal colloid filled in the tubular
body 31 can be used after taking out from the communicated
portion. The type and form of the disposable ampul are not
limited.
The stamp pad and the seal impression pad of the
present invention will now be described.
The stamp pad and the seal impression pad of the
present invention are a stamp pad and a seal impression pad,
impregnated with the metal colloid of the present invention
as an ink. It is possible to use as the stamp pad and the
seal impression pad by sufficiently impregnating with the
metal colloid adjusted to a predetermined concentration. The
patterns made of the metal colloid formed by using the stamp
pad and the seal impression pad of the present invention show
color tone and metal gloss peculiar to metal. Furthermore,


it can also be used as a drawn material wherein optional
patterns are drawn by using an ink with which the stamp pad
or seal impression pad are impregnated.
Furthermore, the drawn material using the ink jet
printer of the present invention will be described.
The drawn material using the ink jet printer of the
present invention is a drawn material which is characterized
by drawing through an ink jet printer using the metal colloid
of the present invention as an ink. The drawn material drawn
by an ink jet printer using the metal colloid of the present
invention as an ink show color tone and metal gloss peculiar
to gold. Specifically, first, a paper wherein patterns are
written on the surface by a commercially available black ink
using a seal impression and a stamp, a colored paper wherein
characters and patterns are drawn on the surface using a
black pen, and a colored paper wherein a hand print and a
foot print are formed using a black ink are prepared. Using
an image scanner, the surface of the paper and that of the
colored paper are scanned and the resulting image data are
inputted into a computer. By an ink jet printer using the
metal colloid of the present invention as an ink, image data
are printed on the paper and the colored paper based on the
inputted image data. Characters and patterns printed on the
paper and the colored paper using the metal colloid of the
present invention show the same shape as that of black


colored characters and patterns drawn and also show metal
gloss and color tone peculiar to metal and are excellent in
brightness.
In this embodiment, using the image scanner, the
surface of the paper and that of the colored paper were
scanned and the resulting image data were inputted into a
computer and then printed using the ink jet printer. Using
the image scanner, not only base papers such as paper and
colored paper, but also a photograph of these base papers,
and a print and a publication in which these patterns and
characters are described may be scanned and the resulting
image data may be inputted into a computer and directly
printed using an ink jet printer to obtain a drawn material.
EXAMPLES
Examples and Comparative Examples of the present
invention will now be described in detail.

Chlorauric acid was prepared as a metal salt, γ-
mercaptopropyltrimethoxysilane was prepared as a protective
agent precursor, and dimethylamineborane was prepared as a
reducing agent, respectively. First, an appropriate amount
of dimethylamineborane was added to 9.00 g of γ-
mercaptopropyltrimethoxysilane. A methanol solution prepared
by dissolving chlorauric acid so as to adjust the metal


concentration to 4.0% by weight was gradually added to
prepare a mixed solution. This mixed solution was prepared
by maintaining at 60°C while stirring the mixed solution
using a magnetic stirrer, and the reductive reaction was
conducted until metal colloidal particles are produced and
show a red color. After the completion of the reductive
reaction, the mixed solution was cooled to room temperature.
After cooling, the mixed solution was desalted by an
ultrafiltration method to obtain a metal colloid containing
water as a dispersion medium. The concentration of this
metal colloid was adjusted by adding an appropriate amount of
water to obtain a metal colloid having a concentration of 50%
by weight wherein metal colloidal particles are dispersed in
water.
A photograph wherein a metal colloid is placed in a
storage container is shown in Fig. 2, and a photograph of
metal colloidal particles is taken by a transmission electron
microscope (TEM) and the resulting photograph is shown in Fig.
3, respectively. Protective agent molecules constituting
metal colloidal particles in the resulting metal colloid were
subjected to TOF-SIMS analysis. By TOF-SIMS analysis,
cluster ions comprising Au and CS were predominantly detected.
As is apparent from the results of TOF-SIMS analysis and NMR
(C,H) analysis, the protective agent particles are
coordination-modified on the surface of Au particles by


sulfur.

Chlorauric acid was prepared as a metal salt, γ-
mercaptopropyltrimethoxysilane, 2-aminoethanol and
Acetylacetone were prepared as a protective agent precursor,
and dimethylamineborane was prepared as a reducing agent,
respectively. First, 3.00 g of γ-
mercaptopropyltrimethoxysilane, 5.00 g of 2-aminoethanol and
12.00 g of acetylacetone were mixed and an appropriate amount
of dimethylamineborane was added to the mixed solution. A
methanol solution prepared by dissolving chlorauric acid so
as to adjust the metal concentration to 4.0% by weight was
gradually added to prepare a mixed solution. This mixed
solution was prepared by maintaining at 60°C while stirring
the mixed solution using a magnetic stirrer, and the
reductive reaction was conducted until metal colloidal
particles are produced and show a red color. After the
completion of the reductive reaction, the mixed solution was
cooled to room temperature. After cooling, the mixed
solution was desalted by an ultrafiltration method to obtain
a metal colloid containing water as a dispersion medium. The
concentration of this metal colloid was adjusted by adding an
appropriate amount of water to obtain a metal colloid having
a concentration of 50% by weight wherein metal colloidal
particles are dispersed in water.


Protective agent molecules constituting metal colloidal
particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. By TOF-SIMS analysis, cluster ions
comprising Au and CS, Au and CN or Au and CO were
predominantly detected. As is apparent from the results of
TOF-SIMS analysis and NMR (C,H) analysis, the protective
agent particles are coordination-modified on the surface of
Au particles by sulfur, nitrogen and oxygen.

In the same manner as in Synthesis Example 1, except
that the metal salt, the protective agent precursor, the
reducing agent and the dispersion medium were replaced by the
compounds shown in the following Table 1 and Table 2, various
metal colloids were obtained. The compounds represented by
symbols (A1) to (H1) in the column of the kind of the
protective agent precursor in Table 1 and Table 2 are shown
in Table 3.
Also the protective agent molecular structure of metal
colloidal particles obtained in Synthesis Examples 3 to 27
was confirmed by analyzing using NMR, TOF-SIMS, FT-IR, SAXS,
visible ultraviolet spectroscopy, SERS and XAFS in
combination.













A metal colloid comprising a water medium having a
concentration of 50% by weight of Example 1 was produced from
the metal colloid produced in Synthesis Example 1.
Comparative Example 1>
First, chlorauric acid was prepared as a metal salt, y-
aminopropyltriethoxysilane was prepared as a protective agent
precursor, and dimethylamineborane was prepared as a reducing
agent.
A methanol solution prepared by prepared by dissolving
9.00 g of γ-aminopropyltriethoxysilane so as to adjust the
gold metal concentration to 4.0% by weight was added.
Subsequently, dimethylamineborane as a reducing agent was
added until metal colloidal particles and show a red color.
The reaction was conducted by maintaining at 60°C while
stirring the mixed solution using a magnetic stirrer. After
cooling, the mixed solution was desalted by an
ultrafiltration method to obtain a metal colloidal solution
comprising a water medium having a concentration of 50% by
weight.
Characters written on a Japanese paper using this metal
colloidal solution showed color tone and metal gloss peculiar
to gold, and metal was not peeled off even when the surface
of characters are rubbed with a cloth.



The metal colloids obtained in Example 1 and
Comparative Example 1 were divided into two samples, and then
one sample was stored at 25°C and the other sample was stored
at 40°C, respectively. Then, the change of viscosity of the
metal colloidal solution with time (storage days) was
examined. The results are shown in Fig. 4.
As is apparent from the results shown in Fig. 4, the
initial viscosity of the metal colloid of Comparative Example
1 was 5 cP when stored at 25°C, and the viscosity was 6 to
6.5 cP after storing for 60 days and thus the viscosity
changed by about 60%. When stored at 40°C, the viscosity
rapidly increased after about 12 days. After storing 60 days,
the viscosity increased to 12 cP and thus the viscosity
changed by 140%. As is apparent from these results, the
metal colloid of Comparative Example 1 is inferior in
stability with time at high temperature. On the other hand,
the initial viscosity of the metal colloid of Example 1 was 5
cP, and the viscosity within 60 days was 6 to 6.5 cP when
stored at 25 and 40°C and thus the viscosity changed by about
30% at most. As is apparent from these results, the metal
colloid of the present invention is excellent in stability
with time even when stored at high temperature.

Each of the metal colloids obtained in Synthesis
Example 1 and Synthesis Example 7 was mixed with a silica sol

to prepare a solution having a colloid concentration of 8% by
weight and the solution was coated to form a film, and then
the film was fired at 300°C to form a metal colloidal thin
film. Using a metal colloid of a comparative sample prepared
by using a protective agent shown in Table 4 below, the same
film was formed. Pencil hardness of these metal colloidal
thin films thus formed was measured. The results are shown
in Table 4.
As is apparent from the results shown in Table 4, all
metal colloid thin film of the present invention showed the
pencil hardness of 7H or more (no scratching occurs when the
pencil hardness is 6H), whereas, the metal colloidal thin
film as the comparative sample showed the pencil hardness of
1H or less (scratching occurs when the pencil hardness is 1H).
The hardness of the thin film of the present invention did
not change even when used under heating.


With respect to the metal colloidal solution of Example


2, permeability immediately after preparation and
permeability after 400 hours were measured. The results are
show in Fig. 5 (permeability immediately after preparation)
and Fig. 6 (permeability after 400 hours), respectively.
As is apparent from the results shown in Fig. 5 and Fig.
6, permeability immediately after preparation and
permeability after 400 hours hardly changed at a wavelength
within a range from 380 to 780 nm and the metal colloidal
solution of the present inventional is excellent in stability
with time.
With respect to these samples, chromaticity change was
also measured. The resulting measuring results are as
follows. In a chromaticity coordinate system, the value of
the x ordinate was 0.6420 at the initiation of the
measurement and the value of the x ordinate was 0.6408 after
400 hours, and thus the x coordinate changed by 0.19%. Also
the value of the y ordinate was 0.3428 at the initiation of
the measurement and the value of the y ordinate was 0.3443
after 400 hours, and thus the y coordinate changed by 0.44%.
As is apparent from these results, the change rate is very
small and thus these samples are excellent in stability with
time. With respect to other metal colloids, the same test
was conducted. As a result, the color tone of all metal
colloids changed by 2% or less.



The metal colloids having a concentration of 50% by
weight obtained in Synthesis Examples 1 to 27 were prepared
and each of the metal colloids having a concentration of 50%
by weight was diluted to prepare metal colloids each having a
concentration of 5% by weight, 10% by weight, 15% by weight,
20% by weight, 25% by weight, 30% by weight and 40% by weight,
respectively. Using each of metal colloids each having a
concentration of 5 to 50% by weight, predetermined characters
were written on a Japanese paper using a writing brush of
India ink, and then air-dried. A photograph of a Japanese
paper wherein characters are written on the surface using a
metal colloid having a concentration of 30% by weight is
shown in Fig. 7. In Fig. 7, a photograph of a paper made of
the material other than that of the Japanese paper wherein
characters are written on the surface is also shown.
In case of using the metal colloid having a
concentration of 30% by weight or more, the written
characters showed color tone and metal specular gloss
peculiar to metal, and metal was not peeled off even when the
surface of the characters are rubbed with a cloth. Also in
case of using the metal colloid having a concentration of 25%
by weight or less, the characters showed metal specular gloss,
but showed color tone which is seemed to be different from
the color tone peculiar to metal. After storing the metal
colloid at room temperature for 3 weeks, characters were


written again on the Japanese paper using the stored metal
colloid. Similar to the case before the storage, the written
characters showed color tone and metal specular gloss
peculiar to metal.

A solution was prepared by mixing each of the metal
colloids each having a concentration of 5 to 50% by weight
used in Example 4 with polyvinyl pyrrolidone, polyvinyl
butyral and polyvinyl alcohol in the proportion of 5 to 15%
based on the weight of metal. Using each of the metal
colloids thus prepared, predetermined characters were written
on a Japanese paper using a writing brush of India ink, and
then air-dried.
In case of using the metal colloid having a
concentration of 25% by weight or more, the written
characters showed color tone and metal specular gloss
peculiar to metal, and metal was not peeled off even when the
surface of the characters are rubbed with a cloth. Also in
case of using the metal colloid having a concentration of 20%
by weight or less, the characters showed metal specular gloss,
but showed color tone which is seemed to be different from
the color tone peculiar to metal. After storing the metal
colloid at room temperature for 3 weeks, characters were
written again on the Japanese paper using the stored metal
colloid. Similar to the case before the storage, the written


characters showed color tone and metal specular gloss
peculiar to metal.

First, a glass cup, a ceramic ware, a coffee cup made
of porcelain and a plastic plate made of polycarbonate were
prepared, respectively. Using the metal colloid prepared in
Example 4, predetermined patterns were drawn on the glass cup
and the ceramic, respectively. On the side of the coffee cup
made of a metporcelain and the surface of the plastic plate
made of polycarbonate, predetermined patterns were drawn,
respectively. A photograph of a glass cup wherein patterns
are drawn on the surface is shown in Fig. 8, and a photograph
of a coffee cup made of porcelain wherein characters are
written on the surface is shown in Fig. 9.
In case of using the metal colloid having a
concentration of 15% by weight or more, the patterns showed
color tone and metal specular gloss peculiar to metal, and
metal was not peeled off even when the surface of the
patterns is rubbed with a cloth. Also in case of using the
metal colloid having a concentration of 10% by weight or less,
the patterns showed metal specular gloss, but showed color
tone which is seemed to be different from the color tone
peculiar to metal. After storing the metal colloid at 40°C
for 3 weeks, characters were written again on the ceramic
ware, the coffee cup made of porcelain and the plastic plate


made of polycarbonate using the stored metal colloid.
Similar to the case before the storage, the pattern showed
color tone and metal specular gloss peculiar to metal

First, the metal colloid prepared in Example 4 was
coated on the surface of an artificial hair, an artificial
eyelash, a plastic model, an amulet case, a skippet, a
memorial card, an invitation card, a greeting card, a doll, a
Buddhist image, a mortuary tablet, a picture frame, clothes
and a woven fabric, respectively. The metal colloid was
coated on the artificial nail by a method of spraying using
an airbrush, while the metal colloid was coated on the entire
surface of the artificial eyelash, the plastic model, the
doll and the Buddhist image using a writing brush. Also
writing desired characters were written on the mortuary
tablet using a wiring brush and the metal colloid was coated
only on the frame portion of the picture frame using a
writing brush, and desired characters or patterns were drawn
on the memorial card, the invitation card, the greeting card,
the amulet case, the skippet, clothes and the woven fabric
using a writing brush. After coating, the dispersion medium
in the metal colloid was sufficiently removed by drying with
an air of a dryer to form a metal colloid-containing coat.
A photograph of a plastic model on which a metal
colloid-containing coat is formed is shown in Fig. 10 A and


the frame portion is shown in Fig. 10 B, respectively. As is
apparent from Fig. 10 A and Fig. 10 B, the metal colloid-
containing coat showed metal gloss and color tone peculiar to
metal and is excellent in brightness and design properties.

First, the metal colloid prepared in Example 4 was
coated on the following jewelries. A gold colloid was coated
on a ring, a ring made of a silver clay, a pierced earring,
an earring, a bracelet, a necklace, a key holder and an
ornamental hairpin using a writing brush, and the gold
colloid was coated on a watch, a hairpin, a broach and a
tiepin by a method f of spraying using an airbrush. A ring
made of a silver clay, an earring and a broach on which a
metal colloid-containing coat is formed are shown in Fig. 11
A, Fig. 11 B and Fig. 11 C, respectively.
As is apparent from Fig. 11 A, Fig. 11 B and Fig. 11 C,
the metal colloid-containing coat of jewelries showed metal
gloss and color tone peculiar to metal and is excellent in
brightness and design properties.

The metal colloid prepared in Example 4, a natural nail
and an artificial nail were prepared, respectively. By a
method of coating the metal colloid using a writing brush for
manicure shown in Fig. 12, the metal colloid was coated on
the surface of the natural nail and the artificial nail.


After coating, the dispersion medium in the metal colloid was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. A natural nail on which a
metal colloid-containing coat is formed by a coating method
is shown in Fig. 13.
As is apparent from Fig. 13, the metal colloid-
containing coat formed on the surface of the natural nail and
the artificial nail showed golden gloss and color tone
peculiar to gold and had a metal specular surface which is
excellent in smoothness.

Using a method of spraying a metal colloid using an
airbrush for manicure shown in Fig. 14, the metal colloid
prepared in Example 4 was sprayed over the surface of a
natural nail and the surface of an artificial nail. After
spraying, the dispersion medium in the metal colloid was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. A natural nail on which a
metal colloid-containing coat is formed by a spraying method
is shown in Fig. 15.
As is apparent from Fig. 15, the metal colloid-
containing coat formed on the surface of the natural nail and
the artificial nail showed golden gloss and color tone
peculiar to gold and had a metal specular surface which has
matted gloss and is excellent in smoothness, unlike the coat


of Example 9 formed by coating using the writing brush.

First, in the same manner as in Example 9, the metal
colloid prepared in Example 4 was coated on the surface of a
natural nail and the surface of an artificial nail using a
writing brush for manicure. After coating, the dispersion
medium in the metal colloid was sufficiently removed by
drying with an air of a dryer to form a metal colloid-
containing coat. Then, a top coating agent was coated on the
metal colloid-containing coat thus formed by a wet-on-wet
coating method and this top coating prevented the metal
colloid-containing coat from being peeled off with ease. The
metal colloid-containing coat formed on the surface of the
artificial nail showed golden gloss and color tone peculiar
to gold and had a metal specular surface which is excellent
in smoothness, similar to the case of the coat obtained in
Example 9.

First, an under coat layer was formed on the surface of
an artificial nail. In the same manner as in Example 9, the
metal colloid prepared in Example 4 was coated on the surface
of the under coat layer using a writing brush for manicure.
The metal colloid-containing coat formed on the surface of
the artificial nail showed golden gloss and color tone
peculiar to gold and had a metal specular surface which is


excellent in smoothness, similar to the case of the coats
obtained in Example 9 and Example 11.

First, an under coat layer was formed on the surface of
an artificial nail. In the same manner as in Example 9, the
metal colloid prepared in Example 4 was coated on the surface
of the under coat layer using a writing brush for manicure.
After coating, the dispersion medium in the metal colloid was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. Then, a top coating agent
was coated on the metal colloid-containing coat thus formed
by a wet-on-wet coating method and this top coating prevented
the metal colloid-containing coat from being peeled off with
ease. The metal colloid-containing coat formed on the
surface of the artificial nail showed golden gloss and color
tone peculiar to gold and had a metal specular surface which
is excellent in smoothness, similar to the case of the coats
obtained in Example 9, Example 11 and Example 12.

In the same manner as in Example 13, except that the
metal colloid was coated only at the tip portion of the nail
using an airbrush, a metal colloid-containing coat was formed
on the surface of an artificial nail. In the same manner as
in Example 13, except that desired patterns were drawn on the
surface of the nail using a writing brush for manicure in


case of coating the metal colloid, a metal colloid-containing
coat was formed on the surface of an artificial nail. The
artificial nail coated with the metal colloid only at the tip
portion using an airbrush and the artificial nail wherein
desired patterns are drawn on the surface of the nail using a
writing brush for manicure showed color tone peculiar to
metal and were excellent in design properties, similar to
Example 9 and Examples 11 to 13.

In the same manner as in Example 13, except that the
metal colloid prepared in Example 4 contains 0.5 to 3% of
fine metal particles having an average particle size of 1 to
10 nm, a metal colloid-containing coat was formed on the
surface of an artificial nail. The resulting artificial nail
on which the metal colloid-containing coat is formed is shown
in Fig. 16.
As is apparent from Fig. 16, the metal colloid-
containing coat formed on the surface of the artificial nail
shows a pink gold color tone and is excellent in design
properties.

In the same manner as in Example 13, except that the
metal colloid obtained in Synthesis Example 19 was used, a
metal colloid-containing coat was formed on the surface of an
artificial nail. The resulting artificial nail on which the


metal colloid-containing coat is formed is shown in Fig. 17 A.
As is apparent from Fig. 17 A, the coat formed on the
surface of the artificial nail has a metal specular surface
and is excellent in smoothness, and also shows a yellow gold
color tone and is excellent in design properties.

In the same manner as in Example 13, except that the
metal colloid obtained in Synthesis Example 20 was used, a
metal colloid-containing coat was formed on the surface of an
artificial nail. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 17 B.
As is apparent from Fig. 17 B, the coat formed on the
surface of the artificial nail has a metal specular surface
and is excellent in smoothness, and also shows a green gold
color tone and is excellent in design properties.

In the same manner as in Example 13, except that the
metal colloid obtained in Synthesis Example 21 was used, a
metal colloid-containing coat was formed on the surface of an
artificial nail. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 17 C.
As is apparent from Fig. 17 C, the coat formed on the
surface of the artificial nail has a metal specular surface
and is excellent in smoothness, and also shows a red gold
color tone and is excellent in design properties.



In the same manner as in Example 13, except that the
metal colloid obtained in Synthesis Example 22 was used, a
metal colloid-containing coat was formed on the surface of an
artificial nail. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 17D.
As is apparent from Fig. 17D, the coat formed on the
surface of the artificial nail has a metal specular surface
and is excellent in smoothness, and also shows a pink gold
color tone and is excellent in design properties.

In the same manner as in Example 13, except that the
metal colloid obtained in Synthesis Example 23 was used, a
metal colloid-containing coat was formed on the surface of an
artificial nail. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 17E.
As is apparent from Fig. 17E, the coat formed on the
surface of the artificial nail has a metal specular surface
and is excellent in smoothness, and also shows a white gold
color tone and is excellent in design properties.

First, an under coating agent was coated on the surface
of an artificial nail and then dried to form an under coat
layer. In the same manner as in Example 9, the metal colloid
prepared in Example 4 was coated on the surface of the under


coat layer using a writing brush for manicure. The
dispersion medium in the metal colloid was removed by drying
with an air of a dryer to form a metal colloid-containing
coat. Then, a top coating agent was coated on the metal
colloid-containing coat thus formed and, before completely
drying the top coating agent, a lame agent as a material was
scattered at desired points and diamond natural stones and
pink sapphire natural stones were set thereon, and then these
materials were fixed by pressing and immobilized by drying
the top coating agent with an air of a dryer. Immobilization
of these materials was enhanced by further coating the top
coating agent. Brightness and design properties were
improved by using the metal colloid-containing coat in
combination of the lame agent and natural gems of diamond and
pink sapphire.

First, the metal colloid prepared in Example 4 was
coated only at the tip portion of an artificial nail using a
writing brush for manicure. After coating, the dispersion
medium in the metal colloid was removed by drying with an air
of a dryer to form a metal colloid-containing coat. Then, a
top coating agent was coated on the metal colloid-containing
coat thus formed and, before completely drying the top
coating agent, pearl and diamond natural stones as materials
were arranged at the desired points, and then these materials


were fixed by pressing and immobilized by drying the top
coating agent with an air of a dryer. Immobilization of
these materials was enhanced by further coating the top
coating agent. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 18 A.
As is apparent from Fig. 18 A, brightness and design
properties were improved by using the metal colloid-
containing coat formed only at the tip portion of the nail in
combination with pearl and natural gems of diamond.

First, desired patterns were drawn on the surface of an
artificial nail with the metal colloid prepared in Example 4
using a writing brush for manicure. After drawing, the
dispersion medium in the metal colloid was removed by drying
with an air of a dryer to form a metal colloid-containing
coat. Then, a top coating agent was coated on the entire
surface of a nail and, before completely drying the top
coating agent, a gold foil powder and diamond and pink
sapphire natural stones as materials were set at the desired
points, and then these materials were fixed by pressing and
immobilized by drying the top coating agent with an air of a
dryer. Immobilization of these materials was enhanced by
further coating the top coating agent. The resulting
artificial nail on which the metal colloid-containing coat is
formed is shown in Fig. 18 B.


As is apparent from Fig. 18 B, brightness and design
properties were improved by using the metal colloid-
containing coat in combination with the gold foil powder and
natural gems of diamond and pink sapphire.

First, a coating solution of an acrylic resin was
coated on one surface of a base material 2 made of a
releasable synthetic paper to form a surface protective layer
4. Then, the gold colloid prepared in Example 4 was coated
on the surface protective layer 4 to form a metal colloid-
containing coat layer 5. Furthermore, a coating solution of
a hot melt type resin was coated on the metal colloid-
containing coat layer 5 to form an adhesive layer 6, thus
obtaining a transfer sheet 1 wherein a transfer layer 3
comprising the surface protective layer 4, the metal colloid-
containing coat layer 5 and an adhesive layer 6 is formed on
the base material 2 shown in Fig. 19.

In the same manner as in Example 24, except that
characters or patterns were drawn by an ink jet printer to
form a metal colloid-containing coat layer 5, a transfer
sheet was produced.

Each of the transfer sheets of Example 24 and Example
25 was thermally transferred under pressure to a paper,


clothes, a leather and a glass to form a metal colloid-
containing coat on the surface. The metal colloid-containing
coat showed metal gloss and color tone peculiar to metal and
was excellent in brightness. The coat was not peeled off
even when rubbed with fingers. The method for thermal
transfer under pressure can be conducted by a conventionally
known method.

A plasma-treated glass sheet measuring 150 mm × 150 mm
× 1 mm was prepared and an ink tank of an ink jet printer was
filled with the Au colloid having a concentration of 50% by
weight obtained in Synthesis Example 13 of Example 4, and
then 5 golden gloss colored lines having a line width of
about 2 mm and a length of 100 mm were drawn on the glass
sheet. The drawn glass sheet was dried at room temperature
and the electrical resistance value of the golden gloss
colored line was measured. As a result, it was 9.6 × 10-6 Ω.
cm.

A plasma-treated glass sheet measuring 150 mm × 150 mm
× 1 mm was prepared and an ink tank of an ink jet printer was
filled with the Au colloid having a concentration of 50% by
weight obtained in Synthesis Example 5 of Example 4, and then
5 golden gloss colored lines having a line width of about 2
mm and a length of 100 mm were drawn on the glass sheet. The


drawn glass sheet was fired in an atmospheric air at 300°C
for 10 minutes and the electrical resistance value of the
golden gloss colored line was measured. As a result, it was
2.5 × 10-6 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0mm was
prepared and spin-coated with the Ru colloid having a
concentration of 40% by weight obtained in Synthesis Example
16 of Example 4 under the conditions of a rotating speed of
200 rpm and 3 minutes to form a coat on the surface of the
alumina sheet. The alumina sheet with the coat formed
thereon was fired in an atmospheric air at 350°C for one
minute and then air-cooled. After cooling to room
temperature, the electrical resistance value of the resulting
coat was measured. As a result, the resistance value was 7.1
× 10-4 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0 mm was
prepared and screen printing was conducted using the Pt
colloid having a concentration of 50% by weight obtained in
Synthesis Example 17 of Example 4 to form a coat measuring 10
mm × 25 mm on the surface of the alumina sheet. The alumina
sheet with the coat formed thereon was fired in an
atmospheric air at 400°C for 10 minutes and then air-cooled.
After cooling to room temperature, the electrical resistance


value of the resulting coat was measured. As a result, the
resistance value was 4.9 × 10-4 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0 mm was
prepared and spin-coated with the Cu colloid having a
concentration of 30% by weight obtained in Synthesis Example
18 of Example 4 under the conditions of a rotating speed of
200 rpm and 3 minutes using to form a coat on the surface of
the alumina sheet. The alumina sheet with the coat formed
thereon was fired in a 2% hydrogen-containing argon gas
atmosphere at 300°C for 10 minutes and then air-cooled.
After cooling to room temperature, the electrical resistance
value of the resulting coat was measured. As a result, the
resistance value was 2.5 × 10-5 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm x 1.0 mm was
prepared and offset printing was conducted using the Ni
colloid having a concentration of 30% by weight obtained in
Synthesis Example 24 of Example 4 to form a coat measuring 10
mm × 25 mm on the surface of the alumina sheet. The alumina
sheet with the coat formed thereon was fired in a 2%
hydrogen-containing argon gas atmosphere at 450°C for one
minute and then air-cooled. After cooling to room
temperature, the electrical resistance value of the resulting
coat was measured. As a result, the resistance value was 5.5


× 10-5 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0mm was
prepared and spin-coated with the Ni/Zn colloid having a
concentration of 30% by weight obtained in Synthesis Example
25 of Example 4 under the conditions of a rotating speed of
200 rpm and 3 minutes using to form a coat on the surface of
the alumina sheet. The alumina sheet with the coat formed
thereon was fired in a 2% hydrogen-containing argon gas
atmosphere at 450°C for 10 minutes and then air-cooled.
After cooling to room temperature, the electrical resistance
value of the resulting coat was measured. As a result, the
resistance value was 9.3 × 10-5 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0 mm was
prepared and spray-coated with the Rh colloid having a
concentration of 30% by weight obtained in Synthesis Example
26 of Example 4 to form a coat on the surface of the alumina
sheet. The alumina sheet with the coat formed thereon was
fired in an argon gas atmosphere at 400°C for 10 minutes and
then air-cooled. After cooling to room temperature, the
electrical resistance value of the resulting coat was
measured. As a result, the resistance value was 2.5 × 10-5 Ω.
cm.


9
An alumina sheet measuring 50 mm x 50 mm x 1.0mm was
prepared and spin-coated with the Ir colloid having a
concentration of 30% by weight obtained in Synthesis Example
27 of Example 4 under the conditions of a rotating speed of
200 rpm and 3 minutes to form a coat on the surface of the
alumina sheet. The alumina sheet with the coat formed
thereon was fired in an argon gas atmosphere at 400°C for 10
minutes and then air-cooled. After cooling to room
temperature, the electrical resistance value of the resulting
coat was measured. As a result, the resistance value was 4.5
× 10-5 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1 mm was
prepared and screen printing was conducted using the Au
colloid having a concentration of 50% by weight obtained in
Synthesis Example 5 of Example 4 to form a coat measuring 10
mm × 25 mm on the surface of the alumina sheet. The alumina
sheet with the coat formed thereon was fired in an
atmospheric air at 15°C for one hour and then air-cooled.
After cooling to room temperature, the electrical resistance
value of the resulting coat was measured. As a result, the
resistance value was 1.3 × 10-4 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1 mm was
prepared and screen printing was conducted using the Au


colloid having a concentration of 50% by weight obtained in
Synthesis Example 5 of Example 4 to form a coat measuring 10
mm × 25 mm on the surface of the alumina sheet. The alumina
sheet with the coat formed thereon was fired in an
atmospheric air at 350°C for one minute and then air-cooled.
After cooling to room temperature, the electrical resistance
value of the resulting coat was measured. As a result, the
resistance value was 2.7 × 10-6 Ω.cm.

First, sodium citrate was prepared as a protective
agent and a reducing agent and 45 g of sodium citrate and 15
g of chlorauric acid were dissolved in 240 g of deionized
water, followed by stirring under reflux at 100°C for one
hour. The resulting reddish violet metal colloid was cooled
and then desalted by an ultrafiltration method to obtain
metal colloidal particles of gold. The resulting metal
colloidal particles were added to a water solvent to prepare
a metal colloid having a concentration of 10% by weight of a
water medium. The above synthesis process was repeated three
times to obtain a metal colloid in a total amount of 150 g.
A trial of synthesizing a metal colloid having a
concentration of more than 10% by weight was made. However,
the resulting synthesized product could not be colloidized
because it is unstable and is aggregated. When using a
medium other than water, the metal colloid was aggregated.


Predetermined characters were written on a Japanese
paper by a writing brush for India ink using a metal colloid
having a concentration of 10% by weight of a water medium,
and then air-dried. However, the characters written on the
Japanese paper showed no gloss because of reddish violet blur
occurred. Then, a solution was prepared by mixing the metal
colloid with polyvinyl alcohol in the proportion of 5 to 15%
based on the weight of metal. Predetermined characters were
written on the Japanese paper by this mixed solution using a
writing brush for India ink, and then air-dried. However,
the characters written on the Japanese paper showed no gloss
because of reddish violet blur occurred.
In the same manner as in Example 6, predetermined
patterns were written on a glass cup and a ceramic ware using
the mixed solution. Also predetermined characteristics were
written on the side of a coffee cup made of porcelain and the
surface of a plastic plate made of polycarbonate. In all
base materials, the coat formed by coating once with the
mixed solution showed metallic reflection gloss, but showed a
purplish gold color which is different from the color tone of
god. When wet-on-wet coating is conducted three times, the
resulting coat showed gold-like metal gloss, but showed color
tone which is different from that peculiar to gold. When the
coated surface was rubbed, the coat was peeled off with ease.
The same coating operation was conducted using a mixed


solution prepared by mixing the metal colloid with a
predetermined amount of a solution containing polyvinyl
alcohol and a predetermined amount of solutions each
containing silane compounds A to C. However, the resulting
coat showed color tone which is different from that of gold
and gloss disappeared. When the coat was rubbed, it was
peeled off with ease. These metal colloids were completely
aggregated within 2 days.

An example of a cartridge for pen filled with the metal
colloid of the present invention as an ink, and a pen
connected with the cartridge for pen will now be described.
As shown in Fig. 20 A, a cartridge 10 for pen is
composed of a tubular body 11 having a closed lower portion,
a lid portion 13 which is joined with the upper portion of
the tubular body 11 and is provided with a continuous hole at
center, and a spherical plug 14 inserted loosely into the
continuous hole of the lid portion 13, and the tubular body
11 is filled with the metal colloid 12 prepared in Example 4
of the present invention. The tubular body 11 and the lid
portion 13 are preferably made of a synthetic resin, and the
spherical plug 14 is preferably made of metal. In the
cartridge 10 for pen, when the spherical plug 14 inserted
loosely is pushed up into the cartridge in the state where
the lid portion 13 faces downward or obliquely downward, a


gap is formed between the lid portion 13 and the spherical
plug 14 and the metal colloid is discharged from the gap due
to gravity.
As shown in Fig. 20 B, a pen 20 comprising the
cartridge 10 for pen incorporated thereinto is composed of a
cylindrical upper shaft barrel 21, a cylindrical lower shaft
barrel 22, the upper end of which can be connected to the
lower end of the upper shaft barrel 21, and a tip 26 which is
connected to the other end of the lower shaft barrel 22. The
inner wall of the lower shaft barrel 22 is provided with a
connection portion 23 which loosely inserts the cartridge 10
for pen and contacts with the lid portion 13, thereby to push
up the spherical plug 14 into the cartridge 10 for pen. In
the connection portion 23, there is provided a core portion
24 capable of being impregnated with the metal colloid
discharging from the cartridge 10 for pen due to gravity
while protruding the other end of the lower shaft barrel 22
when the cartridge 10 for pen is connected to the connection
portion 23 and the spherical plug 14 is pushed up by the
connection portion 23. The tip 2 6 connected to the other end
of the lower shaft barrel 22 serves to eject the metal
colloid, with which the core portion 24 is impregnated, from
the tip. The upper shaft barrel 21, the lower shaft barrel
22 and the connection portion 23 are preferably made of a
synthetic resin. The core portion 24 is preferably made of a


synthetic resin having a structure that pores capable of
being impregnated with the metal colloid are formed.
The cartridge 10 for pen is connected to the pen 20 by
contacting the lid portion 13 of the cartridge with the
connection portion 23 and pushing the connection portion 23
and the plug 14 into the cartridge 10 for pen. In that case,
the metal colloid 12 filled into the cartridge 10 is
discharged from the gap between the lid portion 13 and the
spherical plug 14 and thus the core portion 24 is impregnated
with the metal colloid, which is supplied to the tip 26
through the core portion 24. The pen comprising the
cartridge 10 for pen connected thereto is easy to draw and
was capable of drawing smoothly. This pen is very
advantageous to write desired characters and to draw
predetermined patterns on the desired base material, and the
characters and patterns drawn by the pen showed metal gloss
and color tone peculiar to metal and were excellent in
brightness.

An example of a disposable ampul filled with the metal
colloid of the present invention will now be described.
As shown in Fig. 21, a disposable ampul 30 is composed
of a tubular body 31 having a closed lower portion, a cut
portion 33 joined with the upper portion of the tubular body
31, and a lid portion 32. The cut portion 33 is provided


with a smaller width than that of the tubular body 31 and the
lid portion 32 so that it can be cut by a hand operation.
The tubular body 31, the lid portion 32 and the cut portion
33 are preferably made of a synthetic resin. The disposable
ampul 30 has a structure that a metal colloid 34 is sealed by
thermal contact bonding of the cut portion 33 and the lid
portion 32 after filling the tubular body 31 with a metal
colloid 34 prepared in Example 4 of the present invention.
In the disposable ampul 30 thus obtained, the lid
portion 32 can be easily cut from the cut portion 33 through
the lever rule by laterally rotating the lid portion 32 and
the cut surface is communicated with the inside of the
tubular body 31. The metal colloid filled in the tubular
body 31 can be used after taking out from the communicated
portion.

A stamp pad and a seal impression pad were produced by
sufficiently impregnating with the metal colloid prepared in
Example 4 having a concentration of 30% by weight.
Photographs of the resulting stamp pad and seal impression
pad are shown in Fig. 22. A skippet and a card wherein
patterns are formed using the stamp pad and the seal
impression pad are also shown in Fig. 23 and Fig. 24. As is
apparent from Fig. 23 and Fig. 24, the patterns made of the
metal colloid formed by using the stamp pad or seal


impression pad showed color tone and metal gloss peculiar to
gold.

Using the metal colloid prepared in Example 4 having a
concentration of 30% by weight, a spiral scoring test was
conducted by an ink jet printer apparatus. As the base
material, a paper, a leather and a lumber were used. Using
the paper, a business card, a greeting card, a memorial card
and an invitation card were produced. In case of using the
leather, a leather wallet was drawn. In case of using the
lumber, desired characters were written on a mortuary tablet.
A photograph of a business card, a greeting card and a
leather wallet wherein a metal colloid-containing coat is
formed is shown in Fig. 25. As is apparent from Fig. 25, the
patterns written by an ink jet printer apparatus using the
metal colloid showed color tone and metal gloss peculiar to
gold.

Using the metal colloid prepared in Example 4 as an ink,
characters and patterns were drawn on a colored paper by a
writing brush. The characters and patterns showed metal
gloss and color tone peculiar to metal and were excellent in
brightness. In case of drawing characters or patterns, a pen
filled with the metal colloid described in Example 2 8 as an
ink may be used.



Using the metal colloid prepared in Example 4 as an ink,
a hand print and a foot print were formed on a colored paper.
The hand print and the foot print showed metal gloss and
color tone metal peculiar to metal and were excellent in
brightness.

First, a paper wherein patterns are written on the
surface by a commercially available black ink using a seal
impression and a stamp, a colored paper wherein characters
and patterns are drawn on the surface using a black pen, and
a colored paper wherein a hand print and a foot print are
formed using a black ink were prepared. Using an image
scanner, the surface of the paper and that of the colored
paper were scanned and the resulting image data were inputted
into a computer. By an ink jet printer using the metal
colloid of the present invention as an ink, image data were
printed on the paper and the colored paper based on the
inputted image data. Characters and patterns printed on the
paper and the colored paper using the metal colloid of the
present invention showed the same shape as that of black
colored characters and patterns drawn and also showed metal
gloss and color tone peculiar to metal and were excellent in
brightness.
In Example 44, using the image scanner, the surface of


the paper and that of the colored paper were scanned and the
resulting image data were inputted into a computer and then
printed using the ink jet printer. Using the image scanner,
not only base papers such as paper and colored paper, but
also a photograph of these base papers, and a print and a
publication in which these patterns and characters are
described may be scanned and the resulting image data may be
inputted into a computer and directly printed using an ink
jet printer.

Chlorauric acid was prepared as a metal salt used as a
main component of metal particles, silver nitride and copper
acetate were prepared as a metal salt used as an accessory
component, γ-aminopropyltriethoxysilane was prepared as a
protective agent precursor, and dimethylamineborane was
prepared as a reducing agent, respectively. First,
chlorauric acid, silver nitride and copper acetate were
dissolved in methanol so as to adjust the metal concentration
to 4.0% by weight and to adjust the metal weight ratio
Au:Ag:Cu in the metal concentration to 6:2:1. Then, the
metal solution prepared previously by dissolving the metal
salt was gradually added to 8.00 g of γ-
aminopropyltriethoxysilane and 12.00 g of acetylacetone to
prepare a mixed solution. To the mixed solution, an
appropriate amount of dimethylamineborane as the reducing

agent was added. The reduction reaction was conducted while
maintaining the temperature of the mixed solution at 60°C and
stirring the mixed solution using a magnetic stirrer. After
the completion of the reductive reaction, the mixed solution
was cooled to room temperature. After cooling, the mixed
solution was desalted by an ultrafiltration method and the
concentration was adjusted by appropriately adding water to
obtain a metal colloidal solution having a concentration of
50% by weight, containing water as a dispersion medium.
Protective agent molecules constituting metal colloidal
particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. By TOF-SIMS analysis, cluster ions
comprising Au and CN were predominantly detected. As is
apparent from the results of TOF-SIMS analysis and NMR (C,H)
analysis, the protective agent particles are coordination-
modified on the surface of metal particles by nitrogen. The
content of the accessory component in the metal particles was
examined and was found to be 30% by weight. The silver
content in the accessory component was examined and was found
to be 60% by weight.

Chlorauric acid was prepared as a metal salt used as a
main component of metal particles, silver nitride, copper
acetate and palladium nitrate were prepared as a metal salt
used as an accessory component, 3-aminopropanol was prepared


as a protective agent precursor, and sodium borohydride was
prepared as a reducing agent, respectively. First,
chlorauric acid, chlorauric acid, silver nitride, copper
acetate and palladium nitrate were dissolved in methanol so
as to adjust the metal concentration to 4.0% by weight and to
adjust the metal weight ratio Au:Ag:Cu:Pd in the metal
concentration to 8:1:2:1. Then, the metal solution prepared
previously by dissolving the metal salt was gradually added
to 9.00 g of 3-aminopropanol to prepare a mixed solution. To
the mixed solution, an appropriate amount of sodium
borohydride as the reducing agent was added. The reduction
reaction was conducted while maintaining the temperature of
the mixed solution at 50°C and stirring the mixed solution
using a magnetic stirrer. After the completion of the
reductive reaction, the mixed solution was cooled to room
temperature. After cooling, the mixed solution was desalted
by an ultrafiltration method and the concentration was
adjusted by appropriately adding water to obtain a metal
colloidal solution having a concentration of 50% by weight,
comprising water as a dispersion medium.
Protective agent molecules constituting metal colloidal
particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. By TOF-SIMS analysis, cluster ions
comprising Au and CN were predominantly detected. As is
apparent from the results of TOF-SIMS analysis and NMR (C,H)


analysis, the protective agent particles are coordination-
modified on the surface of metal particles by nitrogen. The
content of the accessory component in the metal particles was
examined and was found to be 35% by weight. The silver
content in the accessory component was examined and was found
to be 30% by weight.

In the same manner as in the reaction of Synthesis
Example 28 or Synthesis Example 29, except that the metal
salt, the protective agent precursor, the reducing agent and
the dispersion medium were replaced by the compounds shown in
Table 5 and Table 6, various metal colloids were obtained.
In the column of the kind of the protective agent precursor
in Table 5 and Table 6, compound represented by symbols (A2)
to (12) are shown in Table 7. Also the protective agent
molecular structure constituting metal colloidal particles in
the metal colloids obtained in Synthesis Examples 30 to 44
was confirmed by analyzing using NMR, TOF-SIMS, FT-IR, SAXS,
visible ultraviolet spectroscopy, SERS and XAFS in
combination.











The metal colloids having a concentration of 50% by
weight obtained in Synthesis Examples 28 to 44 were prepared
and each of the metal colloids having a concentration of 50%
by weight was diluted to prepare dilute metal colloidal
solutions each having a concentration of 5% by weight, 10% by
weight, 15% by weight, 20% by weight, 25% by weight, 30% by
weight and 40% by weight, respectively. Using each of dilute
metal colloidal solutions each having a concentration of 5 to
50% by weight, predetermined characters were written on a
Japanese paper using a writing brush of India ink, and then
air-dried. In case of using a dilute solution of the metal
colloid having a concentration of 30% by weight or less
obtained in Synthesis Example 28, the written characters
showed a yellow gold color tone and metal gloss and were
excellent in brightness and design properties, and the
characters were not peeled off even when the surface of the
characters are rubbed with a cloth. Also in case of using
each of dilute solutions of the metal colloids having a
concentration of 30% by weight or less obtained in Synthesis
Example 33, Synthesis Example 37, Synthesis Example 39 and
Synthesis Example 42, characters were written and then air-
dried on a Japanese paper. The written characters
respectively showed a green gold color tone (Synthesis
Example 33), a red gold color tone (Synthesis Example 37), a


pink gold color tone (Synthesis Example 39) and a white gold
color tone (Synthesis Example 42) and metal gloss and were
excellent in brightness and design properties, and the
characters were not peeled off even when the surface of the
characters are rubbed with a cloth, similarly.
In case of using a dilute metal colloidal solution
having a concentration of 20% by weight or less, the
characters written on the Japanese paper showed metal gloss,
but showed color tone which is seemed to be different from
the color tone peculiar to metal. When characters are
written on a Japanese paper subjected to a surface treatment
for preventing penetration of the metal colloid, or a base
material into which the metal colloid does not penetrate, the
resulting characters written using the metal colloid having a
concentration of 20% by weight or less showed the same metal
gloss and color tone as those obtained in case of using the
metal colloid having a concentration of more than 20% by
weight. After storing the dilute metal colloidal solution at
room temperature for 3 weeks, characters were written again
on the Japanese paper using the stored metal colloid.
Similar to the case before the storage, the written
characters showed color tone and metal specular gloss
peculiar to metal and were excellent in brightness and design
properties.



Chlorauric acid was prepared as a metal salt used as a
main component of metal particles, silver nitride and copper
acetate were prepared as a metal salt used as an accessory
component, Y~mercaptopropyltrimethoxysilane and acetylacetone
were prepared as a protective agent precursor, and
dimethylamineborane was prepared as a reducing agent,
respectively. First, chlorauric acid, silver nitride and
copper acetate were dissolved in methanol so as to adjust the
metal concentration to 4.0% by weight and to adjust the metal
weight ratio Au:Ag:Cu in the metal concentration to 6:2:1.
Then, 3.00 g of y-mercaptotrimethoxysilane was mixed with
12.00 g of acetylacetone and an appropriate amount of
dimethylamineborane was added to the mixed solution. Then,
the metal solution prepared previously by dissolving the
metal salt was gradually added to prepare a mixed solution.
This mixed solution was prepared by maintaining at 60°C while
stirring the mixed solution using a magnetic stirrer, and the
reductive reaction was conducted until metal colloidal
particles are produced and show a red color. After the
completion of the reductive reaction, the mixed solution was
cooled to room temperature. After cooling, the mixed
solution was desalted by an ultrafiltration method to obtain
a metal colloid containing water as a dispersion medium. The
concentration of this metal colloid was adjusted by adding an
appropriate amount of water to obtain a metal colloid having


a concentration of 50% by weight, comprising water as a
dispersion medium.
Protective agent molecules constituting metal colloidal
particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. As is apparent from the results of TOF-
SIMS analysis and NMR analysis, the protective agent
molecules are coordination-modified on the surface of the
metal particles by sulfur and oxygen.

Using the metal colloid of Comparative Example 3,
desired characters were written on a Japanese paper using a
writing brush for India ink and then air-dried. The written
characters showed metal color with a yellow gold color tone
and metal gloss. With respect to the characters obtained by
using the metal colloid of Comparative Example 3, and the
characters obtained by using the metal colloids of Synthesis
Example 28, Synthesis Example 33, Synthesis Example 37,
Synthesis Example 39 and Synthesis Example 42 in Example 45,
color tone, ease of peeling and brightness were visually
evaluated. The ease of peeling was confirmed by the method
of rubbing the surface of characters with a cloth conducted
in Example 45. The results are shown in Table 8.


As is apparent from the results shown in Table 8, the
written characters obtained using the metal colloids of
Example 45 and Comparative Example 3 showed various gold-
based color tones. Regarding the ease of peeling, all
written characters obtained by using any metal colloids were
not peeled off. However, the written characters obtained by
using the metal colloid of Example 45 was excellent in
brightness as compared with the written characters obtained
by using the metal colloid of Comparative Example 3.

First, a glass cup, a ceramic ware, a coffee cup made
of porcelain and a plastic plate made of polycarbonate were
prepared, respectively. Using the dilute metal colloidal
solution prepared in Example 45, desired patterns were drawn


on the glass cup and the ceramic ware. Also, desired
characteristics were written on the side of the coffee cup
made of porcelain and the surface of the plastic plate made
of polycarbonate. The written characters showed metal color
with various gold-based color tones such as yellow gold,
green gold, red gold, pink gold and white gold, and metal
gloss and were excellent in brightness and design properties,
similar to Example 45. The characters and patterns were not
peeled off even when the surface of the characters and
patterns are rubbed with a cloth.

The dilute metal colloidal solution prepared in Example
45 was coated on the surface of an artificial hair, an
artificial eyelash, a plastic model, an amulet case, a
skippet, a memorial card, an invitation card, a greeting card,
a doll, a Buddhist image, a mortuary tablet, a picture frame,
clothes and a woven fabric, respectively. Specifically, the
metal colloid was coated on the artificial hair by a method
of spraying using an airbrush, while the metal colloid was
coated on the entire surface of the artificial eyelash, the
plastic model, the doll and the Buddhist image using a
writing brush. Also writing desired characters were written
on the mortuary tablet using a wiring brush and the metal
colloid was coated only on the frame portion of the picture
frame using a writing brush, and desired characters or


patterns were drawn on the memorial card, the invitation card,
the greeting card, the amulet case, the skippet, clothes and
the woven fabric using a writing brush. After coating, the
dispersion medium in the dilute metal colloidal solution was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. Each metal colloid-
containing coat showed metal color with various gold-based
color tones and metal gloss and was excellent in brightness
and design properties, similar to the characters written in
Example 45.

First, the dilute metal colloidal solution prepared in
Example 45 was coated on the following jewelries. A dilute
metal colloidal solution was coated on a ring, a ring made of
a silver clay, a pierced earring, an earring, a bracelet, a
necklace, a key holder and an ornamental hairpin using a
writing brush, and the colloid was coated on a watch, a
hairpin, a broach and a tiepin by a method of spraying using
an airbrush. After coating, the dispersion medium in the
dilute metal colloidal solution was sufficiently removed by
drying with an air of a dryer to form a metal colloid-
containing coat. Each metal colloid-containing coat formed
on the surface of jewelries showed various gold-based color
tones and metal gloss and was excellent in brightness and
design properties, similar to the characters written in


Example 45.

The dilute metal colloidal solution prepared in Example
45, a natural nail and an artificial nail were prepared,
respectively. By a method of coating the metal colloid using
a writing brush for manicure shown in Fig. 12, the metal
colloid was coated on the surface of the natural nail and the
artificial nail. After coating, the dispersion medium in the
dilute metal colloidal solution was sufficiently removed by
drying with an air of a dryer to form a metal colloid-
containing coat. Each metal colloid-containing coat formed
on the surface of the natural nail and the artificial nail
showed various gold-based color tones and metal gloss and was
excellent in brightness and design properties, similar to the
characters written in Example 45.

Using a method of spraying a metal colloid using an
airbrush for manicure shown in Fig. 14, the dilute metal
colloidal solution prepared in Example 45 was sprayed over
the surface of a natural nail and the surface of an
artificial nail. After spraying, the dispersion medium in
the dilute metal colloidal solution was sufficiently removed
by drying with an air of a dryer to form a metal colloid-
containing coat. Similar to the characters written in
Example 45, each metal colloid-containing coat formed on the


surface of the natural nail and the artificial nail showed
various gold-based color tones and metal gloss and was
excellent in brightness and design properties. The resulting
coat has matted gloss and is excellent in smoothness, unlike
the coat of Example 4 9 formed by coating using a writing
brush for manicure.

First, in the same manner as in Example 4 9, the dilute
metal colloidal solution prepared in Example 45 was coated on
the surface of a natural nail and the surface of an
artificial nail using a writing brush for manicure. After
coating, the dispersion medium in the dilute metal colloidal
solution was sufficiently removed by drying with an air of a
dryer to form a metal colloid-containing coat. Then, a top
coating agent was coated on the metal colloid-containing coat
thus formed by a wet-on-wet coating method and this top
coating prevented the metal colloid-containing coat from
being peeled off with ease. The metal colloid-containing
coat formed on the surface of the artificial nail showed
metal color with various gold-based color tones and metal
gloss and was excellent in brightness and design properties,
similar to the case of the coat obtained in Example 49.

First, an under coat layer was formed on the surface of
an artificial nail. In the same manner as in Example 49, the


dilute metal colloidal solution prepared in Example 45 was
coated on the surface of the under coat layer using a writing
brush for manicure. After coating, the dispersion medium in
the dilute metal colloidal solution was sufficiently removed
by drying with an air of a dryer to form a metal colloid-
containing coat. The metal colloid-containing coat formed on
the surface of the artificial nail showed metal color with
various gold-based color tones and metal gloss and was
excellent in brightness and design properties, similar to the
case of the coats obtained in Example 4 9 and Example 51.

First, an under coat layer was formed on the surface of
an artificial nail. In the same manner as in Example 4 9, the
dilute metal colloidal solution prepared in Example 45 was
coated on the surface of the under coat layer using a writing
brush for manicure. After coating, the dispersion medium in
the dilute metal colloidal solution was sufficiently removed
by drying with an air of a dryer to form a metal colloid-
containing coat. Then, a top coating agent was coated on the
metal colloid-containing coat thus formed by a wet-on-wet
coating method and this top coating prevented the metal
colloid-containing coat from being peeled off with ease. The
metal colloid-containing coat formed on the surface of the
artificial nail showed metal color with various gold-based
color tones and metal gloss and was excellent in brightness


and design properties, similar to the case of the coats
obtained in Example 49, Example 51 and Example 52.

In the same manner as in Example 53, except that the
dilute metal colloidal solution was coated only at the tip
portion of the nail using an airbrush, a metal colloid-
containing coat was formed on the surface of an artificial
nail. In the same manner as in Example 53, except that
desired patterns were drawn on the surface of the nail using
a writing brush for manicure in case of coating the dilute
metal colloidal solution, a metal colloid-containing coat was
formed on the surface of an artificial nail. The artificial
nail coated with the metal colloid only at the tip portion
using an airbrush and the artificial nail wherein desired
patterns are drawn on the surface of the nail using a writing
brush for manicure showed metal color with various gold-based
color tones and metal gloss and was excellent in brightness
and design properties, similar to Examples 49 to 53.

First, an under coating agent was coated on the surface
of an artificial nail and then dried to form an under coat
layer. In the same manner as in Example 49, the dilute metal
colloidal solution prepared in Example 45 was coated on the
surface of the under coat layer using a writing brush for
manicure. The dispersion medium in the dilute metal


colloidal solution was removed by drying with an air of a
dryer to form a metal colloid-containing coat. Then, a top
coating agent was coated on the metal colloid-containing coat
thus formed and, before completely drying the top coating
agent, a lame agent as a material was scattered at desired
points and diamond natural stones and pink sapphire natural
stones were set thereon, and then these materials were fixed
by pressing and immobilized by drying the top coating agent
with an air of a dryer. Immobilization of these materials
was enhanced by further coating the top coating agent.
Brightness and design properties were improved by using the
metal colloid-containing coat formed on the artificial nail
in combination of the lame agent and natural gems of diamond
and pink sapphire.

The dilute metal colloidal solution prepared in Example
45 was coated only at the tip portion of an artificial nail
using a writing brush for manicure. After coating, the
dispersion medium in the dilute metal colloidal solution was
removed by drying with an air of a dryer to form a metal
colloid-containing coat. Then, a top coating agent was
coated on the metal colloid-containing coat thus formed and,
before completely drying the top coating agent, natural
stones of ruby, diamond and sapphire as materials were
arranged at desired points, and then these materials were


fixed by pressing and immobilized by drying the top coating
agent with an air of a dryer. Immobilization of these
materials was enhanced by further coating the top coating
agent. Brightness and design properties were improved by
using the metal colloid-containing coat formed only at the
tip portion of the artificial nail in combination of natural
stones of ruby, diamond and sapphire.

Desired patterns were drawn on the surface of a nail
with the dilute metal colloidal solution prepared in Example
45 using a writing brush for manicure. After drawing, the
dispersion medium in the dilute metal colloidal solution was
removed by drying with an air of a dryer to form a metal
colloid-containing coat on the surface of the nail. Then, a
top coating agent was coated on the entire surface of a nail
and, before completely drying the top coating agent, a gold
foil powder and diamond and pink sapphire natural stones as
materials were set at the desired points, and then these
materials were fixed by pressing and immobilized by drying
the top coating agent with an air of a dryer. Immobilization
of these materials was enhanced by further coating the top
coating agent. Brightness and design properties were
improved by using the metal colloid-containing coat formed on
the artificial nail in combination with the gold foil powder
and natural gems of diamond and pink sapphire.



First, as shown in Fig. 19, a coating solution of an
acrylic resin was coated on one surface of a base material 2
made of a releasable synthetic paper to form a surface
protective layer 4. Then, the dilute gold colloidal solution
prepared in Example 45 was coated on the surface protective
layer 4 to form a metal colloid-containing coat layer 5.
Furthermore, a coating solution of a hot melt type resin was
coated on the metal colloid-containing coat layer 5 to form
an adhesive layer 6, thus obtaining a transfer sheet 1
wherein a transfer layer 3 comprising the surface protective
layer 4, the metal colloid-containing coat layer 5 and an
adhesive layer 6 is formed on the base material 2.

In the same manner as in Example 58, except that, in
case of forming a metal colloid-containing coat layer 5 in
the production of a transfer sheet, characters or patterns
were drawn by an ink jet printer to form the metal colloid-
containing coat layer 5, a transfer sheet was produced.

Each of the transfer sheets of Example 58 and Example
59 was thermally transferred under pressure to a paper,
clothes, a leather and a glass to form a metal colloid-
containing coat on the surface. Similar to characters
written in Example 45, the metal colloid-containing coat


showed metal color with various gold-based color tones and
metal gloss and was excellent in brightness and design
properties. The metal colloid-containing coat as the
transfer film was not peeled off even when rubbed with
fingers. The method for thermal transfer under pressure can
be conducted by a conventionally known method.

As shown in Fig. 20 A, there was prepared a cartridge
10 for pen which is composed of a tubular body 11 having a
closed lower portion, a lid portion 13 which is joined with
the upper portion of the tubular body 11 and is provided with
a spherical continuous hole at center, and a spherical plug
14 having a diameter, which is smaller than the shape of the
continuous hole and is enough to prevent from falling off
from the continuous hole, inserted into the continuous hole
of the lid portion 13, the tubular body 11 being filled with
the dilute metal colloidal solution 12 prepared in Example 45.
As shown in Fig. 20 B, a pen 20 comprising the
cartridge 10 for pen incorporated thereinto was prepared.
This pen 20 is composed of a cylindrical upper shaft barrel
21, a cylindrical lower shaft barrel 22, the upper end of
which can be connected to the lower end of the upper shaft
barrel 21, and a tip 2 6 which is connected to the other end
of the lower shaft barrel 22. The inner wall of the lower
shaft barrel 22 is provided with a connection portion 23


which inserts the cartridge 10 for pen and contacts with the
lid portion 13, thereby to push up the spherical plug 14 into
the cartridge 10 for pen. In the connection portion 23,
there is provided a core portion 24 capable of being
impregnated with the dilute metal colloidal solution
discharging from the cartridge 10 due to gravity while
protruding the other end of the lower shaft barrel 22 when
the cartridge 10 for pen is connected to the connection
portion 23 and the spherical plug 14 is pushed up by the
connection portion 23. The tip 2 6 connected to the other end
of the lower shaft barrel 22 serves to eject the dilute metal
colloidal solution, with which the core portion 24 is
impregnated, from the tip.
The cartridge 10 for pen was connected to the pen 20 by
contacting the lid portion 13 of the cartridge with the
connection portion 23 and pushing the connection portion 23
and the plug 14 into the cartridge 10 for pen. In that case,
the dilute metal colloidal solution 12 filled into the
cartridge 10 is discharged from the gap between the lid
portion 13 and the spherical plug 14 and thus the core
portion 24 is impregnated with the dilute metal colloidal
solution, which is supplied to the tip 2 6 through the core
portion 24. The pen comprising the cartridge 10 for pen
connected thereto is easy to draw and was capable of drawing
smoothly. This pen is very advantageous to write desired


characters and to draw predetermined patterns on the desired
base material, and the characters and patterns drawn by the
pen showed metal color with various gold-based color tones
and metal gloss and were excellent in brightness, similar to
the characters written in Examples 45.

As shown in Fig. 21, there was prepared a disposable
ampul 30 which is composed of a tubular body 31 having a
closed lower portion, a cut portion 33 joined with the upper
portion of the tubular body 31, and a lid portion 32, the cut
portion 33 being provided with a smaller width than that of
the tubular body 31 and the lid portion 32 so that it can be
cut by a hand operation, the disposable ampul having a
structure that the dilute metal colloidal solution 34
prepared in Example 45 is sealed by thermal contact bonding
of the cut portion 33 and the lid portion 32 after filling
the tubular body 31 with the dilute metal colloidal solution
34.
In the disposable ampul 30 thus obtained, the lid
portion 32 can be easily cut from the cut portion 33 through
the lever rule by laterally rotating the lid portion 32 and
the cut surface is communicated with the inside of the
tubular body 31. The metal colloid filled in the tubular
body 31 can be used after taking out from the communicated
portion.



A stamp pad and a seal impression pad were produced by
sufficiently impregnating with the dilute metal colloidal
solution prepared in Example 45 having a concentration of 30%
by weight. Using the stamp pad and the seal impression pad,
patterns were formed on a wallet or a key holder by forming
patterns of a metal colloid-containing coat on a leather, or
a memorial card was produced by forming patterns of a metal
colloid-containing coat on a paper. The patterns made by
using the stamp pad or seal impression pad containing the
dilute metal colloidal solution showed metal color with
various gold-based color tones and metal gloss and were
excellent in brightness, similar to the characters written in
Examples 45.

Using the dilute metal colloidal solution prepared in
Example 45, a spiral scoring test was conducted by an ink jet
printer apparatus. As the base material, a paper, a leather
and a lumber were used. Using the paper, a business card, a
greeting card, a memorial card and an invitation card were
produced. In case of using the leather, a leather wallet was
drawn. In case of using the lumber, desired characters were
written on a mortuary tablet. The patterns drawn by the ink
jet printer apparatus using the dilute metal colloidal
solution showed metal color with various gold-based color


tones and metal gloss and were excellent in brightness and
design properties, similar to the characters written in
Examples 45.

Using the dilute metal colloidal solution prepared in
Example 45 as an ink, characters and patterns were drawn on a
colored paper by a writing brush. The characters and
patterns showed metal color with various gold-based color
tones and metal gloss and were excellent in brightness and
design properties, similar to the characters written in
Examples 45. In case of drawing characters or patterns, a
pen filled with the dilute metal colloidal solution described
in Example 61 as an ink may be used.

Using the dilute metal colloidal solution prepared in
Example 45 as an ink, a hand print and a foot print were
formed on a colored paper. The hand print and the foot print
showed metal color with various gold-based color tones and
metal gloss and were excellent in brightness and design
properties, similar to the characters written in Examples 45.

First, a paper wherein patterns are written on the
surface by a commercially available black ink using a seal
impression and a stamp, a colored paper wherein characters
and patterns are drawn on the surface using a black pen, and


a colored paper wherein a hand print and a foot print are
formed using a black ink were prepared. Using an image
scanner, the surface of the paper and that of the colored
paper were scanned and the resulting image data were inputted
into a computer. By an ink jet printer using the dilute
metal colloidal solution prepared in Example 45 as an ink,
image data were printed on the paper and the colored paper
based on the inputted image data. Characters and patterns
printed on the paper and the colored paper using the dilute
metal colloidal solution of the present invention showed the
same shape as that of black colored characters and patterns
drawn and also showed metal color with various gold-based
color tones and metal gloss and were excellent in brightness
and design properties, similar to the characters written in
Examples 45.
In Example 67, using the image scanner, the surface of
the paper and that of the colored paper were scanned and the
resulting image data were inputted into a computer and then
printed using the ink jet printer. Using the image scanner,
not only base papers such as paper and colored paper, but
also a photograph of these base papers, and a print and a
publication in which these patterns and characters are
described may be scanned and the resulting image data may be
inputted into a computer and directly printed using an ink
jet printer.



Chlorauric acid was prepared as a metal salt used as a
main component of metal particles, y-
aminopropyltriethoxysilane and acetylacetone were prepared as
a protective agent precursor, and dimethylamineborane was
prepared as a reducing agent, respectively. First, a
methanol solution prepared by dissolving chlorauric acid so
as to adjust the gold concentration to 4.0% by weight was
gradually added to 8.00 g of γ-aminopropyltriethoxysilane and
12.00 g of acetylacetone to prepare a mixed solution. To the
mixed solution, an appropriate amount of dimethylamineborane
as the reducing agent was added. This mixed solution was
prepared by maintaining at 60°C while stirring the mixed
solution using a magnetic stirrer, and the reductive reaction
was conducted until metal colloidal particles are produced
and show a red color. After the completion of the reductive
reaction, the mixed solution was cooled to room temperature.
After cooling, the mixed solution was desalted by an
ultrafiltration method to obtain a metal colloid containing
water as a dispersion medium. The concentration of this
metal colloid was adjusted by adding an appropriate amount of
water to obtain a metal colloid having a concentration of 50%
by weight wherein Au colloidal particles are dispersed in
water.
Protective agent molecules constituting Au colloidal


particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. By TOF-SIMS analysis, cluster ions
comprising Au and CN were predominantly detected. As is
apparent from the results of TOF-SIMS analysis and NMR (C,H)
analysis, the protective agent particles are coordination-
modified on the surface of Au particles by nitrogen.

Chlorauric acid was prepared as a metal salt used as a
main component of metal particles, 3-aminoethanol and
acetylacetone were prepared as a protective agent precursor,
and dimethylamineborane was prepared as a reducing agent,
respectively. First, a methanol solution prepared by
dissolving chlorauric acid so as to adjust the gold
concentration to 4.0% by weight was gradually added to 9.00 g
of 3-aminoethanol and 12.00 g of acetylacetone to prepare a
mixed solution. To the mixed solution, an appropriate amount
of dimethylamineborane as the reducing agent was added. This
mixed solution was prepared by maintaining at 60°C while
stirring the mixed solution using a magnetic stirrer, and the
reductive reaction was conducted until metal colloidal
particles are produced and show a red color. After the
completion of the reductive reaction, the mixed solution was
cooled to room temperature. After cooling, the mixed
solution was desalted by an ultrafiltration method to obtain
a metal colloid containing water as a dispersion medium. The


concentration of this metal colloid was adjusted by adding an
appropriate amount of water to obtain a metal colloid having
a concentration of 50% by weight wherein Au colloidal
particles are dispersed in water.
Protective agent molecules constituting Au colloidal
particles in the resulting metal colloid were subjected to
TOF-SIMS analysis. By TOF-SIMS analysis, cluster ions
comprising Au and CN were predominantly detected. As is
apparent from the results of TOF-SIMS analysis and NMR (C,H)
analysis, the protective agent particles are coordination-
modified on the surface of Au particles by nitrogen.

In the same manner as in Synthesis Example 45, except
that the metal salt, the protective agent precursor, the
reducing agent and the dispersion medium were replaced by the
compounds shown in Table 9 and Table 10, various metal
colloids were obtained.

In the same manner as in Synthesis Example 45, except
that the metal salt, the protective agent precursor, the
reducing agent and the dispersion medium were replaced by the
compounds shown in Table 10 and Table 11 and the temperature
at which the mixed solution is prepared was changed to 35°C,
various metal colloids were obtained. In the column of the
kind of the protective agent precursor in Table 9 to Table 11,


compound represented by symbols (A3) to (N3) are shown in
Table 12.















The metal colloids having a concentration of 50% by
weight obtained in Synthesis Examples 45 to 86 were prepared
and each of the metal colloids having a concentration of 50%
by weight was diluted to prepare a metal colloids each having
a concentration of 5% by weight, 10% by weight, 15% by weight,
20% by weight, 25% by weight, 30% by weight and 40% by weight,
respectively. As the base material, an artificial hair, an
artificial eyelash, a plastic model, an amulet case, a
skippet, a memorial card, an invitation card, a greeting card,
a doll, a Buddhist image, a mortuary tablet, a picture frame,
clothes and a woven fabric were prepared, respectively.
Specifically, the metal colloid thus prepared was coated on
the artificial hair by a method of spraying using an airbrush,
while the metal colloid was coated on the entire surface of
the artificial eyelash, the plastic model, the doll and the
Buddhist image using a writing brush. Also writing desired
characters were written on the mortuary tablet using a wiring
brush and the metal colloid was coated only on the frame
portion of the picture frame using a writing brush, and
desired characters or patterns were drawn on the memorial
card, the invitation card, the greeting card, the amulet case,
the skippet, clothes and the woven fabric using a writing
brush. After coating on the base material, the dispersion
medium in the dilute metal colloidal solution was


sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. A photograph of an
invitation card wherein characters are written on the surface
using a metal colloid is shown in Fig. 26 A and a photograph
of a doll, the surface of which is coated with a metal
colloid is shown in Fig. 26 B, respectively.
As is apparent from Fig. 26 A and Fig. 2 6 B, the
resulting metal colloid-containing coat formed article showed
metal gloss and color tone peculiar to metal and was
excellent in brightness and design properties.

As the base material, a ring, a ring made of a silver
clay pierced earring, an earring, a bracelet, a necklace, a
key holder, an ornamental hairpin, a watch, a hairpin, a
broach and a tiepin were prepared, respectively. Then, using
the metal colloidal prepared in Example 68, a gold colloid
was coated on the ring, the ring made of a silver clay, the
pierced earring, the earring, the bracelet, the necklace, the
key holder and the ornamental hairpin using a writing brush.
Using the metal colloidal prepared in Example 68, a gold
colloid was coated on the watch, the hairpin, the broach and
the tiepin by a method of spraying using an airbrush. After
coating on the base material, the dispersion medium in the
dilute metal colloidal solution was sufficiently removed by
drying with an air of a dryer to form a metal colloid-


containing coat. A photograph of a ring wherein the surface
other than the display portion is coated with a metal colloid
is shown in Fig. 27 A, a photograph of a pierced earring, the
surface of which is coated with a metal colloid is shown in
Fig. 27 B and a photograph showing a watch, the surface of
which is coated with a metal colloid is shown in Fig. 27 C,
respectively.
As is apparent from Fig. 27 A to Fig. 27 C, the
resulting metal colloid-containing coat formed article is
jewelry which shows metal gloss and color tone peculiar to
metal and is excellent in brightness and design properties.

The metal colloid prepared in Example 68, a natural
nail and an artificial nail were prepared, respectively. By
a method of coating the metal colloid using a writing brush
for manicure shown in Fig. 12, the metal colloid was coated
on the surface of the natural nail and the artificial nail.
After coating, the dispersion medium in the metal colloid was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. A natural nail wherein a
metal colloid-containing coat is formed on the surface by a
coating method is shown in Fig. 28.
As is apparent from Fig. 28, the metal colloid-
containing coat formed on the surface of the natural nail is
a film which showed golden gloss and color tone peculiar to


gold and had a metal specular surface which is excellent in
smoothness.

Using a method of spraying a metal colloid using an
airbrush for manicure shown in Fig. 14, the metal colloid
prepared in Example 68 was sprayed over the surface of a
natural nail and the surface of an artificial nail. After
spraying, the dispersion medium in the metal colloid was
sufficiently removed by drying with an air of a dryer to form
a metal colloid-containing coat. A natural nail wherein a
metal colloid-containing coat is formed on the surface by a
spraying method is shown in Fig. 29.
As is apparent from Fig. 29, the metal colloid-
containing coat formed on the surface of the natural nail and
the artificial nail showed golden gloss and color tone
peculiar to gold and had a metal specular surface which has
matted gloss and is excellent in smoothness, unlike the coat
of Example 70 formed by coating using the writing brush.

First, in the same manner as in Example 70, the metal
colloid prepared in Example 68 was coated on the surface of a
natural nail and the surface of an artificial nail using a
writing brush for manicure. After coating, the dispersion
medium in the metal colloid was sufficiently removed by
drying with an air of a dryer to form a metal colloid-


containing coat. Then, a top coating agent was coated on the
metal colloid-containing coat thus formed by a wet-on-wet
coating method and this top coating prevented the metal
colloid-containing coat from being peeled off with ease. The
metal colloid-containing coat formed on the surface of the
artificial nail showed golden gloss and color tone peculiar
to gold and had a metal specular surface which is excellent
in smoothness, similar to the case of the coat obtained in
Example 70.

First, an artificial nail was prepared and an under
coat layer was formed on the surface of an artificial nail.
In the same manner as in Example 70, the metal colloid
prepared in Example 68 was coated on the surface of the under
coat layer using a writing brush for manicure. The metal
colloid-containing coat formed on the surface of the
artificial nail showed golden gloss and color tone peculiar
to gold and had a metal specular surface which is excellent
in smoothness, similar to the case of the coats obtained in
Example 70 and Example 72.

First, an artificial nail was prepared and an under
coat layer was formed on the surface of an artificial nail.
In the same manner as in Example 70, the metal colloid
prepared in Example 68 was coated on the surface of the under


coat layer using a writing brush for manicure. After coating,
the dispersion medium in the metal colloid was sufficiently
removed by drying with an air of a dryer to form a metal
colloid-containing coat. Then, a top coating agent was
coated on the metal colloid-containing coat thus formed by a
wet-on-wet coating method and this top coating prevented the
metal colloid-containing coat from being peeled off with ease.
The metal colloid-containing coat formed on the surface of
the artificial nail showed golden gloss and color tone
peculiar to gold and had a metal specular surface which is
excellent in smoothness, similar to the case of the coats
obtained in Example 70, Example 72 and Example 73.

In the same manner as in Example 74, except that the
metal colloid was coated only at the tip portion of the nail
using an airbrush, a metal colloid-containing coat was formed
on the surface of an artificial nail. In the same manner as
in Example 74, except that desired patterns were drawn on the
surface of the nail using a writing brush for manicure in
case of coating the metal colloid, a metal colloid-containing
coat was formed on the surface of an artificial nail. The
artificial nail coated with the metal colloid only at the tip
portion using an airbrush and the artificial nail wherein
desired patterns are drawn on the surface of the nail using a
writing brush for manicure showed color tone peculiar to


metal and were excellent in design properties, similar to
Examples 70 to 74.

In the same manner as in Example 74, except that the
metal colloid prepared in Example 68 contains 0.5 to 3% of
fine metal particles having an average particle size of 1 to
10 nm, a metal colloid-containing coat was formed on the
surface of an artificial nail. The metal colloid-containing
coat formed on the surface of the artificial nail shows a
pink gold color tone and is excellent in design properties.

First, an under coating agent was coated on the surface
of an artificial nail and then dried to form an under coat
layer. In the same manner as in Example 70, the metal
colloid prepared in Example 68 was coated on the surface of
the under coat layer using a writing brush for manicure. The
dispersion medium in the metal colloid was removed by drying
with an air of a dryer to form a metal colloid-containing
coat. Then, a top coating agent was coated on the metal
colloid-containing coat thus formed and, before completely
drying the top coating agent, a lame agent as a material was
scattered at desired points and diamond natural stones and
pink sapphire natural stones were set thereon, and then these
materials were fixed by pressing and immobilized by drying
the top coating agent with an air of a dryer. Immobilization


of these materials was enhanced by further coating the top
coating agent. An artificial nail on which a metal colloid-
containing coat is formed is shown in Fig. 30.
As is apparent from Fig. 30, brightness and design
properties were improved by using the metal colloid-
containing coat in combination of the lame agent and natural
gems of diamond and pink sapphire.

First, the metal colloid prepared in Example 68 was
coated only at the tip portion of an artificial nail using a
writing brush for manicure. After coating, the dispersion
medium in the metal colloid was removed by drying with an air
of a dryer to form a metal colloid-containing coat. Then, a
top coating agent was coated on the metal colloid-containing
coat thus formed and, before completely drying the top
coating agent, pearl and diamond natural stones as materials
were arranged at the desired points, and then these materials
were fixed by pressing and immobilized by drying the top
coating agent with an air of a dryer. Immobilization of
these materials was enhanced by further coating the top
coating agent. The resulting artificial nail on which the
metal colloid-containing coat is formed is shown in Fig. 31.
As is apparent from Fig. 31, brightness and design
properties were improved by using the metal colloid-
containing coat formed only at the tip portion of the nail in

combination with natural gems of pearl and diamond.

First, desired patterns were drawn on the surface of an
artificial nail with the metal colloid prepared in Example 68
using a writing brush for manicure. After drawing, the
dispersion medium in the metal colloid was removed by drying
with an air of a dryer to form a metal colloid-containing
coat. Then, a top coating agent was coated on the entire
surface of a nail and, before completely drying the top
coating agent, a gold foil powder and diamond and pink
sapphire natural stones as materials were set at the desired
points, and then these materials were fixed by pressing and
immobilized by drying the top coating agent with an air of a
dryer. Immobilization of these materials was enhanced by
further coating the top coating agent. Brightness and design
properties were improved by using the metal colloid-
containing coat in combination with the gold foil powder and
natural gems of diamond and pink sapphire.

First, as shown in Fig. 19, a coating solution of an
acrylic resin was coated on one surface of a base material 2
made of a releasable synthetic paper to form a surface
protective layer 4. Then, the gold colloid prepared in
Example 68 was coated on the surface protective layer 4 to
form a metal colloid-containing coat layer 5. Furthermore, a


coating solution of a hot melt type resin was coated on the
metal colloid-containing coat layer 5 to form an adhesive
layer 6, thus obtaining a transfer sheet 1 wherein a transfer
layer 3 comprising the surface protective layer 4, the metal
colloid-containing coat layer 5 and an adhesive layer 6 is
formed on the base material 2.

In the same manner as in Example 80, except that
characters or patterns were drawn by an ink jet printer to
form a metal colloid-containing coat layer 5, a transfer
sheet was produced.

Each of the transfer sheets of Example 80 and Example
81 was thermally transferred under pressure to a paper,
clothes, a leather and a glass to form a metal colloid-
containing coat on the surface. The metal colloid-containing
coat showed metal gloss and color tone peculiar to metal and
was excellent in brightness. The coat was not peeled off
even when rubbed with fingers. The method for thermal
transfer under pressure can be conducted by a conventionally
known method.

A plasma-treated glass sheet measuring 150 mm × 150 mm
× 1 mm was prepared and an ink tank of an ink jet printer was
filled with the Au colloid having a concentration of 50% by


weight obtained in Synthesis Example 55 of Example 68, and
then 5 golden gloss colored lines having a line width of
about 2 mm and a length of 100 mm were drawn on the glass
sheet. The drawn glass sheet was dried at room temperature
and the electrical resistance value of the golden gloss
colored line was measured. As a result, it was 9.8 × 10-6 Ω .
cm.

The glass sheet with lines obtained in Example 83 was
fired by maintaining in an atmospheric air at a temperature
of 300°C for 10 minutes and the electrical resistance value
of the golden gloss colored line formed on the glass sheet
was measured. As a result, it was 2.7 × 10-6 Ω.cm.

Two alumina sheets each measuring 50 mm × 50 mm × 1.0
mm were prepared and screen printing was conducted using the
Au colloid having a concentration of 50% by weight obtained
in Synthesis Examples 72 and 73 of Example 68 to form each
coat measuring 10 mm × 25 mm on the surface of the alumina
sheets. The alumina sheets with the coat formed thereon were
air-dried in an atmospheric air at 25°C for one hour. The
electrical resistance value of the resulting coats was
measured. As a result, the resistance value of the coat
formed using the colloid of Synthesis Example 72 was 7.7 ×
10-6 Ω.cm and the resistance value of the coat formed using


the colloid of Synthesis Example 73 was 9.2 × 10-6 Ω.cm.

Two alumina sheets each measuring 50 mm × 50 mm × 1.0
mm were prepared and offset printing was conducted using the
Au colloid having a concentration of 50% by weight obtained
in Synthesis Example 74 of Example 68 to form each coat
measuring 10 mm × 25 mm on the surface of the alumina sheets.
One alumina sheet with the coat formed thereon was air-dried
in an atmospheric air at 25°C for one hour, and the other
alumina sheet with the coat formed thereon was fired in an
atmospheric air at 450°C for one minute and then air-dried.
After cooling to room temperature, the resistance value of
the resulting coats was measured. As a result, the
resistance value of the air-dried coat was 8.8 × 10-6 Ω.cm
and the resistance value of the fired coat was 2.5 × 10-6 Ω.
cm.

Two glass sheets each measuring 50 mm × 50 mm × 1.0 mm
were prepared and spray-coated with the Au colloid having a
concentration of 50% by weight obtained in Synthesis Example
75 of Example 68 to form each coat measuring 10 mm × 25 mm on
the surface of the glass sheets. One glass sheet with the
coat formed thereon was air-dried in an atmospheric air at
15°C for 30 minutes. The other glass sheet with the coat
formed thereon was fired in an atmospheric air at 350°C for


one minute and then air-dried. After cooling to room
temperature, the resistance value of the resulting coats was
measured. As a result, the resistance value of the air-dried
coat was 3.5 × 10-5 Ω.cm and the resistance value of the
fired coat was 3.7 × 10-6 Ω.cm.

A glass sheet measuring 50 mm × 50 mm × 1.0 mm was
prepared and spin-coated with the Au colloid having a
concentration of 50% by weight obtained in Synthesis Example
76 of Example 68 under the conditions of a rotating speed of
200 rpm and 3 minutes to form a coat on the surface of the
glass sheet. The glass sheet with the coat formed thereon
was air-dried in an atmospheric air at 25°C for one hour.
The electrical resistance value of the resulting coat was
measured. As a result, the resistance value was 7.1 × 10-6 Ω.
cm.

Four alumina sheets each measuring 50 mm × 50 mm × 1.0
mm were prepared and slit coat printing was conducted using
the Au colloid having a concentration of 50% by weight
obtained in Synthesis Examples 77, 78, 79 and 80 of Example
68 to form each coat measuring 10 mm × 25 mm on the surface
of the alumina sheets. The alumina sheets with the coat
formed thereon were air-dried in an atmospheric air at 25°C
for one hour. The electrical resistance value of the


resulting coats was measured. As a result, the resistance
value of the coat formed using the colloid of Synthesis
Example 77 was 1.7 × 10-5 Ω.cm, the resistance value of the
coat formed using the colloid of Synthesis Example 78 was 9.1
× 10-6 Ω.cm, the resistance value of the coat formed using
the colloid of Synthesis Example 79 was 1.6 × 10-5 Ω.cm and
the resistance value of the coat formed using the colloid of
Synthesis Example 80 was 8.7 × 10-6 Ω.cm.

Five alumina sheets each measuring 50 mm × 50 mm × 1.0
mm were prepared and screen printing was conducted using the
Au colloid having a concentration of 50% by weight obtained
in Synthesis Examples 81, 82, 83, 84 and 85 of Example 68 to
form each coat measuring 10 mm × 25 mm on the surface of the
alumina sheets. The alumina sheets with the coat formed
thereon were air-dried in an atmospheric air at 40°C for one
hour. The electrical resistance value of the resulting coats
was measured. As a result, the resistance value of the coat
formed using the colloid of Synthesis Example 81 was 5.7 ×
10-6 Ω.cm, the resistance value of the coat formed using the
colloid of Synthesis Example 82 was 5.1 × 10-6 Ω.cm, the
resistance value of the coat formed using the colloid of
Synthesis Example 83 was 6.6 × 10-5 Ω.cm, the resistance
value of the coat formed using the colloid of Synthesis
Example 84 was 7.0 × 10-6 Ω.cm and the resistance value of


the coat formed using the colloid of Synthesis Example 85 was
5.7 × 10-5 Ω.cm.

An alumina sheet measuring 50 mm × 50 mm × 1.0 mm was
prepared and screen printing was conducted using the Ag
colloid having a concentration of 50% by weight obtained in
Synthesis Example 8 6 of Example 68 to form a coat measuring
10 mm x 25 mm on the surface of the alumina sheet. The
alumina sheet with the coat formed thereon was dried in an
atmospheric air at 60°C for 30 minute. The electrical
resistance value of the resulting coat was measured. As a
result, the resistance value was 4.1 * 10~6 Q-cm.

As shown in Fig. 20 A, there was prepared a cartridge
10 for pen which is composed of a tubular body 11 having a
closed lower portion, a lid portion 13 which is joined with
the upper portion of the tubular body 11 and is provided with
a continuous hole at center, and a spherical plug 14 inserted
loosely into the continuous hole of the lid portion 13, the
tubular body 11 being filled with the dilute metal colloidal
solution 12 prepared in Example 68.
As shown in Fig. 20 B, a pen 20 comprising the
cartridge 10 for pen incorporated thereinto was prepared.
This pen 20 is composed of a cylindrical upper shaft barrel
21, a cylindrical lower shaft barrel 22, the upper end of


which can be connected to the lower end of the upper shaft
barrel 21, and a tip 26 which is connected to the other end
of the lower shaft barrel 22. The inner wall of the lower
shaft barrel 22 is provided with a connection portion 23
which inserts the cartridge 10 for pen and contacts with the
lid portion 13, thereby to push up the spherical plug 14 into
the cartridge 10 for pen. In the connection portion 23,
there is provided a core portion 24 capable of being
impregnated with the metal colloidal discharging from the
cartridge 10 due to gravity while protruding the other end of
the lower shaft barrel 22 when the cartridge 10 for pen is
connected to the connection portion 23 and the spherical plug
14 is pushed up by the connection portion 23. The tip 26
connected to the other end of the lower shaft barrel 22
serves to eject the metal colloid, with which the core
portion 24 is impregnated, from the tip.
The cartridge 10 for pen was connected to the pen 20 by
contacting the lid portion 13 of the cartridge with the
connection portion 23 and pushing the connection portion 23
and the plug 14 into the cartridge 10 for pen. In that case,
the metal colloidal 12 filled into the cartridge 10 is
discharged from the gap between the lid portion 13 and the
spherical plug 14 and thus the core portion 24 is impregnated
with the dilute metal colloidal solution, which is supplied
to the tip 26 through the core portion 24. The pen


comprising the cartridge 10 for pen connected thereto is easy
to draw and was capable of drawing smoothly. This pen is
very advantageous to write desired characters and to draw
predetermined patterns on the desired base material, and the
characters and patterns drawn by the pen showed metal gloss
and color tone peculiar to metal and were excellent in
brightness.

As shown in Fig. 21, there was prepared a disposable
ampul 30 which is composed of a tubular body 31 having a
closed lower portion, a cut portion 33 joined with the upper
portion of the tubular body 31, and a lid portion 32, the cut
portion 33 being provided with a smaller width than that of
the tubular body 31 and the lid portion 32 so that it can be
cut by a hand operation, the disposable ampul having a
structure that the dilute metal colloidal solution 34
prepared in Example 68 is sealed by thermal contact bonding
of the cut portion 33 and the lid portion 32 after filling
the tubular body 31 with the dilute metal colloidal solution
34.
In the disposable ampul 30 thus obtained, the lid
portion 32 can be easily cut from the cut portion 33 through
the lever rule by laterally rotating the lid portion 32 and
the cut surface is communicated with the inside of the
tubular body 31. The metal colloid filled in the tubular


body 31 can be used after taking out from the communicated
portion.

The concentration of the metal colloid prepared in
Example 68 was adjusted to 20% by weight. A stamp pad and a
seal impression pad were produced by sufficiently
impregnating with the resulting metal colloid. Photographs
of the resulting stamp pad and seal impression pad are shown
in Fig. 32 A. A card wherein patterns are formed using the
stamp pad and the seal impression pad is also shown in Fig.
32 B. As is apparent from Fig. 32 B, the patterns made of
the metal colloid formed by using the stamp pad or seal
impression pad showed color tone and metal gloss peculiar to
gold.

The concentration of the metal colloid prepared in
Example 68 was adjusted to 20% by weight. As the base
material, a paper, a leather and a lumber were used. Using
the resulting metal colloid, a spiral scoring test was
conducted by an ink jet printer apparatus. Using the paper,
a business card, a greeting card, a memorial card and an
invitation card were produced. In case of using the leather,
a leather wallet was drawn. In case of using the lumber,
desired characters were written on a mortuary tablet. A
photograph of a greeting card wherein a metal colloid-


containing coat is formed by drawing using an ink jet printer
apparatus is shown in Fig. 33 A and a photograph of a
mortuary tablet wherein a metal colloid-containing coat is
formed by drawing using an ink jet printer apparatus is shown
in Fig. 33 B, respectively. As is apparent from Fig. 33 A
and Fig. 33 B, the patterns written by an ink jet printer
apparatus using the metal colloid showed color tone and metal
gloss peculiar to gold.

Using the metal colloid prepared in Example 68 as an
ink, characters and patterns were drawn on a colored paper by
a writing brush. The characters and patterns showed metal
gloss and color tone peculiar to metal and were excellent in
brightness. In case of drawing characters or patterns, a pen
filled with the metal colloid described in Example 92 as an
ink may be used.

Using the metal colloid prepared in Example 68 as an
ink, a hand print and a foot print were formed on a colored
paper. The hand print and the foot print showed metal gloss
and color tone metal peculiar to metal and were excellent in
brightness.

First, a paper wherein patterns are written on the
surface by a commercially available black ink using a seal


impression and a stamp, a colored paper wherein characters
and patterns are drawn on the surface using a black pen, and
a colored paper wherein a hand print and a foot print are
formed using a black ink were prepared. Using an image
scanner, the surface of the paper and that of the colored
paper were scanned and the resulting image data were inputted
into a computer. By an ink jet printer using the metal
colloid prepared in Example 68 as an ink, image data were
printed on the paper and the colored paper based on the
inputted image data. Characters and patterns printed on the
paper and the colored paper using the metal colloid of the
present invention showed the same shape as that of black
colored characters and patterns drawn and also showed metal
gloss and color tone peculiar to metal and were excellent in
brightness.
In Example 98, using the image scanner, the surface of
the paper and that of the colored paper were scanned and the
resulting image data were inputted into a computer and then
printed using the ink jet printer. Using the image scanner,
not only base papers such as paper and colored paper, but
also a photograph of these base papers, and a print and a
publication in which these patterns and characters are
described may be scanned and the resulting image data may be
inputted into a computer and directly printed using an ink
jet printer.


INDUSTRIAL APPLICABILITY
The metal colloidal particles of the present invention
have been obtained by solving the above problems in a
conventional metal colloid and the method for producing the
same, and are excellent in long-term stability of a colloidal
solution and are suited for thin-filming. Also, the metal
colloidal particles can easily form a metal specular glossy
area on various base materials. Furthermore, the metal
colloidal particles can easily form a metal glossy area
showing various gold-based basic tone color tones on various
base materials.
The metal colloid-containing coat formed article and
the transfer sheet of the present invention comprise a metal
colloid-containing coat wherein a coat having a metal
specular glossy area showing various color tones and having
excellent heat resistance is formed.
In the base material with a conductive film of the
present invention, a conductive film having a metal specular
glossy area with various color tones and excellent heat
resistance, and also having low resistance.
Furthermore, the pen, the brush-pencil, the cartridge
for pen, the disposable ampul, the stamp pad and the seal
impression pad of the present invention are excellent in
quality-retaining property of the metal colloid filled or


impregnated. The drawn material obtained by using them has
color tone and metal gloss peculiar to metal.

(Fig. 1)
Protective agent molecules
Carbon skeleton
X: Protective agent coordination-modified site
X: Protective agent end site
(Fig. 4)
Example
Example
Comparative Example
Comparative Example
Viscosity/cP
Days
(Fig. 5)
Immediately after preparation
Permeability
Wavelength
(Fig. 6)
After 400 hours
Permeability
Wavelength

WE CLAIM:
1. Metal colloidal particles capable of forming a metal
colloid by dispersing in either or both of an aqueous
dispersion medium and a nonaqueous dispersion medium in a
proportion ranging from 0.1 to 95 weight % while mixing,
comprising metal particles of one or more of metal selected
from the group consisting of Au, Ag, Pt, Cu, Pd, Ni, Zn, Ru,
Rh and Ir and a protective agent coordination-modified on the
surface of the particles, the protective agent having a
carbon skeleton containing oxygen and nitrogen in the
molecule, and having a structure of being coordination-
modified on the surface of the metal particles using an atom
or an atomic group of oxygen and nitrogen as an anchor,
wherein the protective agent has one, or two or more
functional groups selected from the group consisting of
alkoxysilyl group, silanol group and hydroxyalkyl group in a
molecular structure.
2. The metal colloidal particles as claimed in claim 1,
wherein oxygen contained in the protective agent is derived
from at least one selected from the group consisting of
carbonyl group, carboxyl group, aldehyde group, amide group
and sulfonyl group.

3. The metal colloidal particles as claimed in any one of
claims 1 or 2, wherein either or both of the alkoxysilyl
group and the hydroxyalkyl group contained in the protective
agent are chelete-coordinated by a chelating agent.
4. The metal colloidal particles as claimed in claim 1,
wherein the metal particles constituting the metal colloidal
particles are made of Au and have an average particle size
within a range from 1 to 60 nm.
5. The metal colloidal particles as claimed in claim 1 or
2, wherein a coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained
by dispersing metal colloidal particles containing Au
colloidal particles as a main component and also containing
0.1 to 10% metal particles having an average particle size of
1 to 10 nm, in addition to the Au colloidal particles, in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a pink gold color tone.
6. The metal colloidal particles as claimed in claim 1 or
2, which are either or both of metal colloidal particles
containing Au colloidal particles as a main component and
also containing Ag particles and Cu particles as impurities,
in addition to Au particles, and metal colloidal particles

containing metal particles made of an alloy containing Au as
a main component and also containing Ag and Cu as impurities,
wherein when the content of impurities in the metal colloidal
particles is from 5 to 40% and the content of Ag in
impurities is from 40 to 60% by weight based on 100% by
weight of impurities, a coat formed by coating, spraying,
printing, ejecting or transferring a metal colloid, which is
obtained by dispersing the metal colloidal particles in a
dispersion medium, and removing the dispersion medium from
the metal colloid, shows a yellow gold color tone.
7. The metal colloidal particles as claimed in claim 1 or
2, which are either or both of metal colloidal particles
containing Au colloidal particles as a main component and
also containing Ag particles and Cu particles as impurities,
in addition to Au particles, and metal colloidal particles
containing metal particles made of an alloy containing Au as
a main component and also containing Ag and Cu as impurities,
wherein when the content of impurities in the metal colloidal
particles is from 5 to 40% and the content of Ag in
impurities is 65% by weight or more based on 100% by weight
of impurities, a coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained
by dispersing the metal colloidal particles in a dispersion
medium, and removing the dispersion medium from the metal

colloid, shows a green gold color tone.
8. The metal colloidal particles as claimed in claim 1 or
2, which are either or both of metal colloidal particles
containing Au colloidal particles as a main component and
also containing Ag particles and Cu particles as impurities,
in addition to Au particles, and metal colloidal particles
containing metal particles made of an alloy containing Au as
a main component and also containing Ag and Cu as impurities,
wherein when the content of impurities in the metal colloidal
particles is from 5 to 40% and the content of Ag in
impurities is 30% by weight or less based on 100% by weight
of impurities, a coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained
by dispersing the metal colloidal particles in a dispersion
medium, and removing the dispersion medium from the metal
colloid, shows a red gold color tone.
9. The metal colloidal particles as claimed in claim 1 or
2, which are either or both of metal colloidal particles
containing Au colloidal particles as a main component and
also containing Ag particles, Cu particles and Pd particles
as impurities, in addition to Au particles, and metal
colloidal particles containing metal particles made of an
alloy containing Au as a main component and also containing

Ag, Cu and Pd as impurities, wherein when the content of
impurities in the metal colloidal particles is from 5 to 40%
and the content of Ag in impurities is 30% by weight or less
based on 100% by weight of impurities, a coat formed by
coating, spraying, printing, ejecting or transferring a metal
colloid, which is obtained by dispersing the metal colloidal
particles in a dispersion medium, and removing the dispersion
medium from the metal colloid, shows a pink gold color tone.
10. The metal colloidal particles as claimed in claim 1 or
2, which are either or both of metal colloidal particles
containing Au colloidal particles as a main component and
also containing Pd particles as impurities, in addition to Au
particles, and metal colloidal particles containing metal
particles made of an alloy containing Au as a main component
and also containing Pd as impurities, wherein when the
content of impurities in the metal colloidal particles is
from 5 to 40%, a coat formed by coating, spraying, printing,
ejecting or transferring a metal colloid, which is obtained
by dispersing the metal colloidal particles in a dispersion
medium, and removing the dispersion medium from the metal
colloid, shows a white gold color tone.
11. A metal colloid wherein the metal colloidal particles
as claimed in claim 1 or 2 are dispersed in either or both of

an aqueous dispersion medium and a nonaqueous dispersion
medium in a predetermined proportion while mixing.
12. A metal colloid wherein the metal colloidal particles
as claimed in claim 1 or 2 are mixed with a sol-gel solution
in a predetermined proportion.
13. The metal colloid as claimed in claim 12, wherein the
sol-gel solution is a solution capable of forming at least
one compound selected from the group consisting of silica,
titania, zirconia, alumina, tantalum oxide and niobium oxide.


The invention discloses a metal colloidal particles capable
of forming a metal colloid by dispersing in either or both of
an aqueous dispersion medium and a nonaqueous dispersion
medium in a proportion ranging from 0.1 to 95 weight % while
mixing, comprising metal particles of one or more of metal
selected from the group consisting of Au, Ag, Pt, Cu, Pd, Ni,
Zn, Ru, Rh and Ir and a protective agent coordination-
modified on the surface of the particles, the protective
agent having a carbon skeleton containing oxygen and nitrogen
in the molecule, and having a structure of being
coordination-modified on the surface of the metal particles
using an atom or an atomic group of oxygen and nitrogen as an
anchor, wherein the protective agent has one, or two or more
functional groups selected from the group consisting of
alkoxysilyl group, silanol group and hydroxyalkyl group in a
molecular structure.

Documents:

03816-kolnp-2006 abstract.pdf

03816-kolnp-2006 claims.pdf

03816-kolnp-2006 correspondence others.pdf

03816-kolnp-2006 description(complete).pdf

03816-kolnp-2006 drawings.pdf

03816-kolnp-2006 form-1.pdf

03816-kolnp-2006 form-3.pdf

03816-kolnp-2006 form-5.pdf

03816-kolnp-2006 international publication.pdf

03816-kolnp-2006 international search authority report.pdf

03816-kolnp-2006 priority document.pdf

03816-kolnp-2006-assignment.pdf

03816-kolnp-2006-correspondence-1.1.pdf

03816-kolnp-2006-correspondence-1.2.pdf

03816-kolnp-2006-form-18.pdf

03816-kolnp-2006-g.p.a.pdf

3816-KOLNP-2006-ABSTRACT 1.1.pdf

3816-KOLNP-2006-ABSTRACT.pdf

3816-KOLNP-2006-AMANDED CLAIMS.pdf

3816-kolnp-2006-assignment.pdf

3816-KOLNP-2006-CANCELLED PAGES.pdf

3816-KOLNP-2006-CLAIMS 1.1.pdf

3816-KOLNP-2006-CORRESPONDENCE 1.1.pdf

3816-kolnp-2006-correspondence.pdf

3816-KOLNP-2006-DESCRIPTION (COMPLETE) 1.1.pdf

3816-KOLNP-2006-DESCRIPTION (COMPLETE).pdf

3816-KOLNP-2006-DRAWINGS.pdf

3816-KOLNP-2006-EXAMINATION REPORT REPLY RECIEVED 1.1.pdf

3816-kolnp-2006-examination report.pdf

3816-KOLNP-2006-FORM 1 1.1.pdf

3816-KOLNP-2006-FORM 1.pdf

3816-kolnp-2006-form 18.pdf

3816-KOLNP-2006-FORM 2 1.1.pdf

3816-KOLNP-2006-FORM 2.pdf

3816-KOLNP-2006-FORM 3 1.1.pdf

3816-kolnp-2006-form 3-1.2.pdf

3816-KOLNP-2006-FORM 3.pdf

3816-kolnp-2006-form 5-1.1.pdf

3816-KOLNP-2006-FORM 5.pdf

3816-KOLNP-2006-FORM-27.pdf

3816-kolnp-2006-gpa.pdf

3816-kolnp-2006-granted-abstract.pdf

3816-kolnp-2006-granted-claims.pdf

3816-kolnp-2006-granted-description (complete).pdf

3816-kolnp-2006-granted-drawings.pdf

3816-kolnp-2006-granted-form 1.pdf

3816-kolnp-2006-granted-form 2.pdf

3816-kolnp-2006-granted-specification.pdf

3816-KOLNP-2006-OTHERS 1.1.pdf

3816-kolnp-2006-others-1.2.pdf

3816-KOLNP-2006-OTHERS.pdf

3816-KOLNP-2006-PA.pdf

3816-KOLNP-2006-PETITION UNDER RULE 137.pdf

3816-kolnp-2006-reply to examination report-1.1.pdf

3816-KOLNP-2006-REPLY TO EXAMINATION REPORT.pdf

3816-kolnp-2006-translated copy of priority document.pdf

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Patent Number 247406
Indian Patent Application Number 3816/KOLNP/2006
PG Journal Number 14/2011
Publication Date 08-Apr-2011
Grant Date 05-Apr-2011
Date of Filing 18-Dec-2006
Name of Patentee MITSUBISHI MATERIALS CORPORATION
Applicant Address 5-1, OTEMACHI 1-CHOME, CHIYODA-KU TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 KIYOSHIMA REIKO C/O JEMCO INC. KASHIMA PLANT, 19-1, HIGASHIFUKASHIBA, KAMISU-MACHI KASHIMA-GUN, IBARAKI-KEN
2 HAYASHI TOSHIHARU 1002-14, MUKOYAMA, NAKA-SHI, IBARAKI-KEN
PCT International Classification Number B22F9/00,B44C 1/17
PCT International Application Number PCT/JP2005/011459
PCT International Filing date 2005-06-22
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-187872 2004-06-25 Japan
2 2004-284027 2004-09-29 Japan
3 2004-235261 2004-08-12 Japan