Title of Invention

PHTHALOCYANINE COMPOUND, PROCESS FOR PRODUCING THE SAME, AND COLORED COMPOSITION CONTAINING THE PHTHALOCYANINE COMPOUND

Abstract To provide a phthalocyanine compound represented by the following general formula (1), which is halogen-free and has green hue, and also has resistance to an organic solvent and an acid: in the above general formula (1), M represents a divalent to tetravalent metal atom or two hydrogen atoms, and rings A1, A2, A3 and A4 each independently represents a benzene ring or a structure represented by the above general formula (2), provided that at least one of rings A1, A2, A3 and A4 is a structure represented by the general formula (2) and, in the above general formula (2), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a tolyl group, or a xylyl group.
Full Text 1
DESCRIPTION
PHTHALOCYANINE COMPOUND AND METHOD FOR PRODUCING THE SAME,
AND COLORING COMPOSITION CONTAINING THE PHTHALOCYANINE
COMPOUND
TECHNICAL FIELD
[0001]
The present invention relates to a phthalocyanine compound which can be used as a
green pigment, and a method for producing the same, and a coloring composition containing
the phthalocyanine compound.
BACKGROUND ART
[0002]
Typical examples of a conventionally known green pigment include a
polyhalogenated copper phthalocyanine. Since this polyhalogenated copper
phthalocyanine has excellent fastness properties but has a large amount of halogen atoms
such as chlorine and bromine atoms in the molecule, there have some fear for the safety and
environmental burden, recently. Therefore, it is required to develop a pigment capable of
coloring green with a compound having no halogen atom.
[0003]
As a method of coloring green with a compound having no halogen atom
(hereinafter referred to as "halogen-free"), for example, there is proposed a method
comprising mixing copper phthalocyanine as a blue pigment with a yellow organic pigment,
thereby performing toning to obtain a green pigment, and using the resulting green pigment
(see, for example, Japanese Unexamined Patent Publication (Kokai) No. 2001-64534).

2
However, this method causes a problem that segregation occurs because two kinds of
pigments, each having a quite different chemical structure, are mixed, and also causes a
problem that hue remarkably varies when exposed to sunlight because light resistance varies
depending on the kind of the pigment mixed.
[0004]
On the other hand, as a halogen-free compound which has green hue itself, for
example, a phthalocyanine compound having an imidazole ring represented by the
following general formula (a) (hereinafter referred to as a "compound (a)") (see, for
example, Russian Journal of General Chemistry, 69 (8), 1321 (1999) and Journal of
Porphyrins and Phthalocyanines, 4, 505 (2000)). However, the above problem such as
segregation is solved by the compound (a) in this method, but there was a problem that
resistance to an organic solvent or an acid is insufficient.
[0005]

[Chemical Formula 1]
wherein M represents a copper atom or two hydrogen atoms, and Ra represents any one of a
hydrogen atom, a methyl group, and a benzyl group.

3
DISCLOSURE OF THE INVENTION
[0006]
An object of the present invention is to provide a phthalocyanine compound which
is halogen-free and has green hue, and also has resistance to an organic solvent and an acid.
[0007]
The present inventors have intensively studied so as to achieve the above object
and found that a compound prepared by introducing imidazolone into phthalocyanine is
halogen-free and has green hue, and also has resistance to an organic solvent and an acid.
[0008]
Namely, the present invention provides a phthalocyanine compound represented by
the following general formula (1):
[0009]

[Chemical Formula 2]
wherein M represents a divalent to tetravalent metal atom or two hydrogen atoms, and rings
A1, A2, A3 and A4 each independently represents a benzene ring or a structure represented
by the following general formula (2), provided that at least one of rings A1, A2, A3 and A4
is a structure represented by the following general formula (2):
[0010]

4

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl
group, a tolyl group, or a xylyl group.
[0011]
The phthalocyanine compound of the present invention has green hue and also has
resistance to an organic solvent and an acid, and is therefore useful as a green pigment.
Also, the phthalocyanine compound of the present invention is halogen-free and therefore
has features such as high safety and low environmental burden. Accordingly, the
phthalocyanine compound of the present invention is used very usefully in place of a
halogenated phthalocyanine-based pigment as an existing green pigment in applications
which require environmental measures.
[0012]
The phthalocyanine compound of the present invention can be used as a coloring
agent in wide applications such as printing inks, coating materials, colored plastics, toners,
ink jet inks, and color filters because of having the features described above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
Fig. 1 is a graph showing an infrared spectrum of 5,6-dicyano benzimidazolone
synthesized in Synthesis Example 1.
Fig. 2 is a graph showing an infrared spectrum of copper
tetrabenzimidazolonoporphyrazine synthesized in Synthesis Example 2.

5
Fig. 3 is a graph showing an optical absorption spectrum in DMSO solution of
copper tetrabenzimidazolonoporphyrazine synthesized in Synthesis Example 2.
Fig. 4 is a graph showing an infrared spectrum of zinc
tetrabenzimidazolonoporphyrazine synthesized in Synthesis Example 3.
Fig. 5 is a graph showing an optical absorption spectrum in a DMSO solution of
zinc tetrabenzimidazolonoporphyrazine synthesized in Synthesis Example 3.
Fig. 6 is a graph showing an infrared spectrum of a mixture (1) of zinc
benzimidazolonoporphyrazine compounds synthesized in Synthesis Example 4.
Fig. 7 is a graph showing an optical absorption spectrum in a concentrated sulfuric
acid solution of a mixture (1) of zinc benzimidazolonoporphyrazine compounds synthesized
in Synthesis Example 4.
Fig. 8 is a graph showing an infrared spectrum of a mixture (2) of zinc
benzimidazolonoporphyrazine compounds synthesized in Synthesis Example 5.
Fig. 9 is a graph showing an optical absorption spectrum in a concentrated sulfuric
acid solution of a mixture (2) of zinc benzimidazolonoporphyrazine compounds synthesized
in Synthesis Example 5.
Fig. 10 is a graph showing an optical absorption spectrum of a baked coating film
obtained in a baking coating material coatability test. (a: Example 1; b: Example 2; c: Example 3;
d: Comparative Example 1; e: Comparative Example 2)
BEST MODE FOR CARRYING OUT THE INVENTION
[0014]
Synthesis Examples of a phthalocyanine compound represented by the following
general formula (1) (hereinafter referred to as a "compound (1)") of the present invention
are described below:

6

[Chemical Formula 4]
wherein M represents a divalent to tetravalent metal atom or two hydrogen atoms, and rings
A1, A2, A3 and A4 each independently represents a benzene ring or a structure represented
by the following general formula (2) (hereinafter referred to as a "benzimidazolone (2)"),
provided that at least one of rings A1, A2, A3 and A4 is benzimidazolone (2):
[0016]

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl
group, tolyl group, or a xylyl group.
[0017]
To synthesize the above compound (1), first, a dicyano benzimidazolone compound
represented by the following general formula (3), which is a dinitrile compound having an
imidazolone ring as the intermediate, is synthesized by the following synthesis method:
[0018]

7

[Chemical Formula 6]
wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl
group, a tolyl group, or a xylyl group.
[0019]
[Synthesis of Dicyano Benzimidazolone Compound]
The dicyano benzimidazolone compound represented by the general formula (3)
(hereinafter referred to as a "compound (3)") can be obtained by reacting a compound
represented by the following general formula (4) (hereinafter referred to as a "compound
(4)") with urea or 1,1-carbonyldiimidazole in an organic solvent such as acetonitrile at 50 to
130°C for about 1 to 6 hours:

[Chemical Formula 7]
wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl
group, a tolyl group, or a xylyl group.
[0021]
The method for synthesizing a compound (4) in which R in the general formula (4)
is a hydrogen atom includes, for example, a method comprising protecting an amino group
of o-phenylenediamine with a tosyl group, brominating moieties at the 4- and 5-positions,
performing deprotection, and reacting with copper cyanide thereby substituting a bromo

8
group with a cyano group. This synthesis method is described in detail in Journal of the
Chemical Society, 1170 (1962), and Chemistry-A European Journal, 9 (5), 1233 (2003). A
compound (3) in which R in the general formula (3) is a hydrogen atom can be obtained by
synthesizing the above compound (3) using this compound (4) in which R in the general
formula (4) is a hydrogen atom.
[0022]
Also, the method for synthesizing a compound (4) in which R is other than a
hydrogen atom in the general formula (4) includes, for example, a method comprising
nitrating moieties at the 4- and 5-positions of o-dibromobenzene, reacting with ammonia
thereby reducing one of nitro groups to an amino group, monoalkylating or monoarylating
the amino group, substituting a bromo group with a cyano group, and reducing a nitro group
with tin chloride. This synthesis method is described in detail in Chemical
Communication, 2236 (2002). A compound (3) in which R in the general formula (3) is
other than a hydrogen atom can be obtained by synthesizing the above compound (3) using
this compound (4) in which R in the general formula (4) is other than a hydrogen atom.
[0023]
The compound (1) can be obtained by the following synthesis method (1) using the
compound (3) obtained by the above synthesis method when all substituents of ring A1, A2,
A3 and A4 in the general formula (1) are benzimidazolones (2), or can be obtained by the
following synthesis method (2) when one to three rings among rings A1, A2, A3 and A4 are
benzimidazolones (2) and the remainder are benzene rings.
[0024]
Synthesis Method (1)
The compound (1) in which all of rings A1, A2, A3 and A4 in the general formula
(1) are benzimidazolones (2) can be obtained by thermocondensing the compound (3)

9
described above with a metal salt corresponding to a divalent to tetravalent metal atom
represented by M in the general formula (1) in an organic solvent at 130 to 250°C. The
phthalocyanine compound obtained by this synthesis is a phthalocyanine compound as a
metal complex represented by the following general formula (5) (hereinafter referred to as a
"compound (5)"). By using two or more kinds of compounds (3), each having different R
in the general formula (3), it is possible to obtain a phthalocyanine compound in which R1,
R2, R3 and R4 in the following general formula (5) are different. In this synthesis method
(1), by synthesizing without using a metal salt corresponding to the divalent to tetravalent
metal atom, it is possible to obtain a metal-free phthalocyanine compound in which M in the
following general formula (5) represents two hydrogen atoms:
[0025]

[Chemical Formula 8]
wherein M represents a divalent to tetravalent metal atom or two hydrogen atoms, and R1 to
R4 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon
atoms, a phenyl group, a tolyl group, or a xylyl group.
[0026]
The divalent to tetravalent metal atom represented by M in the general formula (1)

10
includes, for example, atoms of magnesium, aluminum, titanium, vanadium, iron, cobalt,
nickel, copper, zinc, platinum, and palladium. Among these metal atoms, a copper or zinc
atom is preferable and a zinc atom is more preferable. The divalent to tetravalent metal
atom represented by M in the general formula (1) corresponds to a divalent to tetravalent
metal atom represented by M in the general formula (5).
[0027]
As the metal salt corresponding to the divalent to tetravalent metal atom, for
example, various salts such as halides, acetates, sulfates, nitrates, and carbonates can be
used, and halides and acetates are preferable.
[0028]
The organic solvent used to synthesize the compound (5) includes, for example,
alcohols, glycols, trichlorobenzene, quinoline, a-chloronaphthalene, nitrobenzene, sulfolane,
and N,N-dimethylformamide. The reaction may be conducted without using a solvent.
[0029]
In the case of synthesizing the compound (5), an alkali or an organic amine such as
diazabicycloundecene (hereinafter referred to as "DBU") or cyclohexylamine is preferably
used as a catalyst because the yield is improved.
[0030]
Synthesis Method (2)
A compound (1) in which one to three rings among ring A1, A2, A3 and A4 are
benzimidazolones (2) and the others are benzene rings in the general formula (1) can be
obtained by thermocondensing the compound (3) obtained above, phthalonitrile, and a metal
salt corresponding to a divalent to tetravalent metal atom represented by M in the general
formula (1) in an organic solvent at about 130 to 250°C. The phthalocyanine compound
obtained by this synthesis is a phthalocyanine compound as a metal complex represented by

11
the following general formula (6) (hereinafter referred to as a "compound (6)"). By using
two or more kinds of compounds (3), each having different R in the general formula (3), it is
possible to obtain a phthalocyanine compound in which each benzimidazolone (2) in rings
B1, B2 and B3 in the following general formula (6) is different. In the synthesis method
(2), by synthesizing without using a metal salt corresponding to the divalent to tetravalent
metal atom, it is possible to obtain a metal-free phthalocyanine compound in which M in the
following general formula (6) represents two hydrogen atoms:
[0031]
[Chemical Formula 9]

wherein M represents a divalent to tetravalent metal atom or two hydrogen atoms, and rings
B1, B2 and B3 each independently represents a benzene ring or benzimidazolone (2),
provided that at least one of rings B1, B2 and B3 is benzimidazolone (2).
[0032]
The metal salt corresponding to the divalent to tetravalent metal atom used in this
synthesis method (2), the divalent to tetravalent metal atom, the organic solvent and the
catalyst may be the same as those used in the synthesis method (1).
[0033]
In the above synthesis method (2), when a ratio of the compound (3) and

12
phthalonitrile to be charged as raw materials is varied, hue of the finally obtained compound
(6) varies. By increasing a charging ratio of phthalonitrile, the resulting compound (6)
shows more bluish hue and high chroma. Therefore, the charging ratio of phthalonitrile
can be appropriately selected so as to obtain desired hue and chroma, but is preferably
within a range from 15 to 75 mass% based on the total amount of the compound (3) and
phthalonitrile.
[0034]
A compound (1) in which imidazolone is introduced into phthalocyanine can be
obtained by the above synthesis method (1) or (2). In this compound (1), since
imidazolone has a carbonyl group, unlike a compound (a) as the above-described
phthalocyanine compound having an imidazole ring, it becomes possible to form an
intermolecular hydrogen bond between this carbonyl group and a hydrogen atom bonded
with a nitrogen atom in imidazolone of the other molecule, resulting in excellent resistance
to an organic solvent and an acid.
[0035]
When all of rings A1, A2, A3 and A4 are benzimidazolones (2) in the general
formula (1), hue of the compound (1) becomes green. On the other hand, when one to
three rings among rings A1, A2, A3 and A4 are benzimidazolones (2) and the remaindered
are benzene rings, hue becomes bluish green. As the number of benzene ring increases in
rings A1, A2, A3 and A4, hue becomes more bluish green. Rings A1, A2, A3 and A4 are
preferably composed of benzimidazolone (2) and a benzene ring because chroma is
enhanced. Furthermore, in benzimidazolone (2), R in the general formula (2) is preferably
a hydrogen atom, because the number of moieties, which form the above intermolecular
hydrogen bond, increases and therefore resistance to an organic solvent and an acid is more
enhanced.

13
[0036]
As described above, since hue of the phthalocyanine compound of the present
invention can be varied according to the kind of rings A1, A2, A3 and A4 in the general
formula (1), desired hue can be obtained by appropriately selecting rings A1, A2, A3 and A4
from among benzimidazolone (2) and benzene rings.
[0037]
In the compound (1), phthalocyanine compounds represented by the following
formulas (7-a) to (7-e) are more preferable.
[0038]

14


15
[0039]
By the above synthesis method, the compound (1) is obtained as a green crude
pigment. When the compound is used as a coloring agent, a pigmentation treatment is
preferably conducted. This pigmentation treatment includes, for example, a milling
treatment such as solvent salt milling, salt milling, dry milling, solvent milling, or acid
pasting, or a solvent heating treatment. The particle size of the pigment can be
simultaneously adjusted by these pigmentation treatments.
[0040]
When the phthalocyanine compound of the present invention is used as a green
pigment, the phthalocyanine compound is preferably subjected to the above pigmentation
treatment thereby adjusting the particle size of the pigment within a range from 0.01 to 1 um.
[0041]
The coloring composition of the present invention is a composition containing the
phthalocyanine compound of the present invention as a coloring agent and applications
thereof include printing inks, coating materials, colored plastics, toners, ink jet inks, color
pastes for color filter, and color resists.
[EXAMPLES]
[0042]
The present invention will now be described in detail by way of Examples.
[0043]
[Synthesis Example 1]
In 100 parts by mass of dehydrated acetonitrile, 15 parts by mass of 1,2-diamino-
4,5-dicyanobenzene and 19.5 parts by mass of 1,1-carbonyldiimidazole were added,
followed by reaction while stirring at 70°C for 3 hours. The resulting reaction product was
cooled to room temperature and the precipitated solid was filtered, washed with water and

16
then dried to obtain 16.9 parts by mass (yield: 96.5%) of a peachish white solid.
[0044]
With respect to the peachish white solid obtained in Synthesis Example 1,1 H-
NMR analysis (using a nuclear magnetic resonance spectrometer "JNM-LA300"
manufactured by JEOL Ltd.) in a dimethyl sulfoxide (hereinafter referred to as "DMSO")-
d6 solution and infrared spectrophotometry (using a Fourier transform infrared
spectrophotometer "FT/IR-550" manufactured by JASCO Corporation) were conducted to
obtain the following analytical results. A spectrum obtained by infrared spectrophotometry
is shown in Fig. 1.
[0045]

1 H-NMR (DMSO-d6):  = 7.6l(s), 11.67(s, br)
[0046]

3316 cm-1: N-H stretching vibration of imidazolone
2240 cm-1: CN stretching vibration of cyano group
1709,1726 cm-1: C=O stretching vibration of imidazolone
[0047]
It was confirmed by the above results that the peachish white solid obtained in
Synthesis Example 1 is a dicyano benzimidazolone compound represented by the following
formula (8).
[0048]

17

[Chemical Formula 11]
[0049]
[Synthesis Example 2]
(Synthesis of phthalocyanine compound in which M is a copper atom and all of R1 to R4
are hydrogen atoms in the general formula (5))
In 32 parts by mass of trichlorobenzene, 10 parts by mass of 5,6-dicyano
benzimidazolone obtained in Synthesis Example 1, 1.4 parts by mass of copper (I) chloride
and 10 parts by mass and DBU were added, followed by reaction while stirring at 180°C for
6 hours. The resulting reaction product was cooled to room temperature and the
precipitated solid was filtered. The resulting solid was washed in turn with acetone,
methanol, 10 mass% hydrochloric acid, 8 mass% ammonia in water and water, and then
dried to obtain 7.3 parts by mass (yield: 67.2%) of a green solid.
[0050]
With respect to the green solid obtained above, FAB/MS Analysis (mass
spectrometer manufactured by JEOL Ltd."JMS-LX2000"), infrared spectrophotometry
(using a Fourier transform infrared spectrophotometer "FT/IR-550" manufactured by
JASCO Corporation) and measurement of an optical absorption spectrum in a DMSO
solution (using an automatic recording spectrophotometer "U-3500" manufactured by
Hitachi, Ltd.) were conducted to obtain the following analytical results. A spectrum
obtained by infrared spectrophotometry is shown in Fig. 2 and an optical absorption
spectrum is shown in Fig. 3.
[0051]

18

m/z = 800 (M+H)+
[0052]

3178 cm-1: N-H stretching vibration of imidazolone
1716 cm-1: C=O stretching vibration of imidazolone
[0053]
Optical Absorption Spectrum>
Absorption wavelength: 306,404, 626, 691 nm (in DMSO )
[0054]
It was confirmed by the above results that the green solid obtained in Synthesis
Example 2 is copper tetrabenzimidazolonoporphyrazine represented by the following
formula (9).
[0055]

[Chemical Formula 12]
[0056]
[Synthesis Example 3]

19
(Synthesis of phthalocyanine compound in which M is a zinc atom and all of R to R4 are
hydrogen atoms in the general formula (5))
In 175 parts by mass of 1-pentanol, 15 parts by mass of 5,6-dicyano
benzimidazolone obtained in Synthesis Example 1, 5.0 parts by mass of urea, 3.5 parts by
mass of zinc acetate and 12.5 parts by mass of DBU were added, followed by reaction while
stirring at 140°C for 6 hours. The resulting reaction product was cooled to room
temperature and the precipitated solid was filtered. The resulting solid was washed in turn
with acetone, methanol, 3 mass% sulfuric acid, 8 mass% ammonia in water and water, and
then dried to obtain 4.0 parts by mass (yield: 24.8%) of a green solid.
[0057]
With respect to the green solid obtained above, FAB/MS Analysis (using a mass
spectrometer "JMS-LX2000" manufactured by JEOL Ltd.), infrared spectrophotometry
(using a Fourier transform infrared spectrophotometer "FT/IR-550" manufactured by
JASCO Corporation F) and measurement of an optical absorption spectrum in a DMSO
solution (using an automatic recording spectrophotometer "U-3500" manufactured by
Hitachi, Ltd.) were conducted to obtain the following analytical results. A spectrum
obtained by infrared spectrophotometry is shown in Fig. 4 and an optical absorption
spectrum is shown in Fig. 5.
[0058]

m/z = 801(M+H)+
[0059]

3228 cm-1: N-H stretching vibration of imidazolone
1708 cm-1 : C=O stretching vibration of imidazolone

20
[0060]
Optical Absorption Spectrum>
Absorption wavelength: 303, 361, 622, 691 nm (in DMSO)
[0061]
It was confirmed by the above results that the green solid obtained in Synthesis
Example 3 is zinc tetrabenzimidazolonoporphyrazine represented by the following formula
(10).
[0062]

[Chemical Formula 13]
[0063]
[Synthesis Example 4]
(Synthesis 1 of compounds represented by the formulas (7-a) to (7-e))
In 10 parts by mass of 1-octanol, 1.6 parts by mass of 5,6-dicyano benzimidazolone
obtained in Synthesis Example 1,0.4 parts by mass of phthalonitrile, 0.7 parts by mass of
urea, 0.5 parts by mass of zinc acetate and 0.7 parts by mass of DBU, followed by reaction
while stirring at 170°C for 6 hours. The resulting reaction product was cooled to room
temperature and the precipitated solid was filtered. The resulting solid was washed in turn

21
with acetone, methanol, 10 mass% hydrochloric acid, water and methanol, and then dried to
obtain 1.3 parts by mass of a slightly bluish green solid.
[0064]
With respect to the slightly bluish green solid obtained above, FD/MS Analysis
(using a mass spectrometer "JMS-700" manufactured by JEOL Ltd.), infrared
spectrophotometry (using a Fourier transform infrared spectrophotometer "FT/IR-550"
manufactured by JASCO Corporation) and measurement of an optical absorption spectrum
in a concentrated sulfuric acid (using an automatic recording spectrophotometer "U-3500"
manufactured by Hitachi, Ltd.) were conducted to obtain the following analytical results.
A spectrum obtained by infrared spectrophotometry is shown in Fig. 6 and an optical
absorption spectrum is shown in Fig. 7.
[0065]

m/z = 576, 632, 688, 744, 800
[0066]

3168 cm-1: N-H stretching vibration of imidazolone
1704 cm-1: C=O stretching vibration of imidazolone
[0067]

Absorption wavelength: 311,441, 707, 798 nm (in concentrated sulfuric acid)
[0068]
It was confirmed by the above results that the slightly bluish green solid obtained in
Synthesis Example 4 is a mixture of zinc phthalocyanine and five zinc
benzimidazolonoporphyrazine compounds represented by the following formulas (7-a) to

22
(7-e) (hereinafter referred to as a "mixture (1) of zinc benzimidazolonoporphyrazines").
[0069]

23


24
[0070]
[Synthesis Example 5]
(Synthesis 2 of the formulas (7-a) to (7-e))
In 10 parts by mass of 1-octanol, 1.2 parts by mass of 5,6-dicyano benzimidazolone
obtained in Synthesis Example 1, 0.8 parts by mass of phthalonitrile, 0.7 parts by mass of
urea, 0.6 parts by mass of zinc acetate and 0.7 parts by mass of DBU were added, followed
by reaction while stirring at 170°C for 6 hours. The resulting reaction product was cooled
to room temperature and the precipitated solid was filtered. The resulting solid was
washed in turn with acetone, methanol, 10 mass% hydrochloric acid, water, methanol, and
then dried to obtain 1.4 parts by mass of a slightly bluish green solid.
[0071]
With respect to the bluish green solid obtained above, FD/MS Analysis (using a
mass spectrometer "JMS-700" manufactured by JEOL Ltd.), infrared spectrophotometry
(using a Fourier transform infrared spectrophotometer "FT/IR-550" manufactured by
JASCO Corporation) and measurement of an optical absorption spectrum in a concentrated
sulfuric acid solution (using an automatic recording spectrophotometer "U-3500"
manufactured by Hitachi, Ltd.) were conducted to obtain the following analytical results.
A spectrum obtained by infrared spectrophotometry is shown in Fig. 8 and an optical
absorption spectrum is shown in Fig. 9.
[0072]

m/z = 576, 632, 688, 744, 800
[0073]

3182 cm-1: N-H stretching vibration of imidazolone

25
1702 cm-1: C=O stretching vibration of imidazolone
[0074]

Absorption wavelength: 310,440, 705, 796 nm (in concentrated sulfuric acid solution)
[0075]
It was confirmed by the above results that the bluish green solid obtained in
Synthesis Example 5 is a mixture of zinc phthalocyanine and five zinc
benzimidazolonoporphyrazine compounds represented by the above formulas (7-a) to (7-e)
(hereinafter referred to as a mixture (2) of "zinc benzimidazolonoporphyrazine compounds).
[0076]
[Example 1]
2.2 parts by mass of zinc tetrabenzimidazolonoporphyrazine obtained in Synthesis
Example 3 was added to 40 parts by mass of N,N-dimethylformamide and a solvent heating
treatment was conducted at 150°C for 6 hours. After the heat treatment, the green powder
was filtered and then dried to obtain a green pigment having an average particle size of 0.5
um.
[0077]
Using the resulting green pigment of zinc tetrabenzimidazolonoporphyrazine, the
following baking coating material coatability test and chemical resistance test were
conducted.
[0078]

4 parts by mass of a green pigment, 10 parts by mass of a mixed resin of 70% of an
alkyd resin for baking coating material ("Bekkozol J-524-IM-60" manufactured by
Dainippon Ink and Chemicals, Incorporated.) and 30% of a melamine resin ("Super

26
Bekkamine G-821-60" manufactured by Dainippon Ink and Chemicals, Incorporated.), 7
parts by mass of xylene and 3 parts by mass of n-butanol were dispersed with a paint
conditioner for 2 hours using glass beads as a grinding media. Then, 50 parts by mass of
an acrylmelamine resin was added, followed by mixing with the paint conditioner for 5
minutes. The resulting green coating material composition was applied on a polyester film
using an applicator and then baked at 130°C for 30 minutes. The resulting coating film
showed a glossy green color.
[0079]
With respect to the coating film obtained above, an optical absorption spectrum
was measured using a spectrophotometer (using an automatic recording spectrophotometer
"U-3500" manufactured by Hitachi, Ltd.). Absorption wavelengths of this coating film
were 357, 657, and 713 nm. The optical absorption spectrum obtained by the measurement
is shown in Fig. 10.
[0080]

1 Part by mass of a green pigment and 20 parts by mass of an organic solvent or an
acid described in the following Table 1 were charged in a lidded container, sealed, shaken
for 30 seconds and then allowed to stand for 15 minutes. The lidded container was shaken
again for 30 seconds and allowed to stand for 30 minutes, followed by filtration.
Coloration of the filtrate was visually observed and evaluation was conducted according to
the following criteria.
Good: No coloration of a filtrate was visually confirmed.
Poor: Coloration of a filtrate was visually confirmed.
[0081]
[Example 2]

27
In the same manner as in Example 1, except that a mixture (1) of zinc
benzimidazolonoporphyrazine compounds obtained in Synthesis Example 4 was used as a
green pigment in place of zinc tetrabenzimidazolonoporphyrazine obtained in Synthesis
Example 3, a baking coating material coatability test and a chemical resistance test were
conducted.
[0082]
[Example 3]
In the same manner as in Example 1, except that a mixture (2) of zinc
benzimidazolonoporphyrazine compounds obtained in Synthesis Example 5 was used as a
green pigment in place of zinc tetrabenzimidazolonoporphyrazine obtained in Synthesis
Example 3, a baking coating material coatability test and a chemical resistance test were
conducted.
[0083]
[Comparative Example 1]
In the same manner as in Example 1, except that a chlorinated copper
phthalocyanine pigment ("Fastogen Green S", C.I. Pigment Green 7 manufactured by
Dainippon Ink and Chemicals, Incorporated.) was used as a green pigment in place of zinc
tetrabenzimidazolonoporphyrazine obtained in Synthesis Example 3, a baking coating
material coatability test and a chemical resistance test were conducted.
[0084]
[Comparative Example 2]
In the same manner as in Example 1, except that a brominated copper
phthalocyanine pigment ("Fastogen Green 2YK-CF", C.I. Pigment Green 36 manufactured
by Dainippon Ink and Chemicals, Incorporated.) was used as a green pigment in place of
zinc tetrabenzimidazolonoporphyrazine obtained in Synthesis Example 3, a baking coating

28
material coatability test and a chemical resistance test were conducted.
[0085]
Test results of the green pigments of Examples 1 to 3 and Comparative Examples 1
and 2 are shown in Table 1. With regard to the item of halogen-free in Table 1, a halogen-
free pigment was described "Yes", while a no halogen-free pigment was described as "No".

[0086]
Table 1

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2
Compound Zinc
tetrabenzimidazolono-
porphyrazine Mixture (1) of zinc
benzimidazolono-
porphyrazines Mixture (2) of zinc
benzimidazolono-
porphyrazines Chlorinated copper
phthalocyanine Brominated copper
phthalocyanine
Halogen-free Yes Yes Yes No No
Hue Green Slightly bluish green Bluish green Bluish green Green
Absorption
wavelength of baked
coating film (nm) 357
657
713 355
707 346
642
680 363
646 366
662
Chemical resistance
test
Methanol
Acetone
Ethyl acetate
Xylene
2 mass% HC1 Good
Good
Good
Good
Good Good
Good
Good
Good
Good Good
Good
Good
Good
Good Good
Good
Good
Good
Good Good
Good
Good
Good
Good

29

30
[0087]
As is apparent from the results shown in Table 1, the phthalocyanine compound of
the present invention can be used as a halogen-free green pigment and has resistance to an
organic solvent and an acid, which is equivalent to that of a chlorinated copper
phthalocyanine pigment or a brominated copper phthalocyanine pigment known as an
existing green pigment having high chemical resistance.
INDUSTRIAL APPLICABILITY
[0088]
The phthalocyanine compound of the present invention has green hue and also has
resistance to an organic solvent and an acid, and is therefore useful as a green pigment.
Also, the phthalocyanine compound of the present invention is halogen-free and therefore
has features such as high safety and low environmental burden. Thus, the phthalocyanine
compound of the present invention is used very usefully in place of a halogenated
phthalocyanine-based pigment as an existing green pigment in applications which require
environmental measures.
[0089]
The phthalocyanine compound of the present invention can be used as a coloring
agent in wide applications such as printing inks, coating materials, colored plastics, toners,
ink jet inks, and color filters because of having the features described above.

31
CLAIMS
1. A phthalocyanine compound represented by the following general formula (1):
[Chemical Formula 15]

wherein M represents a divalent to tetravalent metal atom or two hydrogen atoms, and
rings A1, A2, A3 and A4 each independently represents a benzene ring or a structure
represented by the following general formula (2), provided that at least one of rings A1, A2,
A3 and A4 is a structure represented by the following general formula (2):
[Chemical Formula 16]

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a
phenyl group, a tolyl group, or a xylyl group.
2. The phthalocyanine compound according to claim 1, wherein the divalent to
tetravalent metal atom represented by M is a copper or zinc atom in the general formula (1).
3. The phthalocyanine compound according to claim 1, wherein R is a hydrogen
atom in the general formula (2).

32
4. The phthalocyanine compound according to claim 1, wherein all of the rings A1,
A2, A3 and A4 in the general formula (1) are structures represented by the general formula
(2).
5. A dicyano benzimidazolone compound represented by the following general
formula (3), which is a raw material for preparing the phthalocyanine compound
represented by the general formula (1) according to claim 1:
[Chemical Formula 17]

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a
phenyl group, a tolyl group, or a xylyl group.
6. A method for preparing the phthalocyanine compound according to claim 1,
which comprises thermocondensing a dicyano benzimidazolone compound represented by
the general formula (3), phthalonitrile, and a mixture of metal salts corresponding to a
divalent to tetravalent metal atom represented by M in the general formula (1).
7. A method for preparing the phthalocyanine compound according to claim 4,
which comprises thermocondensing a dicyano benzimidazolone compound represented by
the general formula (3), and a mixture of metal salts corresponding to a divalent to
tetravalent metal atom represented by M in the general formula (1).

33
8. A coloring composition containing the phthalocyanine compound according to
claim 1.

To provide a phthalocyanine compound represented by the following general
formula (1), which is halogen-free and has green hue, and also has resistance to an organic
solvent and an acid:

in the above general formula (1), M represents a divalent to tetravalent metal atom or two
hydrogen atoms, and rings A1, A2, A3 and A4 each independently represents a benzene
ring or a structure represented by the above general formula (2), provided that at least one
of rings A1, A2, A3 and A4 is a structure represented by the general formula (2) and, in the
above general formula (2), R represents a hydrogen atom, an alkyl group having 1 to 4
carbon atoms, a phenyl group, a tolyl group, or a xylyl group.

Documents:


Patent Number 259211
Indian Patent Application Number 3064/KOLNP/2007
PG Journal Number 10/2014
Publication Date 07-Mar-2014
Grant Date 03-Mar-2014
Date of Filing 21-Aug-2007
Name of Patentee DAINIPPON INK AND CHEMICALS, INC.
Applicant Address 35-58, SAKASHITA 3-CHOME ITABASHI-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 NAGATA YOSHIAKI C/O DAINIPPON INK AND CHEMICALS, INC., CENTRAL RESEARCH LABORATORIES, 631, SAKADO, SAKURA-SHI, CHIBA-KEN
PCT International Classification Number C09B 47/067
PCT International Application Number PCT/JP2006/302842
PCT International Filing date 2006-02-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2005-169353 2005-06-09 Japan
2 2005-042135 2005-02-18 Japan