Title of Invention

A METHOD FOR PROVIDING A DETERGENT FEE WASHING FUNCTION

Abstract It is an object of the present invention to provide a 5 method for providing detergent-free washing function by which a washing effect approximately same as that in the case of using a detergent can be caused even in the case of washing a fiber or a fiber product without using a detergent and a fiber product capable of washing without 10 using a detergent. The present invention relates to a method for providing a detergent-free washing function to a fiber or a fiber product/which is subjected to hydrophilizetion treatment.
Full Text 1
DESCRIPTION
METHOD OF PROVIDING NON-DETERGENT WASHING FUNCTION AND
FIBER PRODUCT WASHABLE WITHOUT USING DETERGENT
5
[TECHNICAL FIELD]
[0001]
The present invention relates to; a method for
providing detergent-free washing function by which a
10 washing effect approximately same as that in the case of
using a detergent can be caused, even in the case of washing
a fiber or a fiber product without using a detergent, and a
fiber product capable of washing without using a detergent.
15 [BACKGROUND ART]
[0002]
A stained fiber product is washed by using a
detergent in common sense. It is carried out by promoting
separation of staining and blotting components from the
20 surface of a fiber on the effect of a surfactant, a main
component of a detergent. However, it has been pointed out
that environments such as seas, lakes and marshes might be
polluted seriously if a large quantity of detergents is
discharged to the environments. As countermeasures against
25 the problem, recently the components in detergents have
been reconsidered and detergents containing, as main
components, those which cause insignificant effects on
environments or detergents which might bring same washing
effects even in a little amount as those of conventional
30 ones have been developed and commercialized. However, an
immense amount of the detergents have been consumed for
domestic use and industrial use and discharged and how to
solve the adverse effects of the detergents on the
environments has still been a serious problem left unsolved.
35 [0003]

2
To deal with the problem,it has been tried to
improve washing machines or washing methods so as to
develop washing methods achieving similar washing effects
without using any detergents to those in the case of using
5 detergents. For example, Patent Document No 1 discloses a
washing method for having the same washing effect as
detergents without using any detergents containing
hydronium ions, hydroxyl ions and the like by passing a
mixture of water and air via clothes at a high speed.
10 However, this aethod requires a special washing machine and
there are leports that the washing effects are insufficient
to the stains and dirt derived from oily components such as
sebaceous matters.
[0004]
15 [Patent Document No. 1] Japanese Kckai Publication 2000-
237485
[DISCLOSURE OF THE INVENTION]
[PROBLEMS WHICH THE INVENTION IS TO SOLVE]
20 [0005]
In consideration of the above-mentioned presenz
situation, the present invention aims to provide a method
for providing detergent-free washing function by which a
washing effect approximately same as that in the case of
25 using a detergent can be caused even in the case of washing
a fiber or a fiber product without using a detergent and a
fiber product capable of washing without using a detergent.
[MEANS FOR SOLVING THE PROBLEMS]
30 [0006]
Hereinafter the present invention will be described
in details.
Incidentally, in this description, the fiber products
include clothes such as underwear, overcoats, socks, panty
35 hoses, globes, hats and caps, hair bands, neckties and all

3
other common products containing fibers such as
handkerchiefs, towels, face masks, mufflers, sheets, pillow
covers, Futon, cushions, diapers, diaper covers and the
like.
5 [0007]
Based on the results of the enthusiastic
investigations/ inventors of the present invention have
unexpectedly found it possible to provide a detergent-free
washing function by subjecting fibers or fiber products to
10 hydrophilization treatment and consequently have
accomplished the present invention. It is supposedly
attributed to that since almost all of stains and dirt to
be concerned for the fibers or fiber products are oily
components such as sebaceous matters, the bonding force of
15 the components of stains and dirt to the fibers is weakened
by hydrophilization of the fibers or the fiber products and
accordingly, the staining and blotting components can be
separated only by water even without using a surfactant.
With respect to stains other than the oily components,, if
20 washing is carried out by using a large quantity of water,
they can be separated without using a surfactant.
[0008]
In this description, the detergent-free washing
function means to cause an approximately same washing
25 effect even in the case of washing without using a
detergent as that in the case of washing with, using a
detergent; and that the approximately same washing effect
is caused means that the washing effect in the case fibers
or fiber products subjected to hydrophilination treatment
30 by the method for providing the detergent-free washing
function of the present invention are washed without using
a detergent is same as the washing effect in the case
untreated fibers or fiber products are washed by using a
detergent. Practically, for example, it means that in the
35 case object fibers or fiber products are white, the

4
alteration of the whiteness after the fibers or fiber
products, which are subjected, to the hydropailization
treatment by the method for providing tha detergsnt-free
washing function of the present invention., are stained and
S blotted and washed without using a detergent from that
before the fibers or the fiber products are stained and
blotted is within 110% to the alteration of the whiteness
after untreated fibers or fiber products are stained and
blotted and washed using a detergent from that before the
10 fibers or the fiber products are stained and blotted. Also,
it means that in the case the object fibers or fiber
products are colored including white color., the remaining
ratio (%) of oleic acid after the fibers or fiber products,
which are subjected to the hydrophilization treatment by
15 the method for providing the detergent-free washing
function of the present invention, are stained with oleic
acid 10% owf and gelatin 2.5% owf and washed without using
a detergent is within 110% to the remaining ratio (%) of
the olelc acid after untreated fibers or fiber products are
20 stained with oleic acid 10% owf and gelatin 2.5% owf and
washed using a detergent.
[0009]
The above-mentioned hydrophilization treatment is not
particularly limited and it is preferable to carry out the
25 hydrophilization treatment by at least one method selected
from a group consisting of, for example, a method for
introducing a hydrophilic group, a method for introducing a
hydrophilic molecule, a method for improving the surface
physically, and a method for applying a coating agent
30 containing a hydrophilic substance.
(0010]
The above-mentioned method for introducing a
hydrophilic group is not particularly limited and a method
for directly bonding a hydrophilic group, e.g. a polar
35 group such as a carboxyl group, an ammo group, a sulfone

5
group, a hydroxyl group, a phosphoric acid group, an epoxy
group, and an ether residual, group, or groups cowprisiing
these groups to the molecules composing the fibers or fiber
products can be exemplified.
5 [0011]
The above-mentioned method for introducing a
hydrophilic molecule is not particularly limited and
examples of the method are a method for bonding & molecule
comprising a hydrophilic group, e.g a polar group such as
10 a carboxyl group, an amlno group, and a sulfone group, or
groups comprising these groups to the molecules composing
the. fibers or fiber products and a mathod for bonding side
chains with high hydrophzlicity to the fibers or fiber
products by graft polymerization of methacrylamide,
15 hydroxyethyl acrylate, acrylic acid, methacrylic acid or
the like. The method is particularly suitable in the case
the fibers or fiber products are of cellulose type,
polyethylene terephthalate, nylon and the like.
[0012]
20 The above-mentioned method for improving the surface
physically is not particularly limited and examples of the
method axe methods for surface-treating the fibers or fiber
products with plasma treatment, corona treatment, ionizing
and activating beam treatment with UV rays, electron beam,
25 radiation beam, and laser, flame treatment, ozonization,
treatment with enzymes or microorganism, and the like.
The above-mentioned method for applying a coating
agent containing a hydrophilic substance is not
particularly limited and an example of the method is
30 forming a coating on the surface of the fibers or fiber
products by using coating agents obtained by dissolving
hydrophilic substances such as hydrophilic vinyl compounds,
polyalkylene oxide type compounds, and hydrophilic natural
compounds in binder resins such as acrylic resin,
35 methacrylic resin, urethane resin., silicon, resin, glyoxal

6
resin, vinyl acetate resin, vinylidene chloride resin,
butadiene resin, melamine resin, epoxy resin, acryl-silicon
copolymer resin, ethylene-vinyl acetate copolymer resin,
isobutylene-maleic anhydride copolymer resin Also, the
5 coating may be formed by applying these monomers or
oligomers and then making them resins by reaction.
[0013]
The fibers or fiber products to be objects of the
method for providing the detergent-free washing function of
10 the present invention are not particularly limited and
those made of natural fibers such as cellulose type fibers
(cotton), flax, silk, and wool; synthetic fibers such as
polyethylene terephthalate, rayon, polynosic, cupra,
acetate, nylon, vinylon, vinylidene, poly (vinyl chloride),
15 acryl, acrylic type, polyethylene/ polypropylene,
polyurethane, and their blended fibers. Among them, those
containing at least cellulose type fibers are preferable
since the cellulose type fibers are used for many fiber
products such as underwear,
20 [0014]
Hereinafter, the method for providing the detergent-
free washing function of the present invention will be
described more in details in the case the fibers or riber
products containing at least cellulose type fibers. If the
25 fibers or fiber products containing at least cellulose type
fibers are blended fibers of cellulose type fibers and
other fibers, the following hydrophilization treatment may
be carried out in the blended fiber state or the
hydrophilization treatment may be carried out only fcr the
30 cellulose type fibers and then the fibers are biendea with
ocher fibers-
[0015]
With respect to the method for providing the
detergent-free washing function of the present invention,
35 in the case that the above-mentioned fibers or fiber

7
products contain at least the cellulose type fibers, the
moisture absorption ratio of the cellulose type fibers is
preferably adjusted to be 7 1% or higher by the
hydrophilization treatment If it is lower than 7.1%, the
5 bonding force of the oily staining and blotting components
to the fibers ox fiber products is so high, that the
staining and blotting components cannot be removed
sufficiently only by water in some cases. It is more
preferably 7.5% or higher. The moisture absorption ratio
10 is not particularly limited in the upper limit and
generally it is preferably 20%, more preferably 15%.
The above-mentioned moisture absorption ratio can be
calculated according to the following equation (1)
[0016]
15 [Equation (1)]
Moisture absorption ratio (%) = ([official weight] - [bone-
dry weight] - 1) x 100 (1)
In the above-mentioned equation (l), the bone-dry
weight can be calculated, for example, by measuring the
20 weight of an object fiber or fiber product to be measured
and a weighing bottle after the object fiber or fiber
product is put in the weighing bottle and dried at 105°C
for 2 hours and subtracting the previously measured weight
of the weighing bottle from the weight of the fiber or
25 fiber product and the weighing bottle. The official weight
can be calculated, for example, by measuring the weight of
the fiber or fiber product whose bone-dry weight is
measured in the weighing bottle and the weighing bottle
after they are left in atmosphere at 20°C and 65% RH for 24
30 hours and subtracting the weight of the weighing bottle
from the weight of the fiber or fiber product and the
weighing bottle. For the measurement of the bone-dry
weight and the official weight, for example, a small cloth
specimen with a size of about 10 x 20 cm can be used. The
35 weight measurement is repeated until the weight is

8
stabilized.
[0017]
The hydrophilization treatment method in the case the
fibers or fiber products contain at least cellulose type
5 fibers is not particularly limited and. since it can give
high moisture absorption ratio relatively easily, a method
for introducing a carboxyl group is preferable. In this
description, a carboxyl group includes salts such as sodium
salt and potassium salt.
10 [0018]
One preferable embodiment of the method for
introducing a carboxyl group into the above-mentioned
cellulose type fibers will be described. A carboxyl group
may be introduced into cellulose type fibers easily in form
15 of carboxymethyl by, for example, bringing a treatment
solution containing monochloroacetic acid or a
monochloroacetic acid alkali metal salt (e.g. sodium salty
potassium salt) into contact with the cellulose type fibers.
Hereinafter, such introduction of a carboxymethyl group in
20 such a method is referred to as carboxymethylation.
[0019]
In the case of the above-mentioned carboxymethy-ation,
the concentration of the monochloroacetic acid or the
monochloroacetic acid alkali metal salt in the treatment
25 solution may properly be determined so as to achieve aimed
processing degree and it is preferably 10 to 500 g/L, more
preferably 50 to 300 g/L, and even more preferably 100 to
200 g/L.
[0020]
30 In the case of che above-mentioned carboxymethylation,
the treatment solution preferably contains an alkali metal
hydroxide, e.g. sodium hydroxide. Addition of sodium
hydroxide makes it possible to improve carboxymethylation
degree of the treated fibers to be obtained. The reaction
35 degree tends to be increased more as the concentration of

9
sodium hydroxide is increased in the above-mentioned
treatment solution and the concentration of the sodium
hydroxide is preferably 20 g/L or higher. However if a
large quantity of sodium hydroxide is added, the touch of
5 fibers to be obtained tends to be deteriorated, and
therefore, it should be selected carefully.
[0021]
As the method for bringing the above-mentioned
treatment solution into contact with the cellulose type
10 fibers, for example, a solution flowing method for swirling
the fibers in the treatment solution; a method for
immersing fibers in the treatment solution and then padding
(squeezing) the fibers can be exemplified. In terms of the
utilization efficiency, it is effective to decrease the
15 bath ratio (the use ratio of the treatment solution.) and
from this viewpoint, the method for immersing and then
padding the fibers is efficient. The temperature condition
in the case of bringing the treatment solution into contact
with the cellulose type fibers is not particularly limited
20 and it is preferable to be, for example, in a range of 5 to
50°C.
[0022]
The duration for bringing the above-mentioned
treatment solution into contact with the cellulose type
25 fibers may properly toe selected depending on various
conditions such as the aimed carboxymethylation degree, the
concentration of monochloroacetic acid in the treatment
solution, the concentration of sodium hydroxide and the
Like The contact may be carried out at a normal
30 temperature for several hours to several days or the time
needed for the contact may foe shortened by heating
treatment.
[0023]
In the case of clothes such as underwear or those
35 required particularly to have good touch, it is preferable

10
to adjust the concentration of monochloroacetic acid or
monochloroacetic acid alkali metal salt in the treatment
solution, the concentration of the alkali metal hydroxide
in the treatment solution, the treatment temperature and
5 the treatment duration. Among them, if the concentration
of the alkali metal hydroxide in the treatment solution is
increased, cellulose type fibers tend to be damaged,
resulting in hard touch. Accordingly, it is preferable to
lower the concentration of the alkali metal hydroxide in
10 the treatment solution as much as possible and to lower the
treatment temperature so as to suppress the effect of the
alkali metal hydroxide. On the other hand, in order to
achieve a sufficient carboxymethylation degree even in the
state that the concentration of the alkali metal hydroxide
15 is suppressed to low, it is required to set the
concentration of monochloroacetic acid or the
monochloroacetac acid alkali metal salt in the treatment
solution to be relatively high and to prolong the treatment
duration, practically, in the case where the cellulose
20 type fibers is brought into contact with the treatment
solution containing an alkali metal hydroxide in the
concentration of 20 to 100 g/L, monochloroacetic acid or
the monochloroacetic acid alkali metal salt in the
concentration of 100 to 400 g/L at 10 to 40°C for 6 to 48
25 hours, both of the sufficient moisture absorption ratio and
the good touch can be satisfied.
[0024]
The lower limit of the above-mentioned
carboxymethylation degree is preferably 0.1% by mole. If
30 it is less than 0.1% by mole, sufficient moisture
adsorption degree cannot be achieved in some cases. The
lower limit is more preferably 1% by mole. The upper limit
of the carboxymethylation degree is not particularly
limited, however it is preferably 10% by mole, more
35 preferably 5% by mole.

11
[0025]
In this description, carboxymethylation degree is the
ratio (%) of carboxymethylated hydroxyl of the cellulose,
which is the ratio {%} of the number of COO groups after
5 the carboxymethylation to the number of hydroxyl grcups of
untreated cellulose. The number of COO group in the
cellulose type fibers can be calculated by quantitatively
determining Na consumed for the replacement after the
entire COO groups of the cellulose type fibers is converted
10 into COOH groups and then the resulting fibers are immersed
in an aqueous sodium hydroxide solution (0.1 N) . The
quantity of Na consumed for the replacement can
quantitatively be measured by titrating/ for example,
nydrochloric acid {0.1 N) to the aqueous sodium hydroxide
15 solution used for immersion of the treated fiber or fiber
product. More particularly, the following measurement
method can be employed.
[0026]
At first a treated cellulose type fiber (e.g a small
20 cloth specimen) is immersed in 0.3 N hydrochloric acid m
the conditions of bath ratio 1 : 50 and the solution
temperature 20°C for 1 hour to convert the entire COO
groups into COOH groups, deviate red, and dried and then the
remaining HC1 is removed and about 4 g of the specimen is
25 sampled and its bone-dry weight (W (g)) is weighed. Next,
the cellulose fiber whose bone-dry weight is weighed is
immersed in an aqueous solution of 0.1N sodium hydroxide 50
mL {B (mL) } and left at 20°C overnight to replace the
entire COOH groups to COONa. Further, to quantitatively
30 measure Na consumed for the replacement, 0.1 N hydrochloric
acid is titrated to the solution, and the titratxon value is
defined to be X (mL). Phenolphthalein may be used as an
indicator.
[0027]
35 The carboxymethylation degree can be calculated

12
according to the following equation (2) from the bone-dry
weight (W (g)) of the cellulose type fiber; the volume (B
(mL) ) of the aqueous sodium hydroxide solution; and. the
volume (X (mL)) of hydrochloric acid used for the titration
5 [0028]
[Equation 2]
carboxymethylation degree (% by mole) = 162.14 x (B - X) -
[10,000W - 59.04 x (B - X)] - 3 X 100 (2)
As a method for the hydrophilization treatment in the
10 case the fibers or fiber products contain at least
cellulose type fibers/ a method for graft polymerizing of
at least one kind of monomer selected from a group
consisting of methacrylamide, hydroxyethyl acrylate,
acrylic acid, and methacrylic acid is also preferabla.
15 [0029]
As a method for the above-mentioned grafting, for
example, a method for polymerization in the state that the
above-mentioned monomer is brought into contact With the
cellulose type fibers can be exemplified. More
20 particularly, for example/ the cellulose type fibers are
immersed in a solution containing the above-mentioned
monomer and a polymerization initiator (e.g. ammonium
peroxodisulfate) and then squeezed and heated to obtain
cellulose type fibers to which hydrophilic molecules are
25 grafted.
[0030]
The amount of the hydrophilic molecules to be
introduced by the above-mentioned grafting may properly be
selected in consideration of the types, of the hydrophilic
30 molecules and the moisture absorption ratio required for
the cellulose type fibers, and the lower limit of the
grafting ratio is preferably 1%. If it is less than 1%, a
sufficient moisture absorption ratio cannot be obtained m
some cases. The lower limit is more preferably 2%. The
35 upper limit of the grafting ratio is not particularly

13
limited, however it is preferably 30%, more preferably 25%,
and even more preferably 20%.
In this description, the grafting ratio can be
calculated according to the following equation (3) from the
5 bone-dry -weight of the cellulose type fibers before
grafting (the bone-dry weight before treatment) and the
bone-dry weight of the cellulose type fibers after grafting
(the bone-dry weight after treatment).
[0031]
10 [Equation (3) ]
Grafting ratio (%} = ([the bone-dry weight after treatment]
÷ [the bone-dry weight before treatment] - 1} x 100 (3)
In the equation (3), the bone-dry weight can be calculated,
15 for example, by measuring the weight of a small cloth
specimen with a size about 10 x 20 era and a weighing bottle
after it is put in the weighing bottle and dried at 105°C
for 2. hours, and subtracting the previously measured weight
of the weighing bottle from the measured weight of tae
20 specimen and the weighing bottle.
[0032]
According to the method for providing detergenl-free
washing function of the present invention to fiber products,
even if fibers or fiber products are washed without using a
25 detergent, a function of giving an approximately same
effect of washing as that of using a detergent can be
provided. Further, in the case of washing without using a
detergent, the process (rinsing process) for removing a
detergent can be omitted and thus the washing can be
30 completed in a short time. Owing to such shortening of the
washing time, consumption of resources such as water and
electric power can considerably be saved. Further, the
fiber products subjected to the method for providing the
detergent-free washing function of the present invention
35 are also provided with, secondary advantageous effects that

14
the moisture absorption-emission property becomes
remarkably excellent and that the products give comfortable
feeling when they are put on.
[0033]
5 The present, invention also includes fiber products
capable of washing without using a detergent, which
contains a fiber subjected to hydrophilization treatment.
In this description, that capable of washing without
using a detergent means to cause an approximately same
10 washing effect even in the case of washing without using a
detergent as that in the case of washing with using a
detergent, and that the approximately same washing effect
is caused means that the washing effect in the case fiber
products capable of washing without using a detergent of
15 the present invention are washed without using a detergent
is same as the washing effect in the case conation fiber
products are washed by using a detergent. Practically, it
means the same effect of the detergent-free washing
function as described above.
20 [0034]
The fiber products of the present invention capable
of washing without using A detergent contain fibers
subjected to the hydrophilization treatment. The above-
mentioned hydrophilization treatment is not particularly
25 limited and at least one method selected from a group
consisting of a method for introducing a hydrophilic group,
a method for introducing a. hydrophilic molecule, a method
for improving the surface physically, and a method for
applying a coating agent containing a hydrophilic substance.
30 The practical examples of the respective treatment methods
are same as described above in the method for providing the
detergent-free washing function.
[0035]
The fibers subjected to the above-mentioned
35 hydropnilization treatment are not particularly limited and

15
may include those obtained by hydrophilization treatment of
natural fibers such as cellulose type fibers (cotton), flax,
silk, and wool; synthetic fibers such as polyethylene
terephthalate, rayon, polynosic, cupra, acetate, nylon,
5 vinylon, vinylidene, poly(vinyl chloride), acryl, acrylic
type, polyethylene, polypropylene, polyurethane; and their
blended fibers. Among them, those containing at least
cellulose type fibers subjected to the hydrophilizacion
treatment are preferable since the cellulose type fibers
10 are used for many fiber products such as underwear.
[0036]
In the case the fiber products of the present
invention capable of washing without using a detergent
contain the cellulose type fibers subjected to the
15 hydrophilization treatment, the above-mentioned cellulose
type fibers subjected to the hydrophilization treatment are
preferable to have a moisture absorption ratio 7.1% or
higher. If it is less than 7.1%, the bonding force of the
oily staining and blotting components and the fibers is so
20 high that the staning and blotting components cannot be
removed sufficiently only by water in some cases. It is
more preferably 7.5% or higher. The moisture absorption
ratio is not particularly limited in the upper limit and
generally it is preferably 20%, more preferably 15%.
25 [0031]
As the above-mentioned cellulose type fibers
subjected to the hydrophilization treatment, for example,
carboxymethylated cellulose type fibers are preferable.
Especially, in the case the touch is required,
30 carboxymethylated cellulose type fibers obtained by
bringing the cellulose type fibers into contact with a
treatment solution containing an alkali metal hydroxide in
a concentration of 20 to 100 g/L and monochloroacetic acid
or a monochloroacetic acid alkali metal salt in a
35 concentration of 100 to 400 g/L at 10 to 40°C for 6 to 48

16
hours are preferable. In this case, the carboxymethylation
degree is preferably 0.1 to 10% by mole.
[0038]
As the above-mentioned cellulose type fibers
5 subjected to hydrophilization treatment, cellulose type
fibers grafted by at least one kind of monomer selected
from a group consisting of methacrylamide, hydroxyethyl
acrylate, acrylic acid, and methacrylic acid are also
preferable. In this case, the grafted cellulose fiber
10 preferably has a grafting ratio of 1 to 20%.
[0039]
The fiber products of the present invention capable
of washing without using a detergent may further contain
deodorants. In the case a carboxyl group is introduced as
15 the hydrophilization treatment, a high deodorization effect
is provided and addition of the deodorants further improves
the deodonzation effect.
[0040]
The above-mentioned deodorants are not particularly
20 limited and for example, conventional ones such as zinc
oxide type, titanium oxide type, silver type, zeolite type,
and plant extract type can be used. Among them, zinc oxide
type deodorants are preferable for use since they are easy
to be processed to fibers.
25 [0041]
Since the fiber products of the present invention
capable of washing without using a detergent have the
above-mentioned constitution, even if they are washed
without using a detergent, an approximately same washing
30 effect as that in. the case of. washing using a detergeat can.
be achieved. Further, in the case the fiber products of
the present invention capable of washing without using a
detergent are washed without using a detergent, the process
(rinsing process) for removing a detergent can be omitted
35 and thus the washing can be completed in a short time.

17
Owing to such shortening of the washing time, consumption
of resources such as water and electric power can
considerably be saved. Further, the fiber products of the
present invention capable of washing without using a
5 detergent are also excellent remarkably in the moisture
absorption-emission property and comfortable feeling when
they are put on.
[EFFECT OF THE INVENTION]
10 [0042]
The present invention provides a method for providing
detergent-free washing function by which a washing effect
approximately same as that in the case of using a detergent
can be caused even in the case of washing a fiber or a
15 fiber product without using a detergent/ and a fiber
product capable of washing without using a detergent.
[BEST MODE FOR CARRYING OUT THE INVENTION]
[0043]
20 Hereinafter, the present invention will be described
an details with reference to Examples, however the present
invention is not limited to these examples.
[0044]
(Example 1)
25 As an original cloth, common cotton cloth was used
and it was immersed in a treatment solution containing
sodium monochloroacetate (200 g/L) and sodium hydrox:de (70
g/L) at a bath ratio of 1 : 20, squeezed by a padder, and
then kept at 25°C for 2 4 hours for promoting reaction. The
30 unreacted matters were removed by washing with water and
the resulting cotton cloth was dried to obtain treated
cloth.
The treated cloth was found carboxymethylated at 2.67
carboxymethylation degree and having a moisture absorption
35 ratio of 3.9% by respective measurements-

18
[0045]
(Example 2)
As an original cloth, common cotton cloth was used
and it was immersed in an aqueous solution containing
5 methacrylic acid monomer 150 g/L and ammonium
peroxodisulfate 7.5 g/L at 20°C for 1 minute, squeezed by a
padder, and steamed at 100°c for 10 minutes, and after that
the unreacted matters were removed by washing with water
and the resulting cotton cloth was dried to obtain, treated.
10 cloth.
The treated cloth was found having a grafting ratio
of 2.1% and a moisture absorption ratio of 7.8% by
respective measurements.
[0046]
15 (Example 3)
As an original cloth, common cotton cloth which was
dyed to 1.0% owf by using a reactive dye (Smifix Supra:
manufactured by Sumitomo Chemical Co , Ltd.) was used and
at was immersed in a treatment solution containing sodium
20 monochloroacetate (200 g/L) and sodium hydroxide (70 g/L)
at a bath ratio of 1 : 20, squeezed by a padder, and then
kept at 25°C for 2.4 hours foe promoting reaction. The.
unreacted matters were removed by washing with water and
the resulting cotton cloth was dried to obtain treatad
25 cloth.
The treated cloth was found having a moisture
absorption ratio of 8.4% by measurement.
[0047]
(Example 4)
30 As an original cloth, a cloth made of cotton-
polyethylene terephthlate mixed fibers containing 64% by
weight of cotton and 36% by weight of polyethylene
terephthalate was used and it was immersed in a treatment
solution containing sodium monochloroacetate (250 g/L) and
35 sodium hydroxide (70 g/L) at a bath ratio of 1 : 28,

19
squeezed by a padder, and then kept at 25°C for 24 hours
for promoting reaction. The. unreacted matters, were removed
by washing with water and the resulting cloth was dried to
obtain treated cloth.
5 The cotton portion of the treated cloth was found
carboxymethylated at 2.85 carboxymethylation degree and
having a moisture absorption ratio of 8.9% by respective
measurements.
[0048]
10 (Example 5)
As an original cloth, common cotton cloth was used
and it. was immersed in a treatment solution containing
sodium monochloroacetate (2 00 g/L) and sodium hydroxide (70
g/L) at a bath ratio of 1 : 20, squeezed by a padder, and
15 then kept at 100°C for 5 minutes for promoting reaction
The unreacted matters were removed by washing with water
and the resulting cotton cloth was dried to obtain treated
cloth.
The treated cloth was found carboxymethylated at 2.58
20 carboxymethylation degree and having a moisture absorption
ratio of 8.7% by respective measurements
(Example 6)
As an original cloth, common cotton cloth was ased
25 and it was immersed in a treatment solution containing-
sodium monochloroacetate (200 g/L) and sodium hydroxide
(100 g/L) at a bath ratio of 1 : 20, squeezed by a paddex,
and then kept at 25°C for 24 hours for promoting reaction.
The unreacted matters were removed by washing with water
30 and the resulting cotton cloth was dried to obtain treated
cloth.
The treated cloth was found carboxymethylated at 3.83
carboxymethylation degree and having a moisture absorption
ratio of 11.1% by respective measurements.
35 [0050]

20
(Example 7)
AS an original cloth, common, cotton cloth, was used
and it was immersed in a treatment solution containing
sodium monochloroacetate (50 g/L) and sodium hydroxide (150
5 g/L) at a bath ratio of 1 : 20, squeezed by a padder, and
then kept, at 100°C for 5 minutes for prormoting reaction.
The unreacted matters were removed by washing with water
and the resulting cotton cloth was dried to obtain treated
cloth.
10 The treated cloth was found carboxymethylated at 2.63
carboxymethylataon degree and having a moisture absorption
ratio of 8.8% by respective measurements.
[0051]
(Reference Example)
15 As a reference cloth, cotton cloth (an original
cloth) used in Examples was used. The moisture absorption.
ratio of the cotton cloth was 7.0%.
[0052]
(Evaluation)
20 The treated cloths of Examples 1 to 7 and the
reference cloth were subjected to a test of washability to
oleic acid, a test of repeat washing, and a test of
deodorization effect by the following methods.
The results are shown in Table 1.
25 [0053]
(1) Test of washability to oieic acid
After each cloth specimen was stained with oleic acid
10% owf and gelatin 2.5% owf and washed by a common
domestic washing machine (ES-S4A, manufactured by Sharp
30 Corp.) in both cases of only with water and using a
detergent (Attack, manufactured by Kao Corp.) in a
concentration of 0.67 g/L. After each washed cloth
specimen was sun-dried, the oleic acid remaining on the
cloth specimen was extracted by methanol and the amount of
35 the remaining oleic acid, was measured by gas chromatography

21
(GC-17A, manufactured by Shimadzu Corp.) to calculate the
oleic acid remaining ratio (%). Based on the calculated
oleic acid remaining ratio (%), the evaluation was carried
out according to the following criteria.
5 © the oleic acid remaining ratio (%) in the case of
washing only by water was not higher than 80% of the oleic
acid remaining ratio (%) in the case of washing the
reference cloth using a detergent:
O: the oleic acid remaining ratio (%) in the case of
10 washing only by water was not higher than 110% of the oleic
acid remaining ratio (%) in the case of washing the
reference cloth using a detergent
A: the oleic acid remaining ratio (%) in the case of
washing only by water was not higher than 120% of the oleac
15 acid remaining ratio (%) in the case of washing the
reference cloth using a detergent: and
X: the oleic acid remaining ratio (I) in the case of
washing only by water exceeded 12 01 of the oleic acid
remaining ratio (%) in the case of washing the reference
20 cloth using a detergent.
[0054]
(2) Test of repeat washing
After each cloth specimen was immersed in artificial
sweat mainly containing oleic acid 40.6%y triolein 22.4%,
25 cholesterol oleate 17.5%, liquid paraffin 3.6%, cholesterol
2.3%, and gelatin 10.0% at a bath ratio 1.30, squeezed
at 130% squeezing and dried at 105°C for 30 minutes.
The each specimen was washed by a common domestic
washing machine (ES-S4A, manufactured by Sharp Corp.) in
30 both cases of only with water and using a detergent (Attack,
manufactured by Kao Corp.) in a concentration of 0.6? g/L.
After each, washed cloth specimen was sun-dried. The
process was repeated 31 times and whiteness alteration was
investigated for each specimen in the respective cases.
35 The measurement of the whiteness was carried out using a

22
color measuring apparatus (White Eye 3000, manufactured by
Gretag-Macbeth Ltd.). The alteration of the whiteness of
the cloth specimens before and after the test was
calculated and evaluation was carried out according to the
5 following criteria:
©: the alteration of the whiteness in the case of washing
only by water was not higher than 80% of the alteration of
the whiteness in the case of washing the reference cloth
using a detergent:
10 O: the alteration of the whiteness in the case of washing
only by water was not higher than 100% of the alteration of
the whiteness in the case of washing the reference cloth
using a detergent:
A: the alteration of the whiteness in the case of washing
15 only by water was not higher than 120% of the alteration of
the whiteness in. the case of washing the reference cloth
using a detergent: and
X: the alteration of the whiteness in the case of washing
only by water exceeded 120% of the alteration of the
20 whiteness in the case of washing the reference cloth using
a detergent
[0055]
(3) Test of deodorization effect
A. magnetic stirrer was put in a 500 ml. (practical
25 capacity 625 mL) Erlenmeyer flask and each cloth specimen
cut in a size of 4 cm x 5 cm was hung in the Erlenmeyer
flask by attaching a thread to tne specimen and sticking an
end of the thread to the outside of the Erlenmeyer flask
with a cellophane tape. After that, in the case of ammonia
30 deodorization, a 2% ammonia solution or in the case of
acetic acid deodorization, a 3% acetic acid solution was
dropwise added along the inner wall face of the Erlenmeyer
flask by a 5 µL micro-pipette. The Erlenmeyer flask was
plugged quickly with a silicon plug covered with a wrap
35 double and further the wrap was air-tightly covered with a

23
triple-folded rubber band. After that, while being stirrec
by the magnetic starrer, the specimen was left at 23°C for
120 minutes,
After 120 minute-treatment, the silicon plug was
5 unplugged without being separated from the wrap and the ga.
concentration in the Erlenmeyer flask was measured by using
a detector equipped with a sill-con plug for measurement (N)
3 La for ammonia: manufactured by Gastec Corp.; NO. 81 for
acetic acid: manufactured by Gastec Corp.).
10 The same test was carried out in such a manner that
no cloth, specimen was hung in the Erlenrmeyer flasx and the
result was employed as a blank measurement value. The
deodorization ratio (%) was calculated according to the
following equation and evaluation Was carried out according
15 to the following criteria.
[0056]
[Equation 4]
Deodorization ratio (%) - ((blank measurement value - cloth
specimen measurement value) / blank measurement value) x
20 100
(Ammonia deodorization)
O: the deodorization. ratao not lower than 703;
∆: the deodonzataon ratio not lower than 50% and lower
than 70%; and
25 X: the deodorization ratio lower than 50%.
(Acetic acid deodorization)
O: the deodorization ratio not lower than 65%;
∆: the deodorization ratio not lower than 75% and lcwer
than 85%; and
30 X; the deodorization ratio lower than 15%.
[0057]
(4) Evaluation of touch
A sensory test was carried out using the reference
cloth as a standard and the evaluation was carried out
35 according to the following criteria.

24
©: soft approximately as same as the reference cloth;
O: slightly hard as compared with the reference cloth
however soft enough; and
X : apparently hard as compared with, the reference cloth
5 and unsuitable for underwear.

25
[0058]
[Table 1]



26
[INDUSTRIAL APPLICABILITY OF THE INVENTION]
[0059]
The present invention provides a method for providing
detergent-free washing function by which a washing effect
5 approximately same as that in the case of using a detergent
can be caused even in the casa of washing a fiber or a
fiber product without using a detergent, and a fiber
product capable of washing without using a detergent.

27
CLAIMS
1. A method for providing a detergent-free washing
function,
5 which, comprises subjecting a fiber or a fiber product
to hydrophilination treatment.
2. The method for providing a detergent-free washing
function according to Claim 1,
10 wherein the hydrophilization treatment is carried out
by at least one method selected from a group consisting of
a method for introducing a hydrophilic group, a method for
introducing a hydrophilic molecule, a method for improving
the surface physically, and a method for applying a coating
15 agent containing a hydrophilic substance.
3. The method for providing a detergent-free washing
function according to Claim 1 or 2,
wherein the fiber or fiber product contains at least
20 a cellulose fiber, and the moisture absorption ratio of the
cellulose fiber is adjusted to be 7.1% or higher by the
hydrophillzation treatment.
4. The method for providing a detergent-free cashing
25 function according to Claim 3,
wherein a carboxyl group is introduced into the
cellulose fiber by carboxymethylation.
5. The method for providing a detergent-free washing
30 function according to Claim 4,
wherein the cellulose fiber is brought into contact
with a treatment solution containing an alkali metal
hydroxide in a concentration of 20 tc 100 g/L,
monochloroacetic acid or a monochloroacetic acid alkali
35 metal salt in a concentration of 100 to 400 g/L at 10 to

28
40*C for 6 to 48 hours.
6. The method for providing a detergent-free washing
function according to Claim 4 or 5,
5 wherein the carboxymethylation degree is adjusted to
be 0.1 to 10% by mole.
7. The method for providing a detergent-free washing
function according to Claim 3,
10 wherein graft polymerization to the cellulose fiber
is carried but. using at least one kind of monomer selected
from a group consisting of methacrylanude, hydroxsyethyl
acrylate, acrylxc acid, and methacrylic acid.
15 8. The method for providing a detergent-free cashing
function according to Claim 7,
wherein the grafting ratio is adjusted to be 1 to 20%.
9. A fiber product capable of washing without using
20 a detergent,
which contains a fiber subjected to hydrophilization
treatment.
10. The fiber product capable of washing without
25 using a detergent according to Claim 9,
wherein the hydrophilization treatment is carr-ed out
by at least one method selected from a group consisting of
a method for introducing a hydrophilic group, a method for
introducing a hydrophilic molecule, a method for improving
30 the surface physically, and a method for applying a coating
agent containing a hydrophilic substance.
11. The fiber product capable of washing without
using a detergent according to Claim 9 or 10,
35 wherein the fiber subjected to the hydrophilization

29
treatment is a cellulose fiber having a moisture absorption
ratio of 7.1% or higher subjected to the hydrophilization
treatment.
5 12. The fiber product capable of washing without
using a detergent according to Claim 11,
wherein the cellulose fiber subjected to the
hydrophilrzation treatment is a carboxymethylated cellulose
fiber.
10
13. The fiber product capable of washing without
using a detergent according to Claim 12,
wherein the cellulose fiber subjected to the
hydrophilizatlon treatment: is obtainable by bringing a
15 cellulose fiber into contact with a treatment solution
containing an alkali metal hydroxide in a concentration of
20 to 100 g/L, monochloroacetic acid or a monochloroacetic
acid alkali metal salt in a concentration of 100 to 400 g/L
at 10 to 40°C for 6 to 48 hours.
20
14. The fiber product capable of washing without
using a detergent according to Claim 12 or 3-3,
wherein the carboxymethylated cellulose fiber has a
carboxyraethylation degree of 0.1 to 10% by mole
25
15. The fiber product capable of washing without
using a detergent according to Claim. 11,
wherein the cellulose fiber subjected to the
hydrophilization treatment is a cellulose fiber grafted by
30 at least one kind of monomer selected from a group
consisting of methacrylamide, hydroxyethyl acrylate,
acrylic acid, and methacrylic acid.
16. The fiber product capable of washing without
35 using a detergent according to Claim 15,

30
wherein the grafted cellulose fiber has a grafting
ratio of 1 to 20%.

It is an object of the present invention to provide a
5 method for providing detergent-free washing function by
which a washing effect approximately same as that in the
case of using a detergent can be caused even in the case of
washing a fiber or a fiber product without using a
detergent and a fiber product capable of washing without
10 using a detergent.
The present invention relates to a method for
providing a detergent-free washing function to a fiber or a
fiber product/which is subjected to hydrophilizetion
treatment.

Documents:

00172-kolnp-2006-abstract.pdf

00172-kolnp-2006-claims.pdf

00172-kolnp-2006-description complete.pdf

00172-kolnp-2006-form 1.pdf

00172-kolnp-2006-form 3.pdf

00172-kolnp-2006-form 5.pdf

00172-kolnp-2006-international publication.pdf

00172-kolnp-2006-international search authority.pdf

00172-kolnp-2006-others.pdf

00172-kolnp-2006-pct forms.pdf

00172-kolnp-2006-priority document.pdf

172-KO,LNP-2006-FORM-27.pdf

172-KOLNP-2006-CORRESPONDENCE.pdf

172-KOLNP-2006-FORM 27.pdf

172-KOLNP-2006-FORM-27-1.pdf

172-kolnp-2006-granted-abstract.pdf

172-kolnp-2006-granted-assignment.pdf

172-kolnp-2006-granted-claims.pdf

172-kolnp-2006-granted-correspondence.pdf

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

172-kolnp-2006-granted-examination report.pdf

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

172-kolnp-2006-granted-form 18.pdf

172-kolnp-2006-granted-form 3.pdf

172-kolnp-2006-granted-form 5.pdf

172-kolnp-2006-granted-gpa.pdf

172-kolnp-2006-granted-reply to examination report.pdf

172-kolnp-2006-granted-specification.pdf


Patent Number 239969
Indian Patent Application Number 172/KOLNP/2006
PG Journal Number 16/2010
Publication Date 16-Apr-2010
Grant Date 16-Apr-2010
Date of Filing 23-Jan-2006
Name of Patentee GUNZE LIMITED
Applicant Address 1, ZEZE, AONO-CHO, AYABE-SHI, KYOTO 6238511,
Inventors:
# Inventor's Name Inventor's Address
1 OZAKI KZUHITO C/O GUNZE LIMITED, 1, ISHIBURO, INOKURASHINMACHI, AYABE-SHI, KYOTO 6238512, JAPAN
2 OZAWA NANAMI C/O GUNZE LIMITED, 1, ISHIBURO, INOKURASHINMACHI, AYABE-SHI, KYOTO 6238512, JAPAN
3 AKIDA SHINGO C/O GUNZE LIMITED, 262, SO, MIYAZU-SHU, KYOTO 6260043, JAPAN
4 TABATA SHINOBU C/O GUNZE LIMITED, 186, GAKUONJI, SANTOCHO, ASAGO-GUN, HYOGO 6695152, JAPAN
5 KIBUNE SUSUMU C/O GUNZE LIMITED, 262, SO, MIYAZU-SHI, KYOTO 6260043, JAPAN
6 HIRANO SHOICHI C/O GUNZE LIMITED, 1, ISHIBURO, INOKURASHINMACHI, AYABE-SHI, KYOTO 6238512,
7 YUI YOSHINARI C/O GUNZE LIMITED, 1, ISHIBURO, INOKURASHINMACHI, AYABE-SHI, KYOTO 6238512,
PCT International Classification Number D06M 13/188
PCT International Application Number PCT/JP2004/006969
PCT International Filing date 2004-05-21
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-274274 2003-07-14 Japan