JPH0811869B2 - Glue composition for clothing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is capable of finishing clothes to be significantly crisp and hard, as compared with a paste composition, more specifically, a conventional polyvinyl acetate emulsion-based paste. The present invention relates to a paste composition that is also excellent in the ability to remove the paste during washing.

[Conventional technology and its problems]

Conventionally, starch was used as the pasting agent, but various improvements have been made to make it easier to use.Currently, liquid pasting agent has been developed as a stable pasting agent that is easy to dilute in cold water and easy to use. A 2 to 15% solution of carboxymethyl cellulose, starch, polyvinyl alcohol, etc. mixed with an antifoaming agent, a preservative, a brightening agent, a fragrance, etc. is used.

However, these starches, polyvinyl alcohol,
Carboxymethyl cellulose etc. has a glass transition temperature of 80 ° C.
Although it is a hard polymer, it is inexpensive as a sizing agent, but when it is glued to clothes, it often gives rise to the inconvenience of giving a paper-like texture and, in some cases, causing rough skin at the site in contact with the skin. . Further, an aqueous solution of these polymers has a high viscosity even at a low concentration, and has a drawback that it is difficult to handle.

In order to eliminate these drawbacks, polyvinyl acetate emulsion (emulsion) is used to improve the adsorptivity to fibers from a high bath ratio and to make it possible to use it in household washing machines. A novel paste composition for holding a cationic charge in a base has also been proposed (for example, JP-A-53-10793,
53-70191, 53-94688, 52-53086, 54
-160884, 54-160884, 55-103309, 55-
103369, 56-110709, 59-88978, 58-487
No. 5, 58-65073, etc.).

Further, conventionally, in the case of an emulsion containing vinyl acetate, which is insoluble in water, as a main monomer, the de-sticking property in the washing cycle was poor, which was a cause of hardening of clothes and the like. There is also proposed a paste composition in which the polymer is swelled and dissolved by an alkali at the time of washing so that the paste can be easily removed.

However, in the case of these sizing agents mainly composed of polyvinyl acetate, the adhesiveness of the vinyl acetate itself to the fibers (mainly cotton fibers) is low, and there are drawbacks that sufficient hardness and crisp texture cannot be obtained. Has been done.

[Means for solving the problem]

As a result of intensive studies to improve the drawbacks of the conventional vinyl acetate-based paste composition, the present inventors have found that during the emulsion polymerization of the lower fatty acid vinyl ester or during the emulsion polymerization of the lower fatty acid vinyl ester and the unsaturated carboxylic acid. In addition, by coexisting a monomer or polymer of methacrylic acid hydroxyalkyl ester or acrylic acid hydroxyalkyl ester, or a mixture thereof, clothes can be made to be significantly harder and crisper than before, and the skin feels good and the glue removes. The present inventors have found that a sizing composition for clothes having excellent properties can be obtained, and have reached the present invention.

That is, the present invention is one type selected from monomers or polymers of methacrylic acid hydroxyalkyl ester or acrylic acid hydroxyalkyl ester during emulsion polymerization of lower fatty acid vinyl ester or emulsion copolymerization of lower fatty acid vinyl ester and unsaturated carboxylic acid, or The present invention provides a paste composition for clothing, which comprises an emulsion obtained by copolymerizing or graft-polymerizing two or more kinds.

Examples of the lower fatty acid vinyl ester used in the present invention include vinyl acetate, vinyl butyrate, vinyl propionate, and the like. Further, the lower fatty acid vinyl ester (as shown in the following (1) to (7) ( Preferably, vinyl acetate) and a copolymerizable monomer (in this case, lower fatty acid vinyl ester: copolymerizable following monomer = 80: 20 to 10)
0: 0 (weight ratio)) can also be used.

(1) Acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, alkyl ester of methacrylic acid (2) α, β Diesters of ethylenically unsaturated dicarboxylic acids such as dibutyl maleate, diethyl maleate, and their corresponding fumarates, itaconates,
Citraconate (3) Styrene, ethylene (4) Vinyl halides such as vinyl chloride (5) Vinylidene halides such as vinylidene chloride (6) Ethylenically unsaturated carboxylic acid amides of α and β and their N-alkylol derivatives For example, acrylamide and N-methylolamide (7) Lower fatty acid vinyl ester different from the lower fatty acid vinyl ester used above The copolymerizable monomer is preferably an alkyl ester of acrylic acid or methacrylic acid.

As the unsaturated carboxylic acid used in the present invention, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, citraconic acid,
In addition to p-vinylbenzoic acid, etc., itaconic acid, maleic acid,
Mention may be made of alkyl half-esters, partial esters or partial amides of unsaturated polycarboxylic acids such as fumaric acid. Examples of the alkyl half-esters of unsaturated polycarboxylic acid include lower alkyl half-esters having 1 to 6 carbon atoms such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, and monobutyl maleate. Preferred examples of these unsaturated carboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.

In the present invention, various cationic polymers may be coexisted during the polymerization or may be added after the completion of the polymerization for the purpose of improving the adsorptivity to the fiber from a high bath ratio. At that time, examples of the cationic polymer used include cationic cellulose, cationic starch, cationic vinyl polymer and the like.

As the cationic cellulose and the cationic starch, those represented by the following formula (1) are preferable.

(In the formula, A: cellulose or starch residue R: alkylene group or hydroxyalkylene group R ₁ , R ₂ , R ₃ : the same or different, and an alkyl group, an aryl group, an aralkyl group or a nitrogen atom in the formula It may be included to form a heterocycle.

X: anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.) _L : a positive integer. ) Cationic cellulose and cationic starch have a degree of cation substitution of 0.01 to 1, that is, 0.01 to 100 units per anhydrous glycose unit.
It is preferable that one, preferably 0.02 to 0.5, cationic groups are introduced. If the degree of substitution is 0.01 or less, the effect is not sufficient, and the degree of substitution may be 1 or more, but 1 or less is preferable from the viewpoint of reaction yield.

Such cationic cellulose is, for example, hydroxyethyl cellulose under alkaline conditions, such as glycidyl trimethyl ammonium chloride or 3-chloro-2.
It can be obtained by reacting -hydroxypropyltrimethylammonium chloride. It can also be obtained by reacting hydroxyethyl cellulose with 4-chlorobutenetrimethylammonium chloride.

The cationic starch can also be obtained, for example, by reacting the starch with glycidyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl trimethyl ammonium chloride under alkaline conditions. It can also be obtained by quaternizing dimethylaminoethyl or starch. Furthermore, it can be obtained by reacting starch with 4-chlorobutenetrimethylammonium chloride.

Examples of the cationic vinyl polymer include those represented by the following formula (2).

(In the formula, R _{4 is a} hydrogen atom or a methyl group R ₅ , R ₆ , and R ₇ are the same or different, and are a hydrogen atom and a carbon number of 1 to 1.
4, an alkyl group or a substituted alkyl group Y: an oxygen atom or an NH group in an amide bond X: the same as in formula (1), an integer of m: 1 to 10, and a number of 5 to 5000. ) The viscosity of these cationic polymer aqueous solutions is 1%.
5 to 1000 cps (centipoise) (20 ° C) for aqueous solution,
It is preferably 10 to 500 cps.

Examples of the hydroxyalkyl methacrylate and hydroxyalkyl acrylate used in the present invention include hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, and acrylic. Examples thereof include hydroxypropyl acid and hydroxybutyl acrylate.

The relative content of each of these components in the present invention is 20 to 60% by weight of the vinyl ester monomer in the aqueous emulsion.
When contained, the cationic polymer is 0 to 5% by weight (preferably 0.2 to 3% by weight), and the unsaturated carboxylic acid is 0 to 15 parts by weight (preferably 100 parts by weight of the vinyl ester monomer). 0.2 to 5 parts by weight), and one or more polymers or monomers selected from methacrylic acid hydroxyalkyl ester and acrylic acid hydroxyalkyl ester are combined to 1 to 30 parts by weight (100 parts by weight of the vinyl ester monomer). It is preferably 2 to 20 parts by weight). Regarding methacrylic acid hydroxyalkyl ester and acrylic acid hydroxyalkyl ester, when the amount used of these is 1 part by weight or less, the paste removal during washing is not sufficiently improved, and when it is 30 parts by weight or more, the emulsion stability during polymerization is stabilized. It is not preferable because it deteriorates the property.

When the sizing composition of the present invention is used for sizing, the clothes can be markedly harder than conventional vinyl acetate sizing agents and can be finished to have a crisp texture, and a particularly desirable finish feeling for sheets and the like. Can be given.

In the polymerization for obtaining the paste composition of the present invention, generally used nonionic, anionic and cationic emulsifiers can be appropriately used.

Examples of nonionic emulsifiers are _{alkylphenoxypolyethoxyethanols having} C _7-18 alkyl groups and 9-30 or more ethylene oxide units, such as _{heptylphenoxypolyethoxyethanol} , _{octylphenoxypolyethoxyethanol} , _{methyloctylphenoxypolyethoxy.} Ethoxyethanol, nonylphenoxypolyethoxyethanol, dodecylphenoxypolyethoxyethanol, etc., or a polyethoxyethanol derivative of alkylphenol linked by a methylene bond, mercaptans such as nonyl, dodecyl, tetradecyl and C
Lauric acid, a sulfur-floating emulsifier obtained by condensing _{6 to 15} alkylthiophenol with the required amount of ethylene oxide.
Examples include ethylene oxide derivatives of long-chain carboxylic acids such as myristic acid, palmitic acid, oleic acid and tall oil mixed acid, and ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrophobic hydrocarbon chain. . Nonionic emulsifier has an HLB of 12-19,
Preferably, the one of 15-18 is used.

Examples of the anionic emulsifier include sodium salts of sulfuric acid esters of C _8-18 alcohols such as lauryl alcohol, sulfate salts of higher aliphatic alcohols represented by potassium salts, sodium salts of C _8-18 fatty acids, potassium salts, Alternatively, an ethanolamine salt such as triethanolamine (eg, triethanolamine oleate, triethanolamine stearate), a funnel oil, a sulfone compound such as sulfated ricinoleic acid, sodium-t-octylbenzenesulfonate, sodium-t- Exemplified are sulfonated alkylaryl compounds such as octylphenol sulfonate.

Examples of cationic emulsifiers include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl esyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts,
Alkylquinolium salt, alkylisoquinolium salt, stearylamide methylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminoethylpyridinium salt, alkoxymethylpyridinium salt,
Examples thereof include 1-methyl-1-acylaminoethyl-2-alkylimidazoline, diacylaminopropyldimethylammonium salt, diacylaminoethyldimethylammonium salt, dialkyldi (polyoxyethylene) ammonium salt and dialkylmethylpolyoxyethyleneammonium salt.

The composition of the present invention may further contain a nonionic water-soluble polymer in order to obtain a stable emulsion for a long period of time.

Examples of the nonionic water-soluble polymer include polyvinyl alcohol, polyvinylpyrrolidone, modified starch, and cellulose derivatives.

The modified starch that can be used in the present invention is a water-soluble modified starch, and examples thereof include hydroxyethylated starch and hydroxypropylated starch.

The polyvinyl alcohol is a vinyl acetate homopolymer or a completely or incompletely saponified product of a copolymer of vinyl acetate and another monomer, or a polyvinyl alcohol derivative obtained by modifying these with, for example, an aldehyde, and the viscosity of a 5% aqueous solution thereof is 30 ° C. And those of 5 to 10,000 centipoise are exemplified.

Further, the nonionic cellulose derivative is water-soluble hydroxyalkylated cellulose or alkylcellulose, and its 5% aqueous solution has a viscosity of 5 to 1000 centipoise at 30 ° C., such as hydroxyethyl cellulose,
Examples thereof include hydroxypropyl cellulose and methyl cellulose.

The amount of these nonionic water-soluble polymers added is 0 to 10% by weight, preferably 1 to 4% by weight, based on the emulsion system.
Is.

As the polymerization initiator used in the present invention, in addition to 2,2'azobis (2-amidinopropane), hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone Peroxide, peracetic acid, perbenzoic acid, potassium persulfate and the like can be used. The addition amount of the polymerization initiator is preferably 0.01 to 5.0% by weight based on the vinyl ester monomer.

The temperature of the polymerization reaction of the present invention is 40 to 120 ° C., preferably 50.
~ 90 ° C, pH during polymerization is 3-9, preferably 4-8
In the range of. At this time, sodium carbonate as a buffer,
It is preferable to use an inorganic salt such as sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate, sodium chloride or sodium sulfate in an amount of 0 to 2% by weight, preferably 0.1 to 1% by weight.

Therefore, the final emulsion composition of the polymer paste base of the present invention preferably has the following respective component contents.

Vinyl ester monomer; 20-60% by weight, preferably 25-5
0 wt% unsaturated carboxylic acid; 0 to 15 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of vinyl ester monomer Methacrylic acid hydroxyalkyl ester or acrylic acid hydroxyalkyl ester monomer or polymer group 1 type or 2 types or more selected from 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of vinyl ester monomer, nonionic emulsifier, anionic emulsifier, or cationic emulsifier. 0-5 parts by weight, preferably 0.2-2% by weight cationic polymer; 0-5% by weight, preferably 0.2-3
Wt% water-soluble nonionic polymer; 0-10 wt%, preferably 1
-4% by weight Polymerization initiator: 0.01-5% by weight, preferably 0.02-1% by weight, organic salt; 0-2% by weight, preferably 0.1-1% by weight, based on vinyl ester monomer Water, etc. In other words, the preferred paste composition of the present invention is obtained by emulsion-polymerizing each component with the above composition. Although all the components may be added at the same time and reacted, it is more preferable to gradually add the vinyl ester monomer into a reaction vessel charged with a substance other than the vinyl ester monomer.

An emulsion polymerized by another method may be added to the paste composition of the present invention, and even a mixture of a conventional emulsion-based paste agent and the emulsion of the present invention can sufficiently improve the toughness. is there. In that case, the proportion of the emulsion according to the invention in the final composition is 5 to 5 by weight.
It is good to prepare it so as to be 99%, preferably 10 to 95%.

Although the paste composition of the present invention does not contain a water-soluble nonionic polymer such as polyvinyl alcohol, a nonionic modified starch or a nonionic cellulose derivative, it sufficiently exerts an effect as a sizing agent. When used in combination with polyvinyl alcohol, nonionic modified starch, nonionic cellulose derivative, or a conventional vinyl acetate emulsion paste, it can give a preferable texture to the cloth as when it is used alone. That is, the texture has a crisp feel, and is particularly preferred for sheets and the like.

In the paste composition of the present invention, if necessary, additives for general polymer emulsions, for example, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc., ethylene glycol, propylene glycol, ethanol. Anti-freezing agents such as the above, other fragrances, germicides, preservatives, fluorescent dyes, pigments and the like can be added.

In using the paste composition of the present invention, a conventional method of using the paste composition, that is, the amount of water for diluting the paste composition with respect to clothes, that is, a so-called bath ratio is set to about 1 to 1 to 4 It can be used also by the method, and when the above-mentioned cationic polymer is used, it can be used at about 1:10 to 1:40. In particular, such an increase in the bath ratio enables uniform sizing, and when used at home, it can be treated with an electric washing machine.

When the paste composition of the present invention is used for sizing, the ratio of the paste composition to the cloth weight is 0.2 to 6% by weight of the paste composition effective content (solid content) with respect to the clothing weight, and preferably
It is 0.5 to 4% by weight.

〔Example〕

Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these examples. The parts in the examples are parts by weight.

Example 1 A paste base was synthesized using various polymers and monomers, and their basic performances were compared and examined.

<Synthesis of various paste bases> A cationic polymer 6.0 as shown in Table 1 was placed in a 5-neck separable flask equipped with a nitrogen introducing tube, a stirring group, a metered dropping device for monomers, a thermometer, and a reflux condenser. Parts, polyvinyl alcohol (saponification degree 80%, polymerization degree 1500) 3.0
Part, and 100 parts of ion-exchanged water are added and dissolved at 90 ° C., 60
After cooling to 0 ° C, 10 parts of the lower fatty acid vinyl ester monomer shown in Table 1 and 2 parts of Emulgen 147 (manufactured by Kao Corporation) were added, and 0.5 part of sodium carbonate and 2,2'-azobis (2-
Amidinopropane) hydrochloride (0.1 part) and ion-exchanged water (20 parts) were added, and the temperature was raised to 75 ° C. to initiate polymerization.

From 30 minutes to 350 minutes after the initiation of polymerization, 88 parts of lower fatty acid vinyl ester monomer and 2 parts of unsaturated carboxylic acid monomer as shown in Table 1, and one or two kinds of various monomers or polymers (in case of two kinds) Then, 10 parts by weight of 1: 1) were mixed in advance, and the mixture was continuously added dropwise to the polymerization reaction solution. After the dropping was completed, the temperature was raised to 80 ° C. and the reaction was completed after stirring for 1 hour.

Comparative Example 1 In the same manner as in Example 1, a paste base having different polymers and monomer compositions as shown in Table 1 was synthesized.

Table 1 shows the evaluation results of the sizing effect of the sizing materials synthesized in Example 1 and Comparative Example 1. The gluing effect was evaluated by the following method.

(Gluing method) Using a tergotometer-type washing tester, ion-exchanged water (500 ml) and the sizing agent synthesized as described above in solid content of 0.
Put in a 5g washing tank and disperse well, then 60 # cotton broad cloth
Add 20 g and stir and paste at 100 rpm for 3 minutes. After dehydration for 1 minute, it was dried in a constant temperature and humidity room at 20 ° C and 65% relative humidity for one day and then subjected to the following gluing effect test.

(Gluing effect test) The cotton cloth glued by the above method is cut into 2 cm x 2.5 cm, and 10 pieces as one set, using a pure bending tester (manufactured by Kato Tech Co., Ltd.), at 25 ° C, The flexural rigidity was measured in a constant temperature and humidity room at 65% relative humidity.

Example 2 A paste base was synthesized in the same manner as in Example 1 and their basic performances were compared and examined.

<Synthesis of various paste bases> As in Example 1, shown in Table 2 is a 5-neck separable flask equipped with a nitrogen introduction tube, a stirring group, a monomer quantitative dropping device, a thermometer, and a reflux condenser. Such cationic polymer 6.0 parts, polyvinyl alcohol (saponification degree 80%,
Polymerization degree 1500) 3.0 parts and ion-exchanged water 100 parts 90
After dissolving at 60 ° C and cooling to 60 ° C, 10 parts of lower fatty acid vinyl ester monomer shown in Table 1 and 2 parts of Emulgen 147 (manufactured by Kao Corporation) were added, and 0.5 part of sodium carbonate, 2,2'-
Azobis (2-amidinopropane) hydrochloride (0.1 part) and ion-exchanged water (20 parts) were added, and the temperature was raised to 75 ° C. to initiate polymerization.
From 30 minutes to 350 minutes after initiation of polymerization, 90 parts of lower fatty acid vinyl ester monomer as shown in Table 2 and one or two kinds of various monomers or polymers (in the case of two kinds, 1: 1 by weight ratio) A premix of 10 parts was continuously added dropwise to the reaction solution. After the dropping was completed, the temperature was raised to 80 ° C. and the reaction was completed after stirring for 1 hour.

Comparative Example 2 In the same manner as in Example 2, a paste base having different polymers and monomer compositions as shown in Table 2 was synthesized.

The sizing effect of the sizing agents synthesized in Example 2 and Comparative Example 2 was evaluated in the same manner as in Example 1.

 The results are shown in Table 2.

Example 3 A paste base was synthesized in the same manner as in Example 1 and their basic performances were compared and examined.

<Synthesis of various paste bases> As in Example 1, a polyvinyl alcohol (saponification degree) was added to a 5-neck separable flask equipped with a nitrogen introducing tube, a stirring group, a monomer dropping device, a thermometer, and a reflux condenser. 80
%, Polymerization degree 1500) 3.0 parts, and ion exchange water 100 parts were added and dissolved at 90 ° C. and cooled to 60 ° C., then 10 parts of lower fatty acid vinyl ester monomer and Emulgen 147 (Kao) shown in Table 3 were added. 2 parts), 0.5 parts sodium carbonate, 2,
0.1 parts of 2'-azobis (2-amidinopropane) hydrochloride,
20 parts of ion-exchanged water was added, and the temperature was raised to 75 ° C. to start polymerization.

From 30 minutes to 350 minutes after the initiation of polymerization, 88 parts of lower fatty acid vinyl ester monomer and 2 parts of unsaturated carboxylic acid monomer as shown in Table 3 and one or two kinds of various monomers or polymers (in case of two kinds) Then, 10 parts by weight of 1: 1) were mixed in advance, and the mixture was continuously added dropwise to the polymerization reaction solution. After the dropping was completed, the temperature was raised to 80 ° C. and the reaction was completed after stirring for 1 hour.

Comparative Example 3 In the same manner as in Example 3, a paste base having different polymers and monomer compositions as shown in Table 3 was synthesized.

Table 3 shows the evaluation results of the sizing effect of the sizing agents synthesized in Example 3 and Comparative Example 3. The sizing method was as follows.

(Gluing method) Using a wash tub, add 100 ml of ion-exchanged water and 0.5 g of the sizing agent synthesized as described above in solid content, disperse well, and put 20 g of 60 # cotton broad cloth in it for 3 minutes Knead in and paste. After dehydration for 1 minute, it was dried in a constant temperature and humidity room at 20 ° C. and 65% relative humidity for one day and then subjected to the gluing effect test shown in Example 1.

Example 4 The following paste composition was produced using the pigment base synthesized in Example 1, and a texture test was conducted by a paired comparison method with a conventional paste composition.

 The results are shown in Table 5.

Paste composition Emulsion (See Table 4) 91 parts Dibutyl phthalate 3 parts Ethylene glycol 3 parts Silicone emulsion (30% emulsion of 20000 centistokes silicone oil) 0.5 parts Light intensity 0.5 parts Ion-exchanged water 2 parts (Gluing test) Using a normal household washing machine, after adding 6 g of each paste composition as an effective component to 20 tap water, disperse well,
Add 500 g cotton sheets and stir glue for 3 minutes. Dehydrate with a dehydrator for 30 seconds and air dry.

With respect to the tension of the sheets glued by the above method, a tactile test by 10 persons was performed by paired comparison to evaluate the performance of each glued composition.

Evaluation standard +2: There is tension +1: There is some tension 0: Same as the control −1: There is no tension −2: There is no tension

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-53-122890 (JP, A) JP-A-59-1776 (JP, A)

Claims (4)

[Claims] 1. One kind selected from a monomer or polymer of a methacrylic acid hydroxyalkyl ester or an acrylic acid hydroxyalkyl ester during emulsion polymerization of a lower fatty acid vinyl ester or emulsion copolymerization of a lower fatty acid vinyl ester and an unsaturated carboxylic acid, or A paste composition for clothing, comprising an emulsion obtained by copolymerizing or graft-polymerizing two or more kinds. 2. The lower fatty acid vinyl ester is vinyl acetate,
The paste composition for clothes according to claim 1, which is vinyl butyrate or vinyl propionate. 3. The paste composition for clothing according to claim 1, wherein the unsaturated carboxylic acid is methacrylic acid, acrylic acid or crotonic acid. 4. The paste composition for clothing according to claim 1, wherein the methacrylic acid hydroxyalkyl ester and the acrylic acid hydroxyalkyl ester have an alkyl chain length of 1 to 4.