JP3032481B2 - Finishing composition for clothing and method of treating clothing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a finishing composition for clothing and a method for treating clothing, and more particularly, has a very good adsorbability to fibers and is used in the fields of sizing agents, softeners, bleaching agents, detergents and the like. In particular, the present invention relates to a finish composition for clothing suitable for use in the field of conventional pastes and a method for treating clothing using the same.

[0002]

2. Description of the Related Art Conventionally, starch has been used as a paste, but various improvements have been made to make it easier to use. At present, it is easy to dilute in cold water, and as a paste that is easy to use and stable. Liquid glue was developed, carboxymethylcellulose,
A mixture in which an antifoaming agent, a preservative, an optical brightener, a fragrance, and the like are blended in a 2 to 15% by weight aqueous solution of starch, polyvinyl alcohol, or the like is used. However, these sizing agents are hard polymers having a glass transition temperature of 80 ° C. or higher, and are inexpensive as sizing agents. Therefore, it is not suitable as a paste for high-grade clothing. Furthermore, the aqueous solutions of these polymers have the disadvantage that they have high viscosity even at low concentrations and are difficult to handle.

[0003] To eliminate these drawbacks, polyvinyl acetate emulsions have been used to improve the adsorptivity of clothing from high bath ratios to clothing and to enable washing at home. A paste composition in which a paste base retains cationic charge has also been proposed (for example, JP-A-53-70191).
Nos. 53-94688, 52-53086, 59-88978
Nos. 58-4875 and 58-65073).

[0004] In the past, in the case of an emulsion containing water-insoluble vinyl acetate as a main monomer, the ability to remove glue during a washing cycle was poor, and this was a cause of hardening of clothing, etc. There has also been proposed a paste composition in which an unsaturated carboxylic acid is copolymerized so that the polymer swells and dissolves due to an alkali at the time of washing, thereby improving desizing. Furthermore, since copolymerization of an aqueous monomer is also possible, it has been found that the effect of the above-mentioned method further improves the desizing property. However, in the case of these pastes mainly composed of polyvinyl acetate, the adsorptivity of the vinyl acetate portion itself to the fibers (mainly cotton fibers) is not sufficient, and a sufficient tension is obtained when a washing machine with a high bath ratio is used. You have to administer quite a lot of glue.

Further, it has been proposed that a hardness component such as calcium ion or magnesium ion dissolved in water is captured by a chelating agent to improve the adsorptivity to fibers (Japanese Patent Application Laid-Open No. 7-229067). However, the effect on general glue bases is very low, and is greatly affected by the bath ratio, and the effect is not exhibited unless a large amount of chelating agent is administered.

[0006]

DISCLOSURE OF THE INVENTION The present invention greatly improves the adsorptivity of such a conventional sizing agent, and makes it possible to attach fibers, such as clothes and sheets, in a smaller amount than a conventional sizing agent. It is possible to give the property and to achieve the use amount and liquidity adapted to the automatic dosing system of the fully automatic washing machine used for softeners etc., even if the person who prefers stiffness increases the use amount, It is an object of the present invention to provide a finishing agent for clothing, such as a glue, which does not accumulate on clothing even after repeated gluing.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have greatly improved the adsorbing performance of the sizing agent to the fiber, and have succeeded in increasing the amount of the adhesive. Further, the present inventors have found a finishing composition for clothing that does not accumulate on clothing even after repeated sizing, and a method for treating clothing using the same, due to being excellent in the adhesive removal property during washing, and have completed the present invention.

That is, the present invention comprises an emulsion containing a vinyl polymer (i) and a water-soluble polymer (ii) having a cationic group, and the total weight of these polymers (provided that the finishing composition for clothing is When the water-soluble nonionic polymer (iii) is contained, the surfactant content is not more than 1.0% by weight based on the total weight of the polymer (i), the polymer (ii) and the polymer (iii)). An object of the present invention is to provide a finish composition for clothing characterized by the following.

[0009]

Embodiments of the present invention will be described below in detail.

The vinyl polymer (i) used in the present invention comprises :
Lower fatty acid vinyl ester (a) and unsaturated carboxylic acids
(b) and an α, β-unsaturated carboxylic acid copolymerizable therewith.
Acid amide, aromatic mono- and divinyl compounds, acrylic acid
Ester and methacrylate, vinyl cyanide
Compound, vinyl halide and fluorine monomer compound
It is a copolymer with at least one selected from (c).

The lower fatty acid vinyl ester (a) used herein includes vinyl acetate, vinyl butyrate, vinyl propionate and the like, and one or more of these can be used in combination. Is particularly preferred.

The unsaturated carboxylic acids (b) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, citraconic acid And unsaturated carboxylic acids such as p-vinylbenzoic acid; alkyl esters and partial esters (preferably lower alkyl monoesters having 1 to 6 carbon atoms) or parts of unsaturated polycarboxylic acids such as itaconic acid, maleic acid and fumaric acid Amides are mentioned.
Of these, acrylic acid, methacrylic acid, crotonic acid,
Particularly preferred are monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, monobutyl maleate and the like.

An α, β-unsaturated carboxylic acid amide;
Aromatic mono- and divinyl compounds, acrylates and
And methacrylates, vinyl cyanide compounds, halo
As the vinyl genoide and the fluorine-based monomer compound (c),
N, N -dialkylacrylamide, N, N-dialkylmethacrylamide, N-alkylacrylamide, N
Α, β-unsaturated carboxylic acid amides such as -alkylmethacrylamide, N-alkoxyalkylacrylamide, N-hydroxyalkylacrylamide, N-hydroxyalkylmethacrylamide, N-acylalkylacrylamide, N-acylalkylmethacrylamide; styrene; aromatic mono- and divinyl compounds such as α-methylstyrene, chlorostyrene, alkylstyrene and divinylbenzene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, Ethylhexyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, hydroxyethyl acrylate , Acrylic and methacrylic esters such as hydroxyethyl methacrylate;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinylidene chloride; trifluoroethyl methacrylate, 2,2,3,
3-tetrafluoropropyl methacrylate, 2,2,3,3,
Fluorine-based monomers such as 4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate, and perfluorooctyl acrylate are exemplified, and one or more of these can be used in combination.

Among these monomers (c) , α, β-unsaturated carboxylic acid amides are preferred, and the alkyl, alkoxyl, and acyl groups of the α, β-unsaturated carboxylic acid amide have a chain length of 1 carbon atom. ~ 18 are preferred. Specifically, N, N-dimethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N
-Hydroxyethyl methacrylamide, diacetone isoacrylamide and the like are exemplified as preferable ones.
In the case of a dialkyl-substituted product, the two alkyl chains may have different lengths, and a polymer thereof can be used instead of the α, β-unsaturated carboxylic acid amide monomer. In the case of a polymer, its molecular weight is not particularly limited, and may be two or more copolymers selected from the above-mentioned amide monomer group.

The lower fatty acid vinyl ester (a) constituting the vinyl polymer (i), the unsaturated carboxylic acid (b) and the above
The copolymerization ratio of the monomer (c) was 99.9 to 70% by weight of the lower fatty acid vinyl ester (a), 0.1 to 10% by weight of the unsaturated carboxylic acid (b ), and
A proportion of 0 to 20% by weight is preferred. Unsaturated carboxylic acids
By changing the copolymerization ratio of (b) and the above-mentioned monomer (c) , it is possible to adjust the strength, elongation, etc., of the film (film formation), and also to adjust the stability of the copolymerization reaction. be able to.

In producing the emulsion containing the vinyl polymer (i) according to the present invention, the lower fatty acid vinyl ester (a) is used in an amount of 20 to 60% by weight based on the whole raw materials used for synthesizing the emulsion. And more preferably 25 to 50% by weight. Also unsaturated carboxylic acids
(b) is preferably used in a proportion of 0.1 to 15 parts by weight, especially 0.2 to 5 parts by weight, based on 100 parts by weight of the lower fatty acid vinyl ester (a).

Further, the above-mentioned monomer (c) , especially α, β
-Unsaturated carboxylic acid amide is 1 to 30 parts by weight, particularly 2 to 30 parts by weight based on 100 parts by weight of the lower fatty acid vinyl ester (a)
It is preferably used in a proportion of 20 parts by weight. By setting the ratio of the α, β-unsaturated carboxylic acid amide to 1 part by weight or more, the desizing property during washing can be sufficiently improved.
When the amount is 30 parts by weight or less, the stability of the emulsion at the time of copolymerization becomes good.

The finish composition of the present invention contains a water-soluble polymer (ii) having various cationic groups for the purpose of improving the adsorptivity to fibers at a high bath ratio. The water-soluble polymer (ii) having a cationic group may be added during the copolymerization of the monomers constituting the vinyl polymer (i), or may be added during or after the polymerization of these monomers. The content of the water-soluble polymer (ii) having a cationic group in the finish composition of the present invention is preferably 0.001 to 5% by weight, and 0.2 to 5% by weight.
3% by weight is more preferred.

The water-soluble polymer (ii) having a cationic group used in the present invention includes cationic cellulose, cationic starch, cationic vinyl polymer and the like. As the cationic cellulose and the cationic starch, for example, a compound represented by the following general formula (I) is preferable.

[0020]

Embedded image

Wherein A represents a cellulose residue or a starch residue. R ¹ represents an alkylene group having 1 to 12 carbon atoms or a hydroxyalkylene group. R ² , R ³ , R ⁴ : the same or different, and represents an alkyl group, an aryl group or an aralkyl group having 1 to 12 carbon atoms. R ² ,
Any two of R ³ and R ⁴ may form a heterocyclic ring with the nitrogen atom. X ⁻ : represents an anion such as chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid and nitric acid.

N: an integer not less than 1 and not more than the number of hydroxyl groups in cellulose or starch. The cationic cellulose and cationic starch used in the present invention have a degree of cation substitution of preferably 0.01 to 2, that is, 0.01 to 2 cationic groups per anhydroglucose unit are introduced, and 0.05 to 1.5 cationic groups are preferably used. Those introduced are particularly preferred. By setting the degree of cation substitution to 0.01 or more, the adsorptivity to fibers can be sufficiently improved, and may be more than 2, but is preferably 2 or less from the viewpoint of reaction yield.

The cationic cellulose can be obtained, for example, by reacting hydroxyethyl cellulose with glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride under alkaline conditions. It can also be obtained by reacting hydroxyethyl cellulose with 4-chlorobutenetrimethylammonium chloride.

In the case of cationic starch, it can be obtained, for example, by reacting starch with glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride under alkaline conditions. It can also be obtained by quaternizing dimethylaminoethylated starch. Further, it can be obtained by reacting starch with 4-chlorobutenetrimethylammonium chloride.

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

[0026]

Embedded image

Wherein R ^{5 represents a} hydrogen atom or a methyl group. R ⁶ , R ⁷ , R ⁸ : same or different, hydrogen atom, carbon number 1 to
4 represents an alkyl group or a substituted alkyl group. Y represents an oxygen atom or an NH group in an amide bond. X ^-: The meanings of the. p: Indicates the number of 1 to 10. q: Indicates a number of 10 to 10,000. As the water-soluble polymer (ii) having a cationic group, a cationic cellulose or a cationic starch represented by the general formula (I) is preferable. The viscosity of the water-soluble polymer (ii) having a cationic group is preferably such that the viscosity of a 1% by weight aqueous solution at 20 ° C. is 5 to 1000 cps (centipoise), and particularly preferably 10 to 500 cps.

The finishing composition of the present invention contains a water-soluble non-ionic polymer (iii) such as non-ionic modified starch, polyvinyl alcohol or a non-ionic cellulose derivative, so that it can be used more for fabrics. A favorable texture can be given. In addition, the desizing property at that time can be sufficiently satisfied.

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

The polyvinyl alcohol which can be used in the present invention includes a vinyl acetate homopolymer, a completely or incomplete saponified product of a copolymer of vinyl acetate and another monomer,
Alternatively, a polyvinyl alcohol derivative obtained by modifying these with an aldehyde or the like, for example, having a 5% aqueous solution having a viscosity of 5 to 10,000 centipoise at 30 ° C. is exemplified.

The nonionic cellulose derivative which can be used in the present invention is a water-soluble hydroxyalkylated cellulose or alkylcellulose having a 5% aqueous solution having a viscosity of 5 to 10,000 centipoise at 30 ° C., For example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose and the like can be mentioned.

These water-soluble nonionic polymers (iii) are contained in the raw materials for the synthesis of the emulsion in an amount of not more than 10% by weight,
In particular, it is preferable to mix 1 to 4% by weight.

In the copolymerization reaction for obtaining the emulsion containing the vinyl polymer (i) according to the present invention, a surfactant is used as an emulsifier. Examples of the surfactant used in the present invention include a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactant used in the present invention include an alkyl group having 7 to 18 carbon atoms and an alkyl group having 9 to 30 carbon atoms.
Or a polyoxyethylene alkyl phenyl ether having ethylene oxide units of a higher value, such as polyoxyethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene methyl octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl A phenyl ether or the like, or an ethylene oxide adduct of an alkylphenol linked by a methylene bond, a mercaptan such as nonylmercaptan, dodecylmercaptan, or tetradecylmercaptan, or an alkylthiophenol having an alkyl group having 6 to 15 carbon atoms and a necessary amount of ethylene oxide. Surfactants containing condensed sulfur, such as lauric acid, myristic acid, palmitic acid, oleic acid, and tall oil mixed acids. An ethylene oxide adduct of a long chain carboxylic acids, ethylene oxide adducts of polyhydroxy compounds that the etherified or esterified with a hydrophobic hydrocarbon chain. As these nonionic surfactants, those having an HLB of 12 to 19 are preferable, and those having an HLB of 15 to 18 are preferable.
Are particularly preferred.

Specific examples of the anionic surfactant used in the present invention include those having 8 carbon atoms such as lauryl alcohol.
Higher aliphatic alcohol sulfates, such as sodium salts and potassium salts of sulfates of alcohols having a carbon number of 8 to 18;
Sodium, potassium or alkanolamine salts such as triethanolamine salts of fatty acids such as triethanolamine oleate, triethanolamine stearate, funnel oil, sulfonates such as sulfated ricinoleic acid, sodium-t And sulfonated alkylaryl compounds such as -octylbenzenesulfonate and sodium-t-octylphenolsulfonate.

Specific examples of the cationic surfactant used in the present invention include alkyltrimethylammonium salts,
Dialkyldimethylammonium salt, alkyldimethylethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylquinolium salt, alkylisoquinolium salt, stearylamidomethylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminoethylpyridinium Salt, alkoxymethylpyridinium salt, 1-methyl-1
-Acylaminoethyl-2-alkylimidazoline, diacylaminopropyldimethylammonium salt, diacylaminoethyldimethylammonium salt, dialkyldi (polyoxyethylene) ammonium salt, dialkylmethylpolyoxyethyleneammonium salt and the like.

In the finishing composition of the present invention, the content of these surfactants is determined by the total weight of the vinyl polymer (i) and the water-soluble polymer (ii) having a cationic group (provided that the finishing When the agent composition contains the water-soluble nonionic polymer (iii), the total weight of the polymer (i), the polymer (ii) and the polymer (iii)) is preferably 1.0% by weight or less. Should be 0.5% by weight or less. Surfactant content of 1.0
When the amount is more than the weight%, the adsorptivity of the emulsion to the fiber is significantly reduced, and a large amount of the emulsion is required to impart tension to the fiber, which is not preferable. Surfactant content
As a method for reducing the content to 1.0% by weight or less,
When producing an emulsion containing (i) and a water-soluble polymer having a cationic group (ii), a method of adjusting the addition amount of a surfactant used as an emulsifier so as to be the above ratio, or obtained. A method of removing the surfactant in the emulsion by filtration or the like so that the content of the surfactant becomes the above ratio.

As the polymerization initiator used in the copolymerization reaction for obtaining the emulsion according to 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 amount of the polymerization initiator to be added is preferably 0.01 to 5% by weight, more preferably 0.02 to 1% by weight, based on the lower fatty acid vinyl ester (a) constituting the vinyl polymer (i).

The temperature of the copolymerization reaction for obtaining the emulsion according to the present invention is 40 to 120 ° C., preferably 50 to 90 ° C.
And the pH at the time of copolymerization is 3 to 9, preferably 3 to 7. At this time, an inorganic salt such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate, sodium chloride or sodium sulfate is used as a buffer in the raw materials used for the emulsion synthesis. % By weight, preferably 0.1 to 1% by weight.

When emulsion polymerization is carried out to obtain the emulsion according to the present invention, the monomers may be charged all at once into the reaction tank and reacted, but more preferably the lower fatty acid vinyl ester (a) is reacted. It is desirable to charge the mixture in a tank and gradually add the lower fatty acid vinyl ester (a), the unsaturated carboxylic acid (b), and the water-soluble monomer (c) to the tank.

The finish composition of the present invention may contain a polyhydric alcohol for the purpose of improving low-temperature storage stability and a dicarboxylic acid diester for the purpose of exhibiting low-temperature toughness. The polyhydric alcohol used in the present invention includes glycerin, ethylene glycol, propylene glycol and the like. The dicarboxylic diester used in the present invention includes dimethyl, diethyl, dibutyl, diheptyl, dioctyl, diisobutyl and butylbenzyl esters of phthalic acid, and dimethyl, diethyl, dibutyl, diheptyl, dioctyl and diisobutyl esters of adipic acid, and sebacine Examples include dimethyl, diethyl, dibutyl, diheptyl, dioctyl and diisobutyl esters of acids.

Further, a silicone compound, a fragrance, a bactericide, a preservative, a fluorescent dye, a pigment and the like can be added to the finish composition of the present invention, if necessary. The finish composition of the present invention can be used as a finish composition such as a conventionally known paste, and can also be used in combination with a softener, a bleach, a detergent and the like.

In using the finish composition of the present invention as a paste, a method of using a conventional paste composition, that is, a water amount for diluting the paste composition with respect to clothing, that is, a so-called bath ratio of 1 is used.
The method can also be used in a method of about 1 to 1 to 4, or as described above, a water-soluble polymer having a cationic group (i
When i) is used, it can be used in a ratio of about 1:10 to 1:40. In particular, such an increase in the bath ratio enables uniform gluing, and furthermore, when used at home, enables treatment with an electric washing machine.

The ratio of the finish composition to the cloth weight when sizing using the finish composition of the present invention as a paste is as follows:
The effective amount (solid content) of the finish composition is 0.2% of the weight of clothing
-6% by weight, more preferably 0.5-4% by weight.

[0045]

When the finishing composition of the present invention is glued, the adsorbability to clothing is greatly improved as compared with the conventional vinyl acetate-based sizing agent. On the other hand, in addition to giving the same tension with a small amount as compared to the conventional glue, even if people who prefer stiffness to excel in laundering during washing increase the amount of use, it can be applied to clothing even with repeated gluing. This has the effect of not accumulating and accumulating.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The percentages in the examples are on a weight basis unless otherwise specified. The average particle size of the emulsion was measured using LA-910 (refractive index: 1.2) manufactured by Horiba, Ltd. The measurement of viscosity is B
As a method for removing the surfactant in the emulsion using a mold viscometer (Rotor No. 1, 50 ° C., 15 rpm), a Millipore filtration device (Millipore, Pellicon membrane GVPP / GVLP 0005 C5)
Was used.

Example 1 Deionized water was placed in a reactor (2 liter separable flask) equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube.
g, 44 g of the cationized starch described in Table 1 and 7 g of polyvinyl alcohol (Gohsenol GL-05) in an aqueous solution of 425 g,
13 g of a 20% aqueous solution of polyoxyethylene dodecyl ether (number of moles of ethylene oxide added: 50 mol), 57 g of a 5% trisodium phosphate buffer, 16 g of pre-added vinyl acetate, and a pre-added initiator V-50 (Wako Pure Chemical Industries, Ltd.) 1.4 g) and heated to 75 ° C. while blowing nitrogen gas. To this, 500 g of a monomer mixture composed of 94.5% of vinyl acetate, 3% of N, N-dimethylacrylamide and 2.5% of methacrylic acid was added dropwise over 6 hours to carry out emulsion polymerization. From 1 hour after the start of the dropping of the monomer to the end of the dropping, the post-addition initiator V-50 was used.
A 190 g aqueous solution to which 1.0 g was added was sequentially added dropwise to obtain an emulsion having the composition shown in Table 1.

Examples 2 to 3 and Examples 5 to 8 Emulsions having the compositions shown in Tables 1 and 2 were synthesized in the same manner as in Example 1.

COMPARATIVE EXAMPLE 1 Deionized water was placed in a reactor (2 liter separable flask) equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube.
g, 44 g of the cationized starch described in Table 1 and 7 g of polyvinyl alcohol (Gohsenol GL-05) in an aqueous solution of 425 g,
Charge 65 g of a 20% aqueous solution of polyoxyethylene dodecyl ether (number of moles of ethylene oxide added: 50 mol), 57 g of a 5% trisodium phosphate buffer, 16 g of pre-added vinyl acetate, and V-501.4 g of a pre-added initiator, and supply nitrogen gas. 75 while blowing
The temperature was raised to ° C. To this, 500 g of a monomer mixture composed of 94.5% of vinyl acetate, 3.0% of dimethylacrylamide and 2.5% of methacrylic acid was added dropwise over 6 hours to carry out emulsion polymerization. From 1 hour from the start of the dropping of the monomer to the end of the dropping, 190 g of an aqueous solution to which 1.0 g of the post-addition initiator V-50 was added was sequentially dropped to obtain an emulsion having the composition shown in Table 2.

Example 4 An emulsion having the composition shown in Table 1 was obtained by distilling low molecular weight (surfactant) from the emulsion synthesized in Comparative Example 1 by millipore filtration.

Comparative Example 2 The dropping time of the monomer mixture was reduced from 6 hours to 4.5 hours by the method of Comparative Example 1 to obtain an emulsion having the composition shown in Table 2.

Comparative Example 3 Deionized water was added to a reactor (2 liter separable flask) equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube.
50 g, 3 g of the cationized starch described in Table 2 and 1 g of polyoxyethylene nonylphenyl ether (the number of moles of ethylene oxide added: 48 mol) were added, dissolved at 80 ° C., cooled to 60 ° C., and then EDTA / 4Na was added. 25 g was dissolved and nitrogen was introduced. Next, 5 g of vinyl acetate was added, and the first addition initiator V-50 was added.
An initiator solution prepared by dissolving 0.1 g of ion-exchanged water in 10 g was charged and stirred for 20 minutes, and then the liquid temperature was raised to 75 ° C.
After the start of the polymerization, an initiator solution in which 45 g of vinyl acetate, 1.55 g of crotonic acid, and 0.4 g of V-50 were dissolved in 40 g of ion-exchanged water was continuously dropped over 2 hours. After the completion of the continuous dropping, the liquid temperature was raised to 80 ° C., and after aging for 1 hour, the polymerization was terminated.
After cooling to room temperature, the pH of the emulsion was adjusted to 9.0 using a 10% aqueous hydrochloric acid solution to obtain an emulsion having the composition shown in Table 2.

Comparative Example 4 The dropping time was reduced from 6 hours to 4.5 hours by the method of Comparative Example 3 to obtain an emulsion having the composition shown in Table 2.

Test Examples The finishing compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were evaluated for the sizing effect and the sizing property by the following methods. The adsorption rate and the bending rigidity value were measured for a low gluing amount (13 g) and a high gluing amount (30 g), respectively.
The results are shown in Tables 1 and 2.

<Gluing treatment> Using a tergotometer type washing tester, 5000 g of ion-exchanged water and 5 g or 11.5 g of the finishing composition synthesized as described above (solid emulsion amount: 13 g, 30 g) After well-dispersed in a washing tank, 200 g of 60 # cotton broad cloth was put therein, and the mixture was stirred and glued at a rotation speed of 100 rpm for 3 minutes. After dehydrating for 1 minute,
After drying all day and night in a constant temperature and humidity room at 20 ° C and 65% relative humidity,
It was subjected to the following gluing effect test.

<Gluing effect test> The cotton cloth glued by the above-mentioned gluing treatment is cut so as to have a width of 5 cm, and a set of 10 sheets is used as a pure bending tester (manufactured by Kato Tech Co., Ltd.).
Was used to measure the bending stiffness in a thermo-hygrostat at 25 ° C. and 65% relative humidity.

<Measurement of Adhesion Amount of Paste> The adsorption rate of the cotton cloth pasted by the above paste treatment was calculated from the weight before paste and the weight change after paste according to the following formula.

[0058]

(Equation 1)

<Evaluation of Paste Detachability> The finish composition synthesized as described above was mixed with 500 ml of ion-exchanged water in terms of solid content of 5 g, 11.5 g (administration emulsion amount 13 g, 30 g),
After placing in a washing tub and dispersing well, 60 # cotton broad cloth
20 g was added and the mixture was sufficiently immersed and glued for 3 minutes. 1
After dehydration for 20 minutes, it is dried for 24 hours in a constant temperature and humidity room at 20 ° C. and 65% relative humidity, and then pressed at 130 ° C. for 1 minute. The hardness of the cloth after pressing is measured using the above-described pure bending tester, and the hardness at this time is defined as H. Using a pressed cloth tergotometer type washing tester, use a household detergent "New Beads" (manufactured by Kao Corporation) at a concentration of 0.133% at a bath ratio of 30 times, and rotate at a rotation speed of 100 rpm. The mixture was stirred and washed for minutes. The cloth thus washed is dried in a thermo-hygrostat at 20 ° C. and 65% relative humidity all day and night, and then pressed again at 130 ° C. for 1 minute. Similarly, the bending rigidity is measured using a pure bending tester. The hardness at this time is defined as I. Further, the hardness of the cloth before the treatment is measured in advance, and this is designated as J. Using the bending stiffness value of the cloth measured in this manner, the adhesive removal rate was calculated by the following equation.

[0060]

(Equation 2)

[0061]

[Table 1]

[0062]

[Table 2]

Note) * 1 Ratio of each monomer constituting the vinyl polymer (i) to the total amount of monomers VAc: vinyl acetate, MAA: methacrylic acid, CA: crotonic acid, DMMA: dimethylacrylamide, HEM
A: Hydroxyethyl methacrylate * 2 Ratio to total weight of vinyl polymer (i) and water-soluble polymer (ii) having cationic group EM150: Polyoxyethylene dodecyl ether (EO
NP: polyoxyethylene nonyl phenyl ether (EO
Number of moles added 48) * 3 Content in the composition DIBA: diisobutyl adipate, PG: propylene glycol, EDTA / 4Na: ethylenediaminetetraacetic acid / 4 sodium salt

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI D06M 15/327 D06M 15/327 (72) Inventor Yoshihiro Hasebe 1334 Minato 1334, Minato, Wakayama-shi, Wakayama Pref. JP-A-9-195170 (JP, A) JP-A-7-229067 (JP, A) JP-A-5-98572 (JP, A) JP-A-5-98573 (JP, A) JP-A-58-13658 JP, A) JP-A-58-4875 (JP, A) JP-A-55-103369 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 15/00-15/72

Claims (1)

(57) [Claims] 1. A lower fatty acid vinyl ester (a), unsaturated
Carboxylic acids (b) and α, β copolymerizable therewith
-Unsaturated carboxylic amides, aromatic mono- and divinylation
Compounds, acrylic esters and methacrylic esters,
Vinyl cyanide compound, vinyl halide and fluorine type
Vinyl polymerization with one or more (c) selected from monomer compounds
(I) and an emulsion containing a water-soluble polymer (ii) having a cationic group, and the total weight of these polymers (provided that the finishing composition for clothing is a water-soluble nonionic polymer)
(iii), the content of the surfactant with respect to the total weight of the polymer (i), the polymer (ii) and the polymer (iii))
A finishing composition for clothing, which is 0.5 % by weight or less.