JPH09105077A - Clothing treating agent composition and clothing treatment product and treatment of clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of imparting clothing with moderate touch feeling and skin touch and also capable of suppressing crease development of the clothing during its washing and dehydration, containing specific water-soluble polymer(s) or aqueous emulsion(s) and a quaternary ammonium salt. SOLUTION: This treating agent composition contains (a) 0.01-20wt.% of at least one kind selected from among water-soluble polymers or aqueous emulsions including modified starch (derivatives), cellulose derivatives, polyvinyl acetate saponified products (derivatives), sulfonic acid group-bearing polymers (salts) prepared by (co)polymerizing one or two kinds of monomer(s) bearing vinyl group and/or aromatic ring, N-vinyl-2-pyrrolidone (co)polymers (salts), (meth)acrylic acid-based polymers (salts) and copolymers of lower fatty acid vinyl ester, unsaturated carboxylic acid and monomer copolymerizable therewith and (b) 0.05-30wt.% of a quaternary ammonium salt of the formula (1-2 of R<1> , R<2> , R<3> and R<4> are each a 8-25C alkyl or alkenyl, the rest being a 1-3C alkyl or hydroxyalkyl; X<-> is an anion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a treating agent composition for clothing, a treated article for clothing, and a method for treating clothing. More specifically, it imparts an appropriate texture, feel to the clothing, and wetness after washing and dehydration. The present invention relates to a treatment agent composition for clothing, a treated article for clothing, and a method for treating clothing, in which “wrinkles” that mechanically occur during dehydration are treated by treating the clothing in an open state.

[0002]

2. Description of the Related Art Generally, there are liquid sizing agents / softening agents and spray glues, spray type antistatic agents, and the like as treatment agents for clothes which are generally known. Nothing is aimed at positively removing the "wrinkles" that occur. In addition, wrinkle spreading sprays (JP-A-1-292184 and JP-A-1-292185) aimed at removing wrinkles formed on dry clothes are sufficiently effective against wet clothes after dehydration. Not.

On the other hand, with the recent diversification of clothing life, cotton,
The increasing preference for natural fibers such as hemp and wrinkles caused by dehydration as in the past due to changes in lifestyle such as the increase in women with occupations such as housewives are troublesome such as ironing. There is an increasing demand for a treatment agent that can easily remove wrinkles from clothing without requiring any complicated work. However, ironing is indispensable in the conventional spray-type sizing agent in principle, which is very troublesome, and the clothes are hard to be finished, so that they cannot be used for various clothes. Moreover, the antistatic agent cannot sufficiently remove the wrinkles of the clothes.

[0004] Therefore, the problem to be solved by the present invention is to provide a clothing treating agent composition, a clothing treating article, and a clothing treating article which impart appropriate texture and touch to clothing and suppress wrinkles mechanically generated during washing and dehydration. It is to provide a processing method.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have formulated a specific water-soluble polymer or aqueous emulsion and a quaternary ammonium salt in respective specific ranges. The inventors have found that the above objects can be achieved by obtaining a composition by applying the composition to a garment to be treated in a wet state, and have completed the present invention.

That is, the present invention comprises the following component (a) from 0.01 to 20:
The present invention provides a treating agent composition for clothing, characterized in that the content of the component (b) is 0.05 to 30% by weight. Component (a): 1 selected from the group consisting of the following (i) to (ix)
Water-soluble polymer and / or aqueous emulsion polymer (i); modified starch and its derivative polymer (ii); cellulose derivative polymer (iii); polyvinyl acetate saponification product and its derivative polymer (iv); A polymer obtained by polymerizing at least one or more monomers having a vinyl group and / or an aromatic ring and having a sulfonic acid group or a salt thereof Polymer (v); N-vinyl-2-pyrrolidone ( D) homopolymer polymer (vi); the monomer (D) and the monomer (D)
And a salt thereof obtained by polymerizing one or more vinyl monomers (E) copolymerizable with
The mole fraction of (D) is 30% or more. ) Polymer (vii); Acrylic acid or methacrylic acid homopolymers and copolymers and salts thereof Emulsion (viii); Lower fatty acid vinyl ester (F) and unsaturated carboxylic acid (G), or said (F), (G) Aqueous emulsion obtained by copolymerizing these with a copolymerizable monomer (H) Emulsion (ix); Is one or more polymerizable aromatic monomer (I) (co) polymerized? Or the monomer (I)
Of the aqueous emulsion (b) component obtained by copolymerizing one or more of the above (1) and one or more of the monomer (J) copolymerizable with the monomer (I): One or more quaternary ammonium salts represented by I)

[0007]

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(In the formula, one or two of R ¹ , R ² , R ³ and R ⁴ represent an alkyl group or an alkenyl group having 8 to 25 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms. Or a hydroxyalkyl group, X ⁻ represents an anionic group.) The present invention also comprises the above component (a) in an amount of 0.01 to 20% by weight, and
(b) component is contained in an amount of 0.05 to 30% by weight, and as the component (c), water-insoluble silicone having an average particle size of dispersed particles in the range of 0.01 to 10 μm is contained in an amount of 0.01 to 10% by weight. The present invention provides a treatment composition for clothing.

The present invention also provides a treated article for clothing, which is obtained by filling the above-mentioned treating agent composition for clothing into a container equipped with a device for spraying a liquid filled inside thereof to the outside. is there. Further, the present invention provides a method for treating clothing, which comprises spraying the above-mentioned clothing treatment agent composition of the present invention onto wet clothing.

[0010]

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

[Component (a)] Used in the composition of the present invention
The component (a) is one or more water-soluble polymers and / or aqueous emulsions selected from the group consisting of (i) to (ix) described in detail below. <Polymer (i); Modified Starch and Derivatives Thereof> As modified starch, hydroxyalkylated starch (eg, hydroxyethylated starch, hydroxypropylated starch, etc.), carboxyalkylated starch (eg, carboxymethylated starch, etc.), Cationized starch having a quaternary ammonium group, or those obtained by lowering the viscosity thereof with an oxidizing agent (for example, H ₂ O ₂ , NaClO, etc.) or an enzyme is used.

In this case, the degree of substitution indicating the ratio of the introduction of substituents (hydroxyalkyl group, carboxyalkyl group, cation group, etc.) into starch (the number of hydroxyl groups into which the substituent is introduced is based on the total number of hydroxyl groups in starch). Number ratio) is 0.
It is from 0.8 to 0.8, preferably from 0.1 to 0.4. 0.08 substitution degree
If the amount is less than the above range, a precipitate will be formed on storage for a long period of time due to denaturation of the modified starch, and a whitening phenomenon will occur when used for colored clothing. In addition, when the degree of substitution is larger than 0.8, the texture of clothing is deteriorated, which is not preferable. Preferred as the polymer (i) are hydroxyethylated starch and cationized starch having a quaternary ammonium group, and preferably have an average molecular weight of 5,000 to 500,000.

<Polymer (ii); Cellulose Derivative> Cellulose derivatives include hydroxyalkyl cellulose (eg hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.),
Alkyl cellulose (eg, methyl cellulose, ethyl cellulose, etc.), carboxymethyl cellulose, cationized cellulose having a quaternary ammonium group, etc. are used. In this case, the degree of substitution indicating the rate at which a substituent (hydroxyalkyl group, alkyl group, carboxymethyl group, cationic group, etc.) is introduced into cellulose (the number of hydroxyl groups into which the substituent is introduced, relative to the total number of hydroxyl groups in cellulose) 0.5-1.5, preferably 0.6-1.0
It is. Preferred as the polymer (ii) is a cationized cellulose having an average molecular weight of 10,000 to 500,000.
0 is preferable.

<Polymer (iii); Saponified Polyvinyl Acetate and Its Derivatives> A homopolymer of vinyl alcohol is obtained by saponifying polyvinyl acetate at 100 mol%. Incomplete saponification of polyvinyl acetate gives a copolymer of vinyl alcohol and vinyl acetate. (a)
When used as a component, 70-100 mol of polyvinyl acetate
%, Preferably from 85 to 100 mol%, is suitable. Further, a polymer having a saponification degree in such a range can be used as a modified polyvinyl alcohol by modifying the polymer with carboxylic acid or cation. The average molecular weight of the polymer (iii) is preferably 5,000 to 500,000.

<Polymer (iv)> The polymer (iv) used in the composition of the present invention is obtained by polymerizing at least one monomer having at least a vinyl group and / or an aromatic ring, and It is a polymer containing a sulfonic acid group or a salt thereof.

The polymer (iv) can be obtained as a homopolymer or a copolymer by the following methods (a) and (b). (A) A monomer (A) having a vinyl group and / or an aromatic ring and having a sulfonic acid group is polymerized, or the monomer (A) is copolymerized with another copolymerizable monomer (B). Polymerizes. (B) at least one or two or more monomers having a vinyl group and / or an aromatic ring and no sulfonic acid group
(A ′) is polymerized and then sulfonated, or the monomer
(A ′) is copolymerized with another copolymerizable monomer (C) and then sulfonated.

Examples of the monomer (A) used in the above method (a) include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, vinylsulfonic acid, methallylsulfonic acid and sulfopropyl. Methacrylate, α-methylstyrene sulfonic acid, vinyltoluene sulfonic acid, vinylnaphthalene sulfonic acid, indene sulfonic acid and the like, and salts thereof can be mentioned.

As the monomer (B), acrylic acid, methacrylic acid, maleic acid, maleic anhydride, hydroxyethyl acrylic acid, hydroxyethyl methacrylic acid, ethylene, propylene, n-butene, isobutene,
Pentene, isoprene, 2-methyl-1-butene, n-
Hexene, 2-methyl-1-pentene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 2-ethyl-
Examples thereof include 1-butene, styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, indene, butadiene, cyclopentadiene, dicyclopentadiene and the like. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, hydroxyethyl acrylic acid,
Preferred are water-soluble monomers such as hydroxyethyl methacrylic acid and salts of these monomers. Particularly, acrylic acid, methacrylic acid, maleic acid and salts thereof and styrene are preferred.

When the polymer (iv) is obtained as a copolymer by the method (a), the proportion of the above-mentioned monomer (A) having a sulfonic acid group is 30 mol% or more, preferably 30 mol% or more based on all monomers to be subjected to the polymerization. Is blended in an amount of 50 mol% or more.

When the polymer (iv) (copolymer) is obtained by combining the above monomers (A) and (B), the above (A) and (B)
Medium, especially styrene sulfonic acid and sodium acrylate,
A combination of styrene sulfonic acid and styrene is preferred.

On the other hand, when the polymer (iv) is obtained as a copolymer by the method (b), the above-mentioned monomer (A ') having no sulfonic acid group is contained in the total amount of the monomers to be subjected to the polymerization in 60%.
The amount is preferably from 100 to 100 mol%, particularly preferably from 85 to 100 mol%.

Examples of the monomer (A ') used in the above method (b) include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, indene and the like, and one or more of these may be used. It can be polymerized. Of these, styrene is particularly preferred.

In the method (b), the monomer
One or more of (A ′) and another monomer (C) copolymerizable with the monomer (A ′) can be polymerized. In this case, as the monomer (C), for example, acrylic acid,
Methacrylic acid, maleic acid, maleic anhydride, hydroxyethyl acrylic acid, hydroxyethyl methacrylic acid,
Ethylene, propylene, butene, pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl- Examples thereof include 1-butene, butadiene, cyclopentadiene, and dicyclopentadiene.

In the above method (b), polymers such as polystyrene, styrene / ethylene copolymer, styrene / diisobutylene copolymer, styrene / dicyclopentadiene copolymer, styrene / vinyltoluene / α-methylstyrene / indene copolymer are available. Medium polystyrene is most preferred), and the resulting polymer is further sulfonated. The sulfonation is performed by using sulfuric anhydride,
It can be carried out by using a sulfonating agent such as chlorosulfonic acid or sulfuric anhydride / Lewis base complex and applying any sulfonation method.

Upon sulfonation, the sulfonation rate of the polymer (iv) (when one sulfonic acid group is attached to one skeleton derived from a monomer having a vinyl group and / or an aromatic ring, the sulfonation rate is 100%) 60%
If the water content is less than the above range, the water solubility decreases, and it is difficult to remove the water during washing, which is not preferable. The preferred sulfonation rate is 85% or more.

The polymer (iv) containing a sulfonic acid group thus obtained can be contained in the composition of the present invention as it is, but can also be used as a salt. Such salts include lithium as a monovalent salt,
Examples thereof include metal salts such as sodium and potassium, ammonium salts, and organic amine salts such as mono-, di- or triethanolamine, morpholine, ethylamine and butylamine. As divalent salts, alkaline earth metals such as calcium, magnesium and barium. There are salts, organic amine salts such as ethylenediamine and hexamethylenediamine, and examples of trivalent salts include aluminum salts, organic amine salts such as diethylenetriamine, and polyvalent organic amines such as polyethyleneimine. The salt is particularly preferably a sodium salt.

The molecular weight of the polymer (iv) used in the composition of the present invention is preferably from 10 to 6 million, more preferably 50.
The range is 100 to 100,000, particularly preferably 10,000 to 500,000.
When the molecular weight is 1000 or more, the texture of clothes is good, and
A viscosity of less than 6 million is suitable because it has an appropriate viscosity.

<Polymer (v)> The polymer (v) used in the composition of the present invention is a homopolymer of N-vinyl-2-pyrrolidone (D). This polymer (v) is a monomer (D)
Having a weight average molecular weight of 1,000 to 6,000.
0,000 is preferred, more preferably 2,000 to 1,000,000
It is. If the molecular weight of the polymer is 1,000 or more, the hand of the garment is good, and if it is 6,000,000 or less, it has a suitable viscosity, so that it is preferable.

The polymer of the monomer (D) includes, for example, PVP K homopolymer series PVP K-15, K-30, K-60, K-90 (trademarks) manufactured by ISPE Japan Co., Ltd. To be These chemical structures are as follows, for example.

[0030]

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<Polymer (vi)> The polymer (vi) used in the composition of the present invention is a vinyl-based monomer copolymerizable with the above-mentioned N-vinyl-2-pyrrolidone monomer (D) and the monomer (D). A copolymer or a salt thereof obtained by polymerizing one or more kinds of (E) (provided that the monomer (D) has a mole fraction of 30 in the monomer composition of the copolymer or the salt).
% Or more). The weight average molecular weight of the copolymer is preferably from 1,000 to 6,000,000, more preferably
2,000 to 1,000,000. The molecular weight of the copolymer is 1,00
If it is 0 or more, the texture of the clothing is good, and 6,000,000
The following is preferable because it has an appropriate viscosity.

Examples of the monomer that can be used as the monomer (E) include a water-soluble vinyl monomer, a water-insoluble vinyl monomer, and a mixed monomer of both.

Here, as the water-soluble vinyl monomer, specifically, one kind or two or more kinds selected from the monomer group consisting of the following (1) to (11) is used. (1) Acrylic acid and its salts (2) Methacrylic acid and its salts (3) Maleic acid and its salts (4) Maleic anhydride (5) 2-Hydroxyethylacrylic acid and its salts (6) 2-Hydroxyethyl methacryl Acids and their salts (7) 2-hydroxypropylacrylic acid and its salts (8) 2-hydroxypropylmethacrylic acid and its salts (9) Acrylamide, methacrylamide, N, N-dialkylacrylamide and N, N-dialkylmethacrylamide (Alkyl group: alkyl group having 1 to 4 carbon atoms) (10) Monomer represented by general formula (II), acid salt thereof and quaternary ammonium salt thereof

[0034]

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[In the formula, R ^{7 represents a} hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁸ and R ⁹ : the same or different, and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, or a hydroxypropyl group. x: indicates the number of 1 to 5. In this case, as specific examples of the monomer represented by the general formula (II), N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N-dimethylaminomethylacrylic acid Amide,
N, N-dimethylaminomethylmethacrylamide, N, N
-Dimethylaminoethylacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-dimethylaminobutylacrylamide, N, N-dimethylaminobutylmethacrylamide and the like.

When the monomer represented by the general formula (II) is used as an acid salt, for example, an inorganic acid salt such as HCl, H ₂ SO ₄ , H ₃ PO ₄ or p-toluenesulfonic acid salt, glycolic acid, When an organic acid salt such as citric acid or succinic acid is used, or when it is used as a quaternary ammonium salt, the monomer represented by the general formula (II) is converted into CH ₃ Cl, (CH ₃ ) by a conventionally known method. _A quaternary ammonium salt of an alkylating agent such as ₂ SO ₄ is used.

(11) Monomer represented by the general formula (III), its acid salt and its quaternary ammonium salt

[0038]

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[Wherein R ⁷ , R ⁸ and R ⁹ are as defined above. y: Indicates the number of 1 to 5. Examples of the monomer represented by the general formula (III), -N, N-dimethylaminoethyl acrylate, -N, N-acrylic acid
Dimethylaminomethyl, -N, N-dimethylaminobutyl acrylate, -N, N-dimethylaminopropyl acrylate, -N, N-dimethylaminoethyl methacrylate, -N, N-dimethylaminomethyl methacrylate, methacrylic acid -N, N-dimethylaminobutyl, methacrylic acid-N, N-
Dimethylaminopropyl, -N, N-diethylaminoethyl acrylate, -N, N-diethylaminomethyl acrylate, -N, N-diethylaminobutyl acrylate, -N, N-diethylaminopropyl acrylate, methacrylic acid-
N, N-diethylaminoethyl, -N, N-diethylaminomethyl methacrylate, -N, N-diethylaminobutyl methacrylate, -N, N-diethylaminopropyl methacrylate and the like.

Further, the monomer represented by the general formula (III) can be used as an acid salt or a quaternary ammonium salt as in the case of the monomer represented by the general formula (II). Among them, the water-soluble vinyl monomer used as the monomer (E) includes the above (1), (2), (5), (6), (9), (1)
The monomers of (0) and (11) are preferred, and more preferred are (1) and (1).
(2), (10) and (11).

Examples of the water-insoluble monomer in the monomer (E) include vinyl acetate and N-vinyl-2-
Caprolactam, ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-
Examples include pentene and 2-ethyl-1-butene. Of these, vinyl acetate and N-vinyl-2-caprolactam are particularly preferred.

In the monomer composition of the copolymer composed of the two kinds of monomers (D) and (E) as described above, the mole fraction of the monomer (D) is 30% or more, preferably 40% or more, more preferably 50% or more. Is. In the case of a copolymer or a salt thereof in which the monomer (D) has a mole fraction of 30% or more in the monomer composition of the copolymer, good solubility in water is exhibited, and as a result, the object of the present invention can be sufficiently achieved. it can.

As the monomer (E), a water-soluble vinyl monomer, a water-insoluble vinyl monomer or a mixed monomer of both are used, but the use of a water-soluble vinyl monomer is better for the water of the copolymer or its salt. It is preferable because it achieves high solubility.

As the polymer (vi), it is also possible to use a salt of a copolymer of the monomer (D) and the monomer (E). As such salts, the same ones as described in <Polymer (iv)> can be used.

The copolymer of the monomer (D) and the monomer (E) can be obtained by a conventionally known radical polymerization or the like under normal pressure or under pressure. Acetone or the like as a polymerization catalyst,
Also, azobisisobutyronitrile and the like can be used as the polymerization initiator. The polymerization temperature and time vary depending on the polymerization solvent used and the combination of monomers, but generally 40
5 to 20 hours at ~ 90 ° C is suitable.

The polymer (vi) can also be obtained as a commercial product, for example, PV of ISP Japan Co., Ltd.
P / VA copolymer series PVP / VA735 (all are trademarks) and the like, and the chemical structure is, for example, as follows.

[0047]

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The company's copolymer series Copolym
845, Copolymer 937, copolymer958 (all of which are trademarks), and the chemical structure is, for example, as follows.

[0049]

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Furthermore, GAFQUAT 734, GAFQUAT 755N (both are trade marks manufactured by ISPE Japan Co., Ltd.) and the like can be mentioned, and their chemical structures are, for example, as follows.

[0051]

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The following are also examples (all are trademarks, manufactured by ASP Japan Co., Ltd.).

[0053]

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<Polymer (vii)> The polymer (vii) used in the composition of the present invention is a homopolymer of acrylic acid or methacrylic acid, a copolymer of acrylic acid or methacrylic acid, and salts thereof. Hereinafter, acrylic acid or methacrylic acid is described as (meth) acrylic acid. The polymer (vii) is a polymer of (meth) acrylic acid or a salt thereof, a copolymer of (meth) acrylic acid and maleic anhydride, or a copolymer of acrylic acid and methacrylic acid, and has an average molecular weight of 1,000 to 6,000,000. , Preferably 2,000 to 1,000,000.

<Emulsion (viii)> The emulsion (viii) used in the composition of the present invention comprises the lower fatty acid vinyl ester (F) and the unsaturated carboxylic acid (G) or the (F) and (G) and these. It is an aqueous emulsion obtained by copolymerizing with a polymerizable monomer (H).

As the lower fatty acid vinyl ester (F),
Vinyl acetate, vinyl butyrate and vinyl propionate are used, with vinyl acetate being preferred.

As the unsaturated carboxylic acid (G), 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 and the like, alkyl half-esters, partial esters or partial amides of unsaturated carboxylic acids such as itaconic acid, maleic acid and fumaric acid are used. Preferred examples of these unsaturated carboxylic acids include acrylic acid, methacrylic acid and crotonic acid. Further, examples of the alkyl half ester of unsaturated polycarboxylic acid include lower alkyl half ester having 1 to 6 carbon atoms such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, and monobutyl maleate. .

Monomer (H) copolymerizable with (F) and (G) above
As the above, those shown in (H-1) to (H-7) below are used. (H-1) α, β diesters of ethylenically unsaturated dicarboxylic acids, such as dibutyl maleate, diethyl maleate, and corresponding fumarate, itaconate,
Citraconate (H-2) Ethylene (H-3) Vinyl halide such as vinyl chloride (H-4) Vinylidene halide such as vinylidene chloride (H-5) Lower fatty acid vinyl ester different from lower fatty acid vinyl ester (F) Ester (H-6) N, N-dialkyl acrylamide (alkyl has 1 to 12 carbon atoms) (H-7) Two or more selected from those shown in (H-1) to (H-6) above. Compound of 1 or 2 or more selected from the above is emulsion-polymerized to obtain an aqueous emulsion. The average molecular weight of the copolymer is preferably 1,000 to 1,000,000, more preferably 10,000 to 200,000. As a combination of (F), (G), (H), (F) vinyl acetate, (G) acrylic acid, methacrylic acid, (H) (H-5) (H-6) are preferable, and more preferably , (F)
They are vinyl acetate, (G) methacrylic acid, and (H) (H-6).

<Emulsion (ix)> The emulsion (ix) used in the present invention is a polymerizable aromatic monomer (I).
An aqueous emulsion obtained by (co) polymerizing one or more selected from the above, or the monomer (I)
Is an aqueous emulsion obtained by copolymerizing one or two or more of the above and one or more selected from the monomer (J) copolymerizable with the monomer (I).

As the polymerizable aromatic monomer (I), for example, styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, indene and the like are used.

Monomer (J) Copolymerizable with Monomer (I)
The following are used as (J-1) to (J-7).

(J-1) Diesters of α, β ethylenically unsaturated dicarboxylic acids such as dibutyl maleate, diethyl maleate, and corresponding fumarate, itaconate, citracone (J-2) ethylene (J-3 ) Vinyl halides such as vinyl chloride (J-4) Vinylidene halides such as vinylidene chloride (J-5) N, N-dialkylacrylamides (alkyl having 1 to 12 carbon atoms) (J-6) Above (J -1) to (J-5) Two or more compounds selected from those shown in (J-5) One or two or more compounds selected from the above are emulsion polymerized to obtain an aqueous emulsion.

The average molecular weight of the copolymer is from 1,000 to
1,000,000 is preferred, more preferably 10,000-200,00
0. The combination of (I) and (J) is preferably (I) styrene, vinyltoluene, (J) (J-5), (J-6) from the viewpoint of emulsion stability and dispersibility, and more preferably (I) Styrene and (J) (J-5).

As the component (a) of the present invention, the above (i) to
Among the water-soluble polymer or aqueous emulsion of (ix), (ii), (iv), (vii), (viii), (ix) are preferable, and more preferably (ii), (iv), (vii), (viii), and more preferably (ii) and (iv).

The component (a) is incorporated in the composition in an amount of 0.01 to 20% by weight, preferably 0.1 to 5% by weight. In the case of an aqueous emulsion, the amount of pure polymer in the emulsion should be within this range. (a) 0.01% by weight of component
When it is above, a sufficient shaping effect to the clothes can be given, and when it is 20% by weight or less, the texture of the clothes becomes good.

[Component (b)] Used in the composition of the present invention
The component (b) is one or more of the quaternary ammonium salts represented by the general formula (I). In the general formula (I), one or two of R ¹ , R ² , R ³ and R ⁴ has 8 carbon atoms.
It is an alkyl group or an alkenyl group having 25 to 25 carbon atoms, preferably an alkyl group or an alkenyl group having 12 to 18 carbon atoms, and particularly preferably an alkyl group having 12 to 18 carbon atoms. The rest is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group. X ⁻ represents an anion group, and the anion group is a halogen anion group (Cl ⁻ , B
r ⁻ etc.), an alkylsulfate anion group having 1 to 5 carbon atoms (CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , C ₃ H ₇ SO ₄ ^−, etc.) and the like,
Cl ^- is preferred.

Specific examples of the quaternary ammonium salt used as the component (b) include stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, dicetyldimethylammonium chloride and stearyltriethylammonium chloride. To be

The component (b) is incorporated in the composition in an amount of 0.05 to 30% by weight, preferably 0.05 to 5% by weight, more preferably 0.05 to 0.5% by weight, and particularly preferably 0.1 to 0.3% by weight.
(b) When the content of the component is 0.05% by weight or more, a sufficient wrinkle-removing effect can be given to the clothes, and when it is 30% by weight or less, the composition is easy to mix, and when it is 0.5% by weight or less, the texture of the clothes is good. Especially good.

[Component (c)] In the present invention, when a water-insoluble silicone having an average particle size of dispersed particles in the range of 0.01 to 10 μm is blended as the component (c), texture, touch and wrinkle are further suppressed. It is effective and preferable.

As the water-insoluble silicone, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, amino-modified polysiloxane, amide-modified polysiloxane, epoxy-modified polysiloxane, carboxy-modified polysiloxane, polyether-modified polysiloxane, etc. Are used, but dimethyl-modified siloxane and amino-modified siloxane are preferred.
The average molecular weight of such silicone is preferably 1,000 to 1,000,000, and more preferably 2,000 to 100,000.

These water-insoluble silicones have an average particle diameter of dispersed particles of 0.01 to 10 μm, preferably 0.01 to 10 μm.
The thickness is 0.5 μm, more preferably 0.05 to 0.1 μm. Particles having an average particle size of more than 10 μm are not preferable because they may separate in the composition. Further, the water-insoluble silicone is preferably blended in the form of an aqueous emulsion in which the above particles are dispersed. The average particle size of silicone is measured by an electrophoretic light scattering photometer (ELS-800, OTSUKA EL
ECTRONICS Co. Ltd.) and a laser diffraction / scattering particle size analyzer (LA-700 HORIBA).

The component (c) is preferably mixed in the composition in an amount of 0.01 to 10% by weight, more preferably 0.03 to 1% by weight. If it is 0.01% by weight or more, the effect of adding the component (c) can be obtained, and if it is 10% by weight or less, the texture and touch are good, which is preferable.

[Arbitrary Ingredients] Further, in the treatment composition for clothing of the present invention, a plasticizer such as dibutyl phthalate, dibutyl adipate, diisobutyl adipate, tricresyl phosphate, and butyl phthalyl glycolate butyl is optionally added. (0 to 3% by weight in the composition), other, fragrance,
A sterilizing / antibacterial agent, a preservative, a pigment, etc. can be added.

The treatment composition for clothing of the present invention is as described above.
The components (a) and (b), or the components (a), (b) and (c), and optional components to be blended as necessary are contained in the above proportions, but the balance is usually water.

[Treatment Article for Clothing] The treatment agent composition for clothing of the present invention described above can be used in various methods such as a method of immersing clothes, a method of spraying with a spray device or the like, and the like. In terms of enabling the treatment composition for clothing to be more efficient and to have unevenness in the clothing, and a suppressed partial treatment,
It is preferably used in the treatment of clothing in the form of a treated article for clothing filled into a container equipped with a device for spraying the liquid filled therein. By using such a treated article for clothing of the present invention, it is possible to further suppress unevenness during the treatment and to extremely effectively treat the partially treated clothing.

As the container used for the treated article for clothing of the present invention, which is equipped with a device for spraying the liquid filled inside, for example, an aerosol container, a trigger container or a manual pump container is exemplified. . For example, a treated article for clothing obtained by filling the treatment agent composition for clothing of the present invention in an aerosol container is obtained by filling an aerosol can with the propellant and the treatment agent composition for clothing of the present invention according to a conventional method. To be As the propellant, it is preferable to use at least one selected from the group consisting of liquefied propane, liquefied butane and dimethyl ether, or a combination of these with CO ₂ or N ₂ . The weight ratio of the propellant to the clothing treatment agent composition of the present invention is: propellant / clothing treatment agent composition of the present invention = 3/97
〜50 / 50 is preferable, and more preferably 5 / 95-40 / 60
It is.

[Method for Treating Clothing] In the method for treating clothing according to the present invention, the above-mentioned treating agent composition for clothing according to the present invention is a clothing to be treated in a wet state (hereinafter referred to as an object).
Is sprayed onto the surface of the object and the treatment composition for clothing is evenly applied to the surface of the object. At that time, it is preferable to perform such a treatment with the treated article for clothing filled in the specific container as described above. In addition, "in a wet state" means a wet state from after dehydration to completion of drying in the washing process.

The object is not particularly limited, but it is particularly effective for natural fiber woven fabrics such as cotton, hemp, and wool, which tend to wrinkle due to dehydration. In addition, various synthetic fibers such as polyamide, polyester, polyvinyl acetal, polyacrylonitrile, polyvinyl chloride and polypropylene, and semi-synthetic fibers such as rayon and acetate can be used. Further, the treatment composition for clothing of the present invention is sprayed on the object in an amount of about 10 to 150% by weight.

[0079]

EFFECTS OF THE INVENTION According to the present invention, a suitable texture for clothes
It is possible to provide a treatment agent composition for clothes, a treated article for clothes, and a method for treating clothes, which gives a touch to the skin and suppresses wrinkles generated during washing and dehydration.

[0080]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 39 and Comparative Examples 1 to 9 (a) As the component, the polymers or aqueous emulsions shown in Tables 1 to 6, as the component (b), the quaternary ammonium salt shown in Table 7, and the component (c). The water-insoluble silicone shown in Table 8 was added to prepare the treatment composition for clothing shown in Tables 9 to 10. This composition was filled in a trigger type container to prepare a treated article for clothing.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

<Performance Evaluation> The treated articles for clothing of the present invention and the comparative articles obtained by the above method were evaluated for texture, texture and wrinkle suppression by the following methods.

(1) Texture / texture A test piece made of cotton broad # 60 with a size of 20 cm × 20 cm was prepared and washed in a washing machine (water capacity: 40 to 70 liters, rotating speed of rotating blades: 65 to 90 rpm, rotating angle: 180 to 240). °, spin speed of dehydration tank 500 ~ 720 rpm, inner diameter 40 ~ 55 cm) and automatic washing operation using JIS K 3371 (synthetic detergent for clothing) specified detergent (washing 12 minutes →
2 minutes of drainage → 2 minutes of dehydration → 3 to 5 minutes of water supply → 2 minutes of rinsing → 2 minutes of drainage → 2 minutes of dehydration → 3 minutes of centrifugal dehydration). The treatment composition was sprayed onto the test piece so that the weight of the test piece was 50% owf based on the dry weight of the test piece, and drip drying was performed. That is,
The test piece was held at several places so that the vertical direction was vertical without dehydration, and hung at room temperature in a non-ventilated place to dry. The treated test piece thus prepared was evaluated for texture and texture by a paired comparison method using a untreated cloth as a control and a touch test by 10 panelists. The evaluation (Example of the present invention) is +2: Very good, +1: Somewhat good, 0: Neither can be said, -1: Somewhat bad, -2: Very bad, compared with the comparative control. . The evaluation results of the texture and the feel of the skin are shown in Tables 11 to 12, respectively.

[0094]

[Table 11]

[0095]

[Table 12]

(2) Wrinkle Suppression The wrinkle suppression effect was evaluated in the following two ways. The results are shown in Tables 13-14. (2-1) The treated test pieces prepared in the same manner as the texture / texture test of (1) were evaluated according to the following criteria. Judgment Value Judgment Criteria 5 No wrinkles 4 Wrinkles are not noticeable 3 Slight wrinkles remain 2 Equivalent wrinkles remain 1 Significant wrinkles remain (2-2) 20 cm x 20 cm cotton broad # 60 The test piece was folded in two and pressed at 105 ° C. for 30 seconds three times to create wrinkles. Spray the test piece with 100% owf of water,
The model was used as a model for wrinkles after dehydration. The treatment composition was sprayed onto the test piece so that the weight of the test piece was 50% owf with respect to the weight of the dried test piece, and drip drying was performed. Spread the treated test piece prepared in this way on a horizontal surface and put 200 g on both ends.
Was applied to measure the height of wrinkles as shown in FIG.

[0097]

[Table 13]

[0098]

[Table 14]

[Brief description of the drawings]

FIG. 1 is a schematic view showing a test method for a wrinkle suppressing effect in Examples.

[Explanation of symbols]

 1 Test cloth h Wrinkle height

Claims (5)

[Claims] 1. The following component (a) is 0.01 to 20% by weight, and
(b) A treating agent composition for clothing, which comprises 0.05 to 30% by weight of the component. Component (a): 1 selected from the group consisting of the following (i) to (ix)
Water-soluble polymer and / or aqueous emulsion polymer (i); modified starch and its derivative polymer (ii); cellulose derivative polymer (iii); polyvinyl acetate saponification product and its derivative polymer (iv); A polymer obtained by polymerizing at least one or more monomers having a vinyl group and / or an aromatic ring and having a sulfonic acid group or a salt thereof Polymer (v); N-vinyl-2-pyrrolidone ( D) homopolymer polymer (vi); the monomer (D) and the monomer (D)
And a salt thereof obtained by polymerizing one or more vinyl monomers (E) copolymerizable with
The mole fraction of (D) is 30% or more. ) Polymer (vii); Acrylic acid or methacrylic acid homopolymers and copolymers and salts thereof Emulsion (viii); Lower fatty acid vinyl ester (F) and unsaturated carboxylic acid (G), or the (F), (G) Aqueous emulsion obtained by copolymerizing these with a copolymerizable monomer (H) Emulsion (ix); Is one or more polymerizable aromatic monomers (I) (co) polymerized? Or the monomer (I)
Of the aqueous emulsion (b) obtained by copolymerizing one or two or more of the above (1) and one or more of the monomer (J) copolymerizable with the monomer (I): One or more quaternary ammonium salts represented by I). (In the formula, one or two of R ¹ , R ² , R ³ and R ⁴ represent an alkyl group or an alkenyl group having 8 to 25 carbon atoms, and the rest are an alkyl group or hydroxyalkyl having 1 to 3 carbon atoms. Represents a group, X ^- represents an anionic group.) 2. As the component (c), 0.01 is a water-insoluble silicone having an average particle size of dispersed particles in the range of 0.01 to 10 μm.
The treatment composition for clothing according to claim 1, wherein the composition is contained in an amount of -10% by weight. 3. The treating agent composition for clothing according to claim 1, wherein the component (a) is (ii) or (iv). 4. A garment obtained by filling the treatment composition for clothing according to any one of claims 1 to 3 into a container equipped with a device for spraying a liquid filled therein to the outside. Processing goods. 5. A method for treating clothing, which comprises spraying the clothing treatment agent composition according to any one of claims 1 to 3 onto clothing in a wet state.