JP7051202B2 - Finishing agent composition for clothing - Google Patents

Description

The present invention relates to a finishing agent composition for clothing.

It is said that it is inevitable that clothing will lose its appearance and texture when it is new due to repeated wearing and washing. In particular, knit clothing with excellent fashionability is composed of yarns made by twisting single fibers sweetly, so that the single fibers that make up the yarns are misaligned due to wearing or washing, resulting in changes in appearance and deterioration of texture. Likely to happen. That is, the appearance beauty of clothing, which is important for the wearer, is lost. In this way, the used clothing causes a tired appearance and texture change.

Patent Document 1 describes a water-soluble polymer compound selected from the group consisting of (A) a water-soluble processed starch having a specific weight average molecular weight and a derivative thereof, and a water-soluble cellulose derivative having a specific weight average molecular weight, (B) a silicone compound and ( C) A fiber product treating agent composition that restores the morphology of a deteriorated fiber product such as shape loss, elongation, and shrinkage by containing each nonionic surfactant in a specific ratio is disclosed.
Patent Document 2 includes i) a saponified product of polyvinyl acetate having a specific weight average molecular weight, ii) polystyrene sulfonic acid having a specific weight average molecular weight, and iii) a polymer of N-vinyl-2-pyrrolidone having a specific weight average molecular weight. A water-soluble polymer compound (A), a softening agent (B) selected from an inorganic or organic acid salt of a tertiary amine and a silicone compound, and a specific non-polyoxyethylene alkyl ether type. Disclosed is a textile product treating agent composition that restores the morphology of a deteriorated textile product such as shape loss, elongation, and shrinkage by containing the ionic surfactant (C) in a specific ratio.
Patent Document 3 contains a water-soluble polymer compound (A) having a specific weight average molecular weight and an amino-modified silicone compound (B) in specific ratios, whereby the fiber is deteriorated due to shape loss, elongation, shrinkage, etc. A textile treatment agent that restores the form of a product is disclosed.
Patent Document 4 describes (a) one or more cations selected from tertiary amines having a hydrocarbon group having 11 to 36 carbon atoms including an ester, an amide or an ether bond, salts thereof and a quaternary product thereof. A polysiloxane solid at a temperature of 20 ° C. that causes intramolecular and intermolecular cross-linking due to a bond other than (b) a covalent bond with the softening base, and the molded product thereof is at a temperature of 20 ° C. and a relative humidity of 65%. By containing polysiloxane that does not break or plastically deform in the range of elongation 0 to 15%, flexibility that can impart slipperiness and elastic texture to textile products while maintaining an excellent flexibility-imparting effect. The agent is disclosed.

Japanese Unexamined Patent Publication No. 2000-129757 Japanese Unexamined Patent Publication No. 2000-129578 Japanese Unexamined Patent Publication No. 2000-239970 Japanese Unexamined Patent Publication No. 11-22273

The present invention provides a garment finishing agent composition that recovers the shape loss of garments and imparts a texture that is not stiff and stiff.

In the present invention, (A) a polymer polymer containing a structural unit from vinyl acetate (hereinafter referred to as (A) component) is contained in an amount of 5% by mass or more and 50% by mass or less, and (B) a terminal or side chain of a polysiloxane chain. A compound in which a poly (N-acylalkyleneimine) consisting of a repeating unit represented by the following general formula (B1) is bonded to at least one of the silicon atoms via an alkylene group containing a hetero atom (hereinafter, (hereinafter,). B) The present invention relates to a finishing agent composition for clothing, which comprises 0.05% by mass or more and 5% by mass or less of (referred to as a component) and water.

[In the formula, R ^1b is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or an aryl having 6 to 22 carbon atoms. The group indicates a group, and n indicates a number of 2 or 3. ]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a garment finishing agent composition capable of recovering the shape loss of garments caused by repeated wearing and washing and imparting a texture without stiffness and ruggedness.

In the present invention, the term "out of shape" refers to a state in which the surface of the cloth is not firm and the surface is wavy and twisted or tired when the clothes are hung on a hanger or worn.
It is thought that the feeling of twisting and tiredness is caused by, for example, the shape of the body, cuffs, and neck, which is different from the original length and shape due to the expansion and contraction of the body, cuffs, and neck compared to new clothing. ..
Further, in the present invention, "texture" refers to the tactile comfort that a person feels on bare skin, and is not only flexible but also slippery, bulky, elastic, elastic, strained, slimy, etc. It is a mixture of the factors of, and shows a certain direction in the vector of comfort.

[Finishing agent composition for clothing]
<Ingredient (A)>
The component (A) of the present invention is a polymer polymer containing a structural unit from vinyl acetate, and is a polymer in which the structural unit from vinyl acetate occupies a part or all of it.
The proportion of vinyl acetate is preferably 75% by mass or more, more preferably 82% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 99% by mass or less, in all the monomers used for the polymerization of the polymer. Is 97% by mass or less, more preferably 96% by mass or less. In the present invention, the monomer ratio used at the time of production may be the ratio of the constituent units of the polymer polymer as the component (A), including the monomer copolymerizable with vinyl acetate described later.

Other monomer compounds for constituting the vinyl acetate polymer, which is the polymer polymer of the component (A), include unsaturated carboxylic acids having a polymerizable unsaturated bond capable of copolymerizing with vinyl acetate, and unsaturated compounds. A monomer compound selected from a lower alcohol (alcohol having 1 or more and 3 or less carbon atoms) ester of a carboxylic acid and an unsaturated carboxylic acid amide is preferable.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, silicic acid, α-chlorosorbic acid, and citraconic acid. Acrylic acid, methacrylic acid and crotonic acid are preferable.
The proportion of the unsaturated carboxylic acid is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass, based on all the monomers used for the polymerization of the vinyl acetate polymer. % Or less.

Examples of the lower alcohol ester of the unsaturated carboxylic acid include methyl ester, ethyl ester, propyl ester and isopropyl ester of the unsaturated carboxylic acid, such as methyl acrylate, ethyl acrylate, methyl methacrylate and methacryl. Ethyl acetate is preferred.
The proportion of the lower alcohol ester of the unsaturated carboxylic acid is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 25% by mass or less, based on all the monomers used for the polymerization of the vinyl acetate polymer. It is preferably 20% by mass or less.

Examples of the unsaturated carboxylic acid amide include N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N-alkoxyalkylacrylamide, and N-hydroxyalkylacrylamide. , N-Hydroxyalkylmethacrylamide, N-acylalkylacrylamide, N-acylalkylmethacrylamide, and one or more selected from N-hydroxyalkylmethacrylamide. The chain length of the alkyl group, alkoxy group, and acyl group of these amide compounds is preferably 1 or more and 18 or less carbon atoms. Among these, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N-hydroxyethylmethacrylamide, diacetone isoacrylamide. Is preferable.
The proportion of the unsaturated carboxylic acid amide is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 25% by mass or less, more preferably, in the total monomer used for the polymerization of the vinyl acetate polymer. Is 20% by mass or less.

The polymer polymer of the component (A) has a weight average molecular weight of preferably 50,000 or more, more preferably 150,000 or more, still more preferably 300,000 or more, and preferably 500,000 or less, more preferably. Is 450,000 or less, more preferably 400,000 or less. This weight average molecular weight is measured by gel permeation chromatography (GPC). Specifically, it refers to a polystyrene-equivalent molecular weight measured using chloroform, dimethylformamide, tetrahydrofuran, acetone, or a solution in which these solvents are combined, preferably dimethylformamide, as an eluent. More specifically, it is measured by the following method.
5 g of the polymer polymer of the component (A) is placed in a 20 mL volumetric flask, messed up with acetone, and then filtered through a 0.5 μm PTFE membrane filter. The weight average molecular weight is measured by GPC under the following conditions using a filtrate.
Column: α-M + α-M (anion)
Eluent: H ₃ PO ₄ (60 mmol / L) / LiBr (50 mmol / L) / DMF
Flow velocity: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration: 5 mg / mL
Sample amount: 100 μL

The garment finishing agent composition of the present invention contains the component (A) in an amount of 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 50 from the viewpoint of recovering the shape of the garment. It is contained in an amount of% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less.

<Ingredient (B)>
The component (B) of the present invention comprises a repeating unit represented by the following general formula (B1) via an alkylene group containing a hetero atom at least one of the silicon atoms in the terminal or side chain of the polysiloxane chain. It is a compound to which poly (N-acylalkyleneimine) is bound.

[In the formula, R ^1b is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or an aryl having 6 to 22 carbon atoms. The group indicates a group, and n indicates a number of 2 or 3. ]

Examples of the alkylene group containing the hetero atom include an alkylene group having 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms and having 2 to 20 carbon atoms, and a specific example thereof is represented by the following formula. I can list things.

The alkyl group represented by R ^1b in the general formula (1) is preferably one having 1 or more carbon atoms and 10 or less carbon atoms, the cycloalkyl group is preferably one having 3 or more carbon atoms and 6 or less carbon atoms, and the aralkyl group is preferably an aralkyl group. A phenylalkyl group and a naphthylalkyl group are preferable, and as the aryl group, a phenyl group, a naphthyl group, and an alkyl group substituted phenyl group are preferable.

In the component (B), the mass ratio of the polysiloxane chain portion to poly (N-acylalkyleneimine) (polysiloxane chain / poly (N-acylalkyleneimine)) is preferable from the viewpoint of imparting a texture without stiffness. Is 40/60 or more, more preferably 50/50 or more, preferably 98/2 or less, more preferably 94/6 or less, still more preferably 90/10 or less.
Here, the mass ratio can be calculated by using the value obtained by the silicon atomic quantitative analysis by the plasma emission analysis for the content of the polysiloxane chain portion.
Further, the mass ratio may be the mass ratio of the polysiloxane chain used in the reaction at the time of production and poly (N-acylalkyleneimine).

The weight average molecular weight of the component (B) is preferably 20,000 or more, more preferably 50,000 or more, still more preferably 100,000 or more, and preferably 500,000 or less, more preferably 300,000 or less. It is more preferably 200,000 or less, still more preferably 150,000 or less. The weight average molecular weight of the component (B) is a polystyrene weight-equivalent molecular weight obtained by gel permeation type liquid chromatography using chloroform as a developing solvent.

The garment finishing agent composition of the present invention contains the component (B) in an amount of 0.05% by mass or more, preferably 0.07% by mass or more, and more preferably 0.1% by mass from the viewpoint of imparting a texture without stiffness. % Or more, more preferably 0.5% by mass or more, and 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.

In the garment finishing agent composition of the present invention, the mass ratio (A) / (B) of the content of the component (A) and the content of the component (B) is determined from the viewpoint of achieving both shape loss recovery and texture. It is preferably 5 or more, more preferably 10 or more, and preferably 250 or less, more preferably 200 or less.

<Ingredient (C)>
The garment finishing agent composition of the present invention preferably further contains cationized starch as the component (C) from the viewpoint of the dispersion stability of the component (A) in water.
As the starches forming the main skeleton of the cationized starch, the starches described in JP-A-2010-180320 can be used. Specific examples thereof include starches such as corn starch, wheat starch, potato starch and tapioca starch.
The method of introducing a cation group into the starch to obtain a cationized starch is not particularly limited, and examples thereof include a method of reacting starches with a quaternary ammonium alkylation reagent.
Examples of the quaternary ammonium alkylating reagent include a quaternary ammonium compound having a glycidyl group described in JP-A-2010-180320, and glycidyltrimethylammonium chloride is used from the viewpoint of easy availability of the compound. preferable.
Specific examples of the method for producing the quaternary ammonium alkylating reagent include, for example, JP-A-56-36501, JP-A-6-100603, JP-A-2010-180320, JP-A-8-1989901 and the like. The method described in 1 is mentioned.

The degree of substitution of the cationized starch is preferably 0.02 or more, more preferably 0.05 or more, and preferably 0.2 or less, more preferably 0.15 or less.
The degree of substitution of the cationized starch is calculated from the following formula from the nitrogen content (N) mass% of the cationized starch measured by a CHN elemental analyzer (manufactured by Elemental Co., Ltd., trade name: VARIO ELIII). ..
Degree of substitution = 162N / (1400-152N)
This degree of substitution indicates the degree of cationization, and is a value indicating the number of moles of cation groups added per anhydrous monosaccharide unit of starch.

As the cationized starch, a 5 mass% aqueous solution having a viscosity at 50 ° C. of 30 mPa · s or more, further 50 mPa · s or more, and 100 mPa · s or less, further 90 mPa · s or less can be used as the component (A). It is preferable from the viewpoint of forming a protective colloid. The viscosity was determined by using a B-type viscometer. Using 1 rotor, rotate at 12 r / min, and then set the indicated value 1 minute later.

In the garment finishing agent composition of the present invention, the component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further, from the viewpoint of the dispersion stability of the component (A) in water. It is preferably contained in an amount of 1.0% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less.

<Polymer polymer mixture (M)>
In the present invention, it is preferable that the component (A) and the component (C) form a mixture (hereinafter, may be referred to as a polymer polymer mixture (M)). That is, the clothing finishing agent composition of the present invention preferably contains a polymer polymer mixture (M) containing the component (A) and the component (C). The polymer polymer mixture (M) preferably contains polyvinyl alcohol, which is a component (D) described later.

The polymer polymer mixture (M) may not be in a state of being uniformly dissolved in a solution, but may be a lumpy, droplet-like or agglomerate mixture which may be partially or wholly swollen with water. preferable. Further, it is more preferable that the polymer polymer mixture (M) forms a fine particle (hereinafter, may be referred to as a polymer polymer mixed fine particle), more preferably a protective colloid having a cation as a surface charge. That is, the clothing finishing agent composition of the present invention preferably contains mixed fine particles containing the component (A) and the component (C), and the mixed fine particles further contain polyvinyl alcohol as the component (D). It is preferable to include it. The component (A), the component (C), and the component (D) are partially dissolved in the dispersion medium of the polymer polymer mixture (M) without forming the polymer polymer mixture (M). Or it may be dispersed.

In order to make the polymer polymer mixture into fine particles, preferably protective colloids, for example, in an aqueous solution containing the component (C), any of the components (D) and (E) described later, the component (A) It can be obtained by polymerizing a single or a plurality of monomers whose main monomer is vinyl acetate, which is a constituent unit.
Therefore, assuming that the component (A), the component (C) and any component (D) constitute fine particles of the polymer polymer mixture, the component (A), the component (C) and any component (D) The mass ratio of the component (A) to the total of the components is preferably 70% by mass or more, more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less.

The mass ratio of the component (C) to the total of the component (A), the component (C) and any component (D) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably. It is 20% by mass or less, more preferably 10% by mass or less.

<(D) component>
The clothing finishing agent composition of the present invention preferably contains polyvinyl alcohol as the component (D). In particular, when the garment finishing agent composition of the present invention contains the polymer polymer mixed fine particles containing the component (A) and the component (C), from the viewpoint of further improving the storage stability of the emulsion, from the viewpoint of further improving the storage stability of the emulsion. It is preferable that the polymer polymer mixed fine particles further contain the component (D).
The component (D) preferably has a weight average molecular weight of 10,000 or more and 200,000 or less, preferably 100,000 or less. The weight average molecular weight of the component (D) can be measured by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance.
The mass ratio of the component (D) to the total of the component (A), the component (C) and any component (D) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably. It is 10% by mass or less, more preferably 4% by mass or less.

The concentration of the component (D) contained in the finishing agent composition for clothing of the present invention is preferably 0.01% by mass or more, more preferably 0.1, from the viewpoint of the dispersion stability of the component (A) in water. It is by mass or more, more preferably 0.3% by mass or more, and preferably 1.0% by mass or less, more preferably 0.9% by mass or less, still more preferably 0.8% by mass or less.

<(E) component>
The clothing finishing agent composition of the present invention preferably contains a nonionic surfactant as the component (E). In particular, when the garment finishing agent composition of the present invention contains a polymer polymer mixture containing the component (A) and the component (C), it constitutes fine particles, preferably protective colloids, of the polymer polymer mixture. From the viewpoint of stabilization, it is preferable that the liquid composition I described below containing the polymer polymer mixture further contains the component (E). In the present invention, from the viewpoint of forming and stabilizing fine particles, preferably protective colloids, of the polymer polymer mixture, the component (E) is specifically used in Japanese Patent Laid-Open No. 10-195772, column 7, lines 43 to. As the component (E), the one described in column 8, line 40 can be used, preferably a polyoxyethylene alkyl (or alkenyl) which is an ethylene oxide adduct of a saturated or unsaturated alcohol having 7 or more and 22 or less carbon atoms. ) Ether. The average number of moles of oxyalkylene groups added to the polyoxyethylene alkyl (or alkenyl) ether is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and preferably 60 or less, more preferably 50 or less. Is.

In the garment finishing agent composition of the present invention, the component (E) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further, from the viewpoint of the dispersion stability of the component (A) in water. It is preferably contained in an amount of 0.1% by mass or more, preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less.

<(F) component>
The garment finishing agent composition of the present invention preferably contains a cationic surfactant as the component (F) from the viewpoint of improving the texture.
Examples of the cationic surfactant include triethanol, which is a cationic surfactant having an ester bond or an amide bond in its structure, in addition to the alkyltrimethylammonium salt and dialkyldimethylammonium salt included in the following general formula (F1) described later. Di-fatty acid ester quaternary ammonium salt of amine, di-fatty acid ester quaternary ammonium salt of diethanoldimethylamine, fatty acid monoester monoamide salt of N-hydroxyethyl-N-methyl-propanediamine, and alkylbenzyldimethyl quaternary having a benzyl group. Examples thereof include ammonium salts, and examples thereof include alkylpyridinium salts and polyethylene polyamines.
The quaternary ammonium salt is preferably an alkyl sulfate or a chloride salt having 1 or more and 3 or less carbon atoms. Further, the number of carbon atoms of the alkyl group or fatty acid residue (including the carbonyl carbon atom) is preferably 2 or more, more preferably 8 or more, still more preferably 12 or more, and preferably 22 or less, more preferably 18 or less, further. It is preferably 16 or less. In this paragraph, cationic surfactants also include compounds in which the alkyl group or fatty acid residue is replaced with one having an unsaturated bond such as an alkenyl group or an unsaturated fatty acid.

The component (F) may be a quaternary ammonium salt compound represented by the following general formula (F1), and is preferably a quaternary ammonium salt compound having a mono-long chain alkyl-tri-short chain alkyl group.

[In the formula, R ^1f and R ^2f are hydrocarbon groups having 1 or more and 22 carbon atoms, preferably R ^1f is an alkyl group or alkenyl group having 8 or more carbon atoms and 18 or less carbon atoms, and R ^2f has 1 or more carbon atoms. It is an alkyl group of 3 or less, preferably a methyl group. R ^3f and R ^4f are each independently an alkyl group having 1 or more and 3 or less carbon atoms, preferably a methyl group, and Y ⁻ is an anion. ]

In the general formula (F1), Y ⁻ is substituted with a halogen ion, preferably a chloro ion, an alkyl sulfate ester ion having 1 or more and 3 or less carbon atoms, and one or more and three or less alkyl groups having 1 or more and 3 or less carbon atoms. Anions selected from the benzenesulfonic acid ions may be preferable, and chloroions are preferable.

In the garment finishing agent composition of the present invention, the component (F) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0. It contains 3% by mass or more, preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and further preferably 3.0% by mass or less. The blending of the component (F) also has an effect of reducing the adhesion of the component (A) to the finishing agent inlet of the washing machine.

<(G) component>
From the viewpoint of storage stability of the finishing agent composition, the finishing agent composition for clothing of the present invention can contain a water-soluble organic solvent as the component (G). Examples of the water-soluble organic solvent include general water-soluble organic solvents used in liquid softener compositions. The "water-soluble organic solvent" in the component (G) means an organic solvent that dissolves 20 g or more in 100 g of deionized water at 20 ° C. Specific examples of the water-soluble organic solvent include one or more selected from propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. Can be mentioned. Among these, one or more selected from glycerin and propylene glycol are preferable.

In the garment finishing agent composition of the present invention, the component (G) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass, from the viewpoint of storage stability of the finishing agent composition. The above, preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.

From the viewpoint of storage stability of the finishing agent composition, the finishing agent composition for clothing of the present invention has, as the component (G), glycerin (hereinafter referred to as (G1) component) and propylene glycol (hereinafter referred to as (G2) component). ) Is preferably contained, and it is more preferable to contain both the component (G1) and the component (G2).
When both the (G1) component and the (G2) component are contained in the clothing finishing agent composition of the present invention, the mass ratio (G1) / of the content of the (G1) component and the content of the (G2) component. (G2) is preferably 2.0 or more, more preferably 5.0 or more, and preferably 30 or less, more preferably 20 or less, from the viewpoint of storage stability of the finishing agent composition.

The garment finishing agent composition of the present invention can contain components generally known to be contained in a bath treatment adhesive or a softener composition. For example, acid agents and alkaline agents as pH regulators, fragrance components, compounds known as sterilizers and deodorants, antibacterial and antifungal agents marketed under the name Proxel, and grade 4 marketed under the name Sanizol. Bactericides such as ammonium salt compounds, colorants such as pigment dyes, thickeners such as xanthan gum, oils such as hydrocarbons, fatty acid alcohol esters, aliphatic alcohols, organic solvents such as butyl carbitol and 2 ethylhexyl glyceryl ethers. , Dimethylsiloxane, known silicones such as modified products thereof (however, excluding the components (A) to (G)) can be contained to the extent that this effect is not impaired.

The dispersion medium of the finishing agent composition for clothing of the present invention is water, and water sterilized with hypochlorous acid can be used, and it is preferable to use a deionized one. Water may be added separately in preparing a preferable composition in addition to those brought in from the component (A) and the optional component (C). The garment finishing agent composition of the present invention contains water, preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass. Contains less than% by mass.

The pH of the finishing agent composition for clothing of the present invention is preferably 3 or more, more preferably 4 or more, and preferably 8 or less, when measured at 25 ° C. according to item 8.3 of JIS K 3362; 2008. It is preferably 7 or less.

An acid agent or an alkaline agent may be used to adjust the pH, and examples of the acid agent include organic acids such as citric acid and fumaric acid, and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid. In addition to alkali metal hydroxides and alkali metal carbonates, amine compounds can also be used as organic alkaline agents such as monoethanolamine and triethanolamine.

<Manufacturing method of finishing agent composition for clothing>
The finishing agent composition for clothing of the present invention is a liquid composition containing the component (A) and water (hereinafter, may be referred to as liquid composition I) in step I and the liquid obtained in step I. It is preferably produced by a production method comprising the step II of mixing the composition I and the component (B).
As the method for producing a garment finishing agent composition of the present invention, the matters described in the garment finishing agent composition of the present invention can be appropriately applied.

In step I, it is preferable to prepare a liquid composition I containing (A) component, (C) component, (D) component, (E) component, and water.
In step I, the liquid composition I containing the component (A), the component (C), the component (D), the component (E), and water is the component (A), the component (C), (D). It is more preferable to prepare the liquid composition I in which the components are dispersed as the polymer polymer mixture (M), further as fine particles composed of the polymer polymer mixture, and further as protective colloids.

In step I, in a reaction medium, for example, in water, a monomer compound that is a constituent unit of the component (A) is prepared in the presence of an arbitrary component (C), an arbitrary component (D), and an arbitrary component (E). It is preferable to polymerize. Thereby, the liquid composition I containing the polymer polymer mixture (M) can be easily obtained.

In the method for producing a finishing agent composition for clothing of the present invention, in step II, with the fine particles of the polymer polymer mixture (M) containing the component (A), the arbitrary component (C), and the arbitrary component (D). From the viewpoint of controlling the dispersibility of the fine particles of the polymer polymer mixture when mixed with the component (B), it is preferable to further mix the component (F). The component (F) may be blended in the liquid composition I in which the fine particles of the polymer polymer mixture are present in step I, or the liquid composition in which the component (B) is dissolved or dispersed in water (hereinafter, liquid composition). It may be blended with (sometimes called Mono II). Examples of the water used in the step I include water sterilized with hypochlorous acid, deionized water, distilled water, ultrapure water and the like.

In the method for producing a finishing agent composition for clothing of the present invention, the mass ratio (A) / (B) of the component (A) and the component (B) to the component (A) and the component (B) recovers from being out of shape. From the viewpoint of achieving both properties and texture, it is preferably used so as to be preferably 5 or more, more preferably 10 or more, and preferably 250 or less, more preferably 200 or less.

<How to dispose of clothing>
In the method for treating clothing of the present invention, the clothing finishing agent composition is brought into contact with each other in a water bath so as to be 0.1% by mass to 3% by mass with respect to the mass of the clothing, and the shape of the clothing is lost. You can effectively achieve recovery and a non-stiff texture. If the amount of the garment finishing agent composition with respect to the mass of the garment is less than 0.1% by mass, the effect of using the garment finishing agent composition cannot be sufficiently obtained, and if it exceeds 3% by mass, the effect cannot be sufficiently obtained. Economically unfavorable. The amount of the component (A) with respect to the mass of the garment is preferably 0.1% by mass or more, more preferably 0.12 mass, from the viewpoint of imparting the effect of recovering the shape of the garment and imparting a texture without stiffness. % Or more, more preferably 0.15% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass or less, still more preferably 2% by mass or less.

The amount of water that dissolves the clothing finishing agent can generally be determined by the bath ratio. In addition, in this specification, "bath ratio" means the ratio of the mass of clothing and the volume of water containing a finishing agent for clothing, [the volume of water (liter)] / [the mass of clothing (kg)]. When the clothing and the clothing finishing composition are brought into contact with each other while stirring the water in which the clothing finishing agent is dissolved using a washing machine or the like, the rubbing between the clothing is reduced and the generation of fluff and pills is generated. From the viewpoint of suppression, the bath ratio is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, and preferably 90 or less, more preferably 80 or less, still more preferably 60 or less.

<Manufacturing example>
(1) Preparation of Polymer Polymer Mixture (M-1) (Product of the Present Invention) In a polymerization reaction tank under a nitrogen atmosphere, 8.9 parts by mass of cationized starch and 100 parts by mass of ion-exchanged water as components of (C). Was uniformly dissolved at 90 ° C. and then cooled to 60 ° C. Here, the cationized starch was obtained by the reaction of cornstarch with 3- (N, N, N-trimethylammonium chloride) -1,2-propylene oxide (referred to as C-1 in the table). The degree of cation substitution = 0.08, and the viscosity of the 5% aqueous solution at 50 ° C. was 70 mPa · s.
Next, in order to obtain a polymer polymer mixture (M) containing the polymer polymer as the component (A), 10 parts by mass of vinyl acetate and polyvinyl alcohol (weight average molecular weight 66,000, in the table, D-1). 3 parts by mass and 1.5 parts by mass of a nonionic surfactant (polyoxyethylene lauryl ether (average number of added moles 40, HLB18.3), E-1 in the table) were added to the cationized starch. In addition to the aqueous solution containing, add 0.5 part by mass of 3 sodium phosphate, 0.4 part by mass of 2,2'-azobis (2-amidinopropane) hydrochloride, and 20 part by mass of ion-exchanged water, and bring the temperature to 75 ° C. The polymerization was started by heating. Premixed so that the final ratio of vinyl acetate, acrylic acid, N, N-dimethylacrylamide is 95.5 / 2.5 / 2 (mass ratio) over 6 hours after the start of polymerization 100 A mass portion was added dropwise to the reaction solution. After completion of the dropping, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling, the pH of the emulsion is adjusted to 5 using a 10 mass% sodium carbonate aqueous solution, and the polymer polymer mixture (M) and (E) containing the components (A), (C) and (D) are contained. A liquid composition i containing the components and water was obtained. The content of the polymer polymer mixture (M) in the liquid composition i was 50% by mass, and the content of the component (E) was 0.6% by mass. Further, in the polymer polymer mixture (M), the mass ratio of (A) / (C) / (D) was 19 / 1.5 / 0.5. The polymer polymer mixture (M) forms polymer polymer mixed fine particles, specifically, protective colloids in the liquid composition i.
The polymer polymer (A-1 in the table) as the component (A) has a high molecular weight of 95.5 / 2.5 / 2 (mass ratio) for vinyl acetate / acrylic acid / N and N-dimethylacrylamide. It was a molecular polymer (weight average molecular weight 340,000).

(2) Preparation of (B) components (B-1 to B-3)
B-1 to B-3 were produced by the following production methods (i) to (iii).
(I) Mix 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate, and use the mixed solution as a molecular sieve (trade name: Zeolam A-4, manufactured by Tosoh Corporation). Dehydration was performed at 2.0 g for 15 hours. Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100,000, amine equivalent 20,000) and 203 g of ethyl acetate were mixed, and the mixed solution was dehydrated with 15.2 g of molecular sieve for 15 hours. .. 0.77 g (0.005 mol) of diethyl sulfate was added to the above dehydrated ethyl 2-ethyl-2-oxazoline ethyl acetate solution, and the mixture was heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere to undergo terminal reactive poly (N-propionyl). Ethylimine) was synthesized. This terminally reactive poly (N-propionylethyleneimine) solution was collectively added to the above dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and heated and refluxed at 80 ° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g, 95% yield). The mass ratio of polysiloxane chain moiety to poly (N-acylalkyleneimine) in the final product (polysiloxane chain / poly (N-acylalkyleneimine)) is 87/13, and the weight average molecular weight of the final product is 115, It was 000.

(Ii) Mix 93.8 g (0.95 mol) of 2-ethyl-2-oxazoline and 203.3 g of ethyl acetate, and use the mixed solution as a molecular sieve (trade name: Zeolam A-4, manufactured by Tosoh Corporation). Dehydration was performed at 14.8 g for 15 hours. Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30,000, amine equivalent 2,000) and 203 g of ethyl acetate were mixed, and the mixed solution was dehydrated with 15.2 g of molecular sieve for 15 hours. .. 6.17 g (0.04 mol) of diethyl sulfate was added to the above-mentioned ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere, and the terminal-reactive poly (N-propionyl) was added. Ethylimine) was synthesized. This terminally reactive poly (N-propionylethyleneimine) solution was collectively added to the above dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and heated and refluxed at 80 ° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow solid (190 g, 95% yield). The mass ratio of polysiloxane chain moiety to poly (N-acylalkyleneimine) in the final product (polysiloxane chain / poly (N-acylalkyleneimine)) is 50/50, and the weight average molecular weight of the final product is 60, It was 000.

(Iii) 2-Ethyl-2-oxazoline 53.2 (0.53 mol) and 127.5 g of ethyl acetate are mixed, and the mixed solution is molecular sieve (trade name: Zeolam A-4, manufactured by Tosoh Corporation). Dehydration was performed at 9.0 g for 15 hours. Further, 153.75 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 50,000, amine equivalent 2,000) and 312.6 g of ethyl acetate were mixed, and the mixed solution was mixed with 22.7 g of molecular sieve for 15 hours. Dehydration was performed. 9.98 g (0.064 mol) of diethyl sulfate was added to the above dehydrated ethyl 2-ethyl-2-oxazoline ethyl acetate solution, and the mixture was heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere to undergo terminal reactive poly (N-propionyl). Ethylimine) was synthesized. This terminally reactive poly (N-propionylethyleneimine) solution was collectively added to the above dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and heated and refluxed at 80 ° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (200 g, yield 92%). The mass ratio of polysiloxane chain moiety to poly (N-acylalkyleneimine) in the final product (polysiloxane chain / poly (N-acylalkyleneimine)) is 70/30, and the weight average molecular weight of the final product is 70, It was 400 (calculated value).

<Preparation of finishing agent composition for clothing>
Examples 1 to 10 and Comparative Examples 1 to 7
A garment finishing agent composition was prepared according to the blending amounts shown in Table 1. Specifically, it was prepared as follows. An amount of ion-exchanged water (temperature: 25 ° C.) was placed in a 500 mL beaker so that the total amount of the garment finishing agent composition was 400 g. The component (B) or the component (B') below and the component (F) below were added to this beaker and uniformly dissolved, and then the mixture was stirred for 10 minutes. Further, the following component (G) was added and uniformly dissolved, and then the liquid composition i containing the polymer polymer mixture (M) obtained in the above synthesis example was added and stirred for 10 minutes. Further, a fragrance was added and the mixture was stirred for 10 minutes.
Each composition in Table 1 has a total of 100% by mass. The pH of each composition in Table 1 at 25 ° C. was 5. The obtained composition was evaluated for its shape-recovery effect and texture according to the evaluation method described later. The results are shown in Table 1. In Table 1, the water contained in the liquid composition i is included in the water contained in the finishing agent composition for clothing.

The components used in the examples and comparative examples are as follows.
<Ingredient (A)>
(A-1): Polymer polymer having vinyl acetate / acrylic acid / N and N-dimethylacrylamide of 95.5 / 2.5 / 2 (mass ratio) (weight average molecular weight 340,000)
<Ingredient (B)>
(B-1): What was obtained by the above-mentioned production method (i) (B-2): What was obtained by the above-mentioned production method (ii) (B-3): What was obtained by the above-mentioned production method (iii). Things <(B') component (comparative component of (B) component)>
B'-1: Polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., KF-6012
B'-2: Amino-modified silicone, Toray Dow Corning silicone
Made by SM8904
<Ingredient (C)>
C-1: Obtained by the reaction of cationized starch (cornstarch with 3- (N, N, N-trimethylammonium chloride) -1,2-propylene oxide. Cation degree of substitution 0.08, viscosity 70 mPa · s ( 5% aqueous solution, 50 ° C)))
<(D) component>
D-1: PVA (weight average molecular weight 66,000)
<(E) component>
E-1: Nonionic surfactant (polyoxyethylene lauryl ether, average number of moles added 40, HLB18.3)
<(F) component>
F-1: Stearyltrimethylammonium chloride (in the general formula (F1), ^R1f is a stearyl group, ^R2f , ^R3f , ^R4f is a methyl group, and ^Y— is a chloride ion compound).
<(G) component>
G-1: Glycerin G-2: Propylene glycol

<Preparation and processing method of test cloth>
T / C Tenjiku (knit) cloth (50% by mass cotton, 50% by mass polyester, MVS color TOP Tenjiku, Saxmoku, manufactured by Sojitz Fashion Co., Ltd.) 2 kg of commercially available liquid detergent (Attack Bio manufactured by Kao Co., Ltd.) Washed repeatedly 5 times in a fully automatic washing machine (Hitachi Appliances, Inc., NW-7FT) using Gel (registered trademark), manufactured in 2017 (detergent concentration 0.083% by mass, tap water (20 ° C)). Use 40L, standard course (washing 9 minutes-2 rinses-6 minutes dehydration), bath ratio 1/20).
The washed T / C knit cloth was dried in an environment of 25 ° C./40% RH for 12 hours and cut into 6 × 6 cm square test cloth (X1) and 10 × 20 cm square test cloth (X2). Obtained.
Next, 285 g of tap water (carbonate alkalinity: 37 mg / l CaCO ₃ ) and 0.12 g of the clothing finishing agent compositions of Examples 1 to 10 and Comparative Examples 1 to 7 shown in Table 1 are placed in a 500 ml plastic cup, respectively. In addition, a magnetic stirrer and a rotor (cross head rotor double, model number 001.1140, height 14 mm, diameter 40 mm, manufactured by AS ONE) were used for stirring for 1 minute (rotation speed 400 rpm). After stirring, 6 test cloths (X1) and 2 test cloths (X2) (9.5 g) were placed in this solution and stirred for 5 minutes (rotation speed 400 rpm). Then, using a two-layer washing machine (TOSHIBA VH-52G (H)), the test cloths (X1 and X2) are placed in a dehydration tank and dehydrated for 1.5 minutes, and the shape of the cloth is reshaped by hand. It was dried for 12 hours in an environment of 25 ° C./40% RH. After drying, the treated test cloth (X1) was used as a test cloth (X3), and the treated test cloth (X2) was used as a test cloth (X4).

<Evaluation method for shape loss recovery>
The shape loss recovery of each test cloth (X3) treated with the clothing finishing agent compositions of Examples 1 to 10 and Comparative Examples 1 to 7 shown in Table 1 was compared with the following reference samples 1 to 4 to determine the following. The evaluation was made by scoring the standard and calculating the average score. The evaluation was made by five well-trained professional evaluators to judge changes in the appearance of T / C cloth and clothing. In the reference sample 1, the untreated T / C cloth is washed 5 times with the detergent as described above using the fully automatic washing machine, and then the T / C cloth is further washed without detergent in the same manner as described above. The one that was deteriorated by repeated washing was used.
The higher the numerical value, the better the evaluation of shape loss recovery, and specifically, 2.0 or more is preferable.

[Reference sample]
Reference sample 1: Untreated and out of shape T / C Tenjiku cloth Reference sample 2: Test cloth (X3) of Comparative Example 4
Reference sample 3: Test cloth (X3) of Example 4
Reference sample 4: Test cloth (X3) of Example 1
The reference samples 1 to 4 had a strong degree of shape loss in this order. That is, the reference sample 1 had the strongest shape loss, and the reference sample 4 had the most shape loss recovery.

〔criterion〕
0: The appearance is the same as that of the test cloth of the reference sample 1, there is a strong shape loss, and there is no shape loss recovery.
1.0: The appearance is the same as that of the test cloth of the reference sample 2, and the shape is slightly lost and there is no recovery from the shape loss.
2.0: The appearance is the same as that of the test cloth of the reference sample 3, and there is a slight loss of shape, but there is some recovery from the loss of shape.
2.5: The appearance between the test cloths of the reference samples 3 and 4, but rather close to the appearance of the reference sample 3, and has a better shape-recovery property than the reference sample 3.
3.0: The appearance is the same as that of the test cloth of the reference sample 4, and the shape is restored.

<Evaluation method of texture>
The texture of each test cloth (X4) treated with the clothing finishing agent compositions of Examples 1 to 10 and Comparative Examples 1 to 7 shown in Table 1 is compared with the following standard samples 1 to 4 according to the following criteria. The evaluation was made by scoring and calculating the average score. The evaluation was made by five well-trained professional evaluators to judge changes in the texture of T / C cloth and clothing.
The higher the value, the better the texture evaluation, and specifically, 1.5 or more is preferable.

[Reference sample]
Reference sample 1: Test cloth (X4) of Comparative Example 1
Reference sample 2: Test cloth (X4) of Comparative Example 7
Reference sample 3: Test cloth (X4) of Example 3
Reference sample 4: The untreated T / C Tenjiku cloth reference samples 1 to 4 had poor texture in this order. That is, the reference sample 1 was the least stiff, and the reference sample 4 was the least stiff.

〔criterion〕
0: The texture is the same as that of the test cloth of the standard sample 1, and it is stiff.
1.0: It has the same texture as the test cloth of the reference sample 2, and is slightly stiff.
2.0: The texture is the same as that of the test cloth of the reference sample 3, and a slight change in texture is felt, but there is not much stiffness.
2.5: The texture between the test cloths of the reference samples 3 and 4, but rather close to the texture of the reference sample 3, and less stiff than the reference sample 3.
3.0: It has the same texture as the test cloth of the reference sample 4, and is clearly not stiff.

Claims (7)

(A) A polymer polymer containing a structural unit from vinyl acetate (hereinafter referred to as (A) component) is contained in an amount of 10 % by mass or more and 50% by mass or less, and (B) at least a silicon atom at the end or side chain of the polysiloxane chain. A compound (hereinafter referred to as (B) component) to which a poly (N-acylalkyleneimine) consisting of a repeating unit represented by the following general formula (B1) is bonded to one via an alkylene group containing a hetero atom. ) Containing 0.05% by mass or more and 5% by mass or less, and water.
A garment finishing agent composition for recovering the shape of clothing.

[In the formula, R ^1b is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or an aryl having 6 to 22 carbon atoms. The group indicates a group, and n indicates a number of 2 or 3. ] The component (B) has a mass ratio (polysiloxane chain / poly (N-acylalkyleneimine)) of a polysiloxane chain portion to a poly (N-acylalkyleneimine) chain portion of 40/60 or more and 98/2 or less. The clothing finishing agent composition according to claim 1, wherein the weight average molecular weight is 20,000 or more and 500,000 or less. The clothing finishing agent composition according to claim 1 or 2, wherein the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is 5 or more and 250 or less. The clothing finishing agent composition according to any one of claims 1 to 3, further comprising (C) cationized starch (hereinafter referred to as component (C)) in an amount of 0.1% by mass or more and 10% by mass or less. .. The clothing finishing agent composition according to claim 4, which contains polymer polymer mixed fine particles containing the component (A) and the component (C). The clothing finishing agent composition according to claim 5, wherein the polymer polymer mixed fine particles further contain (D) polyvinyl alcohol (hereinafter referred to as (D) component). The clothing finishing agent composition according to claim 5 or 6, wherein the polymer polymer mixed fine particles are protective colloids.