JP2020196958A - Finishing agent composition for clothing - Google Patents

Abstract

To provide a garment finishing agent composition that is excellent in storage stability, and can restore garment shape collapse caused by repeated wearing and washing and impart a texture that is not stiff and rugged.SOLUTION: Provided is a garment finishing agent composition containing (A) a polymer containing a constitutional unit derived from vinyl acetate, (B) a compound in which a particular poly(N-acyl-alkylene-imine) is bonded to at least one of the silicon atoms of a polysiloxane via an alkylene group containing a hetero atom, (C) a cationized starch, (D) dimethyl-polysiloxane, and water.SELECTED DRAWING: None

Description

The present invention relates to a garment finishing agent composition.

It is said that it is inevitable that clothing loses 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 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 worn-out appearance and texture change.

Patent Document 1 describes (A) a water-soluble polymer compound selected from the group consisting of a water-soluble processed starch having a specific weight average molecular weight and its derivative, and a water-soluble cellulose derivative having a specific weight average molecular weight, (B) a silicone compound and ( C) A textile treatment agent composition that restores the morphology of a deteriorated textile product such as shape loss, elongation, and shrinkage by containing each nonionic surfactant in a specific ratio is disclosed.
Patent Document 2 states that i) a saponification 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. 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 is disclosed.
In Patent Document 3, a water-soluble polymer compound (A) having a specific weight average molecular weight and an amino-modified silicone compound (B) are contained in specific ratios, so that the fiber is deteriorated due to shape loss, elongation, shrinkage, etc. Textile treatment agents that restore the form of the product are disclosed.
Patent Document 4 describes (a) one or more cations selected from tertiary amines having hydrocarbon groups having 11 to 36 carbon atoms including esters, amides or ether bonds, salts thereof and quaternized products thereof. A polysiloxane solid at a temperature of 20 ° C. that causes intramolecular and intermolecular cross-linking due to a bond other than (b) covalent bond with the softening base, and the molded product 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 0 to 15% elongation, 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. 11-229273

The present invention provides a garment finishing agent composition which is excellent in storage stability, recovers the shape loss that occurs in garments, and imparts a texture that is not stiff and rugged.

In the present invention, (A) a polymer containing a structural unit derived from vinyl acetate (hereinafter referred to as component (A)) and (B) polysiloxane have at least one silicon atom via an alkylene group containing a heteroatom. , A compound to which a poly (N-acylalkyleneimine) consisting of a repeating unit represented by the following general formula (B1) is bound (hereinafter referred to as component (B)), (C) cationized starch (hereinafter, component (hereinafter, component (B)). C)), (D) Dimethylpolysiloxane (hereinafter referred to as component (D)) and water-containing finishing agent composition for clothing.

[In the formula, R ^1b represents a hydrogen atom or a hydrocarbon group having 1 or more and 22 or less carbon atoms, and n represents a number of 2 or 3. ]

According to the present invention, there is provided a garment finishing agent composition which is excellent in storage stability, can recover the shape loss of garment caused by repeated wearing and washing, and can give a texture without ruggedness and stiffness. Will be done.

In the present invention, "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 garment is hung or worn on a hanger.
It is thought that the feeling of twisting and tiredness is caused by, for example, the shape of the body, cuffs, and neck being stretched or shrunk compared to new clothing, and the length and shape are different from the original. ..
Further, in the present invention, "texture" refers to the tactile comfort that a person feels on bare skin, and not only flexibility but also slipperiness, bulkiness, elasticity, elasticity, stiffness, sliminess, etc. It is a mixture of the above factors and shows a certain direction in the comfort vector.

[Finishing agent composition for clothing]
<Ingredient (A)>
The component (A) of the present invention is a polymer containing a structural unit derived from vinyl acetate, and is a polymer in which the structural unit derived from vinyl acetate occupies a part or the whole.
The proportion of the structural unit derived from vinyl acetate is preferably 75% by mass or more, more preferably 82% by mass or more, still more preferably 90% by mass, in all the monomers used for polymerizing the polymer from the viewpoint of recovering the shape of the clothing. % Or more, preferably 99% by mass or less, more preferably 97% by mass or less, still 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 as the component (A), including the monomer copolymerizable with vinyl acetate described later.

Other monomer compounds for forming the polymer of the component (A) include unsaturated carboxylic acids and unsaturated carboxylic acid lower alcohols (carbon numbers) having a polymerizable unsaturated bond copolymerizable with vinyl acetate. A monomer compound selected from 1 to 3 alcoholic acid esters and unsaturated carboxylic acid amides is preferable.

The unsaturated carboxylic acid is one selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, silicic acid, α-chlorosorbic acid, and citraconic acid. The above can be mentioned, and one or more selected from 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, of all the monomers used for the polymerization of the polymer of the component (A). Is 20% by mass 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, and methyl acrylate, ethyl acrylate, methyl methacrylate, and One or more selected from ethyl methacrylate is preferable.
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, based on all the monomers used for the polymerization of the polymer of the component (A). Hereinafter, it is more 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-Hydroxyalkylmethacrylate, N-acylalkylacrylamide, and one or more selected from N-acylalkylmethacrylate. The chain length of the alkyl group, alkoxy group, and acyl group of these amide compounds is preferably 1 to 18 carbon atoms. Among these, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N-hydroxyethylmethacrylamide, and diacetoneiso One or more selected from acrylamide 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 in all the monomers used for the polymerization of the polymer of the component (A). , More preferably 20% by mass or less.

The 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 300,000 or more, from the viewpoint of recovering the shape of clothing. Is 500,000 or less, more preferably 450,000 or less, still 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 combination of these solvents as the eluent, preferably dimethylformamide. More specifically, it is measured by the following method.
5 g of the polymer of the component (A) is placed in a 20 mL volumetric flask, femaled 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 the filtrate.
Column: TSKgel α-M + TSKgel α-M (manufactured by Tosoh Corporation)
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

In the garment finishing agent composition of the present invention, the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, from the viewpoint of recovering the shape of the garment. Then, it is preferably contained in an amount of 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less.

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

[In the formula, R ^1b represents a hydrogen atom or a hydrocarbon group having 1 or more and 22 or less carbon atoms, and n represents 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 specific examples thereof are represented by the following formulas. Can be mentioned.

R ^1b in the general formula (B1) is a hydrogen atom or a hydrocarbon group having 1 or more and 22 carbon atoms or less, and as a hydrocarbon group having 1 or more and 22 carbon atoms or less, from the viewpoint of imparting a texture without stiffness, Alkyl groups having 1 to 22 carbon atoms, cycloalkyl groups having 3 to 22 carbon atoms, aralkyl groups having 7 to 22 carbon atoms, and aryl groups having 6 to 22 carbon atoms are preferable.
The alkyl group represented by R ^1b in the general formula (B1) is more preferably 1 or more and 10 or less carbon atoms, and the cycloalkyl group is more preferably 3 or more and 6 or less carbon atoms, as an aralkyl group. Is more preferably a phenylalkyl group or a naphthylalkyl group, and the aryl group is more preferably a phenyl group, a naphthyl group or an alkyl group substituted phenyl group. R ^1b in the general formula (B1) is more preferably an alkyl group having 1 or more and 5 or less carbon atoms, and even more preferably an ethyl group.

In the component (B), the mass ratio of polysiloxane to poly (N-acylalkyleneimine) (polysiloxane / poly (N-acylalkyleneimine)) is preferably 0 from the viewpoint of imparting a texture without stiffness. It is 66 or more, more preferably 1 or more, still more preferably 1.5 or more, and preferably 50 or less, more preferably 14 or less, still more preferably 9 or less.
Here, the mass ratio can be calculated by using a value obtained by quantitatively analyzing silicon atoms by plasma emission analysis for the content of polysiloxane.
Further, the mass ratio may be the mass ratio of polysiloxane and poly (N-acylalkyleneimine) used in the reaction during production.

The weight average molecular weight of the component (B) is preferably 20,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and preferably 500,000 from the viewpoint of imparting a texture without stiffness. Hereinafter, it is more preferably 300,000 or less, further preferably 200,000 or less, and even more preferably 150,000 or less. The weight average molecular weight of the component (B) is a polystyrene weight-equivalent molecular weight determined by gel permeation chromatography (GPC) using chloroform as a developing solvent.

The garment finishing agent composition of the present invention preferably contains the component (B) in an amount of 0.05% by mass or more, more preferably 0.07% by mass or more, and further preferably 0, from the viewpoint of imparting a texture without stiffness. .1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass or less. , More preferably 0.5% 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) to the content of the component (B) is determined from the viewpoint of achieving both shape loss recovery and texture. , Preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, even more preferably 50 or more, and preferably 250 or less, more preferably 200 or less, still more preferably 150 or less, still more preferably 100 or less. , More preferably 80 or less.

<Component (C)>
The garment finishing agent composition of the present invention 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 cationic 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 alkylating reagent.
Examples of the quaternary ammonium alkylation reagent include a quaternary ammonium compound having a glycidyl group described in JP-A-2010-180320, and from the viewpoint of easy availability of the compound, glycidyltrimethylammonium chloride is used. preferable.
Specific methods 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 is mentioned.

From the viewpoint of the dispersion stability of the component (A) in water, 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. It is 15 or less.
The degree of substitution of cationized starch is calculated from the following formula from the nitrogen content (N) mass% of cationized starch measured by a CHN elemental analyzer (manufactured by Elemental Co., Ltd., trade name: VARIO ELIII). ..
Substitution = (Molecular weight of glucose-Molecular weight of water) x N ÷ (Atomic weight of nitrogen x 100-Molecular weight of quaternary ammonium alkylating reagent x N)
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, it is necessary to use a 5% by mass aqueous solution having a viscosity at 50 ° C. of 30 mPa · s or more, further 50 mPa · s or more, 100 mPa · s or less, and further 90 mPa · s or less. It is preferable from the viewpoint of improving the dispersion stability in water and forming the component (A) and the 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 clothing 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.

In the garment finishing agent composition of the present invention, the mass ratio (A) / (C) of the content of the component (A) to the content of the component (C) is the viewpoint of the dispersion stability of the component (A) in water. From, preferably 1 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 10 or more, and preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, still more preferably 15. It is as follows.

<Component (D)>
The garment finishing agent composition of the present invention contains dimethylpolysiloxane as the component (D). By containing the component (D), the storage stability is excellent even at a high concentration, and the texture can be improved while maintaining the high recoverability of the shape loss generated in the clothing.

The kinematic viscosity of dimethylpolysiloxane at 25 ° C. is preferably 1 mm ² / s or more, more preferably 1.5 mm ² / s or more from the viewpoint of improving the texture, and from the viewpoint of the balance between shape loss recovery and texture. It is preferably 1000 mm ² / s or less, more preferably 500 mm ² / s or less, and further preferably 300 mm ² / s or less. The kinematic viscosity of the component (D) can be measured by a measuring method (JIS Z 8803) defined by Japanese Industrial Standards.

In the garment finishing agent composition of the present invention, the component (D) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.15% by mass, from the viewpoint of improving the texture. And more preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less.

In the garment finishing agent composition of the present invention, the mass ratio (A) / [(B) + (D)] of the content of the component (A) and the total content of the component (B) and the component (D)]. Is preferably 10 or more, more preferably 20 or more, and preferably 50 or less, more preferably 45 or less, from the viewpoint of improving the texture.

In the garment finishing agent composition of the present invention, the mass ratio (B) / (D) of the content of the component (B) to the content of the component (D) is preferably 1 or more from the viewpoint of storage stability. , More preferably 1.2 or more, still more preferably 1.3 or more, even more preferably 1.4 or more, and from the viewpoint of achieving both shape loss recovery and texture, preferably 10 or less, more preferably 5 or less. , More preferably 3 or less, and even more preferably 2 or less.

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

The complex (M) is not in a state of being homogeneously dissolved in the garment finishing agent composition, but is a lumpy, droplet-like or agglomerate complex in which a part or the whole may be swollen with water. It is preferable to have. Further, it is more preferable that the complex (M) forms fine particles (hereinafter, may be referred to as complex fine particles), more preferably a protective colloid having a cation as a surface charge. That is, the garment finishing agent composition of the present invention preferably contains composite fine particles containing the component (A) and the component (C), and the composite fine particles are further made of polyvinyl as the component (E). It preferably contains alcohol. A part of the component (A), the component (C), and the component (E) may be dissolved or dispersed in the garment finishing agent composition without forming a complex (M).

In order to make the complex (M) into fine particles, preferably protective colloids, for example, in an aqueous solution containing the component (C), any component (E) and the component (F) 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 the arbitrary component (E) constitute the composite fine particles, the total of the component (A), the component (C) and the arbitrary component (E) is relative to the total. The mass ratio of the component (A) 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 the arbitrary component (E) 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.

<Ingredient (E)>
The garment finishing agent composition of the present invention preferably contains polyvinyl alcohol as the component (E). In particular, when the garment finishing agent composition of the present invention contains composite fine particles containing the component (A) and the component (C), the composite fine particles are used from the viewpoint of further improving the storage stability of the emulsion. Further, it is preferable to contain the component (E).
The component (E) 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 (E) can be measured by gel permeation chromatography (GPC) 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 (E) to the total of the component (A), the component (C) and the arbitrary component (E) 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.

When the component (E) is used in the garment finishing agent composition of the present invention, the component (E) is preferably 0.01% by mass or more, more preferably, from the viewpoint of the dispersion stability of the component (A) in water. Is contained in an amount of 0.1% 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. ..

<Component (F)>
The garment finishing agent composition of the present invention preferably contains a nonionic surfactant as the component (F). In particular, when the garment finishing agent composition of the present invention contains a complex containing the component (A) and the component (C), from the viewpoint of forming and stabilizing the composite fine particles, preferably the protective colloid. It is preferable that the liquid composition I described below containing the complex further contains the component (F). In the present invention, from the viewpoint of forming and stabilizing the composite fine particles, preferably the protective colloid, the component (F) is specifically contained in Japanese Patent Application Laid-Open No. 10-195772, column 7, lines 43 to 8, line 40. Can be used as described in. The component (F) is preferably a polyoxyethylene alkyl (or alkenyl) ether which is an ethylene oxide adduct of a saturated or unsaturated alcohol having 7 or more and 22 or less carbon atoms. The average number of moles of oxyethylene 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, when the component (F) is used, the component (F) is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of the dispersion stability of the component (A) in water. It is contained in an amount of 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less.

<Ingredient (G)>
The garment finishing agent composition of the present invention preferably contains a cationic surfactant as the component (G) 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 (G1) described later. Quaternary ammonium salt of difatty acid ester of amine, quaternary ammonium salt of difatty acid ester of diethanoldimethylamine, fatty acid monoester monoamide salt of N-hydroxyethyl-N-methyl-propanediamine, and alkylbenzyldimethylquaternary having a benzyl group. Examples include ammonium salts, and other examples 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. 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 (G) may be a quaternary ammonium salt compound represented by the following general formula (G1), and is preferably a quaternary ammonium salt compound having a mono-long chain alkyl-tri short chain alkyl group.

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

In the general formula (G1), Y ⁻ is substituted with a halide ion, preferably a chloride ion, an alkyl sulfate ion having 1 or more and 3 or less carbon atoms, and 1 or more and 3 or less alkyl groups having 1 or more and 3 or less carbon atoms. Anions selected from benzenesulfonate ions which may be used are preferable, and chloride ions are preferable.

When the component (G) is used in the finishing agent composition for clothing of the present invention, the component (G) is preferably 0.01% by mass or more, more preferably 0.1% by mass, from the viewpoint of improving the texture. % Or more, more preferably 0.3% by mass or more, and preferably 5.0% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.0% by mass or less, still more preferably 2. It is contained in an amount of 0% by mass or less, more preferably 1.0% by mass or less. The blending of the component (G) also has an effect of reducing the adhesion of the component (A) to the finishing agent inlet of the washing machine.

<Ingredient (H)>
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 (H). 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 (H) 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.

When the component (H) is used in the garment finishing agent composition of the present invention, the component (H) is preferably 10% by mass or more, more preferably 15% by mass, from the viewpoint of storage stability of the finishing agent composition. As described above, the content is more preferably 20% by mass or more, 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 (H), glycerin (hereinafter referred to as component (H1)) and propylene glycol (hereinafter referred to as component (H2)). ) Is preferably contained, and it is more preferable to contain both the component (H1) and the component (H2).
When both the component (H1) and the component (H2) are contained in the garment finishing agent composition of the present invention, the mass ratio (H1) / of the content of the component (H1) to the content of the component (H2). (H2) is preferably 2.0 or more, more preferably 5.0 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, from the viewpoint of storage stability of the finishing agent composition. Is.

The garment finishing agent composition of the present invention can contain components generally known to be contained in a bath treatment paste or a fabric softener composition. For example, acid agents and alkaline agents as pH adjusters, fragrance components, compounds known as sterilizers and deodorants, antibacterial and antifungal agents marketed under the name of Proxel, and quaternary grades marketed under the name of 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, fatty alcohols, organics such as butyl carbitol and 2-ethylhexyl glyceryl ether A solvent or the like (provided that the components (A) to (H) are excluded) can be contained to such an extent that this effect is not impaired.

The garment finishing agent composition of the present invention preferably contains water as a dispersion medium. As the water, water sterilized with hypochlorous acid can be used, and it is preferable to use deionized water. Water may be added separately in preparing a preferable composition other than those brought in from the component (A) and the 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 garment finishing composition 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 alkali agents such as monoethanolamine and triethanolamine.

<Manufacturing method of finishing agent composition for clothing>
The garment finishing agent composition of the present invention is a step I for preparing a liquid composition containing the component (A), the component (C) and water (hereinafter, may be referred to as a liquid composition I), and a step I. It is preferable to produce the liquid composition by a production method including step II of mixing the obtained liquid composition I, the component (B), and the component (D).
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 the component (A), the component (C), the component (E), the component (F), and water.
In step I, the liquid composition I containing the component (A), the component (C), the component (E), the component (F), and water is the component (A), the component (C), and the component (E). ) Is dispersed as the complex (M), further as the complex fine particles, and further as the protective colloid, it is more preferable to prepare the liquid composition I.

In step I, the monomer compound which is the constituent unit of the component (A) is polymerized in the reaction medium, for example, water, in the presence of the component (C) and the arbitrary component (E) and the arbitrary component (F). Is preferable. Thereby, the liquid composition I containing the complex (M) can be easily obtained.

In the method for producing a finishing agent composition for clothing of the present invention, in step II, the fine particles of the complex (M) containing the component (A), the component (C), and the arbitrary component (E), and the component (B) From the viewpoint of controlling the dispersibility of the complex fine particles at the time of mixing with, it is preferable to further mix the component (G). The component (G) may be blended with the liquid composition I in which the composite fine particles are present in the step I, and the liquid composition in which the component (B) is dissolved or dispersed in water (hereinafter referred to as the liquid composition II). There is also). 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 garment finishing agent composition of the present invention, it is preferable to use each component so as to have a suitable content of the above-mentioned garment finishing agent composition.

<Clothing processing method>
In the method for treating clothing of the present invention, the finishing agent composition for clothing 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 clothing, and the shape of the clothing is lost. You can effectively achieve recovery and a non-stiff texture. When the amount of the garment finishing agent composition with respect to the mass of the garment is 0.1% by mass or more, the effect of using the garment finishing agent composition can be sufficiently obtained, and when it is 3% by mass or less. Economically preferable.

The amount of water that dilutes the garment 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 clothes and the clothes finishing composition are brought into contact with each other while stirring the water obtained by diluting the clothes finishing agent using a washing machine or the like, the rubbing between the clothes is reduced and the generation of fluff and pills is suppressed. From this point of view, the bath ratio is preferably 10 or more, more preferably 15 or more, further 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 complex (M-1) 8.9 parts by mass of cationized starch and 100 parts by mass of ion-exchanged water were added as components (C) to the polymerization reaction tank under a nitrogen atmosphere at 90 ° C. After uniformly dissolving with stirring, the mixture was 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 was 0.08, and the viscosity of the 5% aqueous solution at 50 ° C. was 70 mPa · s.
Next, in order to obtain the complex (M) containing the polymer which is the component (A), 10 parts by mass of vinyl acetate and 3 parts by mass of polyvinyl alcohol (weight average molecular weight 66,000, E-1 in the table). The cationized starch in which 1.5 parts by mass of a nonionic surfactant (polyoxyethylene lauryl ether (average addition molar number 40, HLB18.3), designated as F-1 in the table) is stirred. In addition to the containing aqueous solution, 0.5 parts by mass of trisodium phosphate, 0.4 parts by mass of 2,2'-azobis (2-amidinopropane) hydrochloride, and 20 parts by mass of ion-exchanged water were added and heated to 75 ° C. And the polymerization was started. After the start of polymerization, 100 parts by mass of a mixture premixed so that the final ratio of vinyl acetate, acrylic acid, N, N-dimethylacrylamide is 95.5 / 2.5 / 2 (mass ratio) is 6 It was added dropwise to the reaction solution over time. After completion of the dropping, the temperature was raised to 80 ° C., stirring was continued for 1 hour, and the mixture was cooled to 25 ° C. to obtain an emulsion. After cooling, the pH of the emulsion is adjusted to 5 using a 10 mass% sodium carbonate aqueous solution, and the complex (M-1) and the component (F) containing the component (A), the component (C) and the component (E) are used. In addition, a liquid composition I containing water was obtained. The content of the complex (M-1) in the liquid composition I was 50% by mass, and the content of the component (F) was 0.6% by mass. Further, in the complex (M-1), the mass ratio of (A) / (C) / (E) was 19 / 1.53 / 0.52. The complex (M-1) formed fine particles of the complex, specifically, a protective colloid in the liquid composition I.
The polymer (A-1 in the table) as the component (A) is a polymer containing 95.5 / 2.5 / 2 (mass ratio) of vinyl acetate / acrylic acid / N and N-dimethylacrylamide (mass ratio). The weight average molecular weight was 340,000).

(2) Preparation of (B) component (B-1)
B-1 was produced by the following production method.
12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate are mixed, and the mixed solution is 2.0 g of molecular sieve (trade name: Zeolam A-4, manufactured by Tosoh Corporation). Dehydration was performed 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-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 to undergo terminal-reactive poly (N-propionyl). Ethylimine) was synthesized. This terminally reactive poly (N-propionylethyleneimine) solution was collectively added to the above-mentioned dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and the mixture was heated under reflux 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 (polysiloxane chain / poly (N-acylalkyleneimine)) of the polysiloxane chain portion to poly (N-acylalkyleneimine) in the final product was 88.6 / 11.4, and the weight average of the final product. The molecular weight was 115,000.

<Preparation of finishing agent composition for clothing>
Examples 1-6, Comparative Example 1 and Reference Example 1
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) and the following component (D) obtained by the above production method are added to this beaker, and when the component (G) is contained, the following component (G) is also added and uniformly dissolved. The mixture was stirred for 10 minutes. When the component (H) is further contained, the following component (H) is also added and uniformly dissolved, and then the liquid composition I containing the complex (M-1) obtained in the above synthesis example is added for 10 minutes. Stirred.
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 storage stability, shape loss 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 Examples, Comparative Examples and Reference Examples are as follows.
<Ingredient (A)>
A-1: Polymer with 95.5 / 2.5 / 2 (mass ratio) of vinyl acetate / acrylic acid / N, N-dimethylacrylamide (weight average molecular weight 340,000)
<Ingredient (B)>
B-1: Obtained by the above production method <Component (C)>
C-1: Obtained by the reaction of cationized starch (cornstarch with 3- (N, N, N-trimethylammonium chloride) -1,2-propylene oxide. Cationic substitution degree 0.08, viscosity 70 mPa · s ( 5% aqueous solution, 50 ° C)))
<Component (D)>
D-1: Dimethylpolysiloxane, KF-96L-2cs (kinematic viscosity (25 ° C) 2 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.)
D-2: Dimethylpolysiloxane, KF-96-20cs (kinematic viscosity (25 ° C) 20 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.)
D-3: Dimethylpolysiloxane, KF-96-100cs (kinematic viscosity (25 ° C) 100 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.)
D-4: Dimethylpolysiloxane, KF-96-500cs (kinematic viscosity (25 ° C) 500mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.)
<Ingredient (E)>
E-1: Polyvinyl alcohol (weight average molecular weight 66,000)
<Component (F)>
F-1: Nonionic surfactant (polyoxyethylene lauryl ether, average number of moles added 40, HLB18.3)
<Ingredient (G)>
G1: stearyltrimethylammonium chloride (In the general formula ^{(G1), R 1 g} is stearyl ^{group, R 2g, R 3g, R} 4g is a methyl group, Y ^- is a compound of chloride ion)
<Ingredient (H)>
H-1: Glycerin H-2: Propylene glycol

<Storage stability>
After preparing each finishing agent composition for clothing, the appearance after standing at room temperature for 60 minutes was visually confirmed, and the storage stability was judged according to the following criteria. The results are shown in Table 1.
[Criteria]
〇: Uniform and no separation.
X: Non-uniform or separated.

<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 Biogel manufactured by Kao Corporation Washed repeatedly 5 times in a fully automatic washing machine (manufactured by Hitachi Appliances Co., Ltd., NW-7FT) using a registered trademark) (made in 2019) (detergent concentration 0.083% by mass, using 40 L of tap water (20 ° C), Standard course (washing 9 minutes-2 rinses-6 minutes dehydration), bath ratio 20).
The washed T / C knit cloth was dried in an environment of 25 ° C./40% RH for 12 hours and cut into 5 × 7 cm squares (X1) and 10 × 20 cm squares (X2). Obtained.
Next, add 285 g of tap water (carbonate alkalinity: 37 mg / L CaCO ₃ ) and 0.12 g of each clothing finishing agent composition to a 500 mL plastic cup, and add a magnet stirrer and a rotor (cross head rotor double, model number). The mixture was stirred for 1 minute (rotation speed 400 rpm) using 001.1140, height 14 mm, diameter 40 mm, manufactured by AS ONE Corporation. 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). After that, using a two-layer washing machine (VH-52G (H) manufactured by Toshiba Lifestyle Products & Services Corporation), the test cloths (X1 and X2) were placed in a dehydration tank and dehydrated for 1.5 minutes to restore the shape of the cloth. It was prepared by hand and dried in an environment of 25 ° C./40% RH for 12 hours. After drying, the treated test cloth (X1) was designated as a test cloth (X3), and the treated test cloth (X2) was designated as a test cloth (X4).

<Evaluation method for shape loss recovery>
The shape loss recovery of each test cloth (X3) treated with each garment finishing agent composition was evaluated by comparing with the following standard samples 1 and 3 and scoring according to the following criteria to obtain an 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 untreated T / C cloth is further washed without detergent in the same manner as described above. The one that became deteriorated by repeating 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 3: Test cloth (X3) of Comparative Example 1
The reference sample 1 was strongly out of shape, and the reference sample 3 was recoverable from the out of shape.

[Criteria]
0: The appearance is the same as that of the test cloth of the reference sample 1, and there is a strong shape loss and no shape loss recovery.
1.0: The shape loss is slightly less than that of the test cloth of the reference sample 1, but the shape loss recovery is low.
2.0: There is less shape loss than the test cloth of the reference sample 1, and there is some shape loss recovery.
2.5: From the test cloth of the reference sample 3, the shape is slightly lost, but the shape is recoverable.
3.0: The appearance is similar to that of the test cloth of the reference sample 3, and the shape is clearly recovered.

<Evaluation method of texture>
The texture of each test cloth (X4) treated with each garment finishing agent composition was evaluated by comparing with the following reference samples 2 and 3 and scoring according to the following criteria to obtain an 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.

[Reference sample]
Reference sample 2: Untreated T / C Tenjiku cloth Reference sample 3: Test cloth (X4) of Comparative Example 1
The reference sample 3 was stiff, and the reference sample 2 was not stiff.

[Criteria]
0: The texture is the same as that of the test cloth of the reference sample 3, and it is stiff.
1.0: Slightly less stiff than the test cloth of the reference sample 3.
2.0: Less stiff than the test cloth of the reference sample 3, and less stiff.
2.5: There is a slight difference in texture from the test cloth of the standard sample 2, but there is no stiffness.
3.0: The texture is the same as that of the test cloth of the reference sample 2, and there is clearly no stiffness.

Claims (10)

The following general formula is used for at least one of the silicon atoms of (A) a polymer containing a structural unit derived from vinyl acetate (hereinafter referred to as component (A)) and (B) a polysiloxane via an alkylene group containing a hetero atom. A compound to which a poly (N-acylalkyleneimine) composed of a repeating unit represented by (B1) is bound (hereinafter referred to as component (B)), (C) cationized starch (hereinafter referred to as component (C)). , (D) Dimethylpolysiloxane (hereinafter referred to as component (D)) and water, a finishing agent composition for clothing.

[In the formula, R ^1b represents a hydrogen atom or a hydrocarbon group having 1 or more and 22 or less carbon atoms, and n represents a number of 2 or 3. ] The clothing finishing agent composition according to claim 1, wherein the component (A) is contained in an amount of 5% by mass or more and 50% by mass or less, and the component (B) is contained in an amount of 0.05% by mass or more and 5% by mass or less. The component (B) has a mass ratio of polysiloxane to poly (N-acylalkyleneimine) (polysiloxane / poly (N-acylalkyleneimine)) of 1.5 or more and 50 or less, and has a weight average molecular weight of 20, The clothing finishing agent composition according to claim 1 or 2, which is 000 or more and 500,000 or less. The clothing finish according to any one of claims 1 to 3, 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. Agent composition. The clothing finishing agent composition according to any one of claims 1 to 4, wherein the kinematic viscosity of the component (D) at 25 ° C. is 1 mm ² / s or more and 1000 mm ² / s or less. The clothing finishing agent composition according to any one of claims 1 to 5, which contains the 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 any one of claims 1 to 6, which contains the component (D) in an amount of 0.05% by mass or more and 5% by mass or less. The clothing finishing agent composition according to any one of claims 1 to 7, which contains fine particles of a complex containing the component (A) and the component (C). The clothing finishing agent composition according to claim 8, wherein the composite fine particles further contain (E) polyvinyl alcohol (hereinafter referred to as component (E)). The clothing finishing agent composition according to claim 8 or 9, wherein the composite fine particles are protective colloids.