JP2014129626A - Finishing agent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a finishing agent composition for clothing capable of preventing decline in flexible feeling by cleaning and wearing clothing, especially fiber product such as knit, not generating remaining stains on the clothing even with low mechanical force cleaning of a washing machine.SOLUTION: A finishing agent composition for clothing contains a constitutional unit derived from (meth)acrylic acid ester having an alkyl group having 1 to 16 carbon atoms of 70 to 100 mass%, a polymer having a glass transition temperature of -40°C or more and less than 0°C (A), cationized starch (B), a non-ion surfactant (C), a cationic compound represented by the general formula (1) and water, and the (C) component contains a non-ion surfactant having a hydrocarbon group having 8 to 16 carbon atoms and a polyoxyalkylene chain having an average addition molar number of an oxyalkylene group having 2 to 4 carbon atoms of 3 to 15 (C1), and the mass ratio of the (A) component to the (D) component, [(A)/(D)] is 5 to 50. RRRNX(1), where Rrepresents a hydrocarbon group having 14 to 20 carbon atoms, Rrepresents a substituent defined with Ror R, Rrepresents an alkyl group having 1 to 4 carbon atoms, a benzyl group and a hydroxyalkyl group having 2 to 4 carbon atoms, and Xrepresents an anion.

Description

  The present invention relates to a finishing composition for clothing and a method for treating clothing using the same.

In recent years, knitwear with excellent fashion has been increasing. The knit clothing is required to have a supple texture as compared to the cloths such as sheets and Y-shirts that are the target clothing of the paste composition. The knit clothing is configured by a knitting method called knit knitting using a yarn obtained by twisting a single fiber sweetly compared to a fabric. Knit knitting gives a flexible texture to the entire garment because the yarns and the single fibers constituting the yarn are easy to move.
Clothing is stretched and twisted by repeated wearing and washing. In particular, knitwear is not only stretched and twisted, but it is easy to damage the supple texture because of the sweet twist. In addition, the “smooth texture” in the present specification indicates a firm texture with elasticity and elasticity while maintaining the smoothness of the surface.

As a cause of damaging the supple texture, it is considered that the yarn is thinned by dropping off of the single fiber in the yarn, and in order to prevent this, bonding between the single fibers is performed. In addition, since single fibers in the yarn fall off mainly due to washing, in recent years, full-automatic washing machines have become capable of being used in full-automatic washing machines, as well as reduced texture, fluff and fluff. A pasting agent and a polymer processing agent that can suppress the occurrence of the above have been proposed.
Since the knit clothing uses a yarn in which single fibers are twisted sweetly, the single fibers are easily removed from the yarn, and fluff and fluff are likely to occur. Therefore, when washing knitted clothing, it has been practiced to immerse and process the knitted clothing in a container such as a wash basin. A cleaning agent has been proposed that can be treated and can suppress the generation of fluff and fluff.

  For example, Patent Document 1 discloses a fiber mainly composed of an aqueous dispersion such as a (meth) acrylic acid ester-based copolymer whose glass transition temperature is −45 ° C. to 20 ° C. and further containing a wetting agent. A processing resin composition is disclosed. Furthermore, this patent document 1 describes nonionic surfactants such as polyoxyethylene alkyl ethers as wetting agents.

  Patent Document 2 discloses a laundry containing a cationic antibacterial agent of a copolymer having a glass transition temperature of 0 to 30 ° C. obtained by emulsion polymerization of a monomer mixture such as (meth) acrylic acid ester using a cationic emulsifier. An antibacterial resin composition for glue is disclosed. Patent Document 2 describes a compound such as lauryltrimethylammonium chloride as a cationic emulsifier.

  Patent Document 3 describes a paste composition containing an emulsion obtained by emulsion polymerization using monomers such as alkyl methacrylate and the like during emulsion polymerization of a lower fatty acid vinyl ester and an unsaturated carboxylic acid. Has been. Further, Patent Document 2 describes that a nonionic emulsifier is used at the time of polymerization, and that a cationic polymer such as cationic starch may coexist at the time of polymerization or may be added after the polymerization is completed.

JP 2008-248432 A JP 2001-226204 A JP-A-3-260174

The present inventors include a finishing composition for clothing as described in Patent Documents 1 to 3, that is, containing a specific polymer, a cationic compound and water, and lowering the texture of knit clothing and generating fluff balls. It has been found that there is a new problem in a garment finishing composition that can suppress the above.
In other words, in low-mechanical washing, which is displayed as a dry course or a fashionable course for a washing machine, if a treatment agent adheres to clothing at a high concentration, the attached treatment agent does not detach and a stain residue appears. The problem of doing.

The present inventors have found out that this problem is caused by anions such as carbonate ions (CO ₃ ²⁻ ) and hydrogen carbonate ions (HCO ₃ ⁻ ) in water that cause carbonate alkalinity. It was. Specifically, the anion exchanges with a counter ion (generally a chlorine ion) of the cationized starch of the cationized starch in the garment finish composition, thereby reducing the surface potential of the cationized starch. As a result, the force of charge repulsion was weakened and the polymer particles were likely to aggregate, and as a result, it was considered that spots were easily developed.
In addition, hand washing and washing machine low mechanical strength courses can be mentioned as washing methods for knitted products, but when compared to normal washing, the force applied to clothing is clearly weaker and the attached treatment agent is less likely to be detached. It is thought to be the cause.

Furthermore, it has been found that another cause is the physical properties of the polymer. That is, at a tap water temperature of about 5 to 40 ° C. usually used for washing, a polymer having a glass transition temperature of less than 0 ° C. exhibits a soft physical property, and the polymer exhibiting the soft physical property aggregates together with the cationized starch. It is thought that it becomes easy to adhere to.
In Patent Documents 1 to 3, in the case of using a polymer having a glass transition temperature of −45 ° C. to 20 ° C. and a quaternary ammonium compound as a wetting agent, CO in tap water is added to the inlet of the washing machine. ₃ ^2- and HCO ₃ ^- is contamination due to anions such no description relates to occur. However, in tap water CO ₃ ^- and HCO ₃ ^- by the anion of such scavenging (capture) preventing stains with by aggregation is not described.

  The present invention is a finish composition for clothing that can suppress a decrease in supple texture due to washing and wearing by imparting an appropriate and firm feeling to clothing, particularly knit products, etc. It is an object of the present invention to provide a finishing composition for clothing that does not cause stain residue on clothing, and a method for treating clothing using the finishing composition for clothing.

The inventors of the present invention provide a polymer dispersed with a specific nonionic surfactant and has a property of supplementing anions such as CO ₃ ²⁻ and HCO ₃ ⁻ in tap water with quaternary ammonium in the molecule. It has been found that by adding a compound having a group at a specific ratio, aggregation of components in the finishing composition for clothing can be suppressed, and a stain residue can be suppressed in low mechanical strength washing.

The present invention provides the following [1] and [2].
[1] Polymer (A) containing 70 to 100% by mass of a structural unit derived from a (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms and having a glass transition temperature of −40 ° C. or higher and lower than 0 ° C. ), A cationized starch (B), a nonionic surfactant (C), a cationic compound (D) represented by the following general formula (1), and water, and the component (C) has 8 carbon atoms. A nonionic surfactant (C1) having ˜16 hydrocarbon groups and a polyoxyalkylene chain having an average addition mole number of oxyalkylene groups of 2 to 4 carbon atoms of 3 to 15, and component (D) A finishing composition for clothing in which the mass ratio [(A) / (D)] of the component (A) to 5 is 50.
_{^{R 1 R 2 R 3 2 N}} + · X - (1)
(In the formula, R ¹ represents a hydrocarbon group having 14 to 20 carbon atoms, R ² represents a substituent defined by R ¹ or R ³ , and R ³ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group. And a hydroxyalkyl group having 2 to 4 carbon atoms, and X ⁻ represents an anion.)

[2] A method for treating clothing, in which the component (A) of the clothing finish composition is brought into contact in a water bath so as to be 0.1 to 1% by mass relative to the mass of the clothing.

  The present invention is a garment finish composition that can suppress a decrease in supple texture due to washing and wearing of textiles, particularly textile products such as knitted fabrics. No clothing finish composition can be provided.

[Clothing finishing composition]
The present invention includes a polymer (70) to 100% by mass of a structural unit derived from a (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms, and having a glass transition temperature of −40 ° C. or higher and lower than 0 ° C. A), a cationized starch (B), a nonionic surfactant (C), a cationic compound (D) represented by the following general formula (1), and water, wherein the component (C) has a carbon number A nonionic surfactant (C1) having a hydrocarbon group of 8 to 16 and a polyoxyalkylene chain having an average added mole number of an oxyalkylene group having 2 to 4 carbon atoms of 3 to 15, and a component (D ) Is a finishing composition for clothing having a mass ratio [(A) / (D)] of component (A) to 5-50.
_{^{R 1 R 2 R 3 2 N}} + · X - (1)
(In the formula, R ¹ represents a hydrocarbon group having 14 to 20 carbon atoms, R ² represents a substituent defined by R ¹ or R ³ , and R ³ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group. And a hydroxyalkyl group having 2 to 4 carbon atoms, and X ⁻ represents an anion.)

According to the garment finish composition of the present invention, in the garment finish composition, which can suppress a decrease in the supple texture due to washing and wearing of garments, particularly textile products such as knitwear, the use of the input of a washing machine. Even in low-mechanical washing of the washing machine, no stain remains on the clothes.
In this specification, “(meth) acrylic acid ester” means “acrylic acid ester or methacrylic acid ester”.

<Polymer (A)>
The polymer (A) in the present invention contains 70 to 100% by mass of a structural unit derived from a (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms (hereinafter also referred to as “monomer (a1)”). A polymer having a glass transition temperature of −40 ° C. or higher and lower than 0 ° C. is preferable.
In this specification, the content of the structural unit derived from the monomer (a1) in the polymer (A) is the ratio of the structural unit derived from the monomer (a1) to the polymer (A), and the monomer (a1) at the time of polymerization. It is possible to obtain | require from the mixture ratio of. That is, since the reaction rate in the case of polymerizing the monomer (a1) is usually about 99 mol%, the content can be calculated from the blending ratio. The same applies to the monomer (a2) and the monomer (a3) described later.

The monomer (a1) is not particularly limited as long as it is a (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms, and if the polymer (A) satisfies the glass transition temperature, one kind may be used alone. Even if it uses, 2 or more types may be used together.
In the present invention, the “(meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms” means “(meth) acrylic acid alkyl ester, wherein the alkyl group is an alkyl group having 1 to 16 carbon atoms”. “Some compound”.
The alkyl group may be linear or branched, including n-isomer, sec-isomer, tert-isomer, and iso-isomer.

The number of carbon atoms of the alkyl group in the case of using an acrylate ester is preferably 2 to 12, more preferably 3 to 10, and further preferably 4 to 8 from the viewpoint of easy adjustment of the glass transition temperature.
Specific examples of the compound include acrylic acid ethyl ester, acrylic acid n-propyl ester, acrylic acid n-butyl ester, acrylic acid iso-butyl ester, acrylic acid tert-butyl ester, acrylic acid n-pentyl ester, and acrylic acid n. -Hexyl ester, acrylic acid n-heptyl ester, acrylic acid n-octyl ester, acrylic acid 2-ethylhexyl ester are preferred, acrylic acid n-butyl ester, acrylic acid iso-butyl ester, acrylic acid tert-butyl ester, acrylic acid 2-ethylhexyl ester is more preferable, and acrylic acid n-butyl ester is still more preferable.

The number of carbon atoms of the alkyl group in the case of using the methacrylic acid ester is preferably 1 to 8, more preferably 1 to 4, more preferably 1 to 2, from the viewpoint of easy adjustment of the glass transition temperature.
Specific compounds include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid n-propyl ester, methacrylic acid n-butyl ester, methacrylic acid iso-butyl ester, methacrylic acid tert-butyl ester, and 2-ethylhexyl methacrylate. Esters are preferred, methacrylic acid methyl esters and methacrylic acid ethyl esters are more preferred, and methacrylic acid methyl esters are even more preferred.
From the viewpoint of adjusting the glass transition temperature of the polymer (A) (hereinafter also referred to as “component (A)”) to a range of −40 ° C. or higher and lower than 0 ° C., a methacrylic ester and an acrylic ester are used in combination. Is preferred.

When using both together, it is preferable to use together the methacrylic acid ester which has a C1-C6 alkyl group, and the acrylic acid ester which has a C2-C6 alkyl group, and C1-C2 It is more preferable to use together the methacrylic acid ester which has an alkyl group, and the acrylic acid ester which has a C3-C5 alkyl group, and the combined use of methacrylic acid methyl ester and acrylic acid n-butyl ester is still more preferable.
The mass ratio [acrylic acid ester / methacrylic acid ester] when the methacrylic acid ester and the acrylic acid ester are used in combination is preferably 99/1 to 55 from the viewpoint of adjusting the glass transition temperature of the component (A) to the above range. / 45, more preferably 80/20 to 56/44.
In this specification, the glass transition temperature (Tg) in the case where the component (A) is a polymer polymerized with only one type of monomer shown in Table 1 (hereinafter also referred to as “homopolymer”) is shown in Table 1. The stated values were used.

When a monomer not listed in Table 1 is used as the component (A), the glass transition temperature (Tg) is “Polymer Handbook, Fourth Edition Volume1, WILEY-INTERSCIENCE, A John Wiley & Sons, Inc., Publication, 1999. The value of the homopolymer described in the above is used.
The glass transition temperature (Tg) when the component (A) is a copolymer obtained by polymerizing n types of monomers is the glass transition temperature [Tg (i)] of the homopolymer of each monomer (i). From this, the glass transition temperature (Tg) of the copolymer was calculated according to the following formula (I). However, the numbers after the decimal point were rounded off, and when the copolymer contained a polyfunctional monomer, the calculation was performed for the monomer excluding the polyfunctional monomer.

(Wherein, Tg is the glass transition temperature (° C.) of the copolymer, Tg (i) is the glass transition temperature of the homopolymer of each monomer (i) constituting the copolymer, and wi is the copolymer) The mass fraction of the monomer (i) constituting

(A) It is preferable that the glass transition temperature (Tg) of a component is -40 degreeC or more and less than 0 degree | times. When the glass transition temperature (Tg) is within this range, it is possible to suppress fluff generated in clothing during wearing or the like. Further, when the glass transition temperature (Tg) is less than 0 ° C., the supple texture of the clothing is not impaired. From the viewpoint of suppressing the generation of fluff, the glass transition temperature (Tg) is preferably −35 ° C. to −5 ° C., more preferably −32 to −5 ° C. In addition, from the viewpoint of preventing the finish composition for clothing from remaining in the finisher inlet of the fully automatic washing machine, the glass transition temperature (Tg) of the component (A) is more preferably -30 ° C to -5 ° C. .
The component (A) may be one or more copolymers of the monomer (a1), but may be a copolymer of (a1) and another monomer other than (a1). Good.
When a monomer other than the above (a1) is used, the proportion of the structural unit derived from the monomer (a1) contained in the component (A) is 70% by mass or more, preferably 80 to 80% from the viewpoint of suppressing the occurrence of fluff in clothing. It is 98 mass%, More preferably, it is 85-95 mass%, More preferably, it is 90-95 mass%.
Examples of the other monomer that may be copolymerized with the monomer (a1) include the following monomer (a2) and monomer (a3).

<Monomer (a2)>
As the monomer (a2), it is preferable to use a (meth) acrylic acid ester having a hydroxyalkyl group having 2 to 4 carbon atoms. By using the monomer (a2), the component (A) adhering to the clothing can be easily detached from the clothing at the time of washing, and a stain residue can be prevented.

In the present invention, the (meth) acrylic acid ester having a hydroxyalkyl group having 2 to 4 carbon atoms is a (meth) acrylic acid hydroxyalkyl ester, wherein the hydroxyalkyl group has 2 to 4 carbon atoms. Say things.
From the viewpoint of further improving the detachability of the component (A) from the clothing (meaning that the component (A) is easily detached from the clothing) in the washing step, and from the viewpoint of preventing stain residue, the number of carbon atoms A hydroxyalkyl group having 2 to 3 carbon atoms is preferable, and a hydroxyalkyl group having 2 carbon atoms is more preferable.

Specific examples of the hydroxyalkyl ester of acrylic acid include acrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxypropyl ester, and acrylic acid 4-hydroxybutyl ester.
Specific examples of the methacrylic acid hydroxyalkyl ester include methacrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxypropyl ester, and methacrylic acid 4-hydroxybutyl ester.
Among these, acrylic acid 2-hydroxyethyl ester and methacrylic acid 2-hydroxyethyl ester are preferred from the viewpoint of detachment of the component (A) from clothing and the prevention of stain residue.
The proportion of the structural unit derived from the monomer (a2) in the component (A) is preferably 1 to 15% by mass from the viewpoint of improving the detachability of the component (A) from the garment and preventing stain residue. More preferably, it is 2-10 mass%, More preferably, it is 3-8 mass%, More preferably, it is 4-7 mass%.

<Monomer (a3)>
As the monomer (a3), it is preferable to use at least one monomer selected from ethylenically unsaturated carboxylic acids and salts thereof. In the present invention, “ethylenically unsaturated carboxylic acid” refers to a compound having a vinyl group or a polymerizable double bond in the molecule and a carboxylic acid group. The ethylenically unsaturated carboxylic acid and its salt preferably have a molecular weight of 200 or less when in the acid form.
By using the monomer (a3), it is possible to improve the detachability of the component (A) adhering to the clothing from the clothing and to prevent a stain residue.
Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable from the viewpoint of availability of raw materials.
Examples of the ethylenically unsaturated carboxylate include alkali metal salts and alkaline earth metal salts of the ethylenically unsaturated carboxylic acid. The ethylenically unsaturated carboxylate may be an ammonium salt or an alkanolamine salt. An ethylenically unsaturated carboxylate may be used individually by 1 type, and 2 or more types may be mixed and used for it.
These ethylenically unsaturated carboxylic acids and salts thereof may be used alone or in combination of two or more.

The proportion of the structural unit derived from the monomer (a3) in the component (A) is preferably from 0.1 to 5% by mass, more preferably from the viewpoint of improving the detachment from clothing and the prevention of stain residue. Is 0.3 to 3% by mass, more preferably 0.4 to 2% by mass, and still more preferably 0.8 to 1.2% by mass.
The component (A) is preferably a copolymer containing the monomer (a1), the monomer (a2) and the monomer (a3) from the viewpoint of suppressing generation of fluff and fluff.
In addition, as (A) component, you may use monomers other than said monomer (a1)-(a3) in the range which does not affect the effect of (A) component.

The weight average molecular weight (Mw) of the component (A) is preferably 50,000 to 500,000, more preferably 100,000 to 450,000, and still more preferably 200,000 to 400,000.
In addition, the weight average molecular weight (Mw) of (A) component says the value by a gel permeation chromatography (GPC) measurement. More specifically, it refers to a molecular weight in terms of polystyrene measured using chloroform, dimethylformamide, tetrahydrofuran, acetone, or a combination of these solvents as an eluent, preferably using dimethylformamide.
The component (A) can be produced by a method such as solution polymerization or emulsion polymerization, but is preferably produced by emulsion polymerization from the viewpoint of ease of handling. Examples of the emulsion polymerization method include the method described in JP-A-2008-88414.

<Cationized starch (B)>
In the present invention, the cationized starch (B) is used for the purpose of enhancing the adsorptivity of the component (A) to clothing and as an emulsion stabilizer when the component (A) is produced by emulsion polymerization or the like. (Hereinafter also referred to as “component (B)”).
As the polysaccharide forming the main skeleton of the cationized starch, starch described in JP 2010-180320 A can be used. Specifically, starches such as corn starch, wheat starch, potato starch, tapioca starch and the like can be mentioned.
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 a polysaccharide and a quaternary ammonium alkylating reagent.

Examples of the quaternary ammonium alkylating reagent include a quaternary ammonium compound having a glycidyl group described in JP 2010-180320 A. From the viewpoint of availability of the compound, glycidyl trimethyl ammonium chloride may be 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, and JP-A-8-198901. The method of description is mentioned.

The nitrogen atom content (hereinafter also referred to as “N mass%”) of the cationized starch as the component (B) is generally 0.01 to 1.5 mass%, but the clothing of the component (A) From the point of further increasing the adsorptivity to, preferably 0.3 to 1.3% by mass, more preferably 0.4 to 1% by mass, still more preferably 0.5 to 0.9% by mass, and still more preferably. It is 0.6-0.8 mass%.
In this specification, N mass% means content (mass%) of the nitrogen atom derived from a quaternary ammonium group with respect to the total mass of (B) component. N mass% is based on the nitrogen determination method (semi-micro Kjeldahl method) described on pages 43-44 of the “Twelfth Amendment Japanese Pharmacopoeia” (published by the Japan Standards Association, published by Daiichi Law Publishing Co., Ltd.). Can be done.
The weight average molecular weight of the cationized starch as the component (B) is preferably 100,000 to 1,900,000, more preferably 300,000 to 1,700,000, and more preferably 500,000 to 500,000 from the viewpoint of suppressing fuzz and generation of fuzz. The number is 1.5 million, more preferably 800,000 to 1.3 million, and still more preferably 900,000 to 1.05 million.

<Nonionic surfactant (C)>
(Nonionic surfactant (C1))
From the viewpoint of dispersion stability when the component (A) in the present invention is diluted, the nonionic surfactant (C) (hereinafter also referred to as “component (C)”) is a hydrocarbon group having 8 to 16 carbon atoms. And a nonionic surfactant (C1) having a polyoxyalkylene chain having an average addition mole number of an oxyalkylene group having 2 to 4 carbon atoms of 3 to 15.
The nonionic surfactant (C1) is an average of aliphatic hydrocarbon groups having 8 to 16 carbon atoms and oxyalkylene groups having 2 to 4 carbon atoms from the viewpoint of dispersion stability when the component (A) is diluted. A polyoxyalkylene alkyl ether having a polyoxyalkylene chain having an addition mole number of 3 to 15 is preferred.

From the viewpoint of dispersion stability when the component (A) is diluted, the number of carbon atoms of the aliphatic hydrocarbon group of the component (C1) is preferably 10-15, more preferably 11-14, and the average number of moles of oxyalkylene groups added. Is preferably 4 to 14, more preferably 5 to 13, and still more preferably 6 to 12.
The preferred surfactant (C1) has an aliphatic hydrocarbon group having 10 to 15 carbon atoms, preferably 11 to 14 carbon atoms, and the oxyalkylene group is an oxyethylene group or an oxyethylene group and an oxypropylene group. It is a nonionic surfactant having a polyoxyalkylene chain which is a combination and has an average added mole number of 4 to 14. More preferably, it has an aliphatic hydrocarbon group having 10 to 15 carbon atoms, preferably 11 to 14 carbon atoms, the average addition mole number of the oxypropylene group is 0 to 3, and the average addition mole number of the oxyethylene group is 4 to 14 It is a nonionic surfactant having a polyoxyalkylene chain.
The more preferable surfactant (C1) has an aliphatic hydrocarbon group preferably having 10 to 15 carbon atoms, more preferably 11 to 14, and the oxyalkylene group is an oxyethylene group or an oxyethylene group and an oxypropylene group. A polyoxyalkylene having an average addition mole number of 4 to 14, an average addition mole number of oxypropylene group of 0 to 3, and an average addition mole number of oxyethylene group of 4 to 14 Alkyl ether.
The component (C1) is preferably used in combination of two or more from the viewpoint of dispersion stability when the component (A) is diluted. From the viewpoint of the effect of reducing the viscosity of the composition, an alkyl group having a branched chain ( In the present invention, in addition to a group having a branch in the alkyl group, a polyoxy having an alkyl group derived from a secondary alcohol or an alkyl group in which the carbon atom of the alkyl group bonded to the oxygen atom is a second carbon atom) An alkylene alkyl ether and a linear alkyl group (that is, in the present invention, an alkyl group derived from a linear primary alcohol, or a linear alkyl group in which the carbon atom of the alkyl group bonded to the oxygen atom is the first carbon atom). It is preferable to use together with the polyoxyalkylene alkyl ether. Specific examples include polyoxyethylene alkyl ethers having a primary linear alkyl group having 12 to 14 carbon atoms, an average addition mole number of oxyethylene groups of 8 to 12, and 12 to 14 carbon atoms. It is preferable to use a polyoxyethylene alkyl ether having a secondary alkyl group and an average addition mole number of oxyethylene groups of 5 to 7 in combination.
In addition, the dispersion stability at the time of dilution of the component (A) has a correlation with the emulsion stability at the time of polymerization of the component (A). If the emulsion stability at the time of polymerization is excellent, the dispersion at the time of dilution even after storage Stability does not deteriorate.

(Nonionic surfactant (C2))
In the present invention, from the viewpoint of emulsion stability of component (A), a nonionic surfactant (C2) having at least one hydrocarbon group having 8 to 16 carbon atoms and an average of 30 to 70 oxyalkylene groups added. ) Is preferably contained.
The nonionic surfactant (C2) has an average added mole number of an aliphatic hydrocarbon group having 8 to 16 carbon atoms and an oxyalkylene group having 2 to 4 carbon atoms from the viewpoint of emulsion stability of the component (A). A polyoxyalkylene alkyl ether having a polyoxyalkylene chain of 30 to 70 mol is preferred.
Further, from the viewpoint of emulsion stability, the aliphatic hydrocarbon group, preferably the linear primary alkyl group, preferably has 10 to 15 carbon atoms, more preferably 11 to 14 carbon atoms, preferably an oxyalkylene group, preferably an oxyethylene group. The average number of moles added is preferably 35 to 65, more preferably 40 to 60, and still more preferably 42 to 52 polyoxyalkylene alkyl ether.

  From the viewpoint of emulsion stability and dilution dispersibility of the component (A), the mass ratio [(C1) / (C2)] of the component (C1) to the component (C2) is preferably 0.5 to 50. Furthermore, from the viewpoint of emulsion stability of the component (A), [(C1) / (C2)] is more preferably 48 or less, still more preferably 45 or less, and still more preferably 40 or less. [(C1) / (C2)] is preferably 2 or more, more preferably 10 or more, still more preferably 15 or more, and still more preferably 18 or more, from the viewpoint of dilution dispersibility of the component (A). .

From the viewpoint of emulsion stability and dilution dispersibility of the component (A), the HLB of the component (C) is preferably 12-20. Furthermore, from the viewpoint of emulsion stability of the component (A), the HLB of the component (C) is preferably 19 or less, more preferably 17 or less. Moreover, from the point of the diluting dispersibility of (A) component, HLB of (C) component becomes like this. Preferably it is 12.5 or more, More preferably, it is 13 or more.
The HLB here can be obtained by the Griffin method. In addition, when using two types of surfactant as (C) component in this specification, let the average value which considered the mass be HLB.
(C) component of this invention may be used at the time of manufacture of the said (A) component, and may be used for the finishing composition for clothing separately from (A) component.

<Cationic compound (D) component>
The finishing composition for clothing of the present invention contains a cationic compound (D) represented by the following general formula (1) (hereinafter also referred to as “component (D)”).
_{^{R 1 R 2 R 3 2 N}} + · X - (1)
(In the formula, R ¹ represents a hydrocarbon group having 14 to 20 carbon atoms, R ² represents a substituent defined by R ¹ or R ³ , and R ³ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group. And a hydroxyalkyl group having 2 to 4 carbon atoms, and X ⁻ represents an anion.)
R ¹ represents a hydrocarbon group having 14 to 20 carbon atoms. The hydrocarbon group having 14 to 20 carbon atoms of R ¹ is highly effective in trapping anions such as carbonate ions (CO ₃ ²⁻ ) and hydrogen carbonate ions (HCO ₃ ⁻ ) in water, and the surface charge on the particle surface Suppresses the decline. When the number of carbon atoms is less than 14, it is impossible to suppress a decrease in surface charge. From the same viewpoint as described above, R ¹ is preferably a hydrocarbon group having 14 to 18 carbon atoms, and more preferably a hydrocarbon group having 16 to 18 carbon atoms. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable.
R ² represents a substituent defined by R ¹ or R ³ , and is preferably R ³ from the viewpoint of adsorption of the polymer (A).

R ³ represents an alkyl group having 1 to 4 carbon atoms, a benzyl group, and a hydroxyalkyl group having 2 to 4 carbon atoms. Specific examples of R ³ include a methyl group, an ethyl group, a hydroxyethyl group, and a benzyl group. From the viewpoint of adsorption of the polymer (A), a methyl group, an ethyl group, and a hydroxyethyl group are preferable.
X ⁻ is an anion, and specific examples include halogen ions such as chlorine ion and bromine ion, methyl sulfate ion, and ethyl sulfate ion.

<Content of each component>
The content of the component (A) in the finishing composition for clothing is preferably 1 to 50% by mass. From the viewpoint of reducing the use amount of the garment finish composition per wash, it is preferably 5% by mass or more, more preferably 10% by mass or more. Moreover, from a viewpoint of suppressing a stain residue, content of (A) component becomes like this. Preferably it is 35 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
The mass ratio [(A) / (D)] of the component (A) to the component (D) is preferably 5 to 50, more preferably 5 to 40, more preferably from the viewpoint of suppressing a stain residue in low mechanical strength washing. Preferably it is 5-35.
The mass ratio [(B) / (D)] of the component (B) to the component (D) is preferably 0.3 to 4, more preferably 0.4, from the viewpoint of suppressing a stain residue in low mechanical strength washing. -3.5, more preferably 0.5-3.5.

As described above, the finish composition for clothing according to the present invention can be suitably used for washing knitted clothing characterized by a supple texture because it can suppress a decrease in supple texture due to washing and wearing.
In the present specification, “knit clothing” refers to clothing formed of knit (knitted fabric), and “knit (knitted fabric)” refers to a fabric configured by connecting loops of yarn.

[Clothing processing method]
In the method for treating garments of the present invention, the component (A) of the garment finish composition is preferably contacted in a water bath so as to be 0.1 to 1% by mass relative to the mass of the garment. Can be effectively suppressed. When the amount of the component (A) of the garment finish composition relative to the mass of the garment is less than 0.1% by mass, the effect of using the garment finish composition cannot be sufficiently obtained. Exceeding mass% is not economically preferable. The amount of the component (A) with respect to the mass of the clothes is preferably 0.12 to 0.8% by mass, more preferably 0.15 to 0.6% by mass, from the viewpoint of imparting a supple texture and suppressing the decrease in the texture. %.
The amount of water in which the garment finish is dissolved can generally be determined by the bath ratio. In the present specification, the “bath ratio” refers to the ratio of the mass of clothing and the volume of water containing the clothing finish, [volume of water (liter)] / [mass of clothing (kg)].

When using a washing machine or the like to stir the water in which the garment finish is dissolved, the garment and the garment finish composition are brought into contact with each other. From the viewpoint of suppression, the bath ratio is preferably 10 to 90, more preferably 20 to 80, and still more preferably 30 to 60.
Moreover, when processing clothing by the said clothing processing method, the adsorption amount with respect to clothing of the (A) component of the said finishing composition for clothing is based on the mass of clothing from a viewpoint of giving a feeling firmly to clothing. Preferably from 0.05 to 0.4% by mass, more preferably from 0.08 to 0.3% by mass, and more preferably from 0.1 to 0% from the viewpoint of imparting a supple texture and imparting a firm feeling to clothing. .2% by mass.

  First, each component was synthesized according to the following synthesis example. Table 2 shows the monomer composition of the component (a ') which is a comparative compound of the component (A) and the component (A).

[Synthesis example of each component]
<Synthesis example of component (A)>
Synthesis Example 1: Synthesis of component (a-1) In a nitrogen atmosphere, 1.1 parts by weight of the cationized starch obtained in Synthesis Example 12 below in a reaction vessel, polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., GL-05) ) 0.2 parts by weight and 48.7 parts by weight of ion-exchanged water were uniformly dissolved at 90 ° C and then cooled to 60 ° C. A nonionic surfactant obtained by adding an average of 12 moles of EO to 0.3 parts by weight of n-butyl acrylate, 0.2 parts by weight of methyl methacrylate and a linear primary alcohol having 12 carbon atoms (hereinafter referred to as “non-ionic surfactant”). , Also referred to as “component (c1-1)” / nonionic surfactant obtained by adding an average of 9 mol of EO to a linear primary alcohol having 12 carbon atoms (hereinafter referred to as “component (c1-2)”) Nonionic surfactant obtained by adding 3 moles of EO to secondary alcohol having 12 to 14 carbon atoms on average (hereinafter also referred to as “component (c1-3)”) / linear chain having 12 carbon atoms The weight ratio of nonionic surfactant (hereinafter also referred to as “component (c2-1)”) obtained by adding 47 mol of EO to primary alcohol on average (weight ratio 31.5 / 0/65 / 3.5) ) 1.68 parts by weight, 2,2′-azo 0.03 part by weight of bis (2-amidinopropane) hydrochloride and 19.4 parts by weight of ion-exchanged water were added, and the mixture was heated to 75 ° C. to initiate polymerization. Mix in advance so that the final ratio of methyl methacrylate, n-butyl acrylate, acrylic acid, 2-hydroxyethyl methacrylate (weight ratio 30/64/1/5) is 5 hours after polymerization starts. An aqueous solution prepared by dissolving 16.2 parts by weight of the soot and 0.05 parts by weight of 2,2′-azobis (2-amidinopropane) hydrochloride in 11.9 parts by weight of ion-exchanged water was dropped into the reaction solution. After completion of the dropwise addition, 0.004 part by weight of 2,2′-azobis (2-amidinopropane) hydrochloride was added and stirring was continued for 1 hour. After cooling, the reaction solution was filtered through 255 mesh to obtain 500 g of a base having a polymer weight of about 20% by mass as the weight of the polymer.

5 g of the obtained base was put into a 20 mL volumetric flask, diluted with acetone, and then filtered through a 0.5 μm PTFE membrane filter. When the molecular weight was measured by GPC using the filtrate, the polymerization average molecular weight was 340,000. The GPC measurement conditions are shown below.
Column: α-M + α-M (anion)
Eluent: H ₃ PO ₄ (60 mmol / L) / LiBr (50 mmol /
L) / DMF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration: 5 mg / mL
Sample volume: 100 μL

Synthesis Example 2: Synthesis of component (a-2) In a nitrogen atmosphere, 0.83 parts by weight of the cationized starch obtained in Synthesis Example 12 below in a reaction vessel, polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., GL-05) ) 0.2 parts by weight and 48.7 parts by weight of ion-exchanged water were uniformly dissolved at 90 ° C and then cooled to 60 ° C. To this, 0.3 parts by weight of n-butyl acrylate, 0.2 parts by weight of methyl methacrylate, surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2- 1) 1.68 parts by weight, 2,2′-azobis (2-amidinopropane) previously mixed so that the weight ratio of the components is (weight ratio 31.5 / 0/65 / 3.5) ) 0.03 part by weight of hydrochloride and 19.4 parts by weight of ion-exchanged water were added, and the mixture was heated to 75 ° C. to initiate polymerization. Mix in advance so that the final ratio of methyl methacrylate, n-butyl acrylate, acrylic acid, 2-hydroxyethyl methacrylate (weight ratio 30/64/1/5) is 5 hours after polymerization starts. An aqueous solution prepared by dissolving 16.2 parts by weight of the soot and 0.05 parts by weight of 2,2′-azobis (2-amidinopropane) hydrochloride in 11.9 parts by weight of ion-exchanged water was dropped into the reaction solution. After completion of the dropwise addition, 0.004 part by weight of 2,2′-azobis (2-amidinopropane) hydrochloride was added and stirring was continued for 1 hour. After cooling, the reaction solution was filtered through 255 mesh to obtain a base having a polymer weight of about 20% by mass. The obtained base was concentrated under reduced pressure using an evaporator to obtain 500 g of a base having a polymer weight of about 30% by mass as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 380,000.

Synthesis Example 3: Synthesis of component (a-3) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 0) / 95/0/5) was synthesized in the same manner as in Synthesis Example 1 using what was previously mixed so that 500 g of the base was obtained as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 350,000.

Synthesis Example 4: Synthesis of component (a-4) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 22) 0.5 / 0/75 / 2.5) was synthesized in the same manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 320,000.

Synthesis Example 5: Synthesis of component (a-5) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 0) / 0/75/25) was used in advance, and synthesized in the same manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 320,000.
Synthesis Example 6: Synthesis of Component (a-6) The amount of cationized starch obtained in Synthesis Example 12 below was changed to 1.7 parts by weight, and the base was synthesized by the same method as in Synthesis Example 1. As a result, 500 g was obtained. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 350,000.

Synthesis Example 7: Synthesis of component (a-7) The final ratio of methyl methacrylate, n-butyl acrylate, acrylic acid, and 2-hydroxyethyl methacrylate was (weight ratio 19/75/1/5). In the same manner as in Synthesis Example 1, 500 g of the base was obtained as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 330,000.

Synthesis Example 8: Synthesis of component (a-8) The final ratio of methyl methacrylate, n-butyl acrylate, acrylic acid, and 2-hydroxyethyl methacrylate was (weight ratio 38/56/1/5). In the same manner as in Synthesis Example 1, 500 g of the base was obtained as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 360,000.

Synthesis Example 9: Synthesis of component (a-9) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 98) 0.5 / 0/0 / 1.5) was mixed in the same manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 320,000.

Synthesis Example 10: Synthesis of component (a-10) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 0) / 0/50/50) was used in a similar manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 320,000.

Synthesis Example 11: Synthesis of component (a-11) Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component weight ratio (weight ratio 0) / 100/0/0) was preliminarily mixed and synthesized in the same manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 330,000.

<Synthesis Example of Component (a ′) (Comparative Compound of Component (A))>
Comparative Synthesis Example 1: Synthesis of component (a′-1):
It was synthesized in the same manner as in Synthesis Example 1 so that the final ratio of methyl methacrylate, n-butyl acrylate, acrylic acid, and 2-hydroxyethyl methacrylate was (weight ratio 49/45/1/5). 500 g of the agent was obtained as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 360,000.
Comparative Synthesis Example 2: Synthesis of component (a′-2):
In advance, the weight ratio of the surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component is (weight ratio 0/0/0/100). Using the mixture, it was synthesized in the same manner as in Synthesis Example 1 to obtain 500 g of the base as the weight of the polymer. When the molecular weight was measured by the same method as in Synthesis Example 1, the polymerization average molecular weight was 350,000.

<Synthesis example of component (B)>
Synthesis Example 12
Caustic soda 0.9 g, ion-exchanged water 45 g, and isopropyl alcohol 100 g were placed in a 500 mL four-necked flask equipped with a propeller-type stirring blade, condenser, and thermometer, and the temperature of this solution was adjusted to 25 ° C. The following operation was performed under stirring conditions. 100 g of corn starch (manufactured by Sanwa Starch Co., Ltd.) was added to the solution over 30 minutes. Further, a mixture of 9.7 g of a 20% aqueous solution of caustic soda and 150 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride was charged into a four-necked flask. After the addition, the temperature was raised to 50 ° C. and stirred for 10 hours. Next, the pH of the reaction solution was adjusted to 7 with a 36% aqueous hydrochloric acid solution, and then cooled to 25 ° C. Further, 2.3 g of 36% hydrochloric acid aqueous solution was added, and then the temperature was raised to 40 ° C. and the viscosity of the reaction solution was 50 to 100 mPa.s. Stir until s. Next, the pH of the reaction solution was adjusted to 5.0 with 5% sodium hydroxide aqueous solution. The reaction product was washed twice with isopropyl alcohol / water (mass ratio 50/50) and dried. When the molecular weight was measured by the GPC method, the weight average molecular weight was 972,000. Moreover, N mass% was 0.67 mass%.

[Examples 1 to 19, Comparative Examples 1 to 6]
According to the compounding amounts shown in Tables 3 and 4, the finishing composition for clothing was prepared. Each composition in Table 3.4 is 100% by mass in total. About the obtained composition, according to the below-mentioned evaluation method, the firm feeling (B value) of the cloth and the stain residue at the time of low mechanical force were evaluated. The results are shown in Tables 3 and 4.

<(A) component>
(A-1): Polymer (a-2) obtained in Synthesis Example 1 above: Polymer (a-3) obtained in Synthesis Example 2 above: Polymer (a-4) obtained in Synthesis Example 3 above : Polymer (a-5) obtained in Synthesis Example 4: Polymer (a-6) obtained in Synthesis Example 5: Polymer (a-7) obtained in Synthesis Example 6: Synthesis Example 7 Polymer (a-8) obtained in the above: Polymer (a-9) obtained in Synthesis Example 8 above: Polymer (a-10) obtained in Synthesis Example 9 above: Polymer obtained in Synthesis Example 10 above (A-11): Polymer obtained in Synthesis Example 11

<(A ′) Component: Comparative Compound of Component (A)>
(A′-1): Polymer obtained in Comparative Synthesis Example 1 (a′-2): Polymer obtained in Comparative Synthesis Example 2

<(B) component>
(B-1): Cationized starch obtained in Synthesis Example 12
(N mass% is 0.67 mass%, weight average molecular weight 972,000)

<(C) component>
-(C1) component (c1-1): polyoxyethylene laurate having an average addition mole number of oxyethylene group of 12
Ryl ether (c1-2): polyoxyethylene lauric acid having an average addition mole number of oxyethylene groups of 9
Ruether (c1-3): The average added mole number of oxyethylene group is 3, and the alkyl group has 1 carbon atom.
Polyoxyethylene alkyl derived from 2-14 linear secondary alcohols
ether

-(C2) component (c2-1): polyoxyethylene lauric acid having an average added mole number of oxyethylene groups of 47
Ril ether

<(D) component>
(D-1): Myristyltrimethylammonium chloride
(R ¹ = myristyl group, R ² = methyl group, R ³ = methyl group)
(D-2): Palmityltrimethylammonium chloride
(R ¹ = palmityl group, R ² = methyl group, R ³ = methyl group)
(D-3): Alkyltrimethylammonium chloride
(R ¹ = stearyl group and palmityl group R ² = methyl group, R ³ = methyl group)
(Alkyl group: stearyl group / palmityl group = 70/30 (mass ratio))

<(D ′) Component: Comparative Compound of (D) Component>
(D′-1): Lauryltrimethylammonium chloride
(R ¹ = lauryl group, R ² = methyl group, R ³ = methyl group)

<Method for Preparing Finishing Composition for Clothing>
A 300 mL beaker was charged with ion-exchanged water (temperature: 25 ° C.) in such an amount that the total amount of the finishing composition for clothing was 200 g. (D) component was thrown into this beaker, and after making it melt | dissolve uniformly, it stirred for 10 minutes. Further, the bases (component (A), component (B) and component (C)) obtained in the above synthesis example were added while stirring (300 rpm) with a turbine-type stirring blade having three 2 cm blades. And stirred for 10 minutes.

<A firm evaluation method>
(1) Test cloth piece T / C knit cloth (65% polyester, 35% cotton, air milling F401-F11, manufactured by Masuda Co., Ltd.) 1.8 kg was used using a commercially available liquid detergent (Kao Corporation Attack Biogel). Laundry was repeated 5 times in a two-tank washing machine (Toshiba Corporation, “Ginga VH-360S1”) (detergent concentration 0.083% by mass, using 36 L of tap water (20 ° C.), washing 10 minutes-dehydration 3 minutes-rinsing 8 minutes (rinsing with running water, water volume 15 L / min)).
A washed T / C knit cloth dried in an environment of 25 ° C./50% RH for 12 hours was cut into a 25 × 15 cm square and used as a test cloth piece.

(2) Treatment method 100% by mass of the composition shown in Table 1 is sprayed on the test cloth piece prepared by the above method with respect to the mass when the test cloth is dried using a spray container (T-7500, manufactured by Canyon). , And dried in an environment of 25 ° C./50% RH for 12 hours.
The dried test cloth piece was allowed to stand for 24 hours in a constant temperature and humidity room at 25 ° C. to 65 RH, and the humidity was adjusted. With an automated pure bending tester (KES-FB2-AUTO-A, manufactured by Kato Tech Co., Ltd.), bending deformation rate: 0.5 cm ^-1 / sec, the maximum pole ratio: ± 2.5 cm ^-1, fabric orientation: in the warp direction of the condition, curvature of fabric at 0.5 to 1.5 cm ^-1 The bending stiffness (B value) was measured.
After the pretreatment, the test cloth piece treated with only tap water without using the composition and similarly conditioned in a constant temperature and humidity room of 25 ° C.-65 RH was used as a control product. The difference (ΔB value) was calculated by the following formula.
The texture preferably has a ΔB value of 0.1 or less, and more preferably 0.07 or less. When the ΔB value is out of this range, a large numerical value indicates that it is hard, and a small numerical value indicates that there is no elasticity, and it can be evaluated that a supple texture is not expressed.
△ B value (gf · cm ² / cm) = (Bending stiffness of the composition-treated product) – (Bending stiffness of the target product)

<Stain residue test method>
(Preparation of spot reference sample 1.5)
50 ml of 20 ° C. tap water was placed in a 500 ml sampler cup (manufactured by Sampler Tech Co., Ltd.) and placed on a shaker (Tokyo Rika Kikai Co., Ltd. MMS-310). To a 6 cm × 6 cm test cloth (Sakai Obex Co., Ltd. non-pachi twill (90% polyester, 10% cotton) GMC900 color G18), 0.3 g of a sample obtained by diluting (a-1) the polymer with tap water was applied 1 Left to stand. After standing still, it was gently put into a 500 ml sampler cup placed on a shaker, and swirling was performed at 50 rpm for 5 minutes. After 5 minutes, the test cloth was attached to the dewatering layer of a two-tank washing machine and dehydrated for 10 seconds. After dehydration, it was dried for 24 hours in an environment of 25 ° C./50% RH.

(Preparation of spot reference sample 2)
50 ml of 20 ° C. tap water was placed in a 500 ml sampler cup (manufactured by Sampler Tech Co., Ltd.) and placed on a shaker (Tokyo Rika Kikai Co., Ltd. MMS-310). 0.15 g of the polymer (a-1) was applied to a 6 cm × 6 cm test cloth (Sakai Obex Co., Ltd. Non-Pachi Twill GMC900 color G18), and allowed to stand for 1 minute. After standing still, it was gently put into a 500 ml sampler cup placed on a shaker, and swirling was performed at 50 rpm for 5 minutes. After 5 minutes, the test cloth was attached to the dewatering layer of a two-tank washing machine and dehydrated for 10 seconds. After dehydration, it was dried for 24 hours in an environment of 25 ° C./50% RH.

(Preparation of spot reference sample 3)
50 ml of 20 ° C. tap water was placed in a 500 ml sampler cup (manufactured by Sampler Tech Co., Ltd.) and placed on a shaker (Tokyo Rika Kikai Co., Ltd. MMS-310). 0.3 g of the polymer (a-1) was applied to a 6 cm × 6 cm test cloth (Sakai Obex Co., Ltd. Non-Pachi Twill GMC900 color G18), and allowed to stand for 1 minute. After standing still, it was gently put into a 500 ml sampler cup placed on a shaker, and swirling was performed at 50 rpm for 5 minutes. After 5 minutes, the test cloth was attached to the dewatering layer of a two-tank washing machine and dehydrated for 10 seconds. After dehydration, it was dried for 24 hours in an environment of 25 ° C./50% RH.

(Stain remaining evaluation method)
50 ml of 20 ° C. tap water was placed in a 500 ml sampler cup (manufactured by Sampler Tech Co., Ltd.) and placed on a shaker (Tokyo Rika Kikai Co., Ltd. MMS-310). 0.3 g of Examples 1 to 19 or Comparative Examples 1 to 6 were applied to a 6 cm × 6 cm test cloth (Sakai Obex Co., Ltd. Non-Pachi Twill GMC900 color G18) and allowed to stand for 1 minute. After standing still, it was gently put into a 500 ml sampler cup placed on a shaker, and swirling was performed at 50 rpm for 5 minutes. After 5 minutes, the test cloth was attached to the dewatering layer of a two-tank washing machine and dehydrated for 10 seconds. After dehydration, it was dried for 24 hours in an environment of 25 ° C./50% RH. After drying, the stain level was evaluated by comparing with the following reference samples 1 to 3 and scoring according to the following criteria to obtain an average score. The evaluation was performed by 10 judges who were engaged in the evaluation of the appearance of the fabric for 5 years or more.
The stain level is 1.5 or less, more preferably less than 1.5.

(Judgment criteria)
Spot level 1: No stain left (new test cloth)
Blemish level 1.5: There is a slight blemish residue that can be barely seen by very close observation
(Reference sample 1.5)
Blemish level 2: Slightly blemish remains (reference sample 2)
Spot level 2.5: between the appearances of reference samples 2 and 3, but rather the reference sun
Close to pull 3. The remaining stain can be confirmed.
Spot level 3: The remaining spot can be easily confirmed (reference sample 3).

  From the above results, the finishing agent for clothing according to the present invention is a clothing finishing agent composition capable of suppressing a decrease in supple texture due to washing and wearing of clothing, particularly textile products such as knits. It is possible to provide a garment finish composition that does not cause stains on clothes even in washing.

Claims (8)

Polymer (A), cation containing 70 to 100% by mass of a structural unit derived from (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms, and having a glass transition temperature of −40 ° C. or higher and lower than 0 ° C. It contains a modified starch (B), a nonionic surfactant (C), a cationic compound (D) represented by the following general formula (1), and water, and the component (C) has 8 to 16 carbon atoms. A nonionic surfactant (C1) having a hydrocarbon group and a polyoxyalkylene chain having an average addition mole number of an oxyalkylene group having 2 to 4 carbon atoms of 3 to 15, A finishing composition for clothing having a mass ratio [(A) / (D)] of A) of 5 to 50.
_{^{R 1 R 2 R 3 2 N}} + · X - (1)
(In the formula, R ¹ represents a hydrocarbon group having 14 to 20 carbon atoms, R ² represents a substituent defined by R ¹ or R ³ , and R ³ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group. And a hydroxyalkyl group having 2 to 4 carbon atoms, and X ⁻ represents an anion.)   The oxyalkylene group of the component (C1) is an oxyethylene group or a combination of an oxyethylene group and an oxypropylene group, the average addition mole number is 4 to 14, and the average addition mole number of the oxypropylene group is 0 to 3. The finishing composition for clothing according to claim 1, wherein the average added mole number of oxyethylene groups is 4-14.   A nonionic surfactant (C2) having a hydrocarbon group having 8 to 16 carbon atoms and a polyoxyalkylene chain having an average addition mole number of 2 to 4 carbon atoms having 30 to 70 carbon atoms, The finish composition for clothing according to claim 1 or 2.   The finishing composition for clothing according to claim 3, wherein the oxyalkylene group of the component (C2) is an oxyethylene group, and the average number of added moles is 35 to 65.   The finishing composition for clothing according to claim 3 or 4, wherein the mass ratio [(C1) / (C2)] of the (C1) component to the (C2) component is 0.5 to 50.   (C) Finishing agent composition for clothes in any one of Claims 1-5 whose HLB of a component is 12-20.   The finishing composition for clothing according to any one of claims 1 to 6, wherein the clothing is knit clothing.   The processing method of the clothing which makes the (A) component of the finishing composition for clothing in any one of Claims 1-7 contact in a water bath so that it may become 0.1-1 mass% with respect to the mass of clothing. .