JP2015101801A - Finishing agent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a finishing agent composition for clothing capable of preventing generation of irregular fuzz or hairball of fiber products such as clothing and having no adhesion of aggregates to the fiber products using a holding part for the finishing agent of a washing machine, and a treatment method of clothing using the finishing agent composition for clothing.SOLUTION: There is provided a finishing agent composition for clothing containing 70 mass% to 100 mass% of a constitutional unit derived from (meth)acrylic acid ester having an alkyl group having 1 to 16 carbon atoms (a1), a polymer having a glass transition temperature of -40°C or more and less than 0°C, cationic starch (B), non-ionic surfactant (C) and water where the (C) component has a polyoxyalkylene addition type non-ionic surfactant having at least one hydrocarbon group having 8 to 16 carbon atoms and average 3 mol to 15 mol of oxyalkylene group added (c1) and the content of the (c1) component is 5.5 pts.mass to 15 pts.mass based on 100 pts.mass of the (A) component and obtained by a manufacturing method including a process I and a process II. There is also provided a treatment method of clothing containing the finishing agent composition for clothing.

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 with a cloth such as a sheet or a Y-shirt which is a target clothing of the paste composition. Knitwear is made up of a knit knitting method using a yarn in which single fibers are sweetly twisted compared to a fabric. Knit knitting gives a supple texture to the entire garment because the yarn and the single fibers that make up the yarn are easy to move.

  The apparel is made of yarn, and the yarn is made of monofilament. The clothing rubs against each other due to use or wear, and the clothing rubs against an object other than clothing such as a chair, thereby causing fuzz and fluff. Further, when the fluff and fluff are generated, irregularities are generated on the surface, and when the irregularities are exposed to light, shadows are generated, so that the color of the clothing looks dull, which is not aesthetically pleasing. In particular, when pills are generated, shadows are prominently generated, which increases aesthetic issues.

  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 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 cationized starch may coexist at the time of polymerization, or may be added after the completion of polymerization.
Patent Documents 3 to 5 include a polymer having a (meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms as a structural unit, a glass transition temperature of −40 ° C. or more and less than 0, and a cationized starch. Disclosed finish compositions are disclosed.

JP 2008-248432 A JP-A-3-260174 JP 2013-151663 A JP2013-151775A JP 2013-151776 A

The present inventors have found that a new problem exists in a finishing composition for clothing that can suppress the occurrence of fluffing and fluffing of clothing.
That is, in a garment finishing composition capable of suppressing the occurrence of fluffing and fluffing of clothing, washing is carried out while being diluted with contact with water having a specific alkalinity in the finishing agent holding part of the washing machine. By flowing into the tank, a part of the garment finish composition aggregates and adheres to the textile product, resulting in an aesthetically unfavorable appearance.

  The present invention is a garment finish composition capable of suppressing the occurrence of fluff and fluff in textile products such as clothing, and the aggregates do not adhere to the textile product when the finisher holding part of a washing machine is used. It is an object of the present invention to provide a finishing composition for clothing and a method for treating clothing using the finishing composition for clothing.

The present inventors have found that the above-mentioned problem is caused by anions such as carbonate ions (CO ₃ ²⁻ ) and hydrogen carbonate ions (HCO ₃ ⁻ ) in water, which cause carbonate alkalinity. 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 repelling the electric charge is weakened, and the polymer particles are easily aggregated by the water flow at the time of dilution. As a result, it is considered that the aggregate of the finishing composition for clothing easily adheres to the fiber product.
Furthermore, the present inventors have found that another cause is the physical properties of the polymer. Specifically, 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 soft physical properties, and the polymer exhibiting the soft physical properties aggregates with cationized starch. Therefore, it was considered that the aggregates easily adhere to the fiber product. From the above findings, the present inventors have reached the present invention.

That is, the present invention provides the following [1] and [2].
[1] 70% by mass or more and 100% by mass or less of a structural unit derived from a (meth) acrylic acid ester (a1) having an alkyl group having 1 to 16 carbon atoms, and a glass transition temperature of −40 ° C. or higher. And a polymer (A) that is less than 0 ° C., a cationized starch (B), a nonionic surfactant (C), and water, and the component (C) is a hydrocarbon having 8 to 16 carbon atoms A polyoxyalkylene addition type nonionic surfactant (c1) having at least one group and having an oxyalkylene group added in an average of 3 mol or more and 15 mol or less, and (c1) relative to 100 parts by mass of component (A) ) A finish composition for clothing having a component content of 5.5 parts by mass or more and 15 parts by mass or less, and obtained by a production method having the following steps I and II.
Step I: Step of preparing a solution by adding cationized starch (B) and nonionic surfactant (C) to an aqueous solvent Step II: (A) for the solution obtained in Step I A step of performing emulsion polymerization by adding a monomer constituting the component and a polymerization initiator, and performing emulsion polymerization by adjusting the pH of the solution to 5.5 or more and 8.5 or less

[2] A method for treating clothing having the following steps 1 to 4.
Process 1: The process of hold | maintaining the said finishing composition for clothing in the finishing agent holding | maintenance part of a washing machine.
Step 2: Water having a carbonate alkalinity of 10 ° C. or more and 60 ° C. or less is added to the finish holding unit for holding the clothing finish composition, and the clothing finish composition and water The step of contacting.
Process 3: The process of putting the said finishing composition for clothes in a finishing agent holding part into a washing tub after the process 2.
Process 4: The process which makes the finishing composition for clothing and clothing contact in the water bath in a washing tub.

  The garment finish composition of the present invention is a garment finish composition that can suppress the occurrence of fuzz and pills in textile products such as garments. It is possible to provide a finishing composition for clothing that does not adhere to an object and a method for treating clothing using the same.

[Clothing finishing composition]
The finishing composition for clothing of the present invention contains 70% by mass or more and 100% by mass or less of a structural unit derived from a (meth) acrylic acid ester (a1) having an alkyl group having 1 to 16 carbon atoms, and It contains a polymer (A) having a glass transition temperature of −40 ° C. or higher and lower than 0 ° C., a cationized starch (B), a nonionic surfactant (C), and water. A polyoxyalkylene-added nonionic surfactant (c1) having at least one hydrocarbon group of 8 or more and 16 or less and having an oxyalkylene group added in an average of 3 mol or more and 15 mol or less; ) A finishing composition for clothing in which the content of component (c1) is from 5.5 parts by weight to 15 parts by weight with respect to 100 parts by weight of component, and is obtained by a production method having the following steps I and II. Finish for clothing Composition.
Step I: Step of preparing a solution by adding cationized starch (B) and nonionic surfactant (C) to an aqueous solvent Step II: (A) for the solution obtained in Step I A step of performing emulsion polymerization by adding a monomer constituting the component and a polymerization initiator, and performing emulsion polymerization by adjusting the pH of the solution to 5.5 or more and 8.5 or less

The garment finish composition of the present invention can suppress the occurrence of fluff and fluff of textile products such as garments, and is also used in textile products when using the finishing agent holding part of a washing machine. The aggregate is not attached.
In the present specification, “(meth) acrylic acid ester” means “acrylic acid ester, methacrylic acid ester, or a mixture thereof”.
Further, in this specification, “fluffing” means a state in which the single fiber is pulled by friction and the single fiber comes off from the yarn (visually, the single fiber protrudes from the surface of the yarn) or wear. Means that the single fiber is cracked and the fiber pieces are peeled off from the surface of the single fiber.
In addition, the “fluff” is a state in which single fibers that have fallen out of the clothing are entangled, become a ball and are reattached to the clothing, a state in which the fluff on the fiber is tangled and become a ball, or a thread The fiber piece which has started to peel off from the single fiber which constitutes is entangled on the fiber to form a ball shape.
Further, in the present specification, the “finishing agent holding part” refers to a section where water is injected at the timing when the finishing agent is introduced in the washing process, and the name varies depending on the manufacturer, but the “finishing agent inlet” Also called. Specifically, it is provided in the “detergent case” or “detergent case” provided in the washing machine, the “softening agent input”, the “soft finish agent” input section, or the washing machine. Refers to an input section labeled "softener input case" or the like.

<Polymer (A)>
The polymer (A) in the present invention contains 70% by mass or more of a structural unit derived from a (meth) acrylic acid ester (hereinafter, also referred to as “monomer (a1)”) having an alkyl group having 1 to 16 carbon atoms. It is a polymer having a glass transition temperature of -40 ° C or higher and lower than 0 ° C.
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 one type is selected if the polymer (A) satisfies the glass transition temperature. It may be used alone or in combination of two or more.
In the present invention, the “(meth) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms” is a (meth) acrylic acid alkyl ester, wherein the alkyl group has 1 to 16 carbon atoms. A compound that is an alkyl group.
The alkyl group may be linear or branched, including n-isomer, sec-isomer, tert-isomer, and iso-isomer.

In the case of using an acrylate ester, the number of carbon atoms of the alkyl group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 12 from the viewpoint of easy adjustment of the glass transition temperature. Below, more preferably 10 or less, still more preferably 8 or less.
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.

In the case of using a methacrylic acid ester, the number of carbon atoms of the alkyl group is preferably 1 or more, and preferably 8 or less, more preferably 4 or less, and further preferably 2 from the viewpoint of easy adjustment of the glass transition temperature. It is as follows.
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 ester which has a C2-C6 alkyl group, C1-C1, It is more preferable to use a methacrylic acid ester having an alkyl group of 2 or less and an acrylic acid ester having an alkyl group having 3 or more and 5 or less carbon atoms, and a combined use of methacrylic acid methyl ester and acrylic acid n-butyl ester. Further preferred.
In the case where methacrylic acid ester and acrylic acid ester are used in combination, the ratio of acrylic acid ester (a1-2) to the total of methacrylic acid ester (a1-1) and acrylic acid ester (a1-2) is (A) From the viewpoint of adjusting the glass transition temperature of the component within the above range, it is preferably 55% by mass or more, more preferably 56% by mass or more, and preferably 99% by mass or less, more preferably 80% by mass or less.
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 homopolymer values described in the above are 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 is calculated according to the following formula (I). However, the numbers after the decimal point are rounded off, and when the copolymer contains a polyfunctional monomer, the calculation is performed for the monomer excluding the polyfunctional monomer.

(In the formula (I), 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 (This is the mass fraction of the monomer (i) constituting the copolymer.)

  (A) The glass transition temperature (Tg) of a component is -40 degreeC or more and less than 0 degreeC. When the glass transition temperature (Tg) is less than −40 ° C. or 0 ° C. or more, fluff generated in clothing during wearing or the like cannot be suppressed. In addition, when the glass transition temperature (Tg) is 0 ° C. or higher, fuzz generated in the clothing during wearing or the like cannot be suppressed, and the supple texture of the clothing may be impaired.

  From the viewpoint of suppressing the occurrence of fluff, the glass transition temperature (Tg) is preferably −30 ° C. or higher, more preferably −25 ° C. or higher, still more preferably −20 ° C. or higher, and preferably −5 ° C. or lower. More preferably, it is -8 degrees C or less, More preferably, it is -10 degrees C or less. Moreover, from the viewpoint of preventing the finish composition for clothing from remaining at the finisher inlet of the fully automatic washing machine, the glass transition temperature (Tg) of the component (A) is more preferably −25 ° C. or higher, − 5 ° C. or lower.

The polymer (A) contains 70% by mass or more and 100% by mass or less of the monomer (a1). Generation | occurrence | production of the fluff of clothing can be suppressed as content of a monomer (a1) exists in the said range. From the viewpoint of suppressing the occurrence of fluff in clothing, the content of the monomer (a1) in the polymer (A) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and Preferably, it is 98 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 94 mass% or less.
The content is a ratio of the structural unit derived from the monomer (a1) to the polymer (A), and can be determined from a blending ratio of the monomer (a1) at the time of polymerization. The same applies to the monomer (a2) and the monomer (a3) described later.
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), a (meth) acrylic acid ester having a hydroxyalkyl group having 2 to 4 carbon atoms is used. By using the monomer (a2), the component (A) adhering to the clothes can be easily detached from the clothes at the time of washing, and the finish composition remains in the holding part of the finish composition of the washing machine. (Hereinafter also referred to as “preventing liquid residue”).
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. It means the following.
From the viewpoint of further improving the detachability of the component (A) from the clothing in the washing step (meaning that the component (A) is easily detached from the clothing) and preventing the liquid residue, A hydroxyalkyl group having 2 or more and 3 or less is preferable, and a hydroxyethyl group having 2 carbon atoms is more preferable.

Specific examples of the acrylic acid hydroxyalkyl ester 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 the detachment of the component (A) from the clothing and the prevention of liquid residue.

  The proportion of the structural unit derived from the monomer (a2) in the component (A) is preferably 1% by mass or more from the viewpoint of improving detachability from the clothing of the component (A) and preventing liquid residue. More preferably 2% by mass or more, further preferably 3% by mass or more, still more preferably 4% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass. Hereinafter, it is more preferably 7% by mass or less.

<Monomer (a3)>
As the monomer (a3), at least one monomer selected from ethylenically unsaturated carboxylic acids and salts thereof is used. In the present invention, “ethylenically unsaturated carboxylic acid” refers to a compound having a vinyl group and a carboxylic acid group in the molecule.
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 liquid residue.

Examples of ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of availability of raw materials, and acrylic acid is more preferable.
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 and 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 0.1% by mass or more, more preferably from the viewpoint of improving detachment from clothes and preventing liquid residue. 0.3% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably. It is 2 mass% or less, More preferably, it is 1.5 mass% or less.
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 or more, more preferably 100,000 or more, still more preferably 200,000 or more, still more preferably 300,000 or more, and preferably 500,000 or less. More preferably, it is 450,000 or less, More preferably, it is 400,000 or less.
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.

<Cationized starch (B)>
In the present invention, 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, the cationized starch (B) ( Hereinafter, it is also referred to as “component (B)”.
As the starches forming the main skeleton of the cationized starch, starches described in JP 2010-180320 A and the like 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 starches with 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% by mass or more and 1.5% by mass or less. ) From the viewpoint of further enhancing the adsorptivity of the component to the clothing, it is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.5% by mass or more, and preferably 1 .3% by mass or less, more preferably 1% by mass or less, still more preferably 0.9% by mass or less, and still more preferably 0.8% by 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 component (B) is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 500,000 or more, and still more preferably, from the viewpoint of suppressing generation of fuzz and fluff. Is 800,000 or more, preferably 1.9 million or less, more preferably 1.7 million or less, still more preferably 1.5 million or less, still more preferably 1.3 million or less, still more preferably 1.1 million or less, and even more preferably 100 10,000 or less.

<Nonionic surfactant (C)>
(Nonionic surfactant (c1))
In the present invention, from the viewpoint of improving the dispersion stability when the component (A) is diluted, the nonionic surfactant (C) (hereinafter also referred to as “component (C)”) has 8 or more carbon atoms, A polyoxyalkylene-added nonionic surfactant (c1) having at least one hydrocarbon group of 16 or less and having an oxyalkylene group added in an average of 3 mol or more and 15 mol or less is used.
As the surfactant (c1), from the viewpoint of dispersion stability when the component (A) is diluted, the surfactant (c1) has at least one aliphatic hydrocarbon group having 8 to 16 carbon atoms and an average of 3 oxyalkylene groups. Preference is given to polyoxyalkylene alkyl ethers added in an amount of from 15 to 15 mol.
From the viewpoint of improving the dispersion stability when the component (A) is diluted, the carbon number of the hydrocarbon group of the component (c1) is preferably 10 or more, more preferably 11 or more, and preferably 15 or less. More preferably, it is 14 or less, and the average added mole number of the oxyalkylene group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 14 or less, more preferably 13 or less, More preferably, it is 12 or less.

As the preferred surfactant (c1), the oxyalkylene group is an oxyethylene group or a combination of an oxyethylene group and an oxypropylene group, the average number of added moles is 3 or more and 15 or less, and the oxypropylene group The average number of moles added is 0 or more and 2 or less, and the average number of moles added of the oxyethylene group is 3 or more and 15 or less.
In addition, the component (c1) is preferably used in combination of two or more different types from the viewpoint of improving the dispersion stability when the component (A) is diluted. From the viewpoint of the effect of reducing the viscosity of the composition, the branched alkyl It is preferable to use together a polyoxyalkylene alkyl ether having a group and a linear alkyl group. In the present specification, the branched alkyl group also includes an alkyl group derived from a secondary alcohol.
As a specific example, a polyoxyethylene alkyl ether having a linear alkyl group having 12 carbon atoms and having an average addition mole number of oxyethylene group of 8 or more and 12 or less, and a second compound having 12 or more and 14 or less carbon atoms. It is preferable to use a polyoxyethylene alkyl ether having a secondary alkyl group and having an average addition mole number of oxyethylene group of 5 or more and 7 or less.

(Nonionic surfactant (c2))
In the present invention, from the viewpoint of improving the emulsion stability of the component (A), it has at least one hydrocarbon group having 8 to 16 carbon atoms, and an average of 30 to 70 mol of oxyalkylene group is added. The polyoxyalkylene addition type nonionic surfactant (hereinafter also referred to as “component (c2)”) may be used together with the component (c1). By using the nonionic surfactant (c2), the dispersion stability when the component (A) is diluted is improved, and the emulsion stability during polymerization and the dispersion stability after storage are also improved.
As the nonionic surfactant (c2), from the viewpoint of emulsion stability of the component (A), it has at least one hydrocarbon group having 8 or more and 16 or less carbon atoms, and an average of 30 moles or more of oxyalkylene groups. , Polyoxyalkylene addition type nonionic surfactant added with 70 mol or less is preferable.

  From the viewpoint of emulsion stability, the carbon number of the hydrocarbon group is preferably 10 or more, more preferably 11 or more, and preferably 15 or less, more preferably 14 or less, and the average addition mole of the oxyalkylene group. The number is preferably 35 or more, more preferably 40 or more, still more preferably 42 or more, and is preferably 65 or less, more preferably 60 or less, and even more preferably 52 or less. An ethylene group is preferred.

  The mass ratio [(c1) / (c2)] of the component (c1) to the component (c2) is preferably 2 or more and 50 or less from the viewpoint of the emulsion stability and dilution dispersibility of the component (A). Furthermore, from the viewpoint of emulsion stability of the component (A), the mass ratio [(c1) / (c2)] is preferably 48 or less, more preferably 45 or less, still more preferably 40 or less, and still more preferably 35 or less. More preferably, it is 30 or less. In addition, from the viewpoint of dilution dispersibility of the component (A), the mass ratio [(c1) / (c2)] is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and still more preferably 15 or more. , More preferably 20 or more, and still more preferably 25 or more.

The component (C) of the present invention preferably has an HLB of 12 or more and 15 or less from the viewpoint of emulsion stability and dilution dispersibility of the component (A). In addition, when using two types of surfactant as (C) component in this specification, let the average value which considered the mass be HLB.
From the viewpoint of emulsion stability of the component (A), the HLB of the component (C) is preferably 14.5 or less, more preferably 14 or less. In addition, from the viewpoint of dilution dispersibility of the component (A), the HLB of the component (C) is preferably 12.5 or more, more preferably 13 or more. The HLB value can be obtained by the Griffin method.

<Method for producing a finishing composition for clothing>
The finishing composition for clothing of the present invention is produced by a production method having the following step I and step II. By producing by this method, a composition having excellent dilution stability can be obtained.

[Step I]
Step I is a step of preparing a solution by adding the cationized starch (B) and the nonionic surfactant (C) to the aqueous solvent.
As the aqueous solvent, water is preferable. Examples of water include distilled water, ion exchange water, and ultrapure water.
In addition, an organic solvent compatible with water may be added as long as the emulsion state during the emulsion polymerization in Step II is not broken. Examples of the organic solvent include alcohols having 2 or 3 carbon atoms such as methanol, ethanol, and isopropyl alcohol, and ketones having 3 or 4 carbon atoms such as acetone and methyl ethyl ketone.
The addition amount of the organic solvent is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and preferably 10 parts by mass or less, based on 100 parts by mass of water. Preferably it is 5 mass parts or less.

In Step I, the order of addition of the cationized starch (B) and the nonionic surfactant (C) to the aqueous solvent is not particularly limited, but the cationized starch (B) is dispersed and suspended or dissolved in the aqueous solvent. Then, it is preferable to add a nonionic surfactant (C). In addition, it is preferable to heat when the cationized starch (B) is dispersed and suspended or dissolved.
The cationized starch (B) and the nonionic surfactant (C) may be added all at once, or may be added by dividing or dropping. When adding the cationized starch (B) and the nonionic surfactant (C), it is preferable to add them while stirring the system. Stirring is preferably performed at a speed that does not cause shear aggregation due to shearing of the cationized starch (B).

  Although there is no particular limitation on the temperature at the time of dissolution of the cationized starch (B), it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of dissolution rate and equipment load. And preferably it is 120 degrees C or less, More preferably, it is 110 degrees C or less, More preferably, it is 100 degrees C or less.

[Step II]
Step II is a step of performing emulsion polymerization by adding the monomer constituting the component (A) and a polymerization initiator to the solution obtained in Step I, and the pH of the solution is 5.5 or more, 8 It is a step of adjusting the viscosity to 5 or less and performing emulsion polymerization of the monomer constituting the component (A).
In the present invention, by adjusting the pH of the solution obtained in step I, the interaction between the component (A) and the component (B) can be increased, and the dilution stability of the resulting polymer can be increased.
In Step II, it is preferable to carry out emulsion polymerization in a solution with controlled pH, and the pH of the solution is preferably controlled using a pH adjuster before the start of emulsion polymerization in Step II.
That is, in step II, it is preferable to adjust the pH of the solution to 5.5 or more and 8.5 or less before adding the polymerization initiator to the solution.
From the viewpoint of increasing the dilution stability of the resulting polymer, the pH during the emulsion polymerization in Step II is preferably 5.5 or more, more preferably 6.0 or more, and still more preferably 6.5 or more, and , Preferably 8.5 or less, more preferably 8.0 or less, still more preferably 7.5 or less.

Examples of the pH adjuster include phosphate buffer, sodium phosphate, sodium hydrogen phosphate, phosphoric acid, sodium citrate carbonate, and sodium bicarbonate. A pH adjuster may be used individually by 1 type, and may be used in combination of 2 or more type.
When using a pH adjuster, the addition time is not particularly limited as long as it is before the start of emulsion polymerization in Step II. In addition, pH of the solution in this invention means the value which measured the solution before the addition of the monomer which comprises (A) component using a pH meter at 20 degreeC.

  Examples of the polymerization initiator used in Step II include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2-amidinopropane). ) Known radical polymerization of azo compounds such as hydrochloride, organic peroxides such as tert-butylperoxyoctoate and dibenzoyl peroxide, inorganic oxides such as sodium persulfate, potassium persulfate and ammonium persulfate An agent can be used. Of these polymerization initiators, azo compounds are preferred. A polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

When using an organic peroxide as a polymerization initiator, it is preferable to use it from the middle of the polymerization from the viewpoint of keeping the viscosity of the reaction mixture during the polymerization of the present invention low.
The amount of the polymerization initiator used is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and still more preferably 0 with respect to 100 parts by mass of the total amount of monomers constituting the component (A). 0.05 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less.

In step II, the method for adding the monomer constituting component (A) to the solution obtained in step I is not particularly limited, and each monomer may be added individually or simultaneously, or both in advance. May be mixed and added. In addition, the monomer and the polymerization initiator constituting the component (A) may be added to the solution all at once, or may be added by a method such as splitting or dropping, but dropping from the viewpoint of copolymerization composition and conversion rate. It is preferable to do so.
The order of addition of the monomer constituting the component (A) and the polymerization initiator is not particularly limited, and the addition of the polymerization initiator may be before or after the addition of the monomer constituting the component (A), or It may be simultaneous.

  The temperature of emulsion polymerization in Step II is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 60 ° C. or higher, and preferably from the viewpoint of emulsion polymerization speed and emulsion state stability. 100 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower.

The polymerization time for emulsion polymerization is preferably 1.5 hours or more, more preferably 2 hours or more, still more preferably 2.5 hours or more, more preferably 3 hours, from the viewpoint of sufficient polymerization and productivity. More preferably, it is 10 hours or less, more preferably 7 hours or less, and even more preferably 6 hours or less.
The emulsion polymerization is preferably performed with stirring. The faster the stirring speed, the smaller the particle size of the polymer can be obtained. However, when the stirring speed is excessively increased, shear aggregation occurs. The emulsion polymerization is preferably carried out with stirring at a speed that does not cause shear aggregation.
It is preferable from the viewpoint of reducing the residual monomer amount that a polymerization initiator is further added after the emulsion polymerization.

<Content of each component>
The content of the component (A) in the garment finishing composition is preferably 1% by mass or more and 50% by mass or less, and the amount of the garment finishing composition used per wash is reduced. Therefore, it is more preferably 5% by mass or more, further preferably 8% by mass or more, and still more preferably 10% by mass or more. In addition, the content of the component (A) in the garment finish composition is more preferably 35% by mass or less, still more preferably 25% by mass or less, and still more preferably, from the viewpoint of reducing adhesion to the finisher inlet. Preferably it is 20 mass% or less.
The amount of component (B) relative to 100 parts by weight of component (A) is preferably 2 parts by weight or more, more preferably 2.5 parts by weight or more, from the viewpoint of emulsion stability and dilution dispersibility of component (A). Preferably it is 3 parts by mass or more, more preferably 4 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 20 parts by mass or less. More preferably, it is 15 parts by mass or less, and still more preferably 10 parts by mass or less.

In this invention, the quantity of (c1) component with respect to 100 mass parts of (A) component is 5.5 mass parts or more and 15 mass parts or less. When the amount of the component (c1) relative to the component (A) is within the above range, the dilution stability of the component (A) is further improved. From the viewpoint of improving the dilution stability, the amount of the component (c1) relative to the component (A) is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 8 parts by mass or more, and preferably Is 14 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 12 parts by mass or less, still more preferably 11 parts by mass or less, and still more preferably 10 parts by mass or less.
The amount of the component (C) containing (c1) with respect to 100 parts by mass of the component (A) is preferably 5.5 parts by mass or more, more preferably 8 from the viewpoint of the emulsion stability and dilution dispersibility of the component (A). It is at least 10 parts by mass, more preferably at least 10 parts by mass, and preferably at most 30 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 15 parts by mass.

  In addition, the garment finish composition of the present invention is a cationic surfactant having a hydrocarbon group having 8 to 18 carbon atoms from the viewpoint of reducing the adhesion of the component (A) to the finishing agent inlet. It is preferable to contain an agent (hereinafter also referred to as “component (D)”). When the carbon number exceeds 18, the effect of suppressing fluff and fluff is reduced, so the carbon number of the hydrocarbon group is preferably 8 or more, and preferably 14 or less, more preferably 12 or less. Specific examples include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, and the like.

  The amount of the component (D) relative to 100 parts by mass of the component (A) is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, and still more preferably from the viewpoint of suppressing generation of fuzz and fluff. 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 25 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less. is there.

Moreover, the finishing composition for garments of the present invention is an alcohol having 2 or more and 6 or less carbon atoms and 6 or less carbon atoms (hereinafter also referred to as “component (E)”) from the viewpoint of enhancing storage stability. It is preferable to contain. Specific examples include ethylene glycol, propylene glycol, glycerin and sorbitol.
Furthermore, arbitrary components, such as a fragrance | flavor, dye, an antifoamer, an antibacterial agent, a disinfectant, antioxidant, a chelating agent, and an antiseptic | preservative, can be used as needed.
As described above, the finish composition for clothing of the present invention can suppress the occurrence of fuzz and fluff of textile products such as clothing, and aggregates are formed on the textile product when using the finisher inlet of a washing machine. Since it does not adhere, it can be suitably used for finishing knit clothing.
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]
The processing method of the clothing of this invention has the following process 1-process 4.
Process 1: The process of hold | maintaining the said finishing composition for clothing in the finishing agent holding | maintenance part of a washing machine.
Step 2: Water having a carbonate alkalinity of 10 ° C. or more and 60 ° C. or less is added to the finish holding unit for holding the clothing finish composition, and the clothing finish composition and water The step of contacting.
Process 3: The process of putting the said finishing composition for clothes in a finishing agent holding part into a washing tub after the process 2.
Process 4: The process which makes the finishing composition for clothing and clothing contact in the water bath in a washing tub.

Process 1: The process of hold | maintaining the finishing composition for clothing of the said invention in the finishing agent holding | maintenance part of a washing machine.
The amount of the garment finishing composition of the present invention charged into the finishing agent holding part is generally 2 g or more and 80 g or less, preferably 5 g or more from the viewpoint of easily realizing the effect of the present invention. More preferably, it is 10 g or more, preferably 60 g or less, more preferably 50 g or less.

In step 2, water having a carbonate alkalinity of 10 ° C. or more and 60 ° C. or less is introduced into the finish holding portion of the washing machine holding the clothing finish composition. This is a step of bringing an object into contact with water.
In step 2, the finish composition for clothing present in the finish holding part and the water may be brought into contact with each other uniformly, and a part of the finish composition for clothing and a part of water are brought into contact with each other. You may make it make it. The flow rate of water charged into the finishing agent inlet is preferably 0.5 L / min or more and 4 L / min or less.
Moreover, if the carbonate alkalinity of water is 10 degrees or more and 60 degrees or less, the effect of the present invention can be enjoyed. In addition, carbonate alkalinity in this specification means the value measured in accordance with the following method.

<Measurement method of carbonate alkalinity>
Take 100 ml of test water in a 200 ml beaker and add 0.15 ml of bromocresol green-methyl red / ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) as an indicator. While stirring this solution with a magnetic stirrer and a rotor (length 30 mm, diameter 8 mm) (rotation speed 200 rpm), titration is performed with 10 mmol / l sulfuric acid until the color of the solution changes from blue to reddish purple. The carbonate alkalinity is calculated by the following formula.
Carbonate alkalinity (degree) = a × 10
(A is the amount (ml) of 10 mmol / l sulfuric acid required for titration. In the above formula, 1 degree means 1 CaCO ₃ mg / l.)

Step 3 is a step of putting the garment finish composition in the finish holding part into the washing tub after Step 2.
After step 2 means after the first contact of the garment finish composition present in the finish holding part and water in step 2.
In this step 3, it is preferable that the garment finish composition is poured into the washing tub by further adding water to the finish holding section where the garment finish composition is present.

Step 4 is a step of bringing the garment finish composition into contact with the garment in the water bath in the washing tub.
The amount of water in the washing tub can generally be determined by the bath ratio. The “bath ratio” in the present specification refers to a ratio between the mass of clothing and the volume of water, a value represented by [volume of water (liter)] / [mass of clothing (kg)].
When the bath ratio is small, fluff and fluff are likely to occur due to rubbing between clothing. Therefore, the bath ratio is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more.
Preferably it is 90 or less, More preferably, it is 80 or less, More preferably, it is 60 or less.
The amount of the garment finish composition used is preferably 0.1% by mass or more, more preferably 0.12% by mass or more, and still more preferably 0.15% by mass or more with respect to the mass of the garment, and Preferably, it is 1 mass% or less, More preferably, it is 0.8 mass% or less, More preferably, it is 0.6 mass% or less.

Moreover, when processing clothing by the said clothing processing method, the adhesion amount with respect to the clothing of the (A) component of the said finishing composition for clothing is clothing from a viewpoint of suppressing generation | occurrence | production of fluff and fluff effectively. Preferably, it is 0.05 mass% or more and 0.4 mass% or less with respect to the mass of this, and from the viewpoint of imparting a supple texture and imparting fluff and fluff suppression effects to the clothing, more preferably it is 0.00. It is 08 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less.
As described above, the method for treating garments of the present invention uses the finish composition for garments of the present invention, so that it is possible to suppress the occurrence of fuzz and pills, and to finish the washing machine. Since the aggregate does not adhere to the fiber product when using the inlet, it can be suitably used for finishing knit clothing.

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]
<Preparation Example of Finishing Solution Stock Solution Containing Component (A)>
The polymer (A) [component (A)] is obtained by polymerizing monomers constituting the component (A) in a solution containing at least a part of the cationized starch (B) and the nonionic surfactant (C). can get. Therefore, the finishing composition of the present invention is prepared based on the component (A) -containing solution after polymerization, and in the present invention, the polymer-containing (A) component-containing solution may be referred to as a finishing stock solution.
Preparation Example 1: Preparation of (a-1) component-containing finishing agent stock solution [Step I]
In a nitrogen atmosphere, 1.1 parts by mass of the cationized starch obtained in Synthesis Example B below, 0.2 parts by mass of polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and ion-exchanged water in a reaction vessel 48.7 parts by mass were uniformly dissolved at 90 ° C. and then cooled to 60 ° C. To this, a nonionic surfactant obtained by adding an average of 12 moles of EO to a straight-chain primary alcohol having 12 carbon atoms (hereinafter also referred to as “component (c1-1)”) / straight chain having 12 carbon atoms. Nonionic surfactant with 9 moles of EO added to primary alcohol (hereinafter also referred to as “(c1-2)” component) / 7 moles of EO added to secondary alcohols with 12 to 14 carbon atoms Nonionic surfactant (hereinafter also referred to as “component (c1-3)”) / nonionic surfactant obtained by adding an average of 47 mol of EO to a linear primary alcohol having 12 carbon atoms (hereinafter referred to as “component (c1-3)”) 1.68 parts by mass that have been mixed in advance so that the mass ratio of “(c2-1) component” is (31.5 / 0/65 / 3.5), and ion-exchanged water 19.4 parts by mass were added and stirred.

[Process II]
Then, after stirring, using a phosphate buffer as a pH adjuster and adjusting the pH to 7.0, 0.3 parts by mass of n-butyl acrylate, 0.2 parts by mass of methyl methacrylate, 2, 2 0.03 part by mass of '-azobis (2-amidinopropane) hydrochloride was added and heated to 75 ° C. to initiate polymerization. Mix in advance so that the final ratio of methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid is (mass ratio 19/75/5/1) over 5 hours after the start of polymerization. An aqueous solution prepared by dissolving 16.2 parts by mass of the soot and 0.05 parts by mass of 2,2′-azobis (2-amidinopropane) hydrochloride in 11.9 parts by mass of ion-exchanged water was dropped into the reaction solution. After completion of the dropwise addition, 0.004 part by mass 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 finishing agent stock solution containing about 20% by mass of the polymer of component (A) [hereinafter referred to as component (a-1)].

5 g of the resulting finishing agent stock solution was placed in 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 weight average molecular weight was 330,000. The GPC measurement conditions are shown below.
Column: α-M + α-M (anion) (two α-M linked)
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

Preparation Example 2: (a-2) Preparation of Component-Containing Finishing Agent Stock Solution The final ratio of methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid (mass ratio 30/64/5/1) Thus, a finisher stock solution containing a polymer of component (A) [hereinafter referred to as component (a-2)] was synthesized in the same manner as in Preparation Example 1. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 340,000.

Preparation Example 3: Preparation of (a-3) Component-Containing Finishing Agent Stock Solution The final ratio of methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid is (mass ratio 38/56/5/1). Thus, a finisher stock solution containing a polymer of component (A) [hereinafter referred to as component (a-3)] was synthesized in the same manner as in Preparation Example 1. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 350,000.

Preparation Example 4: (a-4) Preparation of Component-Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 6.0 and synthesized in the same manner as in Preparation Example 2 (A) polymer [hereinafter (a -4) Finishing agent stock solution containing component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 330,000.

Preparation Example 5: (a-5) Preparation of Component-Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 6.5 and synthesized in the same manner as in Preparation Example 2, and the polymer of component (A) [hereinafter (a -5) A finisher stock solution containing the component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 320,000.

Preparation Example 6: (a-6) Preparation of Component-Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 7.5 and synthesized in the same manner as in Preparation Example 2 (A) polymer [hereinafter (a -6) Finishing agent stock solution containing the component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 330,000.

Preparation Example 7: (a-7) Preparation of Component-Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 8.0 and synthesized in the same manner as in Preparation Example 2, and the polymer of component (A) [hereinafter (a -7) Finishing agent stock solution containing component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 350,000.

Preparation Example 8: Preparation of (a-8) Component-Containing Finishing Agent Stock Solution The mass ratio of surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component is (M) component polymer (hereinafter referred to as (a-8)) synthesized in the same manner as in Preparation Example 2 using a material previously mixed so as to have a mass ratio of 0/100/0/0. Finishing agent stock solution containing “components” was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 330,000.

Preparation Example 9: Preparation of (a-9) Component-containing Finishing Agent Stock Solution Surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component mass ratio (M) Polymer of component (A) (hereinafter referred to as (a-9)) synthesized in the same manner as in Preparation Example 2 using a material previously mixed so as to have a mass ratio of 0/0/75/25 Finishing agent stock solution containing “components” was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 320,000.

Preparation Example 10: Preparation of (a-10) Component-Containing Finishing Agent Stock Solution The mass ratio of surfactant (c1-1) component / (c1-2) component / (c1-3) component / (c2-1) component is A polymer of component (A) synthesized below in the same manner as in Preparation Example 2 using 2.08 parts by mass of a material previously mixed so as to have a mass ratio of 0/0/83/17. A finisher stock solution containing (a-10) component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 320,000.

Preparation Example 11: (a-11) Preparation of Component-Containing Finishing Agent Stock Solution In Step I, 0.83 parts by mass of the cationized starch obtained in Synthesis Example B below was used to synthesize in the same manner as in Preparation Example 2. A stock solution of a finishing agent containing about 20% by mass of the polymer of component (A) [hereinafter referred to as component (a-11)] was obtained.
The obtained finishing agent stock solution containing about 20% by mass of the component (a-11) was concentrated under reduced pressure using an evaporator to finally obtain a finishing agent stock solution having a weight of the component (a-11) of about 30% by mass. When the molecular weight was measured by the same method as in Preparation Example 1, the polymerization average molecular weight was 380,000.

Preparation Example 12: Preparation of (a-12) Component-containing Finishing Agent Stock Solution In Step I, 0.83 parts by mass of the cationized starch obtained in Synthesis Example B below, surfactant (c1-1) component / (c1- 2) Premixed so that the mass ratio of component / (c1-3) component / (c2-1) component is (mass ratio 31.5 / 0/65 / 3.5) 1.12 Using a part by mass, a finishing agent stock solution containing a polymer of component (A) [hereinafter referred to as component (a-12)] synthesized in the same manner as in Preparation Example 2 was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 320,000.

<Synthesis Example of Component (A ′) (Comparative Compound of Component (A))>
Comparative Preparation Example 1: Preparation of Component (a′-1) Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 5.0 and synthesized in the same manner as in Preparation Example 2, and the polymer of component (A) [below A finisher stock solution containing (a′-1) component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 340,000.

Comparative Preparation Example 2: Preparation of (a′-2) Component-containing Finishing Agent Stock Solution The pH in Step II was adjusted to 5.0, and synthesized in the same manner as in Preparation Example 3, and the polymer of component (A) [below A finisher stock solution containing (a′-2) component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 350,000.

Comparative Preparation Example 3 (a′-3) Preparation of Component-Containing Finishing Agent Stock Solution The pH in Step II was adjusted to 9.0 and synthesized in the same manner as in Preparation Example 2, and the polymer of component (A) [below A finisher stock solution containing (a′-3) component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 350,000.

Comparative Preparation Example 4: Preparation of (a′-4) Component-Containing Finishing Agent Stock Solution The final ratio of methyl methacrylate, n-butyl acrylate, methacrylic acid, 2-hydroxyethyl acrylic acid is (mass ratio 46/48/5 / A finisher stock solution containing a polymer of component (A) [hereinafter referred to as component (a′-4)] was synthesized as in 1) by the same method as in Preparation Example 1. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 350,000.

Comparative Preparation Example 5: (a′-5) Preparation of Component-Containing Finishing Agent Stock Solution Mass of Surfactant (c1-1) Component / (c1-2) Component / (c1-3) Component / (c2-1) Component Using a mixture that has been mixed in advance so that the ratio is (mass ratio 0/0/50/50), it was synthesized in the same manner as in Synthesis Example 2, and the polymer of component (A) [hereinafter (a ′ -5) A finisher stock solution containing the component] was obtained. When the molecular weight was measured by the same method as in Preparation Example 1, the weight average molecular weight was 340,000.

<Synthesis example of component (B)>
Synthesis Example B: Synthesis of Component (b-1) Into a 500 mL four-necked flask equipped with a propeller-type stirring blade, condenser, and thermometer, 0.9 g of caustic soda, 45 g of ion-exchanged water, and 100 g of isopropyl alcohol were added. The temperature was adjusted to ° C. The following operations were performed under stirring conditions. Corn starch (Sanwa Starch Co., Ltd.) 100g was added over 30 minutes. Furthermore, a mixture of 9.7 g of a 20% by mass 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 mass% hydrochloric acid aqueous solution, and then cooled to 25 ° C. Furthermore, after adding 2.3 g of 36 mass% hydrochloric acid aqueous solution, it heated up to 40 degreeC and stirred until the viscosity of the reaction liquid became 50-100 mPa * s. Subsequently, the pH of the reaction solution was adjusted to 5.0 with a 5 mass% aqueous sodium hydroxide solution. This reaction product was washed twice with isopropyl alcohol / water (mass ratio 50/50) and dried to obtain a cationized starch [hereinafter referred to as component (b-1)]. When the molecular weight was measured by GPC using standard pullulan as a standard substance for the component (b-1), the weight average molecular weight was 972,000. Moreover, N mass% was 0.67 mass%.

[Examples 1 to 12, Comparative Examples 1 to 6]
Tables 3 to 4 show the finishing solution stock solutions containing (A) component, (B) component, (C) component and water obtained in Preparation Examples 1-12 and Comparative Preparation Examples 1-5. A finishing composition for clothing was prepared according to the blending amount. Each composition of Tables 3-4 will be 100 mass% in total. About the obtained composition, along with the below-mentioned evaluation method, fluffing and fuzziness suppression effect and dilution dispersibility were evaluated. The results are shown in Tables 3-4.

<(A) component, (A ') component>
(A-1) to (a-12): Polymers (a′-1) to (a′-5) obtained in Preparation Examples 1 to 12: Polymers obtained in Comparative Preparation Examples 1 to 5 (B) component>
(B-1): Cationized starch obtained in Synthesis Example B above
(N mass% is 0.67 mass%, weight average molecular weight 972,000)

<(C1) component>
(C1-1): Nonionic surfactant obtained by adding 12 moles of EO to a straight-chain primary alcohol having 12 carbon atoms on average (c1-2): EO added to a straight-chain primary alcohol having 12 carbon atoms Nonionic surfactant added with an average of 9 moles (c1-3): Nonionic surfactant with an average of 7 moles of EO added to a secondary alcohol having 12 to 14 carbon atoms

<(C2) component>
(C2-1): Nonionic surfactant obtained by adding an average of 47 mol of EO to a linear primary alcohol having 12 carbon atoms

<Optional component>
(D-1): Lauryltrimethylammonium chloride (e-1): Propylene glycol

<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. Add the final finishing stock solution (component (A), component (B) and component (C)) obtained in the above synthesis example while stirring (300 rpm) with a turbine-type stirring blade with three 2 cm blades. And stirred for 10 minutes. Furthermore, (E) component and the fragrance | flavor were thrown in and it stirred for 10 minutes.

[Treatment Method for Clothing Finishing Composition]
<Preparation of test cloth>
2 kg of T / C knitted fabric (65% by weight polyester, 35% by weight cotton, air milling F401-F11, brown, manufactured by Masuda Co., Ltd.), a commercially available liquid detergent (attack biogel (registered trademark), Kao Corp., 2012) Washed 5 times using a fully automatic washing machine (Hitachi Appliances Co., Ltd., NW-7FT) (detergent concentration 0.083 mass%, tap water (20 ° C) 40L used, standard course, washing 9) Min-Rinse twice-Dehydration 6 min, bath ratio 1/20).
The washed T / C knitted fabric was dried for 12 hours in an environment of 25 ° C./50% RH and cut into a 10 × 10 cm square to obtain a test fabric (X1).
Subsequently, 300 g of tap water (carbonate alkalinity: 37 mg / lCaCO ₃ ) in a 500 ml glass beaker and 0.30 g of the finishing composition for clothing of Examples 1 to 12 and Comparative Examples 1 to 6 shown in Tables 3 to 4 were added. In addition, the mixture was stirred for 10 minutes using a magnetic stirrer and a rotor (cross head rotor double, model number 001.1140, height 14 mm, diameter 40 mm, manufactured by ASONE) (rotation speed 400 rpm). After stirring, 4 pieces (10 g) of test cloths (X1) were put into this solution and stirred for 5 minutes (rotation speed: 400 rpm). Then, using a two-layer washing machine (TOSHIBA VH-52G (H)), the test cloth (X1) was attached to the inner wall of the dewatering tank, dehydrated for 2 minutes, and dried in an environment of 25 ° C./50% RH for 12 hours. This was designated as test cloth (X2).

<Evaluation method of fuzz and fluff suppression effect>
Appearance / retention tester (manufactured by Daiei Kagaku Seisakusho Co., Ltd., model number) treated with the finishing compositions for clothing of Examples 1 to 12 and Comparative Examples 1 to 6 shown in Tables 3 to 4 “ARP-1”) was used to rub twice with a load of 3.2 N.
The rubbing level of each rubbed test cloth (X2) was evaluated by comparing with the following reference samples 1 to 4 and scoring according to the following criteria to obtain an average score. The evaluation was performed by 10 judges (30's) engaged in evaluation of the appearance of the fabric for 5 years or more.
The fuzz suppression effect is 3.5 or less, preferably 3.0 or less, more preferably less than 3.0.

Reference sample 1: untreated T / C knit cloth (evaluation point: 0)
Reference sample 2: test cloth (X1) (evaluation point: 2.0)
Reference sample 3: test cloth treated with 0.2 g of the garment finish composition of Example 2
(X2) (Evaluation point: 3.5)
Reference sample 4: Test cloth (X2) of Comparative Example 1 (Evaluation point: 5.0)

[Criteria]
0: Appearance equivalent to the test cloth of the reference sample 1 and no fluff or fluff.
1.0: An intermediate appearance between the test cloths of the reference samples 1 and 2, and very slightly fuzzy
There is no hairball.
2.0: Appearance equivalent to the test cloth of Reference Sample 2 and slightly fuzzy,
There is no hairball.
2.5: Appearance between the test cloths of the reference samples 2 and 3, but if anything
Close to the appearance of the reference sample 2 and more fuzzy than the reference sample 2
But there is no hairball.
3.0: Appearance between the test cloths of the reference samples 2 and 3, but if anything
It is close to the appearance of the reference sample 3 and has fuzz but no fluff.
3.5: Appearance equivalent to the test cloth of the reference sample 3, with fuzz, but fuzz
Absent.
4.0: Appearance between the test cloths of the reference samples 3 and 4, but if anything
It is close to the appearance of the reference sample 3, has fuzz, and has a slight fluff.
4.5: Between the appearance of the test cloths of the reference samples 3 and 4, but if anything
It is close to the appearance of the reference sample 4, has fuzz and fluff.
5.0: Appearance equivalent to that of the test cloth of the reference sample 4, with fuzz and fluff.

<Dilution dispersibility evaluation method>
As a preparation, 5 g of a finishing agent composition for clothing shown in Tables 3 to 4 was put in a 5 mL plastic cup (made of polypropylene, Neo Mini Cup, Maruemu Co., Ltd.) (hereinafter referred to as “sample cup”). A 200 mL plastic cup (made of polypropylene, sampler cup, Sampler Tech Co., Ltd.) having 4 holes with a diameter of 5 mm (hereinafter referred to as a perforated cup) was prepared.

Tap water (carbonate alkalinity: 37 degrees (mg / lCaCO ₃ )) adjusted to 20 ° C. was allowed to flow from a tap having a height of 45 cm at a flow rate of 2.5 L / min. The previously prepared perforated cup was fixed so that the bottom of the cup was set 15 cm below the faucet. Apply the sample cup prepared earlier to the running water so that the water from the faucet passes through the cup so that the finish composition does not remain in the cup. I received it in a 5L tub for 2 minutes. After 2 minutes, the water was stopped and the tub was allowed to stand for 5 minutes. After 5 minutes, the liquid in the tub was filtered with a 200 mesh that had been previously conditioned at 25 ° C./50% RH, and dried in a thermostatic bath at 105 ° C. for 1 hour. The dried mesh was conditioned at 25 ° C./50% RH, and the weight of the mesh before and after drying was weighed to calculate the amount of agglomerates generated from the composition.

Aggregate amount (%) = [(mesh weight after drying (g)) − (mesh weight before drying (g))] / [(composition weight (g)) × ((A) component blending amount (mass%) ))] X 100
As dilution dispersibility, the aggregate amount of 0.3% or less is acceptable, and preferably 0.2% or less.

<Dilution dispersibility in washing machine>
T / C knit cloth (65% by mass of polyester, 35% by mass of cotton, air milling F401-F7, black, manufactured by Masuda Co., Ltd.) was cut into a length of 60 cm while being cylindrical with a width of 45 cm, and a test cloth (Y1) did.
7 sheets (about 1 kg) of test cloths (Y1) were put into a fully automatic washing machine (TOSHIBA, AW-70DE), and 28 g of the finishing composition for clothing shown in Tables 3 to 4 was introduced into the inlet of the soft finish. Thereafter, washing was performed using a commercially available liquid detergent (Emar (registered trademark) manufactured by Kao Corporation, manufactured in 2012) (detergent concentration: 0.13% by mass, use of 28 L of tap water (20 ° C.), dry course, washing 6 Min-rinse twice-dehydration 6 min, bath ratio 1/30). The washed test cloth (Y1) was dried in an environment of 25 ° C./50% RH for 12 hours to obtain a test cloth (Y2).
The surface of the dried test cloth (Y2) was observed, and the adhesion state of the white aggregate was evaluated. Dilution dispersibility in a washing machine is represented by the number of test cloths (Y2) to which white agglomerates adhere, and 1 or less passes and 0 is the most excellent.

  As is clear from the above results, the finish composition for clothing of the present invention can suppress the occurrence of fluffing and fluffing of textile products such as clothing, and the fibers when using the finish holding part of the washing machine. Aggregates do not adhere to the product.

Claims (6)

70 to 100% by mass of a structural unit derived from (meth) acrylic acid ester (a1) having an alkyl group having 1 to 16 carbon atoms, and having a glass transition temperature of −40 ° C. or more and 0 ° C. A polymer (A), a cationized starch (B), a nonionic surfactant (C), and water, wherein the component (C) contains at least a hydrocarbon group having 8 to 16 carbon atoms. A polyoxyalkylene addition-type nonionic surfactant (c1) having one and an oxyalkylene group added in an average of 3 mol or more and 15 mol or less, and the component (c1) with respect to 100 parts by mass of component (A) A finish composition for clothing having a content of 5.5 parts by mass or more and 15 parts by mass or less, and obtained by a production method having the following steps I and II.
Step I: Step of preparing a solution by adding cationized starch (B) and nonionic surfactant (C) to an aqueous solvent Step II: (A) for the solution obtained in Step I A step of performing emulsion polymerization by adding a monomer constituting the component and a polymerization initiator, and performing emulsion polymerization by adjusting the pH of the solution to 5.5 or more and 8.5 or less   In the process II, before adding the said polymerization initiator with respect to the solution obtained by the process I, pH of the said solution is adjusted to 5.5 or more and 8.5 or less. Finishing composition.   Furthermore, the finishing composition for clothing of Claim 1 or 2 containing the cationic surfactant (D) which has a C8-C18 hydrocarbon group.   The amount of the said (B) component with respect to 100 mass parts of said (A) component is 2 mass parts or more and 50 mass parts or less, The finishing agent composition for clothing in any one of Claims 1-3. The processing method of the clothing which has the following process 1-process 4.
Process 1: The process of hold | maintaining the finishing composition for clothing in any one of Claims 1-4 in the finishing agent holding | maintenance part of a washing machine.
Step 2: Water having a carbonate alkalinity of 10 ° C. or more and 60 ° C. or less is added to the finish holding unit for holding the clothing finish composition, and the clothing finish composition and water The step of contacting.
Process 3: The process of putting the said finishing composition for clothes in a finishing agent holding part into a washing tub after the process 2.
Process 4: The process which makes the finishing composition for clothing and clothing contact in the water bath in a washing tub.   The method for processing clothing according to claim 5, wherein the clothing is knit clothing.