JP2024010430A - Fiber product treatment agent composition - Google Patents

Abstract

To provide a fiber product treatment agent composition that releases a pleasant fragrance when a user wears the treated fiber product, particularly when the treated fiber product is dampened by moisture due to sweating or the like.SOLUTION: A fiber product treatment agent composition includes the following component (a), component (b), component (c), and water. Component (a): a microcapsule consisting of a shell including a silicon compound, and a core located inside the shell and including a fragrance compound, Component (b): a polymer including a constitutional unit with an anionic group, and Component (c): a cationic surfactant.SELECTED DRAWING: None

Description

The present invention relates to a textile treatment agent composition and a method for producing the textile treatment agent composition.

Consumers are increasingly interested in scents when washing clothes, drying clothes, and wearing clothes, and the market for liquid fabric softeners and fragrance agents that appeal to scent-related content is growing significantly.
However, since textile treatment agent compositions used in general households are processed into textile products through water, the adhesion of the fragrance to the fibers may be insufficient, or the fragrance may disappear over time during or after drying. The scent becomes weaker when it evaporates from the cloth.
In response to such problems, for example, Patent Document 1 discloses a fabric softening composition that contains a specific long-lasting fragrance composition and improves the life of the fragrance on the fabric.

Patent Document 2 describes a sustained-release product that can be used for clothing using a mixture of dibasic acid monoester and/or dibasic acid diester and ethylene glycol or propylene glycol, etc., for the purpose of sustaining the fragrance for a long time. A perfume composition is disclosed. Furthermore, in Patent Document 3, fragrance can be maintained for a long time by using an aqueous liquid containing emulsion particles obtained by emulsifying and dispersing in water a mixture of a fragrance composition and an oil with a melting point of 30°C or higher at normal pressure. It is disclosed that it can be sustained.

On the other hand, attempts have been made to incorporate microcapsules of fragrances as a conventional technique for improving the fragrance retention during wear. Patent Document 4 describes an encapsulated fragrance containing a fragrance composition having a flash point within the range of 50 to 130° C. as a core substance. Additionally, Patent Document 5 describes that fragrance retention is improved by containing microcapsules whose shell structure is silica containing a fragrance produced by a core-shell method in liquid detergents and rinse cycle softeners. ing. Patent Document 6 describes microcapsules with a silica shell as a structure of first and second shells that contain a fragrance produced by a sol-gel reaction, and discloses an example in which the microcapsules are blended into a commercially available fabric softener. There is. Further, Patent Document 7 describes that by using microcapsules containing a fragrance in combination with a polymer containing a specific amine, the fragrance can be uniformly adhered to a plurality of different surfaces at a high concentration.

Patent Document 8 also discloses that, in addition to the usual fragrance persistence, a specific tertiary amine compound, its acid salt, and its quaternized compound are used for the purpose of realizing an excellent odor emitted when the wearer sweats. Component (A) containing one or more selected from the following, Component (B) consisting of microcapsules encapsulating a fragrance containing 90% by mass or more of a fragrance compound with a logP value of 2.0 or more and 6.0 or less, specified. A liquid softener containing component (C) consisting of a fragrance precursor which is an ester of a fragrance and a specific fatty acid ester or fatty acid diester, and water, and having a pH of 2.5 or more and 4.0 or less at 30°C. Compositions are disclosed. Further, Patent Document 9 discloses a textile treatment agent composition that contains a silicate ester compound of a fragrance compound and a specific fragrance, and improves the life of the fragrance on fabric. Patent Document 10 discloses a fragrance composition for softeners containing a silicate ester compound and a specific fragrance with high residual fragrance. A silicate ester compound has the property of releasing a fragrance by hydrolyzing the ester bond by absorbing moisture. Patent Document 11 describes the use of an amine compound with a structural formula containing alkanoylaminopropyl dialkylamine to suppress the volatilization of alcoholic fragrances from textile products, and Patent Document 12 describes the use of an amine compound with a structural formula containing an alkanoylaminopropyl dialkylamine, and Patent Document 12 describes the use of an amine compound with a structural formula containing an alkanoylaminopropyl dialkylamine to suppress volatilization of an alcohol-based fragrance from textile products. A liquid fabric softener composition containing a cationic compound, N-alkanoylaminoalkyl-N-dialkylamine or its salt, and an alcoholic fragrance residue with excellent fragrance persistence is described, and microcapsules are used as the alcoholic fragrance precursor. Contains scented fragrances.

Special Publication No. 11-504994 Japanese Patent Application Publication No. 2003-313580 Japanese Patent Application Publication No. 2012-72539 Japanese Patent Application Publication No. 2006-249326 Special Publication No. 2011-517323 Japanese Patent Application Publication No. 2015-128762 Japanese Patent Application Publication No. 2018-172687 JP2017-008446A JP2009-256818A Japanese Patent Application Publication No. 2011-063674 JP2020-23766A JP2020-23773A

In recent years, some techniques have been proposed for producing fragrances from textile products in a sustained manner, but it is difficult to adsorb fragrances added to textile processing agents to textile products, and textile processing agents for bath treatment such as fabric softeners are difficult to absorb. When blended into a textile product, a hydrophilic fragrance compound with a low logP does not remain on the surface of the textile product but flows. In addition, when spraying or otherwise applying the fragrance directly to textile products, the fragrance compound with high vapor pressure disappears during drying. Microencapsulation of fragrances has been proposed as a means of improving the effectiveness of fragrances, but in order to release the fragrances, it is necessary to physically destroy the capsules, and some of the capsules are released on the fiber surface. Although it is effective in reducing fragrance in situations where moisture is involved, such as when sweating, it is not sufficient and there are still issues. In addition, as a means to improve the effectiveness in situations where moisture is involved, it has been proposed to convert alcohol-based fragrance compounds into silicate esters or fatty acid esters to create fragrance precursors, but there are restrictions on the types of fragrances that can be used. The problem is that there are limits to satisfying the preferences of consumers.

The present invention provides a textile product treatment agent composition that gives off a good fragrance when the treated textile product is moistened with water, for example, due to perspiration during use of the textile product, and a method for producing the same.

The present inventors investigated how to improve the effectiveness of scents in situations where moisture is involved, and found that a specific capsule that adheres to fibers in an aqueous medium and then disintegrates when drying was created using a specific polymer. It has been discovered that by combining this with a cationic surfactant, it not only improves adsorption to textile products, but also produces a noticeable fragrance when the textile products are re-wetted, leading to the present invention.

The present invention relates to a textile treatment agent composition containing the following components (a), (b), (c) and water.
(a) Component: Microcapsule having a shell containing a silicon compound and a core containing a fragrance compound inside the shell (B) Component: Polymer containing a structural unit having an anionic group (c) Component: Cationic surfactant agent

The present invention also provides a method for producing a textile treatment agent composition containing the component (a), component (b), component (c) and water, comprising:
adding and mixing component (a) and component (b) to a mixture containing component (c) and water;
The present invention relates to a method for producing a textile treatment agent composition.

According to the present invention, there is provided a textile product treatment agent composition that gives off a good fragrance when the treated textile product is moistened with water, for example, due to perspiration during use of the textile product, and a method for producing the same. be done.

<Textile treatment agent composition>
<(a) Component>
Component (a) includes a microcapsule having a shell containing silica as a constituent and a core containing a fragrance compound inside the shell. Silica is a substance whose structural unit is silicon dioxide. Hereinafter, microcapsules having a shell containing silica as a constituent and a core containing a fragrance compound inside the shell will also be referred to as silica capsules. A fragrance compound can be incorporated into a silica capsule as a fragrance composition containing a plurality of fragrance compounds.

<Shell>
The shell of the silica capsule of the present invention contains silica as a constituent. The shell of the silica capsule of the present invention is characterized in that a part or substantially all of the structure constituting the shell is made of silica as a constituent component.
The shell of the silica capsule of the present invention is preferably formed by a sol-gel reaction using an alkoxysilane as a precursor.
In the present invention, the term "sol-gel reaction" refers to a reaction in which an alkoxysilane passes through a sol and gel state to form silica, which is a constituent component of the shell, through hydrolysis and polycondensation reactions. Specifically, for example, a tetraalkoxysilane is hydrolyzed, a silanol compound undergoes a dehydration condensation reaction and a dealcoholization condensation reaction to produce a siloxane oligomer, and the dehydration condensation reaction further proceeds to form silica.

Further, the shell of the silica capsule of the present invention may contain an inorganic polymer other than silica as a component within a range that does not impede the effects of the present invention. In the present invention, an inorganic polymer refers to a polymer containing an inorganic element. Examples of the inorganic polymer include polymers consisting only of inorganic elements, polymers whose main chain is composed only of inorganic elements, and which have organic groups as side chains or substituents.
The inorganic polymer is preferably a metal oxide containing a metal element or a metalloid element, and more preferably a reaction similar to the sol-gel reaction of silica using metal alkoxide [M(OR)x] as a precursor. It is a polymer formed by Here, M is a metal or metalloid element, and R is a hydrocarbon group.
Examples of the metal or metalloid element constituting the metal alkoxide include titanium, zirconium, aluminum, and zinc.

The alkoxysilane is preferably tetraalkoxysilane from the viewpoint of increasing the encapsulation rate of the fragrance and the viewpoint of achieving good delivery performance.
From the viewpoint of promoting the sol-gel reaction, the tetraalkoxysilane preferably has an alkoxy group having 1 to 4 carbon atoms, and more preferably tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. One or more types selected from the following, more preferably one or more types selected from tetramethoxysilane and tetraethoxysilane, even more preferably tetraethoxysilane.

(Manufacture of silica capsules)
The shell of the silica capsule of the present invention undergoes a sol-gel reaction in two stages from the viewpoint of increasing the encapsulation rate of fragrance compounds, improving long-term retention, and achieving good delivery performance of fragrance compounds. It is preferable that silica formed by the following methods be included as a constituent component. That is, the silica capsule of the present invention is preferably manufactured by a method including Step 1 and Step 2 below.
Step 1: An emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant and an oil phase component containing a fragrance compound and a tetraalkoxysilane is subjected to a sol-gel reaction under acidic conditions to form a core and , a first shell containing silica as a constituent component, and obtaining an aqueous dispersion containing the silica capsules (1). Step 2: The silica capsules obtained in Step 1 ( A step of further adding tetraalkoxysilane to the aqueous dispersion containing 1) to perform a sol-gel reaction to form a silica capsule having a second shell that encloses the first shell.

[Step 1]
In step 1, an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant and an oil phase component containing a fragrance compound and a tetraalkoxysilane is subjected to a sol-gel reaction under acidic conditions to form a core. and a first shell containing silica as a constituent component, and obtaining an aqueous dispersion containing the silica capsule (1).

Examples of the cationic surfactant in Step 1 include alkylamine salts and alkyl quaternary ammonium salts. The alkylamine salt is preferably a salt of a secondary amine or a tertiary amine, more preferably a salt of a tertiary amine. Alkylamine salts and alkyl quaternary ammonium salts are compounds having at least one long-chain alkyl group, optionally preferably at least one group selected from long-chain alkyl groups, short-chain alkyl groups, and benzyl groups. is preferred. The number of carbon atoms in the long chain alkyl group is preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. The number of carbon atoms in the short chain alkyl group is preferably 1 or more, and preferably 4 or less, more preferably 1 or 2, and still more preferably 1, that is, a methyl group.
Examples of the alkylamine salts include alkylamine salts in which the long-chain alkyl group has the number of carbon atoms within the above range, such as long-chain monoalkyl monomethyl secondary amine salts and long-chain monoalkyldimethyl tertiary amine salts.
Examples of quaternary ammonium salts include long-chain alkyl tri-short-chain alkyl quaternary ammonium salts and di-long-chain alkyl di-short-chain alkyl quaternary ammonium salts in which the long-chain alkyl group and the short-chain alkyl group each have the carbon numbers within the above-mentioned ranges. , long-chain alkyl benzyl di-short-chain alkyl quaternary ammonium salts, and the like.

Examples of the alkylamine salts include alkylamine acetates such as lauryldimethylamine acetate and stearyldimethylamine acetate.
Examples of alkyltrimethylammonium salts include alkyltrimethylammonium chlorides such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride; alkyltrimethylammonium bromides such as lauryltrimethylammonium bromide, cetyltrimethylammonium bromide, and stearyltrimethylammonium bromide; Can be mentioned.
Examples of dialkyldimethylammonium salts include dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride; dialkyldimethylammonium bromides such as distearyldimethylammonium bromide, and the like.
Examples of the alkylbenzyldimethylammonium salt include alkylbenzyldimethylammonium chloride, alkylbenzyldimethylammonium bromide, and the like.
Among these, the cationic surfactant is preferably a quaternary ammonium salt, more preferably an alkyltrimethylammonium salt having an alkyl group having 10 to 22 carbon atoms, and even more preferably an alkyl trimethylammonium salt having an alkyl group having 10 to 22 carbon atoms. Alkyltrimethylammonium chloride having the following alkyl group, more preferably one or more selected from lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, even more preferably cetyltrimethylammonium chloride. be.

In step 1, other emulsifiers may be included in addition to the cationic surfactant within a range that does not impede the effects of the present invention. Other emulsifiers include polymeric dispersants, nonionic surfactants, anionic surfactants, and amphoteric surfactants.

In Step 1, the content of the cationic surfactant in the aqueous phase component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably from the viewpoint of suppressing the formation of emulsifier micelles due to excess emulsifier that does not contribute to the dispersion stability of the emulsion and improving encapsulation efficiency. is 5% by mass or less, more preferably 2% by mass or less.

From the viewpoint of production efficiency, the amount of the oil phase component relative to the total amount of the emulsion obtained in Step 1 is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% or more, and is stable. From the viewpoint of obtaining a suitable emulsion, the content is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

The amount of tetraalkoxysilane added in Step 1 is preferably 10% by mass or more, more preferably 10% by mass or more based on the total amount of fragrance compounds in Step 1, from the viewpoint of promoting the sol-gel reaction and forming a sufficiently dense shell. is 12% by mass or more, more preferably 14% by mass or more, and from the viewpoint of suppressing excessive tetraalkoxysilane from remaining in the fragrance compound, preferably 60% by mass or less, more preferably 50% by mass. The content is more preferably 40% by mass or less, even more preferably 35% by mass or less.

Step 1 preferably includes the following steps 1-1 to 1-4.
Step 1-1: Step of preparing an aqueous phase component containing a cationic activator Step 1-2: Step of mixing fragrance and tetraalkoxysilane to prepare an oil phase component Step 1-3: Step of preparing an oil phase component containing the cationic activator Step 1-4: Mix and emulsify the aqueous phase component obtained in step 1-2 with the oil phase component obtained in step 1-2 to obtain an emulsion. Step 1-4: The emulsion obtained in step 1-3 is - subjecting to a gel reaction to form a silica capsule having a core and a first shell comprising silica;

The stirring means used to prepare the emulsion is not particularly limited, but a homogenizer with strong shearing force, a high-pressure disperser, an ultrasonic disperser, etc. can be used. In addition, homo mixers, "Disper" (product name, manufactured by Primix Co., Ltd.), "Clearmix" (product name, manufactured by M Techniques Co., Ltd.), "Cavitron" (product name, manufactured by Pacific Kiko Co., Ltd.), etc. are used. You can also.

The median diameter D ₅₀ of the emulsion droplets in the emulsion in step 1 is preferably 0.1 μm or more, more preferably 0.2 μm or more, and It is preferably 0.3 μm or more, and from the viewpoint of the physical strength of the silica capsule, it is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 10 μm or less, even more preferably 5 μm or less, and even more preferably 3 μm. It is as follows.
The median diameter _D50 of emulsified droplets can be measured by the method described in Examples.

The initial pH of the sol-gel reaction in step 1 is determined from the viewpoint of maintaining the balance between the hydrolysis reaction and condensation reaction of the tetraalkoxysilane, and from the viewpoint of suppressing the production of a highly hydrophilic sol and promoting the progress of encapsulation. It is preferably 3.0 or more, more preferably 3.3 or more, even more preferably 3.5 or more, and suppresses the simultaneous formation of a silica shell and aggregation of emulsion droplets, and has a dense shell. From the viewpoint of obtaining capsules, it is preferably 4.5 or less, more preferably 4.3 or less, still more preferably 4.1 or less.

Depending on the strength of acidity or alkalinity of the oil phase component containing the fragrance compound, any acidic or alkaline pH adjuster may be used from the viewpoint of adjusting to a desired initial pH.
The pH of the emulsion may be lower than a desired value. In that case, it is preferable to adjust the pH using an alkaline pH adjuster, which will be described later.
That is, step 1-4 may preferably be step 1-4' below.
Step 1-4': Adjust the pH of the emulsion obtained in Step 1-3 using a pH adjuster, perform the first stage sol-gel reaction, and form a silica capsule having a core and a first shell. (1) and obtaining an aqueous dispersion containing the silica capsules (1)

Examples of acidic pH adjusters include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as acetic acid and citric acid, and solutions obtained by adding cation exchange resins to water, ethanol, etc., and preferably hydrochloric acid, sulfuric acid, etc. , nitric acid, and citric acid.
Examples of alkaline pH adjusters include sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine, trishydroxymethylaminomethane, and sodium hydroxide and ammonium hydroxide are preferred. .

The reaction temperature of the sol-gel reaction in step 1 can be selected from any value as long as it is above the melting point of water contained in the aqueous phase and below the boiling point. From the viewpoint of controlling the balance and forming a dense shell, it is preferable to keep the temperature within a certain range. The temperature range is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and preferably 60°C or lower, more preferably 50°C or lower, and still more preferably 40°C or lower.

[Step 2]
In step 2, tetraalkoxysilane is further added to the aqueous dispersion containing the silica capsules (1) obtained in step 1, and a sol-gel reaction is performed to form a silica having a second shell that encloses the first shell. This is the process of forming a capsule.

The amount of tetraalkoxysilane added in Step 2 is preferably 7% by mass or more, more preferably 10% by mass or more, based on the fragrance compound in Step 1, from the viewpoint of forming a second shell that includes the first shell. , more preferably 15% by mass or more, and from the viewpoint of suppressing the formation of silica sol dispersed in the aqueous phase and improving the dispersion stability of silica capsules, preferably 200% by mass or less, more preferably 170% by mass. The content is preferably 150% by mass or less.

In step 2, the tetraalkoxysilane added to the aqueous dispersion containing the silica capsules (1) obtained in step 1 may be added in its entirety at once, or may be added intermittently in divided portions, Although it may be added continuously, it is preferable to add it dropwise continuously from the viewpoint of forming a highly dense second shell.
When tetraalkoxysilane is added dropwise continuously, the dropping time can be set appropriately depending on the scale of production, but from the viewpoint of suppressing separation of the tetraalkoxysilane to be added and the water dispersion, Preferably it is 5 minutes or more, more preferably 10 minutes or more, still more preferably 30 minutes or more, and preferably 1200 minutes or less, more preferably 1000 minutes or less, still more preferably 500 minutes or less.

In the present invention, the total amount of tetraalkoxysilane added, that is, the total amount of tetraalkoxysilane used in step 1 and step 2, is preferably 30% by mass or more, more preferably 35% by mass, based on the fragrance compound in step 1. % or more, more preferably 40% by mass or more, and preferably 250% by mass or less, more preferably 200% by mass or less, still more preferably 150% by mass or less. By adjusting the total amount of tetraalkoxysilane added within the above range, the encapsulated fragrance compound can be retained for a long period of time.

In the present invention, the total amount of the fragrance compound and tetraalkoxysilane in Step 1 is preferably set to the total amount of the water dispersion before addition of the tetraalkoxysilane in Step 2 from the viewpoint of improving the long-term retention of the fragrance compound. is 20% by mass or less, more preferably 18% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and from the viewpoint of production efficiency, preferably 2% by mass or more, more preferably is 3% by mass or more, more preferably 5% by mass or more.
Adjustment of the total amount of the fragrance compound and tetraalkoxysilane in Step 1 with respect to the total amount of the water dispersion before addition of the tetraalkoxysilane in Step 2 is the amount of the fragrance compound and tetraalkoxysilane in Step 1 and the amount obtained in Step 1. Step 1 may be carried out so that the total amount of the water dispersion falls within the above range, or may be carried out by further adding water to the water dispersion obtained in Step 1 to dilute it.

In the present invention, from the viewpoint of production efficiency, in step 2, the aqueous dispersion obtained in step 1 may be diluted with water before adding the tetraalkoxysilane. The total amount of the fragrance compound and tetraalkoxysilane in Step 1 is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass, relative to the total amount of the aqueous dispersion obtained in Step 1 before dilution. % or more, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.
The dilution ratio is preferably 2 times or more, more preferably 2.5 times or more, and preferably 20 times or less, more preferably 10 times or less, and more preferably 7 times or less.

The reaction temperature of the sol-gel reaction in step 2 can be arbitrarily selected as long as it is above the melting point and below the boiling point of water contained as a dispersion medium, but it is important to consider the balance between the hydrolysis reaction and condensation reaction in the sol-gel reaction. From the viewpoint of controlling and forming a dense shell, the temperature is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and preferably 60°C or lower, more preferably 50°C or lower, and Preferably it is 40°C. The sol-gel reaction in step 1 and the sol-gel reaction in step 2 may be performed at different reaction temperatures.

In the present invention, in step 2, an organic polymer may be further added to the aqueous dispersion obtained in step 1 for the purpose of stabilizing the aqueous dispersion and suppressing aggregation. Here, the organic polymer means a compound having a weight average molecular weight of 5,000 or more.
Examples of the organic polymer include nonionic polymers, cationic polymers, and anionic polymers.
The nonionic polymer means a water-soluble polymer that has no charge in water. By using a nonionic polymer, it is possible to impart functions to the silica capsule according to the intended use of the silica capsule.
As used herein, the term "water-soluble polymer" refers to a polymer whose dissolved amount is 1 mg or more when the polymer is dried at 105° C. for 2 hours to reach a constant weight and is dissolved in 100 g of water at 25° C.

Examples of nonionic polymers include polymers having structural units derived from nonionic monomers, water-soluble polysaccharides (cellulose-based, gum-based, starch-based, etc.), and derivatives thereof.
Nonionic monomers include (meth)acrylates having hydrocarbon groups derived from aliphatic alcohols having 1 to 22 carbon atoms; styrenic monomers such as styrene; (meth)acrylates containing aromatic groups such as benzyl (meth)acrylate; Vinyl acetate; Vinyl pyrrolidone; Vinyl alcohol; Polyalkylene glycol (meth)acrylates such as polyethylene glycol mono(meth)acrylate; Alkoxypolyalkylenes such as methoxypolyethylene glycol mono(meth)acrylate and octoxypolyethylene glycol mono(meth)acrylate Examples include glycol mono(meth)acrylate; (meth)acrylamide and the like. Note that (meth)acrylate means acrylate or methacrylate. Similarly, (meth)acrylic means acrylic or methacrylic.

Examples of the cationic polymer include polymers containing a quaternary ammonium base, polymers having nitrogen-based cation groups, and polymers that may become cationic by adjusting the pH. By using a cationic polymer, it is possible to alleviate the tendency for the silica capsules (1) obtained in step 1 to aggregate in the aqueous dispersion, and it is possible to suppress the generation of coarse particles and the like in the subsequent step 2.
Examples of cationic polymers include poly(diallyldimethylammonium chloride), poly(acrylic acid-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-acrylic acid-co- polydiallyldimethylammonium salts such as diallyldimethylammonium chloride) and their copolymers, poly(2-(methacryloyloxy)ethyltrimethylammonium chloride), polyethyleneimine, polyallylamine, cationized cellulose, cationized guar gum, cationized tara gum, cationized Examples include fenugreek gum and cationized locust Bingham gum. Among these, polydiallyldimethylammonium salts and copolymers thereof are preferred, such as poly(diallyldimethylammonium chloride), poly(acrylic acid-co-diallyldimethylammonium chloride), and poly(acrylamide-co-acrylic acid-co-diallyldimethyl). ammonium chloride) is more preferable, and poly(diallyldimethylammonium chloride) is even more preferable.

The cationic group equivalent of the cationic polymer is preferably 1 meq/g or more, more preferably 3 meq, from the viewpoint of dispersibility of the silica capsule (1), suppressing the formation of coarse particles, and improving long-term retention. /g or more, more preferably 4.5 meq/g or more, and preferably 10 meq/g or less, more preferably 8 meq/g or less. The cationic polymer may contain an anion group, but in that case, the anion group equivalent contained in the cationic polymer is preferably 3.5 meq/g or less, more preferably 2 meq/g or less, and even more preferably 1 meq/g. g or less. In the present invention, the cationic group equivalent of the cationic polymer is calculated based on the monomer composition.

Examples of the anionic polymer include polymers containing a monomer unit having a carboxyl group, polymers containing a monomer unit having a sulfonic acid group, and polymers that become anionic by adjusting the pH.
Examples of anionic polymers include poly(meth)(acrylic acid), poly(maleic acid), poly((meth)acrylic acid-co-maleic acid), poly((meth)acrylic acid-co-maleic anhydride), Poly((meth)acrylic acid-co-isobutylene), poly((meth)acrylic acid-co-styrene), poly(isobutylene-co-maleic acid), poly(styrene-co-maleic acid), carboxymethyl cellulose, etc. Can be mentioned. Note that (meth)acrylic acid means acrylic acid or methacrylic acid.

The amount of the organic polymer added is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, based on the aqueous dispersion obtained in Step 1. , and preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less.

The silica capsules obtained in step 2 are obtained in a dispersed state in water. Depending on the application, this may be used as is, but in some cases, the silica capsule may be separated and used. As a separation method, a filtration method, a centrifugation method, etc. can be adopted.

<Core>
The core of the silica capsule according to the invention contains a perfume compound.
In the present invention, from the viewpoint of fragrance release when the fibers become wet with moisture such as perspiration, the logP of the total amount of fragrance compounds is 2.0 or more and 5.0 or less, and the vapor pressure at 25°C is 0.01 or more and 8 It is preferable that the proportion of fragrance compounds having a concentration of .00 or less is 25% by mass or more.

In the present invention, the logP value is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol/water partition coefficient P is the ratio of the equilibrium concentrations of compounds in each solvent when a trace amount of the compound is dissolved as a solute in a solvent consisting of two liquid phases of 1-octanol and water and a partition equilibrium is reached. and is generally expressed in the form of their logarithm logP with respect to base 10. Today, the value of "calculated logP" (sometimes referred to as ClogP) is widely used, which is calculated by a calculation program that uses fragment values of atomic groups determined by the number of atoms and the type of chemical bonds that make up a compound molecule. In the present invention, the ClogP value is also used when selecting a compound.

In the present invention, a value calculated using the software EPI Suite (registered trademark; The Estimations Programs Interface for Windows version 4.11) jointly developed by the US Environmental Protection Agency and Syracuse Corporation is used as the value of ClogP.

In the present invention, the vapor pressure at 25° C. is determined by actual measurement or vapor pressure estimation from the boiling point, and if the chemical substance is solid at room temperature, it is estimated from the melting point. Vapor pressure is estimated by several known methods (Antoine method, Modified Grain method, Mackay method, etc.), but in the present invention, it is estimated by the method incorporated in the EPI suite available from the U.S. Environmental Protection Agency (EPA). The value calculated using MPBPWIN, which is the average value of the value calculated by the Antoine method and the value calculated by the Grain method, is displayed in the calculation results as "Selected VP". If there is, the average value is used, and if there is no indication as "Selected VP", the value calculated by the Modified Grain method is used.

Examples of fragrance compounds having a logP of 2.0 or more and 5.0 or less and a vapor pressure of 0.01 or more and 8.00 or less at 25°C include γ-undecalactone, 2-cyclohexylidene-2-phenylacetonitrile , damascenone, δ-damascone, α-methyl-β-(pt-butylphenyl)-propionaldehyde, β-ionone, myrrhaldehyde, ethyltricyclo[5.2.1.0-2,6]decane- 2-carboxylate (furtate), citronellol, geraniol, α-ionone, patchouli alcohol, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, methyl dihydrojasmonate, Hexyl cinnamic aldehyde, amyl cinnamic aldehyde, allylcyclohexyl propionate, dimethylbenzyl carbinyl butyrate, tricyclodecenyl propionate, amyl salicylate, γ-methyl ionone, α-damascone, β-damascone, Neroline Yarayara, 2,4, 6-trimethyl-4-phenyl-1,3-dioxane, phenylhexanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, dodecahydro -3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, γ-nonalactone, methyl β-naphthylketone, eugenol, ryral, dimethylbenzylcarbinyl acetate, iso-damascone, 2-cyclohexylidene -2-phenylacetonitrile, γ-decalactone, α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, 7-methyl-3,5-dihydro-2H-benzodioxepinone, tricyclodecynyl acetate (acetic acid tricyclodecenyl), tricyclodecynylpropionate, allyl 2-pentyloxyglycolate, 1-(2-tert-butylcyclohexyloxy)-2-butanol, citronellyloxyacetaldehyde, indole, 4-methyl- 3-decen-5-ol, para-menthane-8-thiol-3-one, 3-(para-tert-butylphenyl)-propanal, ethyl cinnamate, 5-methyl-3-heptanone oxime, methyl anthra Nilate, terpineol, β-caryophyllene, citronellyl acetate, geranyl acetate, neryl acetate, p-t-butylcyclohexyl acetate, tetrahydrogeraniol, 2-isobutyl-4hydroxy-4-methyltetrahydropyranol (phlorosa), α-dynascone, cisjasmone , bicyclo[3.2.1]octan-8-one-1,5-dimethyl-oxime, 2,4-dimethyl-4,4α,5,9β-tetrahydroindeno[1,2-d]-m-dioxin, 3-(para-ethylphenyl)-2,2-dimethylpropanal, ethyl-2-tert-butylcyclohexyl-carbonate, hexyl benzoate, 4-acetoxy-3-amyltetrahydropyran, dodecylaldehyde, dihydro-β-ionone , methylcyclooctyl carbonate, ethyl methylphenylglycidate, isoeugenol, methylisoeugenol, diphenyl oxide, 2,2,5-trimethyl-5-pentylcyclopentanone, thymol, neroline bromeliad, 5,6-dimethyl- 8-isopropenyl, bicyclo'4,4,0]-1-decen-3-one, 3-(4-isopropylphenyl)-propanal, 4-isopropylcyclohexanemethanol, methyl methylanthranilate, dodecanenitrile 3- One example is dodecenal.

Moreover, as the fragrance compound of component (a), a fragrance compound having a logP value lower than 2.0 can also be used. Fragrance compounds with logP values lower than 2.0 include, for example, coumarin (1.5), phenylethyl alcohol (1.6), cis-3-hexenol (1.6), raspberry ketone (1.5), helio Examples include tropine (1.8), benzyl alcohol (1.1), and the like. Note that the numbers in parentheses are logP values.

Moreover, as the fragrance compound of component (a), a fragrance compound having a logP value higher than 5.0 can also be used. Examples of fragrance compounds with a logP value higher than 5.0 include 2-[2-(4-methyl-3-cyclohexen-1-yl)propyl]cyclopentanone (5.1), 7-acetyl-1, 2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene (5.2), acetylcedrene (5.2), nerolidol (5.7), Examples include caryophyllene (6.3). Note that the numbers in parentheses are logP values.

Moreover, as the fragrance compound of component (a), a fragrance compound having a vapor pressure lower than 0.01 Pa can also be used. Examples of fragrance compounds having a vapor pressure lower than 0.01 Pa include 1,4-dioxacycloheptadecane-5,17-dione (0.0000585) and ethylene brassylate (0.0000585). Note that the numbers in parentheses are vapor pressures.

Moreover, as the fragrance compound of component (a), a fragrance compound having a vapor pressure higher than 8.00 Pa can also be used. Examples of fragrance compounds with a vapor pressure higher than 8.00 Pa include ethyl 2-methylbutyrate (1070), ethyl-2-methylpentanoate (384), limonene (193), and allyl 2-pentyloxyglycolate (19). .7), 2,4-dimethyl-3-cyclohexenylcarboxaldehyde (46.9), linalool (11.1), linalyl acetate (17.5), tetrahydrolinalool (9.51), 1,8-cineole (208), isobornyl acetate (14.3), ocimene (358), cis-3-hexenol (125), tripral (46.9), and styralyl acetate (14.9). Note that the numbers in parentheses are vapor pressures.

In addition, the microcapsules of component (a) may encapsulate one or more types selected from a diluent, a solvent, and a solidifying agent in addition to the fragrance compound. Examples of the diluent or solvent include ethylene glycol, propylene glycol, dipropylene glycol, and glycerin, and also include fatty acid alcohols, lower alcohol esters of fatty acids, and glycerin esters of fatty acids.

[Silica capsule]
The silica capsule of the present invention, for example, the silica capsule produced as described above, adheres to a textile product in an aqueous medium and then breaks at the end of the process in which water evaporates from the textile product, allowing the contents to penetrate into the textile product. can.

The silica capsule of the present invention is preferably a core containing the fragrance compound, from the viewpoint that the silica capsule stably retains the encapsulated substance in the textile product treatment composition and breaks down upon drying after adhering to the textile product in an aqueous medium. A silica capsule has a first shell that encloses the core, and a second shell that encloses the first shell.
The first shell of the silica capsule of the present invention includes the core, contains silica as a constituent, and preferably has an average thickness of 5 nm or more and 20 nm or less, and the second shell includes the first shell and contains silica as a component. as a constituent component, and preferably has an average thickness of 10 nm or more and 100 nm or less.
The average thickness of the first shell and second shell of the silica capsule can be measured by transmission electron microscopy (TEM) observation. Specifically, the thicknesses of the first shell and the second shell are actually measured on a photograph under observation using a transmission electron microscope. This operation is performed by changing the field of view five times. The average thickness distribution of the first shell and the second shell is determined from the obtained data. The standard magnification of a transmission electron microscope is 10,000 times or more and 100,000 times or less, but it is adjusted as appropriate depending on the size of the silica capsule. Here, as a transmission electron microscope (TEM), for example, the product name "JEM-2100" (manufactured by JEOL Ltd.) can be used.

The median diameter D ₅₀ of the component (a) and the silica capsule according to the present invention is preferably 0.1 μm or more, more preferably 0.1 μm or more, from the viewpoint of improving long-term retention and dispersion stability of the silica capsule. 5 μm or more, more preferably 1 μm or more, and from the viewpoint of improving the physical strength of the silica capsule and improving long-term retention, preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and more More preferably, it is 10 μm or less.
Component (a) and the median diameter _D50 of the silica capsule can be measured by the method described in the Examples.

The silica capsules according to the present invention are preferably blended as a silica capsule slurry when preparing a textile treatment agent composition. From the viewpoint of improving the dispersibility of the silica capsule slurry in the components mixed when preparing the textile treatment agent composition, the silica capsule slurry contains a cationic surfactant, a nonionic surfactant, and an anionic surfactant. A surfactant selected from the group consisting of surfactants may also be added.

Note that the silica capsule of component (a) may be partially aggregated to the extent that the fragrance is not impaired.

The textile treatment agent composition of the present invention preferably contains component (a) as a fragrance compound contained in component (a), preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and still more preferably 0. .1% by mass or more, and preferably 3.0% by mass or less, more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less.

In addition, in the present invention, the polymer or cationic surfactant containing a structural unit having an anionic group incorporated into component (a) during the manufacturing process of component (a), such as the silica capsule of the present invention, is the component (b). , shall not be included as component (c).

<(b) component>
Component (b) is a polymer containing a constitutional unit having an anionic group, such as an anionic polymer and an amphoteric polymer containing a constitutional unit having an anionic group and a constitutional unit having a cationic group.

Component (b) includes a polymer made of an anionic monomer or a copolymer of an anionic monomer and a monomer copolymerizable with the anionic monomer. Examples of the copolymerizable monomer include cationic monomers and nonionic monomers. The cationic monomer is, for example, a monomer having a cationic group such as a quaternary ammonium group, an amino group, or a quaternary phosphonium group in its molecule. The nonionic monomer is, for example, a monomer having an unsaturated bond copolymerizable with an anionic monomer and having no ionic group.

Examples of the anionic monomer include monomers having anionic groups such as a carboxyl group, a sulfate group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group in the molecule. The anionic monomer is preferably a monomer having an anion group selected from a carboxyl group and a sulfonic acid group, and more preferably a monomer having a carboxyl group.

The anionic polymer is preferably a polymer containing a structural unit having at least one anionic group selected from a carboxy group and a sulfonic acid group.
A polymer containing a structural unit having a carboxyl group can be obtained by polymerizing a vinyl monomer having a carboxyl group or a salt thereof. The polymer containing a structural unit having a carboxy group preferably contains a structural unit derived from at least one carboxy group-containing vinyl monomer selected from acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Examples of polymers containing structural units having carboxyl groups include acrylic acid monopolymer (polyacrylic acid), methacrylic acid monopolymer (polymethacrylic acid), acrylic acid/maleic acid copolymer, methacrylic acid/maleic acid copolymer, acrylic acid /maleic anhydride copolymer, methacrylic acid/maleic anhydride copolymer, and salts thereof.
A polymer containing a structural unit having a sulfonic acid group can be obtained by polymerizing a vinyl monomer having a sulfonic acid group or a salt thereof. Examples of polymers containing structural units having sulfonic acid groups include styrenesulfonic acid or its salts, 2-acrylamido-2-methylpropanesulfonic acid or its salts, (meth)allylsulfonic acid or its salts, vinylsulfonic acid or its salts, etc. Contains structural units derived from vinyl monomers containing sulfonic acid groups such as salts and naphthalenesulfonic acid. Examples of the polymer containing a structural unit having a sulfonic acid group include salts of aromatic sulfonic acid formalin condensates such as sodium salts of β-naphthalene sulfonic acid formalin condensates.

Among component (b), the anionic polymer is more preferably one or more selected from polymers containing a structural unit having a carboxy group, and even more preferably acrylic acid polymer, acrylic acid-maleic acid copolymer, acrylic acid- One or more types selected from maleic anhydride copolymers and salts thereof. The anionic polymer preferably contains acrylic acid as a constituent monomer, and the proportion of acrylic acid in the constituent monomers is preferably 40 mol% or more and 100 mol% or less.

Examples of cationic monomers copolymerizable with anionic monomers include 2-(N,N-dimethylamino)ethyl methacrylate, 2-(N,N-dimethylamino)ethyl acrylate, and N-{3-(N, N-dimethylamino)propyl}acrylamide, N-{3-(N,N-dimethylamino)propyl}methacrylamide, 2-(methacryloyloxy)ethyldimethylethylammonium ethyl sulfate, 2-(methacryloyloxy)ethyltrimethylammonium chloride , (meth)acrylamidopropyltrimethylammonium chloride, 4-vinylbenzyltrimethylammonium chloride, and the like. Cationic monomers include 2-(N,N-dimethylamino)ethyl, 2-(N,N-dimethylamino)ethyl methacrylate, N-{3-(N,N-dimethylamino)propyl}acrylamide, N -{3-(N,N-dimethylamino)propyl}methacrylamide is preferred.

Examples of the nonionic monomer copolymerizable with the anionic monomer include methacrylates such as ethyl methacrylate, N,N-dimethylacrylamide, diacetone acrylamide, styrene, vinyl acetate, and the like.

Among component (b), the amphoteric polymer includes a structural unit having an anionic group and a structural unit having a cationic group. One structural unit of the amphoteric polymer may have an anionic group and a cationic group. The amphoteric polymer may be a polymer whose constituent units have an anionic group and a cationic group.

Examples of the structural unit having a cationic group of the amphoteric polymer include those derived from the above-mentioned cationic monomer. The amphoteric polymer is preferably one or more selected from copolymers of acrylic acid and dialkyldiallylammonium salts, copolymers of acrylic acid, acrylamide, and dialkyldiallylammonium salts, and the like. Examples of the copolymer of acrylic acid and dialkyl diallylammonium salt include copolymers obtained by copolymerizing equimolar amounts of acrylic acid and dialkyl diallylammonium salt.

The salt of component (b) is a metal salt, an ammonium salt, an ammonium salt having an alkyl or alkenyl having a total carbon number of 1 to 22, a pyridinium salt substituted with an alkyl or alkenyl having a total of 1 to 22 carbon atoms, a total carbon number of 1 to 22 Examples include the following alkanol ammonium salts and basic amino acids, with alkali metal salts such as sodium salts and potassium salts being preferred.

The proportion of the anionic group-containing structural units constituting the polymer of component (b) is preferably 20 mol% or more, more preferably 50 mol% or more, and even more preferably 80 mol% of all the structural units of component (b). % or more, and preferably 100 mol% or less, and may be 100 mol%.
The structural unit having an anionic group can be formed from a monomer having an anionic group, for example. Examples of the monomer having an anionic group include monomers selected from acrylic acid, maleic acid, maleic anhydride, and salts thereof. The structural units of component (b) can further optionally contain structural units formed from other monomers known to be copolymerizable with these monomers.
When component (b) contains acrylic acid and optionally maleic acid and/or maleic anhydride as constituent monomers, the ratio of the constituent units of maleic acid and/or maleic anhydride to acrylic acid is preferably the molar ratio of the monomers. is 0 or more, more preferably 0.1 or more, and preferably 0.6 or less, more preferably 0.5 or less. Furthermore, when the polymer of component (b) contains acrylic acid as constituent monomers, optionally maleic acid and/or maleic anhydride, and optionally other monomers copolymerizable with these, acrylic acid, maleic acid and The molar ratio of other copolymerizable monomers to the total amount with/or maleic anhydride is preferably 0.5 or less, more preferably 0.2 or less, still more preferably 0.1 or less. The molar ratio may be a blending ratio during polymerization, or may be one determined by a known measuring method for the polymer after polymerization.

The weight average molecular weight of component (b) may be, for example, 2,000 or more, further 5,000 or more, and 2,000,000 or less, further 500,000 or less. If the weight average molecular weight of component (b) is not available as a catalog value, it is measured by GPC (gel permeation chromatography) under the following conditions.
1. Conversion standard material: Value obtained using polyacrylic acid (AMERICAN STANDARDS CORP) standard sample as a calibration curve2. Eluent: 0.2 mol/L phosphate buffer/CH ₃ CN = 9/1 (volume ratio),
pH=7
3. Column: PWXL+G4000PWXL+G2500PWXL (manufactured by Tosoh Corporation)
4. Detector: RI
5. Sample concentration: 5mg/mL
6. Injection volume: 0.1mL
7. Measured concentration: 40℃
8. Flow rate: 1.0mL/min

The textile treatment agent composition of the present invention contains component (b) preferably at least 0.0005% by mass, more preferably at least 0.0001% by mass, even more preferably at least 0.0015% by mass, and preferably at least 0.0015% by mass. The content is 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less.

In the textile treatment agent composition of the present invention, the mass ratio of the content of component (b) to the content of component (a) in the composition [component (b)/component (a)] is preferably 1/ It is 2000 or more, more preferably 1/1000 or more, still more preferably 1/500 or more, and preferably 1/4 or less. Here, the content of component (a) is the content as a fragrance compound contained in component (a).

<(c) component>
Component (c) is preferably at least one compound selected from a tertiary amine represented by the following general formula (C1), an acid salt thereof, and a quaternized product of the amine. Component (c) is a component that is added to the composition separately from component (a). Component (c) refers to something that is present in the composition without being included in component (a).

[In the formula, the R ^c1 group is a hydrocarbon group having a total carbon number of 12 to 28, which may be separated by one or more selected from ester groups, amide groups, and ether groups, and the R ^c2 group and Each R ^c3 group is independently a group selected from an R ^c1 group, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl ether alkylene group having 4 to 6 carbon atoms. It is. ]

In the general formula (C1), the R ^c1 group has a total carbon number of 12 or more, preferably 14 or more, and 28 or less, preferably 28 or more, separated by one or more selected from ester groups, amide groups, and ether groups. is preferably a hydrocarbon group of 26 or less. In this case, the hydrocarbon group may be either saturated or unsaturated. That is, preferable R ^c1 groups include the groups shown in (i) to (iii) below.
(i) A saturated hydrocarbon group with a total carbon number of 12 or more, preferably 14 or more, and 28 or less, preferably 26 or less, separated by one or more selected from ester groups, amide groups, and ether groups ) Has one or more double bonds with a total carbon number of 12 or more, preferably 14 or more, and 28 or less, preferably 26 or less, separated by one or more selected from ester groups, amide groups, and ether groups. Unsaturated hydrocarbon group (iii) A mixture of the above groups (i) and (ii)

Preferred R ^c2 groups and R ^c3 groups are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl ether alkylene having 4 to 6 carbon atoms. Examples include groups selected from the group consisting of:

Component (c) is, for example, a fatty acid or a fatty acid lower alkyl ester having a total of 12 to 28 carbon atoms, an alkanolamine having an alkanol group having 2 or 3 carbon atoms, or an aminoalkylamine having an alkylamine group having 2 or 3 carbon atoms. It can be obtained by an esterification reaction, amidation reaction, or transesterification reaction with an amine such as, or by reacting the alkanolamine with an alkylene oxide having 2 or 3 carbon atoms and then performing the reaction. can.

As the fatty acid or fatty acid lower alkyl ester, fatty acids having a total number of carbon atoms of 12 to 28 or lower alkyl esters thereof (alkyl group having 1 to 3 carbon atoms) are suitable, and one type or a mixture of two or more types may be used. Can be done.
Fatty acids or fatty acid lower alkyl esters may be prepared using fatty acids as known in the Oil Chemistry Handbook (4th edition, Japan Oil Chemists' Society, Maruzen Co., Ltd., November 20, 2001), etc., as necessary. Alternatively, it may be a single fatty acid or a fatty acid mixture containing fatty acids with different chain lengths or unsaturated fatty acids derived from natural fats and oils such as coconut oil, palm oil, and beef tallow. Mixtures of different types of fatty acids, such as fatty acids derived from natural fats and oils, can be prepared by hydrogenation of unsaturated bonds, isomerization of unsaturated bonds, adjustment of the alkyl chain length by distillation, bottom cutting, top cutting, or multiple processes. Those obtained by mixing fatty acids can be used.

The aminoalkylamine mentioned above is preferably an amine having at least two or more types of amino groups selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Further, the alkanolamine described above essentially has a hydroxy group in its molecule, and amines having primary to tertiary amino groups are preferred. More specific examples include dialkyl monoalkanolamines (preferably dimethyl monoethanolamine or dimethyl monopropanolamine), monoalkyl dialkanolamines (preferably methyldiethanolamine or methyldipropanolamine), or trialkanolamines (preferably tri-alkanolamines). di(aminoalkyl)alkylamines (e.g. N-methyl-N,N-di(3-aminopropyl)amine), dialkylaminoalkylamines (e.g. N,N-dimethyl -N-(3-aminopropyl)amine), alkylaminopropylmonoalkylalkanolamine (preferably N-methyl-N-(2-hydroxyethyl)-N-(3-aminopropyl)amine). , but not limited to these. More preferably N-methyldiethanolamine, triethanolamine, N-methyl-N-(2-hydroxyethyl)-N-(3-aminopropyl)amine, N,N-dimethyl-N-( 3-aminopropyl)amine and N,N-dimethyl-N-(2-hydroxyethyl)amine.

Examples of the acid salt of the tertiary amine represented by the general formula (C1) include acid salts neutralized with inorganic acids and organic acids. Preferred inorganic acids are hydrochloric acid, sulfuric acid, and phosphoric acid, and preferred organic acids are monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, or monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms, or These are alkyl sulfate esters having 6 to 36 carbon atoms, or polyoxyalkylene alkyl sulfates (alkyl group having 6 to 36 carbon atoms). More preferably methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-)xylene sulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, citric acid, benzoic acid, salicylic acid, carbon These are alkyl sulfate esters having 12 to 36 carbon atoms, or polyoxyalkylene alkyl sulfates (alkyl group having 12 to 36 carbon atoms).

As the quaternized product of the tertiary amine represented by the general formula (C1), the tertiary amine represented by the general formula (C1) is 4 Examples include graded compounds. Methyl chloride is preferred as the alkyl halide, dimethyl sulfate and diethyl sulfate are preferred as the dialkyl sulfate, and ethylene oxide is preferred as the alkylene oxide. In addition, the quaternization reaction using an alkylating agent can be carried out in the presence of a solvent (e.g., ethanol); Therefore, it can also be carried out without a solvent.

Component (c) may be a component containing one or more selected from the following components (c1) and (c2). These are preferable when the textile treatment agent composition of the present invention is used as a liquid softener composition.
Component (c1): A tertiary amine compound represented by the following general formula (C2) and its acid salt.
Component (c2): A quaternized product of a tertiary amine compound represented by the following general formula (C2). In this case, the organic group bonded to the nitrogen atom through quaternization is R ^c14 , and the counter ion is X ^- .
[R ^c11 -C(=O)-O-(C _p H _2p O) _r -C _q H _2q ] _m N(R ^c12 ) _3-m (C2)
[In the formula, R ^c11 is a hydrocarbon group having 11 or more and 23 or less carbon atoms,
R ^c12 is a group selected from a hydrocarbon group having 1 to 3 carbon atoms and a HO-(C _p H _2p O) _r -C _q H _2q group,
m is a number of 1 or more and 3 or less, p and q are each independently a number of 2 or 3, and r is a number of 0 or more and 5 or less.
When a plurality of R ^c11 , R ^c12 , p, q, and r exist in the same molecule, they may be the same or different. Further, the total number of carbon atoms in R ^c11 -C(=O)-O-(C _p H _2p O) _r -C _q H _2q is 14 or more and 28 or less. ]

R ^c11 in the general formula (C2) has 11 to 23 carbon atoms, and is preferably an acyclic hydrocarbon group having 13 to 21 carbon atoms from the viewpoint of softening the textile product.
Specific examples of R ^c11 include straight-chain or branched alkyl groups having 13 to 21 carbon atoms, straight-chain or branched alkenyl groups having 13 to 21 carbon atoms, and preferably 13 to 21 carbon atoms. Examples include a group selected from a straight-chain alkyl group and a straight-chain alkenyl group having 13 to 21 carbon atoms.

Component (c1) is preferably a mixture of compounds in which R ^c11 in the general formula (C2) is composed of different substituents, and is a mixture of a compound in which R ^c11 is an alkyl group and a compound in which R c11 is an alkenyl group. It is more preferable that
The ratio of the compound consisting of an alkyl group and the compound consisting of an alkenyl group can be determined depending on the composition of the fatty acid or fatty acid ester used as the raw material. The amount of alkyl groups and the amount of alkenyl groups can be adjusted by hydrogenating a raw material having an alkenyl group or by hydrogenating a compound in which R ^c11 is an alkenyl group.

The unsaturated group contained in the alkenyl group has a cis form and a trans form. The molar ratio of the cis isomer to the trans isomer [cis isomer/trans isomer] is preferably 30/70 or more and 99/1 or less, and more preferably 50/50 or more and 97/3 or less from the viewpoint of availability of the alkenyl group. It is. In the present invention, the ratio of the cis isomer to the trans isomer can be calculated from the integral ratio of ¹ H-NMR.

p and q in general formula (C2) are each a number of 2 or 3. From the viewpoint of retaining the water absorbency of the treated fabric, p is preferably 2. From the viewpoint of ease of manufacture, q is preferably 2.
In general formula (C2), r is a number of 0 or 1, preferably 0, from the viewpoint of softening the textile product.
From the viewpoint of water absorption, R ^c12 is preferably a HO-(C _p H _2p O) _r -C _q H _2q group, and more preferably a HO-C ₂ H ₄ group.
m is preferably 1 or more and 2 or less from the viewpoint of water absorption.

Component (c1) is a tertiary amine compound represented by the general formula (C2) and its acid salt as described above, but the pH of the textile treatment agent composition of the present invention, for example, the liquid softener composition Accordingly, almost all of the component (c1) may be present in the composition in the form of an acid salt.
When the tertiary amine compound constituting component (c1) is present as an acid salt, examples of the acid include inorganic acids and organic acids.
Inorganic acids include hydrochloric acid and sulfuric acid.
Examples of organic acids include alkyl sulfuric acids having 1 to 3 carbon atoms, monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, and monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms. . Specific examples of organic acids include methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-)xylene sulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, citric acid, and benzoic acid. acid, and salicylic acid.

The method for producing the amine compound represented by the general formula (C2), which is the component (c1), is not particularly limited, but includes, for example, an esterification reaction between an alkanolamine compound represented by the following general formula (C2-1) and a fatty acid; Alternatively, it can be obtained by a transesterification reaction between an alkanolamine compound represented by the general formula (C2-1) and a fatty acid ester.
As the fatty acid, fatty acids derived from palm kernel oil, coconut oil, beef tallow, rapeseed oil, and sunflower oil can be used, and the fatty acid ratio may be adjusted, or fatty acids from different origins can be used in combination. You can.

[HO-(C _p H _2p O) _r -C _q H _2q ] _n N(R ^c13 ) _3-n (C2-1)
[In the formula, R ^c13 is a group selected from hydrocarbon groups having 1 to 3 carbon atoms, n is a number of 1 to 3, and p, q, and r have the same meanings as in the above general formula (C2). represent. ]

As an example of the esterification reaction, for example, the method described on pages 8 to 9 of Japanese Patent Publication No. 2000-510171 can be applied.
As an example of the transesterification reaction, for example, the method described in paragraphs [0013] to [0016] of JP-A-7-138211 can be applied.

Component (c2) is a quaternized product of the tertiary amine compound represented by the general formula (C2), and is a quaternized product of the tertiary amine compound represented by the general formula (C2) and an alkylating agent. It can be obtained by a grading reaction. Examples of R ^c14 in the component (c2) include a methyl group, an ethyl group, and a benzyl group, and preferably a methyl group or an ethyl group. Further, examples of the counter ion X ⁻ in component (c) include chlorine ion, bromide ion, methyl sulfate ion, and ethyl sulfate ion.

The textile treatment agent composition of the present invention contains component (c) preferably at least 1% by mass, more preferably at least 3% by mass, even more preferably at least 5% by mass, and more preferably at most 20% by mass. The content is preferably 18% by mass or less, more preferably 15% by mass or less.

In the textile treatment agent composition of the present invention, the mass ratio of the content of component (c) to the content of component (a) in the composition [component (c)/component (a)] is preferably 1/ It is 50 or more, more preferably 1/1 or more, and preferably 200/1 or less, more preferably 100/1 or less. Here, the content of component (a) is the content as a fragrance compound contained in component (a).

<Components that may be contained in the textile treatment agent composition of the present invention>
The textile treatment agent composition of the present invention can further contain the following components.

<(d) component>
The textile treatment agent composition of the present invention can contain, as component (d), a perfume compound other than the perfume compound included in component (a).
In the present invention, even if the fragrance compound is the same as the fragrance compound encapsulated in the microcapsules of the component (a), the fragrance compound that is not encapsulated in the microcapsules of the component (a) is treated as the component (d). . That is, the fragrance compound of component (d) is a fragrance compound dispersed in the textile product treatment agent composition, and these fragrance compounds are sometimes referred to as external fragrance.

There is no particular restriction on the fragrance compound that can be used as the component (d), and the same fragrance compound as the fragrance compound used for the component (a) may be used. Component (d) can be blended into the textile treatment agent composition of the present invention as a fragrance composition containing a plurality of fragrance compounds.
Examples of fragrance compounds that can be used as the component (d) include the fragrances and patents described in "Basic Knowledge of Fragrances and Perfumes, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005, 4th edition." In addition to perfume compounds that are known to be incorporated into fabric softeners and the like through literature, it is also possible to use perfume ingredients or perfume compositions prepared independently by perfume manufacturers.
Component (d) includes, for example, β-ionone (4.4), γ-undecalactone (3.1), γ-nonalactone (2.1), γ-methylionone (4.8), ambroxane ( 4.8), IsoE Super (5.2), Ethyl Vanillin (1.6), Ethylene Brassylate (4.7), Eugenol (2.7), Cashmeran (manufactured by IFF) (4.5), Coumarin (1.5), geraniol (3.5), o,t-butylcyclohexyl acetate (4.4), citronellyl acetate (4.6), dimethylbenzylcarbinyl acetate (3.4), sandal mysore core ( 4.7), methyl dihydrojasmonate (3.5), dihydromircenol (3.5), dimethyltetrahydrobenzaldehyde (2.9), Javanol (manufactured by Givaudan) (4.7), Neroline Yarayara (3.3) ), Habanolide (manufactured by Firmenich) (4.9), Flutate (Kao Corporation) (3.6), Peonyl (manufactured by Givaudan) (4.3), Hexylcinnamic aldehyde (4.8), Heliotropin (1 .8), methyl β-naphthyl ketone (2.9), methyl anthranilate (2.3), raspberry ketone (1.5), limonene (4.8), and Lilial (4.4). can. Note that the numbers in parentheses are logP values.

In addition, the textile processing agent composition of the present invention may contain a diluent and a retention agent for the fragrance compound. Examples of diluents and retention agents include dipropylene glycol, isopropyl palmitate, diethyl phthalate, penzyl benzoate, liquid paraffin, isoparaffin, and fats and oils.
When using a diluent and a retention agent, the amount of the diluent and retention agent relative to the total of component (d), the diluent, and the retention agent is preferably 0% by mass or more and 20% by mass or less. Note that these diluents and retention agents can also be used for the fragrance compound encapsulated in microcapsules as component (a).

By using component (d) in combination with component (a), it becomes possible to design fragrances with a higher degree of freedom than before. Therefore, when a textile product is treated with the textile product treating agent composition of the present invention containing component (d) in combination, a fresh and rich fragrance can be imparted, for example.

When the textile treatment agent composition of the present invention contains component (d), its content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, preferably 2.5% by mass from the viewpoint of storage stability (hereinafter also referred to as storage stability) of the textile treatment agent composition and aroma balance with other fragrance components. The content is more preferably 2.0% by mass or less, and even more preferably 1.8% by mass or less. The content of component (d) in the textile treatment agent composition can be adjusted depending on the product.

In addition, when the textile product treatment agent composition of the present invention contains the (d) component, the total content of the (a) component and (d) component is determined from the viewpoint of sufficiently imparting fragrance to the textile product. , preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, from the viewpoint of storage stability and aroma balance with other fragrance ingredients. Preferably it is 2.8% by mass or less, more preferably 2.5% by mass or less, still more preferably 2.0% by mass or less.

<(e) Component>
The textile treatment agent composition of the present invention comprises, as component (e), a polyoxyalkylene alkyl ether having an alkyl group having 8 to 24 carbon atoms, and a polyoxyalkylene alkenyl having an alkenyl group having 8 to 24 carbon atoms. It can contain one or more nonionic surfactants selected from ethers.

As component (e), at least one kind selected from nonionic surfactants represented by the following general formula (4) is preferable.

R ^1e -A- [(R ^2e O) _p -R ^3e ] _q (4)
[In the formula, R ^1e is an alkyl group or alkenyl group having 8 or more carbon atoms, preferably 10 or more, and 24 or less, preferably 18 or less, more preferably 16 or less, and R ^2e has 2 or more carbon atoms. or 3 alkylene group, preferably an ethylene group, R ^3e is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, p is 2 or more, preferably 5 or more, more preferably 10 or more, and The number is 100 or less, more preferably 80 or less, even more preferably 60 or less, and the addition form may be either random addition or block addition. A is -O-, -COO-, -CONH-, -NH-, -CON< or -N<, and when A is -O-, -COO-, -CONH- or -NH-, q is 1 and q is 2 when A is -CON< or -N<. ]

Specific examples of the compound of general formula (4) include compounds represented by the following formulas (4-1) to (4-4).

R ^1e -O-(C ₂ H ₄ O) _r -H (4-1)
[In the formula, R ^1e has the above meaning. r is a number of 8 or more, preferably 10 or more, and 100 or less, preferably 60 or less. ]
R ^1e -O-(C ₂ H ₄ O) _s / (C ₃ H ₆ O) _t -H (4-2)
[In the formula, R ^1e has the above meaning. s and t are each independently a number of 2 or more, preferably 5 or more, and 40 or less, and (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. . ]
R ^1e -O-(C ₂ H ₄ O) _x1 -(C ₃ H ₆ O) _y -(C ₂ H ₄ O) _x2 -H (4-3)
[In the formula, R ^1e has the above meaning. x1, y, and x2 are the average number of added moles, x1 is 1 to 13, y is 1 to 4, x2 is 1 to 13, and (C ₂ H ₄ O) and (C ₃ H ₆ O) and (C ₂ H ₄ O) are block adducts. ]

[In the formula, R ^1e has the above meaning. B is -N< or -CON<, u and v are each independently a number from 0 to 40, and u+v is a number from 5 to 60, preferably 40 or less. R ^4e and R ^5e each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

When the textile treatment agent composition of the present invention contains component (e), its content is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, even more preferably The content is 2.0% by mass or more, and preferably 5.0% by mass or less, more preferably 4.5% by mass or less, and still more preferably 4.0% by mass or less.

<(f) component>
The textile treatment agent composition of the present invention may contain an inorganic salt as component (f) from the viewpoint of improving storage stability.
From the viewpoint of improving storage stability, the inorganic salt is preferably one or more selected from sodium chloride, calcium chloride, and magnesium chloride.
When the textile treatment agent composition of the present invention contains component (f), the content is preferably 0.005% by mass in the composition from the viewpoint of improving the dispersibility of the textile treatment agent composition. The above, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, and from the viewpoint of improving the storage stability of the textile treatment agent composition, preferably 1.0% by mass or less, more It is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

<(g) Component>
The textile treatment agent composition of the present invention may contain an ester of a polyhydric alcohol and a fatty acid as the component (g) from the viewpoint of improving storage stability.
As the ester of a polyhydric alcohol and a fatty acid, an ester compound of a polyhydric alcohol having 3 or more and 6 or less carbon atoms and having 3 or more and 6 hydrides and a fatty acid having 12 or more and 22 or less carbon atoms is preferable.
More specifically, the number of carbon atoms is preferably 3 or more, more preferably 4 or more, and preferably 6 or less, and preferably 3 or more, more preferably 4 or more, and preferably 6. It is an ester compound of a polyhydric alcohol having a carbon number of 12 or more, more preferably 14 or more, even more preferably 16 or more, and preferably 22 or less, more preferably 20 or less carbon atoms.
(g) The polyhydric alcohol constituting the component is one selected from glycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, arabitol, pentaerythritol, sorbitan, sorbitol, xylitol, and mannitol. One or more types are preferable, and one or more types selected from pentaerythritol and sorbitan are more preferable.
(g) The fatty acids constituting the component include saturated fatty acids such as lauric acid, myristic acid, stearic acid, and palmitic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, and linolenic acid, palm oil fatty acids, and fatty acids derived from vegetable oils such as hydrogenated palm oil fatty acids, fatty acids derived from animal oils such as beef tallow fatty acids and hydrogenated beef tallow fatty acids, and one or more fatty acids selected from saturated fatty acids, fatty acids derived from vegetable oils, and fatty acids derived from animal oils. The above are more preferred, and one or more selected from stearic acid, hydrogenated palm oil fatty acid, and hydrogenated beef tallow fatty acid is even more preferred.
Component (g) in the present invention includes an ester compound of pentaerythritol and a fatty acid having 16 to 22 carbon atoms (hereinafter also referred to as "pentaerythritol fatty acid ester"), and an ester compound of sorbitan and a fatty acid having 16 to 22 carbon atoms. One or more selected from ester compounds (hereinafter also referred to as "sorbitan fatty acid esters") are preferred.

When the textile treatment agent composition of the present invention contains component (g), the content of component (g) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more in the composition. , more preferably 0.5% by mass or more, even more preferably 0.7% by mass or more, and preferably 5.0% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less. .

<(h) component>
The textile treatment agent composition of the present invention may contain an amphoteric surfactant as component (h).

Component (h) is not particularly limited as long as it can be generally incorporated into liquid softener compositions, and examples include alkyl (carbon number 12 to 22) amidopropylcarbobetaine, alkyl (carbon number Amidopropyl sulfobetaine (number 12 to 22), alkyl (carbon number 12 to 22) carbobetaine, alkyl (carbon number 12 to 22) sulfobetaine, alkyl (carbon number 10 to 18) dimethylamine oxide, etc. It will be done.

When the textile treatment agent composition of the present invention contains component (h), the content of component (h) is determined from the viewpoint of reducing the viscosity of the textile treatment agent composition and improving the bactericidal property. In the composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and storage stability From the viewpoint of suppressing a decrease in the flexibility effect, the content is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2.5% by mass or less.

<(i) Component>
The textile treatment agent composition of the present invention may contain a water-insoluble silicone compound as component (i). As used herein, the term "water-insoluble" in component (i) means that the amount of the silicone compound dissolved in 1 L of ion-exchanged water at 20° C. is 1 g or less.
Specific examples of component (i) include dimethylpolysiloxane, quaternary ammonium-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, carboxy-modified dimethylpolysiloxane, and polyoxyalkylene-modified Examples include silicone compounds such as dimethylpolysiloxane and fluorine-modified dimethylpolysiloxane.

Component (i) is selected from dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, and polyoxyalkylene (polyoxyethylene and/or polyoxypropylene, preferably polyoxyethylene)-modified dimethylpolysiloxane. One or more types are preferred. The weight average molecular weight of component (i) is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and preferably 1,000,000 or less. Component (i) has a viscosity at 25° C. of preferably 2 mm ² /s or more, more preferably 500 mm ² /s or more, even more preferably 1,000 mm ² /s or more, and preferably 1 million mm ² /s or less. The weight average molecular weight of component (i) is a value measured by gel permeation chromatography using polystyrene as a standard substance.

The amino equivalent of the amino-modified dimethylpolysiloxane (amino equivalent is the molecular weight per nitrogen atom) is preferably 1,500 g/mol or more, more preferably 2,500 g/mol or more, and even more preferably 3,000 g/mol. and preferably 40,000 g/mol or less, more preferably 20,000 g/mol or less, and even more preferably 10,000 g/mol or less.

When the textile product treatment agent composition of the present invention contains component (i), the content of component (i) is preferably 0.00 to 100% in the composition from the viewpoint of imparting a refreshing finish to the textile product. The content is 1% by mass or more, more preferably 0.5% by mass or more, and from the viewpoint of dispersibility, preferably 5% by mass or less.
Further, when the textile treatment agent composition of the present invention contains component (i), the content of component (i) is preferably 0.001% by mass or more in the composition from the viewpoint of suppressing foaming. Preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass. % or less.

<(j) component>
The textile treatment agent composition of the present invention can contain an acid agent as component (j) from the viewpoint of adjusting the pH of the textile treatment agent composition.
Examples of acid agents include inorganic acids and organic acids, and specific examples of inorganic acids include hydrochloric acid and sulfuric acid. Specific examples of organic acids include monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms, and alkyl sulfuric acids having 1 to 3 carbon atoms. can be mentioned. More specifically, methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-)xylene sulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, ethylenediaminetetraacetic acid, citric acid. , benzoic acid, and salicylic acid.
Among these, acid agents selected from hydrochloric acid and monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms are preferred, and acid agents selected from hydrochloric acid and citric acid are more preferred.
When the textile treatment agent composition of the present invention contains an acid agent, the content can be adjusted as appropriate, and is preferably an amount that provides a pH within the range described below and does not impair storage stability. .

<(k) component>
The textile treatment agent composition of the present invention may contain a fatty acid having 12 or more and 22 or less carbon atoms from the viewpoint of improving the softening effect.
The fatty acid of component (k) may be contained as an unreacted product during the synthesis of component (c) or a decomposed product of component (c).
Component (k) is preferably a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, and specific examples include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, and erucic acid. , and behenic acid, and more preferably fatty acids selected from palmitic acid, stearic acid, oleic acid, and linoleic acid.

When the textile treatment agent composition of the present invention contains component (k), the content of component (k) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more in the composition. , more preferably 0.1% by mass or more, and preferably 0.3% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less.

<(l) component>
The textile treatment agent composition of the present invention may contain a water-soluble organic solvent as component (l) from the viewpoint of storage stability and viscosity.
Examples of the water-soluble organic solvent include common water-soluble organic solvents used in textile treatment agent compositions. Note that the "water-soluble organic solvent" in component (l) refers to an organic solvent that dissolves 20 g or more in 100 g of deionized water at 20°C.
Specific examples of the water-soluble organic solvent include propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. Among these, water-soluble organic solvents selected from ethylene glycol, ethanol, and propylene glycol are preferred.

If the textile treatment agent composition of the present invention is sufficiently stabilized by other components and has a low viscosity, it may not contain the water-soluble organic solvent as component (l).
When the textile treatment agent composition of the present invention contains component (l), the content of component (l) is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably The content is 5% by mass or less, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more.

<(m) component>
In the textile treatment composition of the present invention, a chelating agent may be used as the component (m) from the viewpoint of suppressing hue change, fading of dye, and deterioration of fragrance during long-term storage of the textile treatment composition. preferable. Note that component (m) in the present invention may also have a function as the acid agent.

Specific examples of chelating agents include ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, and L-glutamic acid-N,N-diacetic acid. Examples include acetic acid, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid, and salts thereof. As the salt, alkali metal salts and ammonium salts are preferred, and sodium salts and potassium salts are more preferred.

When the textile treatment agent composition of the present invention contains component (m), the content of component (m) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more in the composition. and, preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass. % or less.

<(n) component>
The textile treatment agent composition of the present invention can contain, as component (n), microcapsules other than component (a) that encapsulate a perfume compound, or a perfume precursor.
By using component (n) in combination with component (a) and component (d), it becomes possible to design fragrances with a higher degree of freedom than before. Component (n) includes a silicate ester compound described in JP-A No. 2014-125685 as a sustained-release fragrance, an alcohol-based fragrance compound described in Japanese Patent Application Publication No. 8-502522, and an aliphatic monocarboxylic acid or an aliphatic Ester compounds with dicarboxylic acids can be used.

When the textile treatment agent composition of the present invention contains component (n), the content of component (n) is preferably 0.15% by mass or more, more preferably 0.3% by mass or more in the composition. , more preferably 0.45% by mass or more, and preferably 0.65% by mass or less, more preferably 0.6% by mass or less, still more preferably 0.55% by mass or less.

When the textile product treatment agent composition of the present invention contains component (n), the total content of component (a), component (d), and component (n) is determined from the viewpoint of sufficiently imparting fragrance to textile products. In the composition, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and a balance between storage stability and flavor intensity palatability. From this point of view, the content is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less.

Note that the mass % of the component (n) is calculated based on the mass of the perfume compound contained in the microcapsules of the component (n) and the perfume compound constituting the perfume precursor of the component (n).

<(o) component>
In the textile treatment agent composition of the present invention, an antioxidant such as butylated hydroxytoluene (BHT) can be used from the viewpoint of suppressing deterioration of the base material, and also prevents aesthetics and discoloration during long-term storage. From this point of view, dyes and pigments commonly used in textile treatment agent compositions can also be used. Furthermore, an antibacterial and antifungal agent commercially available under the trade name of Proxel can also be used. Furthermore, benzoic acid and its salts can also be used as antibacterial and antifungal agents.

<Other ingredients, etc.>
The textile treatment agent composition of the present invention preferably contains water. Preferably, it is a liquid composition containing water. Water is usually the balance of the composition and is used so that the ingredients total 100% by weight. The textile treatment agent composition of the present invention contains water, preferably 60% by mass or more, more preferably 65% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.

The textile treatment agent composition of the present invention has a pH at 20°C of preferably 2.0 or more, more preferably 2.2 or more, and preferably 4.0 or less, more preferably 3.8 or less. be. The method for measuring pH was described in the Examples.

The textile processing agent composition of the present invention is suitable for textile products, and textile products include clothing, fabrics, bedding, towels, and the like.
The textile treatment agent composition of the present invention can be used for softening treatment of textile products. For example, the textile treatment agent composition of the present invention may be a textile softener composition or a textile fabric softener composition.

The textile treatment agent composition of the present invention can be produced by mixing component (a), component (b), component (c), and water. The textile treatment agent composition of the present invention is produced by, for example, producing component (a) by a method including step 1 and step 2, and adding the obtained component (a) to component (b), component (c) and water. It can be manufactured by mixing with In these manufacturing methods, the above-mentioned optional components can be mixed as appropriate.

<Processing method for textile products>
The present invention provides a method for treating textile products, in which a treatment liquid obtained by mixing components (a), (b), (c) and water is brought into contact with textile products.
The (a) component, (b) component, and (c) component used in the textile product treatment method of the present invention are the (a) component, (b) component, ( c) ingredients may be used. Preferred embodiments of component (a), component (b), component (c), etc. are also the same as in the textile treatment agent composition of the present invention. The matters described for the textile product treatment agent composition of the present invention can be appropriately applied to the fiber treatment method of the present invention.

In the method for treating textile products of the present invention, it is preferable that the treatment liquid is obtained by mixing the textile product treatment agent composition of the present invention and water.

<Fragrance compounds>
Model fragrance A-1, a fragrance composition having the composition shown in Table 1-1, and model fragrance A-2, a fragrance composition having the composition shown in Table 1-2, were used as fragrance compounds to be encapsulated in microcapsules. there was.

<(a) Component>
(a-1): Silica capsules obtained in Synthesis Example 1 below (a-2): Silica capsules obtained in Synthesis Example 2 below

<Synthesis Example 1> Synthesis of (a-1) (Step 1)
A water phase component was obtained by diluting 3.0 g of Cortamine 60W (trade name, manufactured by Kao Corporation, cetyltrimethylammonium chloride, effective content: 30% by mass) with 750 g of ion-exchanged water. To this aqueous phase component, an oil phase component prepared by mixing 200 g of model fragrance A-1 with the mixing ratio shown in Table 1 and 50 g of tetraethoxysilane (hereinafter also referred to as "TEOS") was added, and a homomixer was added. (Manufactured by HsiangTai, model: HM-310, hereinafter the same) was used to emulsify the mixture at a rotation speed of 8,500 rpm to obtain an emulsion. The median diameter _D50 of the emulsified droplets at this time was 1.4 μm.
After adjusting the pH of the obtained emulsion to 3.8 using a 1% aqueous sulfuric acid solution, it was transferred to a separable flask equipped with a stirring blade and a cooler, and heated at 200 rpm for 24 hours while maintaining the liquid temperature at 30°C. By stirring, an aqueous dispersion containing silica capsules (1-1) having a core made of model fragrance A-1 and a first shell made of silica was obtained.

(Step 2)
While stirring the aqueous dispersion obtained in Step 1 at a liquid temperature of 30° C., 21 g of TEOS was added dropwise over 420 minutes. After dropping, stirring was continued for an additional 17 hours and then cooled to form a second shell that included the first shell, and contained silica capsules (A-1) in which model fragrance A was encapsulated with amorphous silica. An aqueous dispersion was obtained. The median diameter _D50 of the silica capsule (A-1) was 2.1 μm. The median diameter _D50 of the emulsified droplets and silica capsules (A-1) was measured using a laser diffraction/scattering particle size distribution measuring device "LA-960" (trade name, manufactured by Horiba, Ltd.). A flow cell was used for the measurement, the medium was water, and the refractive index was set at 1.40-0i. An emulsion or an aqueous dispersion containing silica capsules was added to a flow cell, measurement was performed at a concentration where the transmittance was around 90%, and the median diameter D ₅₀ was determined on a volume basis.
Note that the thickness of the first shell was approximately 5 nm, and the thickness of the second shell was 5 to 30 nm.

<Synthesis Example 2> Synthesis of (a-2) (Step 1)
A water phase component was obtained by diluting 3.0 g of Cortamine 60W (trade name, manufactured by Kao Corporation, cetyltrimethylammonium chloride, effective content: 30% by mass) with 750 g of ion-exchanged water. To this aqueous phase component, an oil phase component prepared by mixing 200 g of model fragrance A-2 with the mixing ratio shown in Table 1 and 50 g of tetraethoxysilane (hereinafter also referred to as "TEOS") was added, and a homomixer was added. (Manufactured by HsiangTai, model: HM-310, hereinafter the same) was used to emulsify the mixture at a rotation speed of 8,500 rpm to obtain an emulsion. The median diameter _D50 of the emulsified droplets at this time was 1.4 μm.
After adjusting the pH of the obtained emulsion to 3.8 using a 1% aqueous sulfuric acid solution, it was transferred to a separable flask equipped with a stirring blade and a cooler, and heated at 200 rpm for 24 hours while maintaining the liquid temperature at 30°C. By stirring, an aqueous dispersion containing silica capsules (1-1) having a core made of model fragrance A-2 and a first shell made of silica was obtained.

(Step 2)
While stirring the aqueous dispersion obtained in Step 1 at a liquid temperature of 30° C., 21 g of TEOS was added dropwise over 420 minutes. After dropping, stirring was continued for an additional 17 hours and then cooled to form a second shell that encloses the first shell, containing silica capsules (A-2) in which model fragrance A is encapsulated with amorphous silica. An aqueous dispersion was obtained. The median diameter _D50 of the silica capsule (A-2) was 2.1 μm. The median diameter D ₅₀ of the emulsified droplets and silica capsules (A-2) was measured using a laser diffraction/scattering particle size distribution measuring device "LA-960" (trade name, manufactured by Horiba, Ltd.). A flow cell was used for the measurement, the medium was water, and the refractive index was set at 1.40-0i. An emulsion or an aqueous dispersion containing silica capsules was added to a flow cell, measurement was performed at a concentration where the transmittance was around 90%, and the median diameter D ₅₀ was determined on a volume basis.
Note that the thickness of the first shell was approximately 5 nm, and the thickness of the second shell was 5 to 30 nm.

<(b) component>
(b-1): Poise 520 (manufactured by Kao Corporation), sodium salt of acrylic acid-maleic acid copolymer, acrylic acid/maleic anhydride = 71/29 (mole ratio), weight average molecular weight 30,000 (b-2) : Poise 521 (manufactured by Kao Corporation), sodium salt of acrylic acid-maleic acid copolymer, acrylic acid/maleic anhydride = 44/56 (mole ratio), weight average molecular weight 20,000 (b-3): Marquat 3940 (Japan) Manufactured by Lubrizol Co., Ltd., acrylic acid-diallyldimethylammonium salt-acrylamide copolymer, acrylic acid/diallyldimethylammonium chloride/acrylamide = 30/30/40 (mole ratio), weight average molecular weight = 150,000)

<(c) component>
(c-1): Reaction mixture obtained in Synthesis Example 3 below (c-2): Reaction mixture (c-3) obtained in Synthesis Example 4 below: N-(3) obtained in Synthesis Example 5 below. -alkanoylaminopropyl)-N,N-dimethylamine

<Synthesis Example 3> Synthesis of (c-1) Triethanolamine and a fatty acid represented by R ¹ COOH are subjected to an esterification reaction at a reaction molar ratio (fatty acid/triethanolamine) of 1.65/1. An esterification reaction product containing an amine compound represented by formula (c1) was obtained.
The esterification reaction product contained 5% by mass of unreacted fatty acids (the composition is as described below). After performing a quaternization reaction with dimethyl sulfuric acid so that the methyl group was 0.96 equivalent to the amine of the amine compound in the esterification reaction product, 10% by mass of ethanol was added.

The obtained reaction product was analyzed for the composition ratio of each component by HPLC method, and as a result of quantitative determination using tetraoctylammonium bromide as an internal standard, the obtained reaction product was found to have the following component (c11-1): It was a mixture (100% by mass in total) consisting of component (c11-2), components (c21-1) to (c21-3), and unreacted fatty acids. The quaternization rate was 86%. The quaternization rate can be determined from the amine value.

The content in parentheses is the quaternary ammonium ion moiety (excluding CH ₃ OSO ₃ ^- ) of component (c11-1), component (c11-2), and components (c21-1) to (c21-3). (part) and the content ratio of each component in the total amount of unreacted fatty acids.

The composition of R ¹ COOH used in the reaction for producing (c-1) is shown below.
Palmitic acid: 45% by mass
Stearic acid: 25% by mass
Fatty acid with 18 carbon atoms and one unsaturated group: 27% by mass
Fatty acid with 18 carbon atoms and two unsaturated groups: 3% by mass
The composition was determined by analyzing the fatty acids used as raw materials by gas chromatography, and determining the area percentage of each fatty acid as mass percentage. The mass ratio of the cis/trans form of the unsaturated group is 85/15 (integral ratio according to ¹ H-NMR).

<Synthesis Example 4> Synthesis of (c-2) Triethanolamine and a fatty acid represented by RCOOH are subjected to an esterification reaction at a reaction molar ratio (fatty acid/triethanolamine) of 1.87/1. I got something.
The esterification reaction product contained 1% by mass of unreacted fatty acids (composition is as described below). After performing a quaternization reaction with dimethyl sulfuric acid so that the methyl group was 0.96 equivalent to the amine of the amine compound in the esterification reaction product, ethanol was added.

The obtained reaction product was analyzed for the composition ratio of each component by HPLC method, and as a result of quantitative determination using tetraoctylammonium bromide as an internal standard substance, the obtained reaction product was component (c) (c- 2) Contained 66% by mass of ingredients, 15% by mass of ethanol, 17% by mass of unreacted amine salt (as methyl sulfate), 1% by mass of unreacted fatty acid, trace amounts of quaternized triethanolamine, and other trace components. . In addition, component (c-2), which is component (c), is a hydrocarbon group in which R ^c11 is R in the following RCOOH composition in general formula (C2), and r = 0, q = 2, and m = 1, the plurality of R ^c12 are both hydroxyethyl groups (structure of r=0, q=2), the organic group added by quaternization is R ^c14 is a methyl group, and X ^- is The compound that is methyl sulfate ion is 22% by mass in (c-2), and in the general formula (C2), R ^c11 is a hydrocarbon group having the composition of RCOOH below, r = 0, q = 2, and m = 2, R ^c12 is a hydroxyethyl group (r = 0, q = 2 structure), R ⁴ is a methyl group, and X ^- is a methyl sulfate ion, in (c-2) 58% by mass, in the general formula (C2), R ^c11 is a hydrocarbon group which is R in the composition of RCOOH below, r = 0, q = 2 and m = 3, and R ⁴ is a methyl group, , the compound in which X ⁻ is a methyl sulfate ion was 20% by mass in (c-2). Moreover, the quaternization rate was 80% by mass.

The composition of RCOOH used in the reaction to produce (c-2) is shown below.
Oleic acid: 80% by mass
Linoleic acid: 10% by mass
Linolenic acid: 2% by mass
Stearic acid: 2% by mass
Palmitic acid: 6% by mass
The composition was determined by analyzing the fatty acids used as raw materials by gas chromatography, and determining the area percentage of each fatty acid as mass percentage.
Note that the values in the recipe table are converted to the concentration of component (c-2).

<Synthesis Example 5> Synthesis of (c-3) A mixed fatty acid having a beef tallow hydrogenated fatty acid composition and N-aminopropyl-N,N-dimethylamine were mixed in a usual method at a molar ratio of fatty acid/amine = 0.95/1. A dehydration condensation reaction was performed to obtain N-(3-alkanoylaminopropyl)-N,N-dimethylamine.

<(d) component>
(d-1): Flavor composition listed in Table 2

<(e) Component>
(e-1): Compound in which 30 mol of ethylene oxide is added to lauryl alcohol on average. That is, in the general formula (4-1), R ^1e is a linear alkyl group having 12 carbon atoms and is bonded to an oxygen atom. A nonionic surfactant in which the carbon atom of ^1e is a primary carbon atom and r is 30

<(f) component>
(f-1): Calcium chloride

<(i) Component>
(i-1): Aqueous emulsion of dimethylpolysiloxane produced in Synthesis Example 6 below.

<Synthesis Example 6> Synthesis of (i-1) 5 g of polyoxyethylene lauryl ether with an average added mole number of 5 moles was added to 300 g of dimethylpolysiloxane (viscosity 500,000 mm ² /s at 25°C) while applying high shear force. and continued stirring at high shear for an additional 10 minutes. Thereafter, 30 g of ion-exchanged water was added, then 2 g of polyoxyethylene lauryl ether sodium sulfate with an average added mole of 2 moles, and 15 g of polyoxyethylene myristyl ether with an average added mole of 40 moles, and further under high shear force, Stirring was continued for 30 minutes, and then 248 g of water was added and stirred to obtain an aqueous emulsion of dimethylpolysiloxane [(i-1)]. The volume average particle diameter of the emulsified particles in (i-1) was 500 nm. Further, the content of dimethylpolysiloxane in (i-1) was 50% by mass. The volume average particle diameter was measured by dispersing an aqueous emulsion in ethanol and using an electrophoretic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., model ELS-8000) at 20°C.

<(j) component>
(j-1): 10% by mass hydrochloric acid aqueous solution

<(l) component>
(l-1): Propylene glycol

<(m) component>
(m-1): Trisodium methylglycine diacetate

<(o) component>
(o-1): Proxel BDN (manufactured by Arch Chemical Japan)

<pH adjuster>
In order to adjust the pH of the textile treatment agent composition, sodium hydroxide or hydrochloric acid, which is the component (j), was used as necessary.

<Example 1 and Comparative Example 1>
[Preparation of liquid textile treatment agent composition]
A liquid textile treatment agent composition was prepared by mixing each component so as to have the composition shown in Table 3. Specifically, it is as follows. Note that the mass % of the composition in the table is the mass % of the active ingredient (component (a) is mass % as a fragrance compound).
In a 300 mL beaker, add ion-exchanged water in an amount equivalent to 85% by mass of the amount required to make 200 g of the liquid textile treatment agent composition, component (e), component (i), and (j). The components (l), (m), and (o) were added, and the temperature of the ion-exchanged water was adjusted to 60±2° C. using a water bath. A mixed solution was obtained by stirring using a stirring blade as necessary so that the component (e) was uniformly dissolved in the ion-exchanged water. In addition, the stirring blade is a stirring blade arranged so that the long side is in the direction of 90 degrees with respect to the rotation center axis of the stirring rod with a diameter of 5 mm, the number of blades is 3, the long side of the blade is / short side = 3 cm / 1.5 cm, and the blade was installed at an angle of 45 degrees with respect to the rotating surface.

The mixed liquid whose temperature was controlled to 60±2° C. was stirred using the stirring blade (300 r/m). Component (c), which had been heated and dissolved at 65° C., was added thereto over 3 minutes, and after the addition was completed, the mixture was stirred for 15 minutes.
Next, using a 5°C water bath, the mixture was cooled to a temperature of 30±2°C. A pre-mixed mixture of components (a) and (b) was added to this, and then components (d) and (f) were sequentially added and stirred for 5 minutes. Further, ion-exchanged water was added to the finished product (200 g) and stirred for 5 minutes to obtain a liquid textile treatment agent composition.
The visible light transmittance of the obtained liquid textile treatment agent composition was measured. Specifically, a glass cell with an optical path length of 10 mm was used as a measurement cell, ion-exchanged water was placed in a control cell, and measurement was performed using an ultraviolet-visible spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation). The visible light transmittance (wavelength 660 nm) of the liquid textile treatment agent compositions obtained in Examples and Comparative Examples were all less than 10%, indicating that they were emulsion-type liquid textile treatment agent compositions.

The pH of the liquid textile treatment agent composition was measured as follows.
A composite electrode for pH measurement (general-purpose sleeve type, manufactured by HORIBA) was connected to a pH meter (pH meter D-51 manufactured by HORIBA), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol/L) was used as the pH electrode internal solution.
Next, each of pH 1.68 standard solution (oxalate standard solution), pH 4.01 standard solution (phthalate standard solution), and pH 6.86 (neutral phosphate standard solution) was filled into a 100 ml beaker. It was immersed in a constant temperature bath at 30°C for 30 minutes. The pH measuring electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and a calibration operation was performed in the order of pH 6.86 → pH 4.01 → pH 1.68. Note that when measuring the alkaline region, a pH 9.18 standard solution (borate standard solution) is used for calibration instead of the pH 1.68 standard solution.
A 100 ml beaker was filled with the sample, and the temperature was adjusted to 30°C in a 30°C constant temperature bath. A pH measurement electrode was immersed in the sample, which had been kept at a constant temperature, for 3 minutes, and the pH was measured.

〔evaluation〕
In advance, using a commercially available weak alkaline detergent (Kao Corporation, Attack), 17 pieces of underwear (Gunze Corporation, men's round neck short sleeve shirt, L size) were washed in a fully automatic washing machine NW-6CY manufactured by Hitachi, Ltd. Excessive drug was removed by repeated washing and drying indoors. The washing conditions for each wash were: detergent concentration of 0.0667% by mass, tap water of 47 L, water temperature of 20° C., washing for 10 minutes, rinsing twice, and dehydration for 6 minutes.

A treatment solution prepared by dispersing 0.867g (10g/1.5kg of underwear) of a liquid textile treatment agent composition in 4L of tap water was poured into an electric bucket N-BK2-A manufactured by Panasonic Corporation, and then the above-mentioned method was added. A piece of underwear that had been washed was added and stirred for 5 minutes. Thereafter, the underwear finished with the liquid textile treatment agent composition was dehydrated for 3 minutes in the dehydration tank of a two-tub washing machine manufactured by Hitachi, Ltd., and then hung on a hanger in a room at 20°C and 40% RH for 24 hours. Dry for an hour. This operation was performed three times for each liquid textile treatment agent composition, and five pieces of underwear each finished with the liquid textile treatment agent composition were prepared.

(1) Effective feeling of scent A piece of cloth measuring 20 cm x 20 cm was cut from the prepared underwear and used for scent evaluation. The evaluation method is to first smell the scent in a dry state, then use a sprayer to soak the cloth with water at 10-20% o. w. f After moistening, the cloth was folded into four. After allowing it to stand still for a few seconds, the cloth was opened and the scent was smelled at the intersection of the folds, and the difference in scent intensity when dry and when wet was evaluated to determine the effectiveness of moisture scenting. The evaluation was carried out by five panelists who specialize in evaluating scents.
The evaluation was performed according to the following criteria, and the average value of the five evaluations was taken as the evaluation result.

<Evaluation criteria>
(Evaluation criteria for scent intensity)
3: Large difference in scent intensity 2: Small difference in scent intensity 1: No difference in scent intensity (evaluation criteria for scent expressiveness)
3: Feels strong and fresh 2: Feels weak and fresh 1: Does not feel fresh at all

Claims (4)

A textile processing agent composition containing the following components (a), (b), (c) and water.
(a) Component: Microcapsule having a shell containing a silicon compound and a core containing a fragrance compound inside the shell (B) Component: Polymer containing a structural unit having an anionic group (c) Component: Cationic surfactant agent The textile treatment agent composition according to claim 1, wherein component (b) is a polymer containing a structural unit having at least one anionic group selected from a carboxy group and a sulfonic acid group. The textile treatment agent composition according to claim 1 or 2, which contains component (b) in an amount of 0.0005% by mass or more and 1% by mass or less. A method for producing a textile treatment agent composition containing the following components (a), (b), (c) and water, comprising:
adding and mixing component (a) and component (b) to a mixture containing component (c) and water;
A method for producing a textile treatment agent composition.
(a) Component: Microcapsules having a shell containing a silicon compound and a core containing a fragrance inside the shell (b) Component: Polymer containing a structural unit having an anionic group (c) Component: cationic surfactant