JP5863113B2 - Textile treatment composition - Google Patents

Description

  The present invention relates to a fiber product treating agent composition containing an antioxidant, in which discoloration is suppressed.

As a method of deodorizing and deodorizing textile products, attempts have been made to reduce bad odors by sensory deodorization, physical deodorization, chemical deodorization, biological deodorization, etc. Is planned.
Antioxidants have been found as having a deodorizing effect. However, there exists a problem that the processing agent for textiles discolors by mix | blending antioxidant.
In contrast, Japanese Patent Application Laid-Open No. 2010-144143 discloses a method of suppressing coloring of an antioxidant by adding a specific silicon compound to a softener composition containing an antioxidant. Japanese Patent Application Laid-Open No. 2011-137252 discloses a method for suppressing discoloration of appearance by combining a specific aldehyde fragrance, a specific antioxidant, a specific amine compound, and the like in a liquid softener composition for clothing. It is disclosed.
However, the method disclosed in Japanese Patent Application Laid-Open No. 2010-144143 does not have a sufficient coloring suppression effect, and the method disclosed in Japanese Patent Application Laid-Open No. 2011-137252 is limited to a specific antioxidant.

JP 2010-144143 A JP 2011-137252 A

  Therefore, an object of the present invention is to provide a treating agent composition for textiles that contains an antioxidant and has an excellent discoloration suppressing effect.

The present inventors have found that the discoloration suppressing effect of the composition can be obtained by blending a specific glucan called highly cyclic branched dextrin into the treatment composition for textiles containing an antioxidant.
The present invention has been completed based on such novel findings.

The present invention
(A) an antioxidant;
(B) a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000, wherein the inner branched cyclic structure portion is α-1,4-glucoside A fiber product comprising a glucan which is a cyclic structure part formed by a bond and an α-1,6-glucoside bond, and the outer branched structure part is an acyclic structure part bonded to the inner branched cyclic structure part A treating agent composition is provided.

  In the treatment composition for textile products of the present invention, the discoloration suppressing effect of the composition can be obtained by blending the highly cyclic branched dextrin as the component (B).

[Component (A)]
The antioxidant that is the component (A) contained in the fiber product treating agent composition of the present invention is not particularly limited as long as it is a compound that is generally known to have an antioxidant effect. (A) A component may be used individually by 1 type, or may use 2 or more types together. Specific examples of the component (A) include 2,6-di-t-dibutyl-4-hydroxytoluene (BHT), t-butyl-p-hydroxyanisole (BHA), p-methoxyphenol, β-naphthol, and phenyl. -Α-naphthylamine, tetramethyldiaminodiphenylmethane, γ-oryzanol, vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol), vitamin C (L-ascorbic acid), trehalose, 2,2'- Ethylidenebis (4,6-di-t-butylphenol), tris (tetramethylhydroxypiperidinol) 1/3 citrate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Quercetin, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, etc. And the like. Among these, at least one selected from phenolic antioxidants is preferable, and 2,6-di-t-dibutyl-4-hydroxytoluene, t-butyl-p-hydroxyanisole, 2,2′-ethylidenebis. At least one selected from (4,6-di-t-butylphenol), p-methoxyphenol and γ-oryzanol is preferred. More preferred are 2,6-di-t-dibutyl-4-hydroxytoluene, p-methoxyphenol, 2,2′-ethylidenebis (4,6-di-t-butylphenol), and more preferred is 2,6. -Di-t-dibutyl-4-hydroxytoluene.
In the treatment composition for textile products of the present invention, the amount of component (A) is not particularly limited, but is preferably 0.001 to 5% by mass, more preferably 0.005 to 4% by mass, and still more preferably. It is 0.01-3 mass%. When it is less than 0.001% by mass, there is no sufficient deodorizing effect. Even if more than 5 mass% is blended, the deodorizing effect is not particularly improved.
In the case of the softener composition, the amount of component (A) is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and still more preferably 0.1 to 3% by mass.
In the case of a spray-type fiber treatment agent, the amount of component (A) is preferably 0.001 to 2% by mass, more preferably 0.005 to 1% by mass, and still more preferably 0.01 to 0.5% by mass. It is.

[Component (B)]
Component (B) contained in the textile product treating agent composition of the present invention is a glucan having an inner branched cyclic structure portion and an outer branched structure portion, and having a polymerization degree in the range of 50 to 10,000, The inner branched cyclic structure portion is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is the inner branched cyclic structure portion. It is a glucan, which is an acyclic structure moiety bound to. Such a glucan is also called highly branched cyclic dextrin or cluster dextrin, and the component (B) is also referred to as “highly branched cyclic dextrin” in this specification.
The highly branched cyclic dextrin contained in the fiber product treating agent composition of the present invention has a molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and a large number of glucan chains in the cyclic portion. Mainly contains dextrin having a weight average polymerization degree of about 2500.
The inner branched cyclic structure portion of the highly branched cyclic dextrin contained in the treatment composition for textile products of the present invention is composed of about 10 to 100 glucoses. The outer branch structure part which consists of a branched glucan chain has couple | bonded.

For example, the degree of polymerization of the highly branched cyclic dextrin contained in the treatment composition for textile products of the present invention is in the range of 50 to 5000.
For example, the degree of polymerization of the inner branched cyclic structure portion of the highly branched cyclic dextrin contained in the textile product treatment composition of the present invention is in the range of 10-100.
For example, the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin contained in the textile product treatment composition of the present invention is 40 or more.
For example, the degree of polymerization of each unit chain of the outer branched structure portion of the highly branched cyclic dextrin contained in the textile product treating agent composition of the present invention is 10 to 20 on average.

The highly branched cyclic dextrin contained in the textile product treatment composition of the present invention is produced, for example, by using starch as a raw material and an enzyme called a branching enzyme. Starch, which is a raw material, is composed of amylose in which glucose is linearly bound by α-1,4-glucoside bonds and amylopectin having a structure that is complicatedly branched by α-1,6-glucoside bonds. It is a macromolecule with many connected structures. Branching enzyme, an enzyme used, is a glucan chain transferase widely distributed in animals, plants, and microorganisms. It acts on the seam portion of the cluster structure of amylopectin and catalyzes the reaction of cyclizing it.
More specifically, the highly branched cyclic dextrin contained in the textile product treating agent composition of the present invention has an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104, and has a polymerization degree. It is a glucan in the range of 50 to 10,000. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.

The highly branched cyclic dextrin contained in the fiber product treating agent composition of the present invention has a specific structure as described above and has a high degree of polymerization (molecular weight), and α-cyclodextrin (n = 6). , Β-cyclodextrin (n = 7), γ-cyclodextrin (n = 8) and the like are different from general cyclodextrins in which 6 to 8 glucoses are bound.
As a specific example of the highly branched cyclic dextrin contained in the treatment composition for textile products of the present invention, “Cluster Dextrin” (registered trademark) of Glico Nutrition Foods Co., Ltd. may be mentioned.
In the treatment composition for textile products of the present invention, the amount of component (B) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and still more preferably. It is 0.05-3 mass%. When the blending amount of the component (B) is more than 0.01% by mass, an excellent yellowing suppression effect can be exhibited. When the blending amount of the component (B) is more than 10% by mass, stability at high temperature storage may be deteriorated.
In the case of a softener composition, the amount of component (B) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and still more preferably 0.5 to 3% by mass.
In the case of a spray-type fiber treatment agent, the amount of component (B) is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and still more preferably 0.05 to 1% by mass. .
In addition, instead of highly cyclic branched dextrin, 6-8 glucoses such as α-cyclodextrin (n = 6), β-cyclodextrin (n = 7), γ-cyclodextrin (n = 8) are generally bonded. Even if a typical cyclodextrin is blended in a fiber product treating agent composition, an excellent yellowing suppression effect equivalent to the fiber product treating agent composition of the present invention cannot be obtained.
Moreover, the ratio ((A) / (B)) of the content of the component (A) and the content of the component (B) in the treating agent composition for textile products is not particularly limited, but is preferably 5 or less, It is more preferably 3 or less, and particularly preferably within the range of 1 or less. When the ratio of the content of the component (A) and the content of the component (B) is 5 or less, an excellent yellowing suppression effect is exhibited.

[Component (C)]
The processing agent composition for textiles of the present invention can further contain (C) a nonionic surfactant. (C) The storage stability of the processing agent composition for textiles of this invention can be improved with a component. (C) A component may be used individually by 1 type, or may use 2 or more types together. Nonionic surfactants include those derived from higher alcohols, higher amines or higher fatty acids. More specifically, polyoxyalkylene alkyl ethers and polyoxyethylene fatty acid alkyls having an alkyl group or alkenyl group having 8 to 36 carbon atoms and an average of 5 to 100 moles of alkylene oxide having 2 to 4 carbon atoms added thereto. (C1-3) ester, polyoxyethylene alkylamine having an average addition mole number of oxyethylene group of 5 to 100 mole, alkyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms, oxyethylene group Hardened castor oil having an average addition mole number of 5 to 100 moles, an ester of a fatty acid having an alkyl group or alkenyl group having 8 to 24 carbon atoms and a polyhydric alcohol, an alkyl group or alkenyl group having 8 to 24 carbon atoms An average of 5 to 20 moles of alkylene oxide having 2 to 4 carbon atoms in fatty acid and polyhydric alcohol An ester of the pressurizing and polyoxyalkylene alkyl ether. The alkyl group or alkenyl group may be linear or branched. Among them, polyoxyalkylene alkyl ethers having an alkyl group or alkenyl group having 8 to 36 carbon atoms, preferably 10 to 14 carbon atoms, and having an average of 5 to 100 moles of alkylene oxide having 2 to 4 carbon atoms added thereto, Hardened castor oil having an average added mole number of ethylene groups of 5 to 100 moles, esters of fatty acids having 8 to 24 carbon atoms or alkyl groups or alkenyl groups and polyhydric alcohols, alkyl groups or alkenyls having 8 to 24 carbon atoms An ester of a fatty acid having a group and a polyoxyalkylene alkyl ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to a polyhydric alcohol is preferable, having 8 to 36 carbon atoms, preferably 10 to 14 carbon atoms An alkylene oxide having an alkyl group or an alkenyl group and having 2 to 4 carbon atoms on average 5 to 10 Mol, preferably polyoxyalkylene alkyl ethers obtained by averaging 5 to 60 mols is more preferable.
In the treatment composition for textiles of the present invention, the amount of component (C) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.03 to 8% by mass, and 0.05 -5 mass% is further more preferable.
In the case of a softener composition, the amount of component (C) is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and still more preferably 0.5 to 5% by mass.
In the case of a spray type fiber treatment agent, the amount of component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass. .
Further, the ratio (A) / (C) of the content of the component (A) and the content of the component (C) in the fiber product treating agent composition of the present invention is not particularly limited, but is preferably 2 or less. Is more preferably 1 or less, and particularly preferably 0.5 or less. When the ratio of the content of the component (A) and the content of the component (C) is 2 or less, the storage stability can be further improved.

[Component (D)]
The treatment composition for textiles of the present invention can further contain (D) at least one of a cationic surfactant, an amphoteric surfactant, and an anionic surfactant. With the component (D), the storage stability of the treatment composition for textile products of the present invention can be enhanced. (D) A component may be used individually by 1 type, or may use 2 or more types together. The treatment composition for textile products of the present invention preferably contains a cationic surfactant.
As the cationic surfactant, a hydrocarbon group having 10 to 26 carbon atoms which may be separated by an ester group or an amide group (hereinafter sometimes referred to as “long-chain hydrocarbon group” in the present specification) is a molecule. At least one compound selected from the group consisting of 1 to 3 amine compounds, salts thereof and quaternized compounds thereof, and polyoxyethylene alkylmethylammonium having an average addition mole number of oxyethylene groups of 5 to 100 mol Examples include salts. Among them, a tertiary amine acid salt or a quaternized product thereof having at least one hydrocarbon group having 10 to 26 carbon atoms which may be separated by an ester group or an amide group in the molecule is preferable. In the fiber product treating agent composition of the present invention, the amount of the cationic surfactant is not particularly limited, but is preferably 0.01 to 30% by mass.
When applied as a softening agent composition, an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group or an amide group, a salt thereof and a quaternary thereof At least one compound selected from the group consisting of compounds is preferred. In particular, the carbon number of the long-chain hydrocarbon group is preferably 17 to 26, and more preferably 19 to 24. When the number of carbon atoms is 10 or more, flexibility is good, and when it is 26 or less, handling properties are good.
The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is the long chain carbonization. The center of the hydrogen group is preferably distributed around the median.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long chain hydrocarbon group may be separated by an ester group (—COO—) or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.
When it has this dividing group, the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places. When having two or more splitting groups, each splitting group may be the same or different.
In addition, when it has a splitting group in a carbon chain, the carbon atom which a splitting group shall count to carbon number of a long-chain hydrocarbon group.
The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
As the amine compound, a secondary amine compound or a tertiary amine compound is preferable, and a tertiary amine compound is more preferable.

［式中、Ｒ¹〜Ｒ³はそれぞれ独立に、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７〜２１の炭化水素基である。）、−（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７〜２１の炭化水素基である。）、水素原子、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨ（Ｙ）ＯＨ、又は−（ＣＨ₂）_nＮＨ₂であり、Ｒ¹〜Ｒ³のうちの少なくとも１つは、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴、又は−（ＣＨ₂）_nＮＨＣＯＲ⁵である。］ More specifically, examples of the amine compound include compounds represented by the following general formula (D1).

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms. to 21 is a hydrocarbon _{group), -.. (CH 2} ) n NHCOR 5 (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, the number of carbon atoms 1 to 4 alkyl group, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ , and at least one of R ^{1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms. , —CH ₂ CH (Y) OCOR ⁴ , or — (CH ₂ ) _n NHCOR ⁵ . ]

Wherein (D1), the number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ is preferably 17 to 26, 19 to 24 is more preferable. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In —CH ₂ CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable.
R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When R ⁴ is more present in compounds of the formula (D1), may be R ⁴ of said plurality of mutually identical, may be different.
Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0 / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, a cis isomer and a trans isomer are present, and the mass ratio of the cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.

Specific examples of fatty acids used as R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partial Examples include hydrogenated beef tallow fatty acid (iodine value of 10 to 60). Among them, a fatty acid prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c) It is preferable to use a composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100.
(B) The ratio (mass ratio) of cis isomer / trans isomer is 40/60 to 100/0, more preferably 70/30 to 90/10.
(C) The fatty acid having 18 carbon atoms is 60 mass% or more, preferably 80 mass% or more, the fatty acid having 20 carbon atoms is less than 2 mass%, and the fatty acid having 21 to 22 carbon atoms is less than 1 mass%. .

In — (CH ₂ ) _n NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferable.
R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When R ⁵ is more present in compounds of the formula (D1), may be R ⁵ of said plurality of mutually identical, may be different.
Specific examples of R ⁵ include the same as R ⁴ .

At least one of R ^{1 to} R ³ is a long-chain hydrocarbon group (a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ , or — (CH ₂ ) _n NHCOR ⁵ ). Two are preferably long-chain hydrocarbon groups.
When one or two of R ^{1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH or — (CH ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ . Among these, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable. Y in —CH ₂ CH (Y) OH is the same as Y in —CH ₂ CH (Y) OCOR ⁴ . _{N in} — (CH ₂ ) _n NH ₂ is the same as n in — (CH ₂ ) _n NHCOR ⁵ .

［式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、炭素数１０〜２６の炭化水素基である。Ｒ⁹及びＲ¹⁰はそれぞれ独立に、炭素数７〜２１の炭化水素基である。］ Preferable examples of the compound represented by the general formula (D1) include compounds represented by the following general formulas (D1-1) to (D1-8).

[Wherein, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R ^{1 to} R ³ .
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ . When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, it may be different.

The salt of an amine compound is obtained by neutralizing an amine compound with an acid. The acid used for neutralization of the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be performed by a known method.
A quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for the quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound, and a salt of a quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion is formed. . The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of the amine compound can be performed by a known method.

  The component (D) is preferably at least one selected from the group consisting of the compound represented by the general formula (D1), a salt thereof, and a quaternized product thereof, and the general formulas (D1-1) to (D1- 8) At least one selected from the group consisting of a salt thereof and a quaternized product thereof is more preferable, and at least one selected from the group consisting of (D1-4) to (D1-6), a salt thereof and a quaternized product thereof. Species are more preferred.

As the compound represented by the formula (D1), a salt thereof, and a quaternized product thereof, a commercially available product may be used, or a product produced by a known method may be used.
For example, a compound represented by the general formula (D1-2) (hereinafter referred to as “compound (D1-2)”) and a compound represented by the general formula (D1-3) (hereinafter referred to as “compound (D1-3)”). Can be synthesized by a condensation reaction of the fatty acid composition or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid and methyldiethanolamine. At that time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (D1-2) / compound (D1-3)” is synthesized such that the mass ratio is 99/1 to 50/50. It is preferable to do.
Furthermore, when the quaternized product is used, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (D1-2) / a quaternized compound (D1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

A compound represented by the general formula (D1-4) (hereinafter referred to as “compound (D1-4)”), a compound represented by the general formula (D1-5) (hereinafter referred to as “compound (D1-5)”). ) And the compound represented by the general formula (D1-6) (hereinafter referred to as “compound (D1-6)”) are synthesized by a condensation reaction of the fatty acid composition or fatty acid methyl ester composition and triethanolamine. be able to. At that time, the content ratio of each component to the total mass of the compounds (D1-4), (D1-5), and (D1-6) is 1 to 60 masses of the compound (D1-4) from the viewpoint of flexibility. %, The compound (D1-5) is preferably 5 to 98% by mass, the compound (D1-6) is preferably 0.1 to 40% by mass, the compound (D1-4) is 30 to 60% by mass, the compound ( It is more preferable that D1-5) is 10 to 55% by mass and the compound (D1-6) is 5 to 35% by mass.
In addition, when using the quaternized product, it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction proceeds sufficiently. The abundance ratio of each of the quaternized compounds (D1-4), (D1-5) and (D1-6) is a mass ratio from the viewpoint of flexibility, and the quaternized compound (D1-4) is 1 to 4. 60% by mass, the quaternized compound (D1-5) is preferably 5 to 98% by mass, and the quaternized compound (D1-6) is preferably 0.1 to 40% by mass. ) Is 30 to 60% by mass, the quaternized compound (D1-5) is 10 to 55% by mass, and the quaternized compound (D1-6) is 5 to 35% by mass. preferable. In addition, when the compounds (D1-4), (D1-5), and (D1-6) are quaternized, esteramine that is not quaternized generally remains after the quaternization reaction. At that time, the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.

  A compound represented by the general formula (D1-7) (hereinafter referred to as “compound (D1-7)”) and a compound represented by the general formula (D1-8) (hereinafter referred to as “compound (D1-8)”) ) From the adduct of the above fatty acid composition, N-methylethanolamine and acrylonitrile. Org. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (D1-7) / compound (D1-8)" may be 99/1-50/50 by mass ratio. When the quaternized product is used, it is preferable to use methyl chloride as a quaternizing agent, which is represented by “a quaternized compound (D1-7) / a quaternized compound (D1-8)”. It is preferable to synthesize the abundance ratio such that the mass ratio is 99/1 to 50/50.

5-30 mass% is preferable with respect to the total mass of a softening agent composition, content of a cationic surfactant is more preferable, 5-25 mass% is more preferable, and 8-22 mass% is especially preferable. When it is 5% by mass or more, a sufficient flexibility imparting effect can be obtained. Storage stability is favorable in it being 30 mass% or less.
When the textile product treating agent composition is applied as a spray-type textile treating agent, the cationic surfactant has in the molecule a hydrocarbon group having 10 to 14 carbon atoms which may be separated by an ester group or an amide group. Amine compound having two, its salt and its quaternized compound, amine compound having one hydrocarbon group having 10 to 18 carbon atoms which may be separated by an ester group or amide group in its molecule, its salt and its 4 At least one compound selected from the group consisting of grades is preferred. Especially, the amine compound which has two C10-14 hydrocarbon groups which may be divided | segmented by the ester group or the amide group in a molecule | numerator, its salt, and its quaternization thing are especially preferable. The content of the cationic surfactant is preferably 0.01 to 10% by mass, more preferably 0.03 to 8% by mass, and 0.05 to 5% by mass with respect to the total mass of the spray-type fiber treatment agent. Particularly preferred.

Examples of amphoteric surfactants include alkyldimethylamine oxide having an alkyl group having 10 to 24 carbon atoms, alkanoylamidopropyldimethylamine oxide having an alkanoyl group having 10 to 24 carbon atoms, and N having an alkyl group having 10 to 24 carbon atoms. -Alkyl-N, N-dimethyl-N- (2-hydroxy-3-sulfopropyl) ammonium betaine, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine having an alkyl group having 10 to 24 carbon atoms N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxy-3-sulfopropyl) ammonium betaine having an alkanoyl group having 10 to 24 carbon atoms, N- having an alkanoyl group having 10 to 24 carbon atoms Alkanoylaminopropyl-N, N-dimethyl It can be exemplified Le -N- carboxymethyl ammonium betaine. As for content of an amphoteric surfactant, 0.01-10 mass% is preferable with respect to the total mass of the processing agent composition for textiles.
In the case of a softener composition, the amount of amphoteric surfactant is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass.
In the case of a spray type fiber treatment agent, the amount of amphoteric surfactant is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass. .

Examples of the anionic surfactant include alkylbenzene sulfonate having an alkyl group having 10 to 15 carbon atoms, alkyl sulfate ester salt having an alkyl group having 10 to 24 carbon atoms, and α-olefin sulfonate having 10 to 24 carbon atoms. An α-sulfo fatty acid methyl ester salt having 10 to 24 carbon atoms of a fatty acid, a polyoxyethylene alkyl sulfate ester salt having an alkyl group having 10 to 24 carbon atoms and an oxyethylene group having a number average added mole number of 1 to 6 Can be mentioned. Among these, alkylbenzene sulfonates having an alkyl group having 10 to 15 carbon atoms are preferable. As for content of an anionic surfactant, 0.01-25 mass% is preferable with respect to the total mass of the processing agent composition for textiles.
In the case of the softener composition, the amount of the anionic surfactant is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and still more preferably 0.1 to 3% by mass. .
In the case of a spray-type fiber treatment agent, the amount of the anionic surfactant is preferably 0.01 to 3% by mass, more preferably 0.03 to 2% by mass, and still more preferably 0.05 to 1% by mass. is there.

[Optional ingredients]
The processing agent composition for textiles of the present invention may contain other components other than the components (A) to (D) as necessary within a range not impairing the effects of the present invention.
As this other component, a well-known component can be suitably mix | blended in the processing agent composition for textiles. For example, water, water-soluble solvents, sugar compounds, silicones, fragrances, dyes and / or pigments, preservatives, ultraviolet absorbers, antibacterial agents, and the like can be contained.
The treatment composition for textiles of the present invention is preferably an aqueous composition and preferably contains water.
As water, any of tap water, ion exchange water, pure water, distilled water, and the like can be used. Of these, ion-exchanged water is preferred.
Water is preferably blended in the fiber composition treating agent composition of the present invention in an amount of 50% by mass or more, more preferably 60% by mass or more. When the water content is equal to or higher than the lower limit, handling properties are good.

It is preferable that the processing agent composition for textiles of this invention contains a water-soluble solvent in addition to water.
The water-soluble solvent is preferably one or more selected from the group consisting of lower (1 to 4 carbon atoms) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (X) It is preferable to blend the components.
^{_{R 11 -O- (C 2 H 4}} O) y - (C 3 H 6 O) z -H ··· (X)
In the formula, R ¹¹ is an alkyl group or alkenyl group having 1 to 6 (preferably 2 to 4) carbon atoms. y and z are average addition mole numbers, y is 1-10, Preferably it is 2-5, z shows the number of 0-5, Preferably it is 0-2.
Among the above-mentioned water-soluble solvents, ethanol, ethylene glycol, butyl carbitol, propylene glycol, dipropylene glycol monomethyl ether, and diethylene glycol monobutyl ether are preferable.
The water-soluble solvent is preferably mixed in the fiber product treating agent composition in an amount of 0 to 30% by mass, more preferably 0.01 to 25% by mass, and still more preferably 0.1 to 20% by mass.

  The sugar compound is preferably one or more selected from the group consisting of sugar compounds having a degree of polymerization of 40 or less from the viewpoint of improving stability. Preferred sugar compounds include monosaccharides, disaccharides, oligosaccharides, or sugar alcohols. Specifically, glucose, fructose, galactose, arabinose, ribose, maltose, isomaltose, cellobiose, lactose, sucrose, talose, maltotriose, isomaltotriose, and oligosaccharides obtained from partial hydrolysis of natural polysaccharides, In addition, it is a compound (sugar derivative) in which a substituent is introduced into these sugars. The monosaccharide or oligosaccharide preferably has 1 to 40 repeating units of the sugar skeleton (polymerization degree), more preferably 1 to 20, and 1 to 5 (that is, monosaccharide and polymerization degree of more than 1 and less than 5 Are particularly desirable. Examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyalkyl group, an amine group, a quaternary ammonium group, and a carboxyl group. Among these, an alkyl group, an alkenyl group, and an alkoxyl group are particularly preferable. desirable. The substituent is preferably an alkyl group, alkenyl group or alkoxy group having 1 to 18 carbon atoms, more preferably an alkyl group, alkenyl group or alkoxy group having 1 to 12 carbon atoms, and particularly preferably 1 carbon atom. -6 alkyl group, most preferably an alkyl group having 1 to 3 carbon atoms. The sugar compound is selected from monosaccharides or oligosaccharides having a polymerization degree of 1 to 5 and compounds in which the hydrogen atom of at least one hydroxyl group of the monosaccharide or oligosaccharide having a polymerization degree of 1 to 5 is substituted with an alkyl group. One or more selected from the above are preferred. Examples of the sugar alcohol include erythritol, threitol, pentitol, hexitol, dulcitol, sorbitol, mannitol, boremitol, perseitol, xylitol, maltitol, lactitol and the like.

There is no restriction | limiting in particular in the kind of a silicone compound, According to the objective, it can select suitably. The molecular structure of the silicone compound may be linear, branched, or cross-linked. The silicone compound may be a modified silicone compound, and the modified silicone compound may be modified with one organic functional group or modified with two or more organic functional groups. It may be.
The silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, for example, dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol. Examples thereof include modified silicone and amino-modified silicone.
Among these, polyether-modified silicone, amino-modified silicone, dimethyl silicone and the like are preferable from the viewpoint of versatility and deodorizing and deodorizing effect, and polyether-modified silicone and amino are particularly preferable from the viewpoint of effect and handling during production. Modified silicone is preferred. Specific examples of the polyether-modified silicone include, for example, a copolymer of alkylsiloxane and polyoxyalkylene. In addition, as carbon number of the alkyl group of the said alkylsiloxane, 1-3 are preferable, and as carbon number of the alkylene group of the said polyoxyalkylene, 2-5 are preferable. Among these, the polyether-modified silicone is preferably a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of ethylene oxide and propylene oxide, etc.). Specific examples of such a polyether-modified silicone include, for example, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and the like.

前記一般式（Ｉ）中、Ｍ、Ｎ、ａ、及びｂは、平均重合度を表し、Ｒは、水素又はアルキル基を表す。ここで、Ｍは、１０〜１０，０００であることが好ましく、１００〜３００がより好ましい。Ｎは、１〜１，０００であることが好ましく、１〜１００がより好ましい。更に、Ｍ＞Ｎであることが好ましい。ａは、２〜１００であることが好ましく、２〜５０がより好ましい。ｂは、０〜５０であることが好ましく、０〜１０がより好ましい。Ｒは、水素又は炭素数１〜４のアルキル基であることが好ましい。
前記一般式（Ｉ）で表されるポリエーテル変性シリコーンは、一般に、Ｓｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンと、例えば、ポリオキシアルキレンアリルエーテル等の炭素−炭素二重結合を末端に有するポリオキシアルキレンアルキルエーテルとを、白金触媒下、付加反応させることにより製造することができる。したがって、前記ポリエーテル変性シリコーン中には未反応のポリオキシアルキレンアルキルエーテルやＳｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンがわずかに含まれる場合がある。Ｓｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサンは反応性が高いため、前記ポリエーテル変性シリコーン中での存在量としては、３０ｐｐｍ以下（Ｓｉ−Ｈの量として）であることが好ましい。

In the general formula (I), M, N, a, and b represent the average degree of polymerization, and R represents hydrogen or an alkyl group. Here, M is preferably 10 to 10,000, and more preferably 100 to 300. N is preferably 1 to 1,000, and more preferably 1 to 100. Furthermore, it is preferable that M> N. a is preferably 2 to 100, and more preferably 2 to 50. b is preferably 0 to 50, and more preferably 0 to 10. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The polyether-modified silicone represented by the general formula (I) generally has an organohydrogenpolysiloxane having a Si-H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Therefore, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

前記一般式（ＩＩ）中、Ａ、Ｂ、ｈ、及びｉは、平均重合度であり、Ｒは、アルキル基を表し、Ｒ’は、水素又はアルキル基を表す。ここで、Ａは、５〜１０，０００であることが好ましく、Ｂは、２〜１０，０００であることが好ましい。ｈは、２〜１００であることが好ましく、ｉは、０〜５０であることが好ましい。Ｒは、炭素数１〜５のアルキル基であることが好ましい。Ｒ’は、水素又は炭素数１〜４のアルキル基であることが好ましい。
前記一般式（ＩＩ）で表される線状ポリシロキサン−ポリオキシアルキレンブロック共重合体は、反応性末端基を有するポリオキシアルキレン化合物と、該化合物の反応性末端基と反応する末端基を有するジヒドロカルビルシロキサンとを反応させることにより製造することができる。このようなポリエーテル変性シリコーンは、側鎖のポリオキシアルキレン鎖が長く、ポリシロキサン鎖の重合度が大きいものほど粘度が高くなるので、製造時の作業性改善及び水性組成物への配合を容易にするために、水溶性有機溶剤とのプレミックスの形で配合に供することが好ましい。該水溶性有機溶剤としては、例えば、エタノール、ジプロピレングリコール、ブチルカルビトール等が挙げられる。
前記ポリエーテル変性シリコーンとしては、より具体的には、例えば、東レ・ダウコーニング（株）製の、ＳＨ３７７２Ｍ、ＳＨ３７７５Ｍ、ＦＺ−２１６６、ＦＺ−２１２０、Ｌ−７２０、ＳＨ８７００、Ｌ−７００２、Ｌ−７００１、ＳＦ８４１０、ＦＺ−２１６４、ＦＺ−２２０３、ＦＺ−２２０８、信越化学工業（株）製の、ＫＦ３５２Ａ、ＫＦ６１５Ａ、Ｘ−２２−６１９１、Ｘ−２２−４５１５、ＫＦ−６０１２、ＫＦ−６００４等、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製のＴＳＦ４４４０、ＴＳＦ４４４１、ＴＳＦ４４４５、ＴＳＦ４４５０、ＴＳＦ４４４６、ＴＳＦ４４５２、ＴＳＦ４４６０等が挙げられる。

In the general formula (II), A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group. Here, A is preferably 5 to 10,000, and B is preferably 2 to 10,000. h is preferably 2 to 100, and i is preferably 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting with dihydrocarbylsiloxane. Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.
More specifically, examples of the polyether-modified silicone include SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, and L-, manufactured by Toray Dow Corning Co., Ltd. 7001, SF8410, FZ-2164, FZ-2203, FZ-2208, manufactured by Shin-Etsu Chemical Co., Ltd., KF352A, KF615A, X-22-6191, X-22-4515, KF-6012, KF-6004, etc. Examples include TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 manufactured by Momentive Performance Materials Japan GK.

式（ＩＩＩ）中、Ｒ₁、Ｒ₆は互いに同一でも、異なっていてもよく、メチル基、水酸基、水素のいずれかを表す。Ｒ₂は、−（ＣＨ₂）_n−Ａ₁、及び−（ＣＨ₂）_n−ＮＨＣＯ−（ＣＨ₂）_m−Ａ₁のいずれかを表す。Ａ₁は、−Ｎ（Ｒ₃）（Ｒ₄）、及び−Ｎ⁺（Ｒ₃）（Ｒ₄）（Ｒ₅）・Ｘ^-のいずれかを表す。Ｒ₃〜Ｒ₅は、互いに同一であってもよいし、異なっていてもよく、水素原子、炭素数１〜１２のアルキル基、フェニル基、及び−（ＣＨ₂）_n−ＮＨ₂のいずれかを表す。Ｘ^-は、フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン、硫酸メチルイオン、及び硫酸エチルイオンのうちのいずれかを表す。ｍ及びｎの値は、互いに同一であってもよいし、異なっていてもよく、０〜１２の整数を表す。ｐ及びｑの値は、ポリシロキサンの重合度を表し、互いに同一であってもよいし、異なっていてもよく、ｐは０〜２００００、好ましくは１０〜１００００、ｑは１〜５００、好ましくは１〜１００を表す。 The amino-modified silicone is a silicone oil in which an amino group is introduced into the terminal or side chain of the dimethyl silicone skeleton, and a substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be substituted in addition to the amino group. Moreover, the form of oil may be sufficient, and the form of the amino modified silicone emulsion which emulsified the nonionic surfactant or the cationic surfactant as an emulsifier may be sufficient. A preferred amino-modified silicone oil or base oil in the case of an emulsion is represented by the following general formula (III).

In formula (III), R ₁ and R ₆ may be the same as or different from each other and each represents a methyl group, a hydroxyl group, or hydrogen. R ₂ represents any _one of — (CH ₂ ) _n —A ₁ and — (CH ₂ ) _n —NHCO— (CH ₂ ) _m —A ₁ . A ₁ represents any _one of —N (R ₃ ) (R ₄ ) and —N ⁺ (R ₃ ) (R ₄ ) (R ₅ ) · X ⁻ . R _{3 to} R ₅ may be the same or different from each other, and are any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and — (CH ₂ ) _n —NH ₂ . Represents. X ⁻ represents any one of fluorine ion, chlorine ion, bromine ion, iodine ion, methyl sulfate ion, and ethyl sulfate ion. The values of m and n may be the same as or different from each other, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane and may be the same or different from each other. p is 0 to 20000, preferably 10 to 10000, q is 1 to 500, preferably 1-100 are represented.

For amino-modified silicone oil used in the textile treating agent composition of the present invention preferably has a kinematic viscosity at 25 ° C. is 50~20000mm ² / s, more preferably 100~10000mm ² / s . When the kinematic viscosity is in this range, a high texture imparting effect is exhibited, manufacturability is good, and the composition is easy to handle, which is preferable.
Commercially available amino-modified silicones can be used. For example, amino-modified silicone oils sold by Toray Dow Corning Co., Ltd. as SF-8417, BY16-892, BY16-890. From Shin-Etsu Chemical Co., Ltd., KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S and the like can be mentioned.
The amino-modified silicone emulsion type is sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, FZ-4672, and sold by Shin-Etsu Chemical Co., Ltd. in the Polon series. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52 are listed.
The kinematic viscosity of the dimethyl silicone is not particularly limited but is preferably 1~100,000,000mm ² / s, more preferably ^{10~10,000,000mm 2 / s, 100~1,000,000mm 2 /} s Is more preferable. Further, it may be an oil or an emulsion.

  A fragrance | flavor can be added to the processing agent composition for textiles of this invention in order to provide a fragrance. Although not particularly limited, a list of perfume ingredients used can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993).

A dye and / or a pigment can be blended for the purpose of improving the appearance of the treatment composition for textiles of the present invention. Preferably, it is one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant / acid mordant dyes.
Specific examples of the dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).
From the viewpoint of the storage stability of the fiber composition treating agent composition of the present invention and the dyeing property to fibers, the composition has at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amide group in the molecule. Acid dyes, direct dyes, and reactive dyes are preferable, and the blending amount thereof is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.
Examples of the dye used in the fiber product treating agent composition of the present invention include JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, and JP-A-8-27669. The dyes described in Kaihei 9-250085, JP-A-10-77576, JP-A-11-43865, JP-A-2001-181972, or JP-A-2001-348784 can also be used. .

The preservative can be used mainly in the treatment composition for textiles of the present invention in order to enhance the antiseptic power and sterilizing power and maintain the antiseptic property during long-term storage.
Examples of the preservative include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
Examples of isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazoline-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone. 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, or a mixture thereof. Of these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2 More preferred is a mixture with -methyl-4-isothiazolin-3-one, especially preferred is a mixture of about 77% by weight of the former and about 23% by weight of the latter.
Examples of benzisothiazolone-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio-2,2-bis ( Benzmethylamide) or a mixture thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like.
It is preferable that the compounding quantity of antiseptic | preservative in the processing agent composition for textiles of this invention is 0.0001-1 mass% with respect to the total amount of the processing agent composition for textiles. When the blending amount of the preservative is less than the lower limit, it is difficult to obtain the effect of adding the preservative, and when it exceeds the upper limit, the storage stability may be lowered.

An ultraviolet absorber is a chemical | medical agent with the effect which protects an ultraviolet-ray, it is a component which absorbs an ultraviolet-ray, converts into infrared rays, visible light, etc., and discharge | releases.
Examples of the ultraviolet absorber include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate, dipropylene glycol salicylate , Salicylic acid derivatives such as octyl salicylate, myristyl salicylate; methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl, p-methoxycinnamic acid Cinnamic acid derivatives such as butyl; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2′-dihydroxy-4-methoxybenzophenone; urocanic acid, Ouro Examples include azole compounds such as ethyl kanate; 4-t-butyl-4′-methoxybenzoylmethane.

The antibacterial agent is a component having an effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of an unpleasant odor derived from the degradation product of the microorganism.
Antibacterial agents include, for example, cationic fungicides such as quaternary ammonium salts (benzalkonium chloride, didecyldimethylammonium chloride), diclosan, triclosan, bis- (2-pyridylthio-1-oxide) zinc, polyhexa Examples include methylene biguanidine hydrochloride, 8-oxyquinoline, polylysine and the like.

  In addition to the above-mentioned compounds, as a function improver, a shrinkage inhibitor, an anti-wrinkle agent, a shape retention agent, a drape retention agent, an iron property improvement agent, an oxygen bleaching inhibitor, a whitening agent, a whitening agent, and a fabric softening Clay, antistatic agent, dye transfer inhibitor such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis (2-sulfostyryl) biphenyl disodium (Cino Pearl CBS manufactured by Ciba Specialty Chemicals) X) fluorescent whitening agents, dye fixing agents, anti-fading agents such as 1,4-bis (3-aminopropyl) piperazine, stain removers, fiber surface modifiers such as cellulase, amylase, protease, lipase, keratinase, etc. Silk protein powders and surface modified products that can give silk texture and functions such as Emulsified dispersion, specifically K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (upper hair), silkgene G Soluble S (Ichimaru Falcos), alkylene terephthalate and / or nonionic polymer compound comprising an alkylene isophthalate unit and a polyoxyalkylene unit, such as FR627 manufactured by Kyoyo Chemical Industry, SRC-1 manufactured by Clariant Japan, etc. Can be blended.

[PH]
The pH of the fiber product treating agent composition of the present invention is not particularly limited. However, in the case of a softener composition, the hydrolysis of the cationic surfactant of the component (C) accompanying storage aging is suppressed. From the viewpoint, the pH at 25 ° C. is preferably in the range of 1 to 6, and more preferably in the range of 2 to 4. In the case of a spray type fiber treatment agent, the pH at 25 ° C. is preferably 3 to 8, more preferably 4 to 7, from the viewpoint of suppressing damage to the fiber product.
When adjusting pH, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytin PH adjusting agents such as acids, short-chain amine compounds such as ethylenediaminetetraacetic acid and dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates and alkali metal silicates can be used.

[viscosity]
In the case of a softener composition, the viscosity of the textile product treating agent composition of the present invention is preferably less than 1000 mPa · s (B-type viscometer, manufactured by TOKIMEC, 25 ° C., the same applies hereinafter). Considering the increase in viscosity due to storage aging, the viscosity immediately after production is more preferably less than 800 mPa · s, and further preferably less than 500 mPa · s. When it is in such a range, the usability such as handling property at the time of loading into the washing machine is good. In the case of a spray-type fiber treatment agent, the viscosity at 25 ° C. is preferably 10 mPa · s or less, and more preferably 5 mPa · s or less from the viewpoint of handling properties. The viscosity can be adjusted by the amount of component (B) and water, the type and amount of component (C), and the like.

[Production method]
The preparation method of the processing agent composition for textiles of this invention is not specifically limited. In the case of the softener composition, it can be produced by a known method, for example, a method similar to the conventional method for producing a softener composition using a cationic surfactant as the main agent.
For example, an oil phase containing the components (A) and (C) and an aqueous phase containing the component (B) are mixed under a temperature condition equal to or higher than the melting point of the component (C) to prepare an emulsion, and then If necessary, it can be produced by adding and mixing other components to the obtained emulsion. The oil phase can be prepared by mixing the component (A), the component (C) and an optional component as necessary at a temperature equal to or higher than the melting point of the component (C). An aqueous phase can be prepared by mixing water, (B) component, and an arbitrary component as needed. In order to enhance the effect, an oil phase containing the component (C) and an aqueous phase are mixed under a temperature condition equal to or higher than the melting point of the component (C) to prepare an emulsion, and then the component (A) is added. A solution prepared by previously mixing a solution dissolved in a water-soluble solvent and an aqueous solution of the component (B) is added, and if necessary, it is produced by adding and mixing other components to the obtained emulsion. It is preferable.
In the case of a spray type fiber treatment agent, it can be prepared according to a conventional method. For example, it can prepare by mixing said each component with water as needed. In order to enhance the effect, a solution prepared by dissolving the component (A) in a water-soluble solvent and an aqueous solution of the component (B) are mixed in advance, and the aqueous solution of the component (C) and an optional component is added thereto, A method of mixing is preferred.

[Usage and usage]
Although the use of the treatment composition for textile products of the present invention is not particularly limited, it can be applied to a cleaning composition, a bleaching composition, a softener composition, a spray-type fiber treatment agent, and the like. Especially, it is preferable to apply as a softening agent composition or a spray type fiber treatment agent.
The method for treating textiles such as clothing with the treating composition for textiles of the present invention is not particularly limited, and conventionally known detergents, finishing agents (softeners, glues, etc.), spray type fiber treatments. It can be performed in the same manner as the agent.
In the case of the softener composition, the method for using the treatment composition for textile products of the present invention is not particularly limited. For example, the composition of the present invention is dissolved in rinsing water at the stage of washing. Alternatively, there is a method in which the composition of the present invention is dissolved in water using a container such as a tub, and further garment is added to dip treatment. In that case, it is diluted to an appropriate concentration and used. In that case, the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, when performing the flexible treatment, it is preferably used in such an amount that the concentration of the component (C) is 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm with respect to the total amount of water used. Is used in such an amount.

In the case of a spray-type fiber treatment agent, the method of using the treatment composition for textile products of the present invention is not particularly limited. For example, the treatment agent composition is accommodated in a trigger-type spray container or a dispenser type pump spray container, This can be done by spraying directly on the textile. After spraying, you may perform a drying process as needed. The fiber product is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and macula covers. The amount of the treatment composition applied to the fiber product is preferably 0.5 to 10 g, more preferably 1 to 5 g, per 100 g of the fiber product.
The spray type fiber treatment agent is preferably contained in a trigger type spray container (hereinafter referred to as trigger container). The trigger container is not particularly limited, and is generally the same as the trigger container used for the fiber treatment product used for imparting a scent or deodorizing effect to a textile product such as clothing. Can be used. As the trigger container, a pressure accumulating trigger container is preferable from the viewpoint of good spray properties and spray pattern and no occurrence of after-draw. Further, the amount of spraying once is 0 from the viewpoint of preventing the fiber product sprayed with the treating agent composition from causing stains and giving a preferable effect without giving the hand excessive fatigue. It is preferable that it is 2-0.6g.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, the component blending amounts are all expressed by mass% (in terms of pure content, unless otherwise specified).

[(A) component]
A-1: Butylated hydroxytoluene (trade name Ionol CP, manufactured by Japan Chemtech Co., Ltd.)
A-2: 2,2′-ethylidenebis (4,6-di-t-butylphenol) (Aldrich)
A-3: p-methoxyphenol (trade name MQ-F, manufactured by Kawaguchi Chemical Industry Co., Ltd.)
A-4: γ-Oryzanol (trade name Oriza Gamma V, manufactured by Ichimaru Falcos Co., Ltd.)

[Component (B)]
B-1: Cluster dextrin (registered trademark, manufactured by Glico Nutrition Foods Co., Ltd.)
The main component of Cluster Dextrin (registered trademark) has a molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and a weight average polymerization degree of 2500 having many glucan chains bonded to the cyclic portion. About dextrin. The cyclic structure portion is composed of about 16 to 100 glucoses, and many non-cyclic branched glucan chains are bonded to the cyclic structure.
B-2: Hydroxypropyl-β-cyclodextrin (trade name Celdex HP-β-CD, manufactured by Nippon Shokuhin Kako Co., Ltd.)

[Component (C)]
C-1: Polyoxyethylene isotridecyl ether EO 60 mol (added ethylene oxide to BASF Rutensol TO3 (EO 60 mol indicates that the average number of added moles of ethylene oxide is 60))
C-2: Polyoxyethylene lauryl ether EO 20 mol (trade name EMALEX 720 manufactured by Nippon Emulsion Co., Ltd. (EO 20 mol indicates that the average number of added moles of ethylene oxide is 20))
C-3: Polyoxyethylene lauryl ether EO 8 mol (trade name New Coal 1100 manufactured by Nippon Emulsifier Co., Ltd. (EO 8 mol indicates that the average number of added moles of ethylene oxide is 8))
C-4: Glycerol monostearate (trade name EMALEX GMS-F manufactured by Nippon Emulsion Co., Ltd.)

[(D) component]
D-1: Cationic surfactant (compound described in Example 4 of JP-A-2003-12471)
D-2: Cationic surfactant (compound described in Example 1 of JP-A-2002-167366)
D-3: Cationic surfactant produced by the following procedure: Tertiary as described in Example 1 of JP-A-5-230001, except that hardened beef tallow fatty acid was used instead of stearic acid and it was not quaternized. 300 g of amine (compound represented by the general formula (D1-7)) was obtained.
As a result of measuring the acid value, saponification value, hydroxyl value, total amine value, tertiary amine value of the obtained reaction product and examining the composition of the reaction product, 86% by mass of the dialkyl product and 10% of the monoalkylamide product were obtained. The mass% and unreacted fatty acid were 4 mass%. Moreover, from the analysis by gas chromatography, 0.1 mass% of unreacted N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine was contained in the reaction product. Finally, 53 g of 99% synthetic ethanol (Japan Ethanol Co., Ltd.) was added to prepare an ethanol solution having a solid content of 85% by mass.
D-4: Didecyldimethylammonium salt (trade name ARCARD 210, manufactured by Lion Akzo)
D-5: N-lauroylamidopropyl-N, N-dimethylamine oxide (trade name Softazoline LAO, manufactured by Kawaken Fine Chemical Co., Ltd.)
D-6: linear alkyl (C10-14) benzenesulfonic acid (trade name Rypon LH-200, manufactured by Lion Corporation)

[Other common ingredients]
E-1:
・ 95% synthetic ethanol (genuine chemistry)
In the softener composition, the amount used was 3%.
・ Calcium chloride (trade name: granular calcium chloride, manufactured by Tokuyama Corporation)
In the softener composition, the amount used was 0.5%.
-Fragrance | flavor component The fragrance | flavor composition A shown by the following Table 1 was mix | blended so that it might become the quantity of 0.8 mass% in a softening agent composition.
-Isothiazolone solution (Rohm and Haas brand name: Caisson CG-ICP)
In the softener composition, the amount used was 100 ppm.
E-2:
・ 95% synthetic ethanol (genuine chemistry)
In the spray-type fiber treatment agent, the amount used was 10%.
-Fragrance | flavor component The fragrance | flavor composition B by which a composition is shown by following Table 1 was mix | blended so that it might become the quantity of 0.2 mass% in a spray type fiber processing agent.

表中の数値は質量％を表す。

The numerical values in the table represent mass%.

[Method for preparing softener composition]
Using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amounts of the respective components are adjusted as shown in Table 2 below. Was prepared. First, (A) component, (C) component, (D) component, and also the fragrance | flavor composition which is a common component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (B) was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of the ion-exchange water for balance is equivalent to the remainder obtained by subtracting the total amount of the oil phase mixture and the component (B) from 980 g. Next, the oil phase mixture heated above the melting point of the component (C) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of the component (C) is added in two portions. And stirred. Here, the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, calcium chloride as a common component is added, and if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5. In addition, ion exchange water was added so that the total mass became 1,000 g, and the intended softener composition was obtained.

[Evaluation of appearance changes]
70 g of the softening agent composition was put in a lightweight glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed to obtain a sample for evaluation, which was held at 40 ° C. for 60 days.
About the sample after the said durability test, the liquid color tone in 25 degreeC was compared with the 5 degreeC preservation | save goods. The evaluation was performed by visual evaluation and averaging by 20 panelists based on the following criteria. In terms of product value, a value of Δ or more was considered acceptable.
<Evaluation criteria>
◎ ◎ ◎: 1-2 people out of 20 who evaluated that a change in color tone was recognized ◎ ◎: 3-4 people out of 20 people who evaluated a change in color tone ◎: Change in color tone was recognized 5 to 6 people out of 20 who evaluated that the color was evaluated: ○: 7 to 8 people who evaluated that the color change was recognized Δ: 9 out of 20 people who evaluated that the color change was recognized -10 people x: 11 or more people who evaluated that a change in color was recognized

[Preparation method of spray fiber treatment agent]
Using a 500 ml beaker, a solution in which component (A) is dissolved in 95% synthetic ethanol, which is a common component, and an aqueous solution of component (B) are mixed in advance, and component (C) and other common components are mixed there. A suitable amount of ion-exchanged water in which the components are dissolved (diluted sulfuric acid (reagent 0.1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 0.1 mol / L, Kanto Chemical) is added in an appropriate amount, if necessary). Was adjusted to 0, and the amount of ion-exchanged water was adjusted so that the total amount would be 400 g) under stirring conditions to obtain the desired spray fiber treatment agent. About each spray type fiber processing agent, the external appearance change was evaluated similarly to the softening agent composition.

Claims (9)

(A) an antioxidant;
(B) a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000, wherein the inner branched cyclic structure portion is α-1,4-glucoside A fiber product comprising a glucan which is a cyclic structure part formed by a bond and an α-1,6-glucoside bond, and the outer branched structure part is an acyclic structure part bonded to the inner branched cyclic structure part Treatment composition.   The content of the component (A) is 0.001 to 5% by mass, the content of the component (B) is 0.01 to 10% by mass, and (A) / (B) is 5 or less. Item 2. A treating agent composition for textiles according to Item 1.   (A) The processing agent composition for textiles of Claim 1 or 2 whose component is a phenolic antioxidant.   (C) The processing agent composition for textiles in any one of Claims 1-3 which further contain a nonionic surfactant.   The component (A) is 2,6-di-t-dibutyl-4-hydroxytoluene (BHT), p-methoxyphenol, or 2,2′-ethylidenebis (4,6-di-t-butylphenol). The processing agent composition for textiles in any one of Claims 1-4.   The component (C) is a polyoxyalkylene alkyl ether having an alkyl group or alkenyl group having 8 to 36 carbon atoms and having an average of 5 to 100 moles of alkylene oxide having 2 to 4 carbon atoms added thereto. The processing agent composition for textiles in any one of -5.   (D) The processing agent composition for textiles according to any one of claims 1 to 6, further comprising at least one of a cationic surfactant, an amphoteric surfactant, and an anionic surfactant.   (D) The processing agent composition for textiles of Claim 7 containing a cationic surfactant as a component.   The spray type fiber processing agent formed by filling the processing agent composition for textiles according to claim 7 into a spray container.