JP7601574B2 - Fiber treatment composition - Google Patents

Description

The present invention relates to a highly transparent fiber treatment composition. In particular, the present invention relates to a highly transparent fiber treatment composition with excellent deodorizing properties.

As a fiber treatment agent, a silicone-based composition is known that is used in combination with a cationic surfactant or a cationic water-soluble polymer to improve the texture (softness and smoothness) of cotton or synthetic fiber clothing (Patent Documents 1 and 2). Some of these compositions contain a nonionic surfactant and one or more water-soluble solvents to make the appearance transparent (Patent Document 3). On the other hand, when the composition is used for repeated washing, odorous components are also adsorbed to the fibers, so odors are generated and accumulated in the clothing.
As a technique that is effective in suppressing odors in clothing, there is the addition of antibacterial compounds such as halogeno-o-hydroxydiphenyl compounds and antioxidants (Patent Documents 4 and 5). However, although this is capable of suppressing odors caused by bacteria, it has little effect on deodorizing odors that occur with repeated washing.
In addition, there is a technology for imparting deodorizing properties to a liquid finishing composition for textile products that is based on a silicone compound and a cationic compound by blending a specific zinc compound (Patent Document 6). However, such a composition has low deodorizing properties for clothes that are repeatedly washed, particularly for underwear made of a synthetic fiber blend, and further low deodorizing properties for body odor of clothes after wearing.

JP 2000-154476 A JP 2009-155739 A JP 2004-131895 A JP 2005-187973 A JP 2007-254902 A JP 2009-57647 A

Therefore, the objective of the present invention is to provide a highly transparent fiber treatment composition with excellent deodorizing properties.

As a result of intensive research into the above problem, it was found that a fatty acid zinc salt such as zinc ricinoleate can impart high deodorizing properties to clothing. However, a fatty acid zinc salt such as zinc ricinoleate is a compound that is not soluble in water and is poorly soluble in commonly used solvents. In order to utilize such a fatty acid zinc salt such as zinc ricinoleate in a fiber treatment agent, it is desirable to dissolve it and make it uniform. Therefore, the stabilization technology required to maintain a highly transparent appearance in a composition containing a fatty acid zinc salt such as zinc ricinoleate was investigated, and the present invention was discovered.

The present invention relates to, for example, the following items [1] to [5].
[1] (A) a zinc salt of a fatty acid having 8 to 22 carbon atoms,
(B) one or more water-soluble solvents selected from the group consisting of monohydric alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, and (C) a polyoxyalkylene alkyl ether represented by the following formula (1) or (2):
R _a -O-(C ₂ H ₄ O) _r -H (1)
(In the formula, R _a represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and r represents the average number of moles added, which is 2 to 30.)
R _b -O-(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t -H (2)
(In the formula, R _b represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, s and t represent the average number of moles added, s is 2 to 30, and t is 1 to 20.)
and the ratio of the total amount of the components (B) and (C) to the component (A) is 25 or more.
[2] The fiber treatment composition according to [1] above, further comprising (D) an amine compound represented by the following formula (3):
R ₁ (R ₂ )N-(CH ₂ ) _m -N(R ₃ )R ₄ (3)
(In the formula, R ₁ to R ₄ each independently represent a hydrocarbon group having 1 to 4 carbon atoms which may have a hydroxyl group or an amino group, and m is an integer ranging from 2 to 6.)
[3] (A) a zinc salt of a fatty acid having 8 to 22 carbon atoms,
(B) one or more water-soluble solvents selected from the group consisting of monohydric alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups; (C) a polyoxyalkylene alkyl ether represented by the following formula (1) or (2):
R _a -O-(C ₂ H ₄ O) _r -H (1)
(In the formula, R _a represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and r represents the average number of moles added, which is 2 to 30.)
R _b -O-(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t -H (2)
(In the formula, R _b represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, s and t represent the average number of moles added, s is 2 to 30, and t is 1 to 20.)
and (D) an amine compound represented by the following formula (3):
R ₁ (R ₂ )N-(CH ₂ ) _m -N(R ₃ )R ₄ (3)
(In the formula, R ₁ to R ₄ each independently represent a hydrocarbon group having 1 to 4 carbon atoms which may have a hydroxyl group or an amino group, and m is an integer ranging from 2 to 6.)
and the ratio of the total amount of the components (B) and (C) to the component (A) is 5 or more.
[4] The fiber treatment composition according to any one of [1] to [3] above, wherein the component (A) is zinc ricinoleate.
[5] The fiber treatment composition according to any one of [1] to [4] above, further comprising (E) a silicone compound.

According to one aspect of the present invention, a highly transparent fiber treatment composition with excellent deodorizing properties can be provided. In this specification, transparency is evaluated based on whether or not the composition has a uniform appearance and the degree of turbidity. For example, if the composition has a uniform appearance, it can be determined that the composition has high transparency even if it is slightly turbid.

[Component (A)]
By incorporating component (A) in the fiber treatment composition of the present invention, it becomes possible to eliminate odors that build up with repeated washing and odors that adhere to clothing when worn.
Component (A) is a zinc salt of a fatty acid having 8 to 22 carbon atoms, such as zinc behenate, zinc caprate, zinc stearate, zinc ricinoleate, etc. Of these, zinc ricinoleate is preferred in terms of its adsorption to clothing and/or the stability of the salt with zinc.
In the fiber treatment composition of the present invention, the component (A) may be used alone or in combination of two or more kinds.
The amount of component (A) to be blended is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and even more preferably 0.5 mass % or more, based on the total mass of the fiber treatment composition.

[Component (B)]
By incorporating component (B) in the fiber treatment composition of the present invention, component (A) can be present in a finely divided state in the solvent.
Component (B) is one or more water-soluble solvents selected from the group consisting of monohydric alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups. Specific examples include ethanol, isopropanol, glycerin, butyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, 1,3-butylene glycol, and diethylene glycol monobutyl ether.
Among these, from the viewpoints of economy and safety to the human body and the environment, preferred examples include ethanol, glycerin, propylene glycol, 1,3-butylene glycol, diethylene glycol monobutyl ether, and the like.
In the fiber treatment composition of the present invention, the component (B) may be used alone or in combination of two or more kinds.
The amount of the (B) component is not particularly limited as long as it is an amount that can achieve the purpose of the blending, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total mass of the fiber treatment composition. In addition, the mass ratio B/A of the (B) component to the (A) component is preferably 15 or more, and more preferably 30 or more.

In the fiber treatment composition of the present invention, when a polyether-modified silicone is used as component (E) described below, component (B) is preferably ethanol, diethylene glycol monobutyl ether, or a combination thereof, which can also be finely emulsified with respect to component (E).
The mass ratio B/E of the component (B) to the component (E) is preferably 0.3 or more. By mixing the components (B) and (E) in amounts such that the mass ratio B/E is 0.3 or more, the component (E) can be made sufficiently fine. Even if a large amount of the component (B) is used, the concentration of the component (E) becomes low, which is not economical, so the mass ratio B/E is preferably 10 or less, more preferably 5 or less.

[Component (C)]
By incorporating component (C) in the fiber treatment composition of the present invention, the solubility of component (A) can be improved.
The component (C) is a polyoxyalkylene alkyl ether represented by the following formula (1) or (2).
R _a -O-(C ₂ H ₄ O) _r -H (1)
(In the formula, R _a represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and r represents the average number of moles added, which is 2 to 30.)
R _b -O-(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t -H (2)
(In the formula, R _b represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, s and t represent the average number of moles added, s is 2 to 30, and t is 1 to 20.)
In formula (1), R _a is preferably an alkyl group or alkenyl group having 12 to 18 carbon atoms, and more preferably an alkyl group or alkenyl group having 12 to 16 carbon atoms. The alkyl group or alkenyl group in R _a may be linear or branched.
In the formula (1), r is preferably 3 to 20, and more preferably 3 to 15.
In formula (2), R _b is preferably an alkyl group or alkenyl group having 12 to 18 carbon atoms, and more preferably an alkyl group or alkenyl group having 12 to 16 carbon atoms. The alkyl group or alkenyl group in R _b may be linear or branched.
In the formula (2), s is preferably an integer of 3 to 20, and more preferably an integer of 3 to 15.
In formula (2), t is preferably 1 to 10, and more preferably 1 to 5.
In formula (2), (C ₂ H ₄ O) and (C ₃ H ₆ O) may be a random adduct or a block adduct.
In the fiber treatment composition of the present invention, the component (C) may be used alone or in combination of two or more kinds.

The amount of component (C) is not particularly limited as long as the purpose of the blending can be achieved, but is preferably 5 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 5 to 30 mass %, relative to the total mass of the fiber treatment composition. In addition, with respect to the ratio with respect to component (A), the mass ratio C/A of component (C) to component (A) is preferably 15 or more.
Furthermore, in order to improve the dispersion and/or solubility of component (A), in the fiber treatment composition of the present invention, the ratio of the total amount of components (B) and (C) to component (A) is preferably not less than 25, and more preferably not less than 30. However, when the fiber treatment composition of the present invention contains component (D) described below, the ratio of the total amount of components (B) and (C) to component (A) may be 5 or more.

[Component (D)]
The fiber treatment composition of the present invention may contain an amine compound represented by the following formula (3) as component (D). By containing component (D) in the fiber treatment composition of the present invention, the solubility of component (A) can be improved. Furthermore, by containing component (D), higher transparency can be imparted to the fiber treatment composition of the present invention.
R ₁ (R ₂ )N-(CH ₂ ) _m -N(R ₃ )R ₄ (3)
(In the formula, R ₁ to R ₄ each independently represent a hydrocarbon group having 1 to 4 carbon atoms which may have a hydroxyl group or an amino group, and m is an integer ranging from 2 to 6.)
The number of hydroxyl or amino groups in each of R ₁ to _{R 4 may} be _one or more, but preferably one.
The hydrocarbon groups of R ₁ to R ₄ may be linear or branched.
R ₁ to R ₄ may each independently be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl group, a 2-methyl-3-hydroxypropyl group, a 2-methyl-2-hydroxypropyl group, a 1,1-dimethyl-2-hydroxyethyl group, an aminomethyl group, a 2-aminoethyl group, a 3-aminopropyl group, a 2-aminopropyl group, a 4-aminobutyl group, a 3-aminobutyl group, a 2-aminobutyl group, a 2-methyl-3-aminopropyl group, a 2-methyl-2-aminopropyl group, or a 1,1-dimethyl-2-aminoethyl group.

The component (D) is preferably N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N'-trimethyl-2-hydroxyethylethylenediamine, N,N,N'-triethyl-2-hydroxyethylethylenediamine, N,N,N'-trimethyl-3-hydroxypropylethylenediamine, N,N,N'-trimethyl-2-hydroxypropylethylenediamine, N,N-diethyl-N'-methyl-2-hydroxyethylethylenediamine, N,N,N'-trimethyl -2-hydroxyethylpropylenediamine, N,N,N'-trimethyl-2-hydroxyethylbutylenediamine, N,N-dimethyl-N',N'-bis(2-hydroxyethyl)ethylenediamine, N,N-diethyl-N',N'-bis(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N',N'-bis(3-hydroxypropyl)ethylenediamine, N,N-dimethyl-N',N'-bis(2-hydroxypropyl)ethylenediamine, N,N-dimethyl-N',N'-bis(3-hydroxypropyl)ethylenediamine N,N-dimethyl-N',N'-bis(2-hydroxypropyl)propylenediamine, N,N-diethyl-N',N'-bis(2-hydroxypropyl)ethylenediamine, N,N-diethyl-N',N'-bis(2-hydroxypropyl)propylenediamine, N,N,N'-trimethyl-2-aminoethylethylenediamine, N,N,N'-triethyl-2-aminoethylethylenediamine, N,N,N'-trimethyl-3-aminopropylethylenediamine The compound is at least one compound selected from the group consisting of N,N,N'-trimethyl-2-aminopropylethylenediamine, N,N-diethyl-N'-methyl-2-aminoethylethylenediamine, N,N,N'-trimethyl-2-aminoethylpropylenediamine, N,N,N'-trimethyl-2-aminoethylbutylenediamine, N,N-dimethyl-N',N'-bis(2-aminoethyl)ethylenediamine, and N,N-diethyl-N',N'-bis(2-aminoethyl)ethylenediamine.
The amount of component (D) is not particularly limited as long as the purpose of the blend can be achieved, but is preferably 0.01 to 5 mass %, and more preferably 0.1 to 2 mass %, relative to the total mass of the fiber treatment composition. When the amount of component (D) is within the range of 0.01 to 5 mass %, component (A) is taken up and solubilized, and not only does it impart a highly transparent appearance to the fiber treatment composition, but it can also allow component (A) to be uniformly adsorbed onto clothing.

[Component (E)]
In the fiber treatment composition of the present invention, a silicone compound generally used in treating fiber products may be blended as component (E). The silicone compound is not particularly limited as long as it can impart smoothness to the fiber product when adsorbed thereon.
Examples of silicone compounds commonly used in the treatment of textile products include dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, epoxy polyether-modified silicone, carboxy-modified silicone, polyglycerol-modified silicone, carbinol-modified silicone, amino-modified silicone, aminopolyether-modified silicone, polyether-long-chain alkyl-aralkyl-modified silicone, and the like. These can be used alone or in combination of two or more.
The molecular structure of the silicone compound may be linear, branched, or crosslinked. The modified silicone compound may be modified with one type of organic functional group, or may be modified with two or more types of organic functional groups.
The kinetic viscosity of the silicone compound at 25° C. is preferably 10 to 100,000,000 ^{mm 2} /s, and more preferably 1,000 to 100,000 mm ² /s. A kinetic viscosity in this range is preferable in terms of ease of blending and the slipperiness of fabrics treated with the composition of the present invention.

The silicone compound may be used as an oil.
From the viewpoint of high adsorption effect to fibers and improvement of softness and smoothness, the silicone compound is preferably nonionic, and more preferred examples include dimethyl silicone, carbinol-modified silicone, polyglycerol-modified silicone, epoxy-modified silicone, polyether-modified silicone, amino-modified silicone, and aminopolyether-modified silicone. Among these, particularly preferred silicone compounds include polyether-modified silicone, aminopolyether-modified silicone, and dimethyl silicone from the viewpoint of imparting softness and preventing discoloration and appearance. These silicone compounds have less squeaky feeling and good softness compared to low molecular weight dimethyl silicone without polyether group.
A preferred polyether-modified silicone is a copolymer of an alkyl (carbon number 1 to 3) siloxane and a polyoxyalkylene (the alkylene group preferably has 2 to 5 carbon atoms). Of these, a copolymer of a dimethylsiloxane and a polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of polyoxyethylene and polyoxypropylene, etc.) is preferred. Examples of such a copolymer include compounds represented by the following general formula (I) or (II).

（式中、Ｍ、Ｎ、ａ及びｂは平均重合度であり、Ｒは水素又はアルキル基を表す。）
ここで、Ｍは１０～１００００、好ましくは１００～３００、Ｎは１～１０００、好ましくは１～１００、かつＭ＞Ｎであることが好ましく、ａは２～１００、好ましくは２～５０、ｂは０～５０、好ましくは０～１０である。Ｒとしては水素又は炭素数１～４のアルキル基が好ましい。
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。従って、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、ポリエーテル変性シリコーン中の存在量として３０ｐｐｍ以下（－Ｈの量として）で存在していることが好ましい。

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

（式中、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５～１００００、Ｂは２～１００００であることが好ましく、ｈは２～１００、ｉは０～５０が好ましい。Ｒとしては炭素数１～５のアルキル基が好ましい。Ｒ’としては水素又は炭素数１～４のアルキル基が好ましい。また、式（ＩＩ）で表されるブロック共重合体の重量平均分子量は、柔軟性及び滑らかさ付与の観点から１５，０００～１００，０００，０００であることが好ましい。
上記式（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。

(In the formula, A, B, h, and i are average degrees of polymerization, R represents an alkyl group, and R′ represents hydrogen or an alkyl group.)
Here, A is preferably 5 to 10,000, 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. Furthermore, the weight average molecular weight of the block copolymer represented by formula (II) is preferably 15,000 to 100,000,000 from the viewpoint of imparting flexibility and smoothness.
The linear polysiloxane-polyoxyalkylene block copolymer represented by the above formula (II) can be produced by reacting a polyoxyalkylene compound having a reactive terminal group with a dihydrocarbylsiloxane having a terminal group that reacts with the reactive terminal group of the polyoxyalkylene compound.

A specific example of the polyether-modified silicone oil is DOWSIL® (manufactured by Dow Toray Co., Ltd.). Examples of ^{the TM} series (including those in the catalog of the former Dow Corning Toray Co., Ltd.) include FZ-2164, FZ-2154, FZ-2191, L-7001, FZ-2120, L-7002, SH3749, SH3771, SH3772, SH3775, CF1188N, SF8410, FZ-2104, FZ-7604, FZ-2161, and FZ-2222; KF352A, KF6008, KF615A, KF6016, and KF6017 manufactured by Shin-Etsu Chemical Co., Ltd.; and TSF4450 and TSF4452 manufactured by Momentive Japan Co., Ltd. Specific examples of aminopolyether-modified silicone oils include DOWSIL® manufactured by Dow Toray Co., Ltd. Examples of ^{the TM} series include FZ-3789, SILSTYLE 104, SILSTYLE 201, and SILSTYLE. These can be used alone or in combination of two or more.
The amount of the silicone compound is not particularly limited, but from the viewpoints of smoothness and viscosity of the composition, it is preferably 0.1 to 50% by mass, more preferably 3 to 50% by mass, and particularly preferably 6 to 15% by mass, based on the total mass of the fiber treatment composition, which can provide excellent effects such as smoothness and good uniform adsorption.

[Component (F)]
The fiber treatment composition of the present invention may contain a cationic water-soluble polymeric compound as component (F). Such a water-soluble polymeric compound has the effect of adsorbing the silicone compound to the fiber.
As the cationic water-soluble polymeric compound, those that have cationic properties when dissolved in water can be used, but as the cationic water-soluble polymeric compound, in particular, a water-soluble polymeric compound having one or more cationic groups selected from an amino group, an amine group, and a quaternary ammonium group is preferred. In this specification, the water-soluble polymer refers to a polymeric compound that is transparent and not cloudy when 1 g of the polymeric compound is added to 100 g of water at 25°C. The cationic water-soluble polymeric compound preferably has a cationic degree of 0.1% or more, for example, 0.1 to 35%, and particularly preferably 2.5% or more, for example, 2.5 to 15%. If the cationic degree satisfies such conditions, the effect of adsorbing the coexisting silicone compound to the fiber can be excellent, and the case where a large amount of the compound is required and is not economical can be prevented.
Here, the degree of cationization is defined as a value calculated by the following formula (A) when the polymer compound is a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, or a nonionic polymer partially modified or substituted with a cationic group (such as cationized cellulose), or as a value calculated by the following formula (B) when the polymer compound is a copolymer of a cationic monomer and an anionic monomer, or a copolymer of a cationic monomer, an anionic monomer, and a nonionic monomer.

Cationization degree (%) = X × Y × 100 Formula (A)
[X: atomic weight of the cationized atom (such as nitrogen) in the cationic group of the polymer compound, and Y: moles of the cationic group contained in 1 g of the polymer compound]
Cationization degree (%)=X×(Y−Z)×100 Formula (B)
[X: atomic weight of a cationized atom (such as nitrogen) in a cationic group of a polymer compound, Y: number of moles of a cationic group contained in 1 g of a polymer compound, Z: number of moles of anionic groups contained in 1 g of a polymer compound (anionic groups of Z include a carboxyl group and a sulfonic acid group contained in a monomer unit in a polymer chain. Specifically, it is a carboxylic acid in acrylic acid. However, it does not include a counter ion of the cationic group.)]
As an example of calculating the degree of cationization, the case of MERQUAT 280 (manufactured by NALCO) represented by the following formula (III) will be shown.

塩化ジメチルジアリルアンモニウムとアクリル酸との質量比＝８０：２０
Ｘ：１４（窒素原子の原子量）
Ｙ：４．９５×１０^-3（カチオン性基の１ｇ中の重量：０．８ｇとカチオン性基の分子量より算出）
Ｚ：２．７８×１０^-3（アニオン性基の１ｇ中の重量：０．２ｇとアニオン性基の分子量より算出）
式（２）より、
カチオン化度（％）＝ １４×（４．９５×１０^-3－２．７８×１０^-3）×１００＝３．０である。

Mass ratio of dimethyldiallylammonium chloride to acrylic acid = 80:20
X: 14 (atomic weight of nitrogen atom)
Y: 4.95×10 ⁻³ (calculated from the weight of cationic groups per 1 g: 0.8 g and the molecular weight of the cationic groups)
Z: 2.78×10 ⁻³ (calculated from the weight of anionic groups in 1 g: 0.2 g and the molecular weight of the anionic groups)
From the formula (2),
Degree of cationization (%)=14×(4.95×10 ⁻³ −2.78×10 ⁻³ )×100=3.0.

Therefore, according to the above-mentioned method for calculating the degree of cationization, the degree of cationization of a polymer of a nonionic monomer or a polymer of an anionic monomer is 0%.
The cationic water-soluble polymer preferably has a weight average molecular weight of 1,000 to 5,000,000, more preferably 3,000 to 1,000,000, and even more preferably 5,000 to 500,000, as measured by gel permeation chromatography using polyethylene glycol as a standard substance. This makes it possible to suppress an increase in viscosity and ensure excellent usability.
Specific examples of water-soluble cationic polymer compounds include polymers of dimethyldiallylammonium chloride such as Merquat 100 (manufactured by Lubrizol), Adeka Catioace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidol EC-004, and Daidol EC-315D (manufactured by Daido Kasei Kogyo Co., Ltd.), copolymers of dimethyldiallylammonium chloride and acrylamide such as Merquat 550 (manufactured by Lubrizol), copolymers of dimethyldiallylammonium chloride and acrylic acid such as Merquat 280 (manufactured by Lubrizol), and Leoguard MGP and Leoguard KGP (Lion Corporation). Examples of the polymerizable compound include cationized cellulose such as LUVIQUAT-FC905 (manufactured by BASF), imidazolinium chloride-vinylpyrrolidone copolymer such as LUVIQUAT-FC905 (manufactured by BASF), polyethyleneimine such as LUGALVAN-G15000 (manufactured by BASF), cationized polyvinyl alcohol such as Poval 11-98 (manufactured by Kuraray Co., Ltd.), natural polymer derivatives having an amino group such as chitosan, and copolymers of diethylamino methacrylate-ethylene oxide or the like with a vinyl monomer having a hydrophilic group added thereto, but the polymerizable compound is not limited to these examples as long as it is a polymer compound that has cationic properties when dissolved in water.
Among these, from the viewpoint of not interfering with the feel such as flexibility imparted by the silicone, those which impart small stiffness to the fiber when the cationic polymer is adsorbed alone are preferred.
A particularly preferred polymer is a cationic polymer obtained by polymerizing dimethyldiallylammonium salt.
The cationic water-soluble polymeric compound may be used alone or in combination.
The amount of the cationic water-soluble polymer compound is not particularly limited, but is preferably in a range that does not impart stiffness to the textile product, for example, 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, relative to the total mass of the fiber treatment composition. By using such a range, it is possible to enhance the adsorption promoting effect of silicone, to provide sufficient effects such as softness and smoothness, and to suppress an increase in viscosity, making the composition easy to use.

[Other optional ingredients]
<Fragrance>
The fiber treatment composition of the present invention may contain a perfume to add fragrance to the composition. Lists of perfume raw materials that may be used are available from various sources, such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic Fragrances: Chemistry and Product Knowledge", Genichi Indo, Chemical Daily Co. (1996) and "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1997). (1994), "Encyclopedia of Fragrance", edited by the Japan Fragrance Association, Asakura Publishing Co., Ltd. (1989), "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996), and "Flower oils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is incorporated herein by reference.

<Dye and/or Pigment>
Dyes and pigments, respectively, may be included to improve the appearance of the fabric treatment composition.
Both the dyes and pigments can be used without any particular restrictions from components known in the field of fiber treatment agents. Specific examples of dyes that can be added are described in Dyes Handbook (edited by the Organic Synthetic Chemistry Association, published July 20, 1970 by Maruzen Co., Ltd.) and the like. In addition, dyes described in JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, JP-A-9-250085, JP-A-10-77576, JP-A-11-43865, JP-A-2001-181972, JP-A-2001-348784, and the like can also be used.
Preferably, the dye is at least one water-soluble dye of red, blue, yellow or purple selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant/acid mordant dyes.
The dye and the pigment may be used alone or in combination of two or more kinds.
The amount of each of the dye and pigment to be added is not particularly limited as long as the purpose of the addition can be achieved, but it is preferably 1 to 50 ppm, and more preferably 1 to 30 ppm, based on the total mass of the fiber treatment composition.

<Preservatives>
The preservative may be added mainly to enhance the preservative and bactericidal power of the fiber treatment composition and to maintain the preservative properties during long-term storage.
As the preservative, any component known in the field of fiber treatment agents can be used without particular limitation, specific examples of which include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, phenol-based phenol compounds, and 2-bromo-2-nitro-1,3-propanediol.
Examples of the isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-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, and mixtures thereof. Among these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is more preferred, and a mixture of about 77% by mass of the former and about 23% by mass of the latter or a diluted solution thereof (e.g., an isothiazolone solution) is particularly preferred, and a specific example thereof is Caisson CG-ICP manufactured by DDP Specialty Products Japan, Ltd.
Examples of benzisothiazolone-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and related compounds such as dithio-2,2-bis(benzmethylamide), and mixtures thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferred, and specific examples include Nippacide manufactured by Clariant Co., Ltd., and Proxel BDN, Proxel GXL, Proxel XL, Proxel LV, Proxel CRL, Proxel NBZ, Proxel AM, and Proxel B20 manufactured by Lonza Co., Ltd.
Examples of benzoic acids and phenol compounds that can be used include benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, benzyl parahydroxybenzoate, 3-methyl-3-isopropylphenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, and 2,6-di-tert-butyl-p-cresol.
The content of the preservative is not particularly limited as long as the purpose of the blending can be achieved, but is preferably 0.0001 to 1 mass % based on the total mass of the fiber treatment composition. When the content is 0.0001 mass % or more, the blending effect of the preservative can be sufficiently obtained, and when it is 1 mass % or less, the high storage stability of the fiber treatment composition can be sufficiently maintained.

<Antibacterial Agent>
The antibacterial agent can impart an antibacterial effect to clothing when fibers are treated with the fiber treatment composition, and can be blended to improve the storage stability of the composition.
As the antibacterial agent, any component known in the field of fiber treatment agents can be used without particular limitation. Specific examples of the alkyl trimethyl ammonium salts include alkyl trimethyl ammonium salts having 12 to 16 carbon atoms (Lipocard C12-37W, Lipocard C50, Lipocard C16Cl salt, Lipocard C16MS salt, etc., manufactured by Lion Specialty Chemicals), dialkyl dimethyl ammonium salts (Lipocard 210-80E, manufactured by Lion Specialty Chemicals, Carboquat MW50, etc., manufactured by Lonza), dialkyl methyl polyammonium propionates (Bardap 26, manufactured by Lonza), diclosan (Tinosan HP100, etc., manufactured by BASF), triclosan, benzalkonium chloride (Barquat MS100, Barquat MB80, etc., manufactured by Lonza), benzethonium chloride, bis-(2-pyridylthio-1-oxide) zinc, 8-oxyquinoline, biguanide compounds (Lonza), Examples of the antibacterial agent include Proxel IB, chlorhexidine hydrochloride, and polylysine.
Among these, C12-16 alkyltrimethylammonium salts, benzalkonium chloride, biguanide compounds, and chlorohexidine hydrochloride are preferred.
The content of the antibacterial agent is not particularly limited as long as the purpose of the blending can be achieved, but it is preferably 0.001 to 5% by mass based on the total mass of the fiber treatment composition.

<Ultraviolet absorbing agent>
An ultraviolet absorber may be incorporated in the fiber treatment composition to protect the composition from ultraviolet rays.
UV absorbers are components that absorb UV rays, convert them into infrared rays or visible light, etc., and release them to provide UV protection.
As the ultraviolet absorbing agent, any component known in the field of liquid fabric softeners can be used without particular limitation. Specific examples include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; salicylic acid derivatives such as ethylene glycol salicylate, dipropylene glycol salicylate, octyl salicylate, and myristyl salicylate; cinnamic acid derivatives such as methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, and butyl p-methoxycinnamate; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2,2'-dihydroxy-4-methoxybenzophenone; azole compounds such as urocanic acid and ethyl urocanate; and 4-t-butyl-4'-methoxybenzoylmethane.
The content of the ultraviolet absorbing agent is not particularly limited as long as the purpose of the blending can be achieved, but it is preferably 0.001 to 5% by mass based on the total mass of the fiber treatment composition.

<Antifoaming agent>
When a defoaming agent is blended into the fiber treatment composition of the present invention, foaming during fiber treatment and foaming during weighing of the composition can be suppressed. Examples of defoaming agents include silicone-based defoaming agents, alcohol-based defoaming agents, ester-based defoaming agents, mineral oil-based defoaming agents, vegetable oil-based defoaming agents, and synthetic oil-based defoaming agents, with silicone-based defoaming agents being preferred. Examples of silicone-based defoaming agents include oil-based defoaming agents, compound-based defoaming agents, self-emulsifying defoaming agents, emulsion-based defoaming agents, powder-based defoaming agents, and solid-based defoaming agents, with self-emulsifying defoaming agents and emulsion-based defoaming agents being preferred. The amount of defoaming agent blended is not particularly limited, but can be 0.1 ppm to 1.0 mass % based on the total mass of the composition, and more preferably 1 ppm to 0.05 mass %.

＜Other＞
In addition to the optional components described above, additives used in ordinary fiber treatment agents can be used within the scope of the present invention, so long as they do not impair the effects of the present invention. Specific examples of such additives include cationic surfactants, oils such as liquid paraffin and higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives, ultraviolet absorbers, fluorescent whitening agents, and the like. In addition, antioxidants and reducing agents for improving the stability of the fragrance and color tone of the fiber treatment agent composition, opacifiers (polystyrene emulsions, etc.), opacifying agents, shrink prevention agents, washing wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, oxygen bleaching inhibitors, whitening agents, whitening agents, fabric softening clays, antistatic agents, dye transfer inhibitors (polyvinylpyrrolidone, etc.), polymer dispersants, dirt release agents, scum dispersants, fluorescent whitening agents (4,4-bis(2-sulfostyryl)biphenyl disodium, etc.), dye fixatives, anti-fading agents (1,4-bis(3-aminopropanediol), etc.), and other additives may be used. In addition, it is possible to appropriately blend in the following: agents that impart the texture and functionality of silk, such as enzymes such as cellulase, amylase, protease, lipase, and keratinase; stain removers; fiber surface modifiers (enzymes such as cellulase, amylase, protease, lipase, and keratinase); foam inhibitors; and components that impart the texture and functionality of silk, such as moisture absorption and release properties (silk protein powder, surface-modified products thereof, and emulsified dispersions, specifically K-50, K-30, K-10, A-705, S-702, L-710, and FP series (Idemitsu Petrochemicals); hydrolyzed silk liquid (Jomo); and Silkgen G Soluble S (Ichimaru Falcos)); stain inhibitors (nonionic polymeric compounds consisting of alkylene terephthalate and/or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry Co., Ltd. and SRC-1 manufactured by Clariant, etc.), and pH adjusters, which will be described later. When an anionic surfactant or an anionic polymer compound is added, it is advisable to add it in an amount lower than the content of the cationic polymer compound of component (F), taking into consideration the adsorption effect of the silicone compound.
When an antioxidant is added, from the viewpoint of the appearance and storage stability of the fiber treatment composition, preferred are BHT (butyl hydroxytoluene), methoxyphenol, tocopherol compounds, etc. The antioxidant is preferably used in an amount of 0.01 to 1.0 mass%.

<Water>
The fiber treatment composition is preferably a liquid aqueous composition containing water.
As the water, any of tap water, ion-exchanged water, pure water, distilled water, etc. can be used, with ion-exchanged water being preferred.

[pH of composition]
The pH of the fiber treatment composition of the present invention (measured at 25° C. using a glass electrode) is not particularly limited, but is preferably in the range of 4 to 8, and more preferably in the range of 5 to 7. In order to adjust the pH to within this range, a pH adjuster such as hydrochloric acid, sulfuric acid, phosphoric acid, alkylsulfuric acid, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine or other short-chain amine compounds, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates or other pH adjusters can be used as necessary.

[Viscosity of composition]
The viscosity of the fiber treatment composition of the present invention (at 25°C, using a Brookfield viscometer with a No. 2 rotor, reading after 10 revolutions) is not particularly limited, but in the case of a product to be added to rinse water in the rinsing step of laundry, it is preferably 500 mPa·s or less, while in the case of a product filled in a trigger spray container or dispenser container and sprayed directly onto a fiber product, a viscosity of 100 mPa·s provides good usability.

[Method of preparing the composition]
The method for preparing the fiber treatment composition of the present invention is not particularly limited, and the fiber treatment composition of the present invention can be prepared by mixing each component. For example, the (A) component and the (B) component are placed in a container such as a glass beaker and stirred, and then the (C) component is added while stirring. The (D) component and other optional components are not particularly limited, and may be added after the (C) component is added.

[Method of using the composition]
The application and method of use of the fiber treatment composition of the present invention are not particularly limited, but when used on natural fiber products such as cotton or chemical fiber products such as polyester, the composition may be placed in the detergent or fabric softener inlet of a washing machine to treat clothes in the washing machine, or may be placed in a trigger spray container to spray on clothes. In either case, as long as component (A) adheres or adsorbs at 0.001% or more per fabric weight, high deodorizing performance can be imparted to any fabric.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In the examples, the amounts of ingredients are all expressed as mass % (based on the pure content unless otherwise specified).

[Component (A)]
A-1: Zinc ricinoleate (TEGOSORB Conc50, EVONIK)
A-2: Zinc stearate (reagent, Fujifilm Wako Pure Chemical Industries, Ltd.)
A-3 (Comparative Example): Zinc gluconate (reagent, Fujifilm Wako Pure Chemical Industries, Ltd.)

[Component (B)]
・B-1: 95% ethanol (reagent, from Japan Alcohol Sales)
B-2: Butyl carbitol (reagent, Tokyo Chemical Industry Co., Ltd.)

[Component (C)]
C-1: Polyoxyethylene alkyl ether (C12-14, EO10) (EMALEX710, Nippon Emulsion)
C-2 (Comparative Example): Polyoxyethylene alkyl ether (C13, EO40) (Leocol TDA-400-75, Lion Specialty Chemicals)

[Component (D)]
D-1: N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (reagent, Tokyo Chemical Industry Co., Ltd.)

[Component (E)]
E-1: Polyether modified silicone (DOWSIL ^™ CF1188N, manufactured by Dow Toray Co., Ltd.)
E-2: Polyether modified silicone (DOWSIL ^™ SH3775, manufactured by Dow Toray Co., Ltd.)
E-3: Aminopolyether modified silicone (DOWSIL ^™ FZ-3789, manufactured by Dow Corning Toray Co., Ltd.)

[Component (F)]
F-1: Dimethyldiallylammonium chloride polymer (MERQUAT ^™ 100, manufactured by Lubrizol Corporation)

[Other optional ingredients]
G-1: A fragrance composition containing fragrance ingredients in the composition shown in Table 1 below.

[Method for preparing fiber treatment composition]
In a 100 mL glass beaker, component (A) was added, followed by component (B), and the mixture was stirred with a stirrer of about 3 cm. Next, component (C) was added while stirring the mixture of components (A) and (B), and then water was added while stirring the mixture after the addition of component (C), and then component (D) was added. When components (E), (F), and (G) were added, they were added to the mixture before the addition of water and stirred. In all cases, an appropriate amount of sulfuric acid (reagent) was added to adjust the pH to 7, and finally the balance was made with water. The compositions of the prepared fiber treatment compositions are shown in Tables 2 and 3 below.

<Evaluation of odor of clothing after wearing (Evaluation 1)>
The clothes to be washed were AIRism (UNIQLO: manufactured by Fast Retailing Co., Ltd.) made of 90% polyester and 10% polyurethane, and the washing was carried out under the following conditions. In a Panasonic drum washing machine NA-VX700, Top NANOX was placed in the detergent inlet, the fiber treatment composition prepared according to the above preparation method was placed in the finishing agent inlet, and the clothes were washed using the automatic cycle (cloth weight: 1 kg). After washing, the dried clothes were worn for 8 hours a day, and the odor of the clothes after wearing was evaluated by 6 evaluators based on the following 6-stage odor intensity standard. The results are shown as the average of the 6 evaluators and are shown in the "Evaluation 1" section in Table 2 below. A score of less than 3 points was considered to be acceptable.
(6-level odor intensity scale)
5 points: strong odor, 4 points: strong odor, 3 points: easily detectable odor, 2 points: weak odor, 1 point: not detectable odor, 0 point: no odor.

<Evaluation of odor accumulation due to repeated washing (Evaluation 2)>
Airism (UNIQLO: manufactured by Fast Retailing Co., Ltd.) made of 90% polyester and 10% polyurethane was worn during the day, and the clothes were repeatedly washed under the following conditions. In a Panasonic drum washing machine NA-VX700, Top NANOX was set in the detergent inlet, the fiber treatment composition prepared according to the above preparation method was set in the finishing agent inlet, and 10 pieces of wet artificially soiled cloth of 20 cm x 20 cm were washed 10 times on the automatic cycle (the total amount of cloth was 1 kg for the worn clothes and the artificially soiled cloth). The odor of the clothes after repeated washing was evaluated by six evaluators based on the following six-level odor intensity standard. The results are shown as the average of the six evaluators and are shown in the "Evaluation 2" section in Table 3 below. A score of less than 3 points was considered to be acceptable. The wet artificially soiled cloth was purchased from the Laundry Science Association.
(6-level odor intensity scale)
5 points: strong odor, 4 points: strong odor, 3 points: easily detectable odor, 2 points: weak odor, 1 point: not detectable odor, 0 point: no odor.

[Method of evaluating fiber treatment composition]
<Appearance Evaluation (Evaluation 3)>
The fiber treatment composition prepared according to the above-mentioned preparation method was transferred to a transparent glass bottle with a sealable lid and allowed to stand at room temperature for 24 hours, and its appearance was evaluated according to the following criteria. △ or better was considered to be acceptable. The results are shown in the "Evaluation 3" section in Tables 2 and 3 below.
×: Precipitation △: Uniform appearance, but slightly cloudy 〇: Uniform appearance, almost clear, but slightly cloudy ◎: Uniform appearance, clear

表中、各成分の組成における数値は質量％を表す。

In the table, the numerical values for the composition of each component represent mass %.

表中、各成分の組成における数値は質量％を表す。

In the table, the numerical values for the composition of each component represent mass %.

Claims (3)

(A) a zinc salt of a fatty acid having 8 to 22 carbon atoms,
(B) one or more water-soluble solvents selected from the group consisting of monohydric alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups;
(C) a polyoxyalkylene alkyl ether represented by the following formula (1) or (2):
R _a -O-(C ₂ H ₄ O) _r -H (1)
(In the formula, R _a represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and r represents the average number of moles added, which is 2 to 30.)
R _b -O-(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t -H (2)
(In the formula, R _b represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, s and t represent the average number of moles added, s is 2 to 30, and t is 1 to 20.)
and (D) an amine compound represented by the following formula (3):
R ₁ (R ₂ )N-(CH ₂ ) _m -N(R ₃ )R ₄ (3)
(In the formula, R ₁ to R ₄ each independently represent a hydrocarbon group having 1 to 4 carbon atoms which may have a hydroxyl group or an amino group, and m is an integer ranging from 2 to 6.)
Contains
The blending amount of (C) is 3 to 30 mass %,
The blending amount of (D) is 0.1 to 5 mass %, and
A fiber treatment composition, in which the ratio of the total amount of components (B) and (C) to component (A) is 5 or more. 2. The fiber treatment composition according to claim 1 , wherein component (A) is zinc ricinoleate. The fiber treatment composition according to claim 1 or 2 , further comprising (E) a silicone compound.