TW202104429A - Silicone composition and fiber treatment agent - Google Patents

Abstract

Provided is a silicone composition that contains (A) an organopolysiloxane having a specific group bound to a silicon atom and having a viscosity of 20-20,000 mPa.s at 25 DEG C and (B) a specific alkylether carboxylic acid or a salt thereof, and that provides excellent flexibility and water absorptivity to the surface of fibers treated therewith.

Description

Polysiloxane composition and fiber treatment agent

The present invention relates to polysiloxane compositions. In detail, it relates to a silicone composition that can impart high flexibility and water absorption to fibers, and a fiber treatment agent containing the silicone composition.

In the past, as a treatment agent for imparting softness or smoothness to various fibers or fiber products, dimethylpolysiloxane, epoxy-containing polysiloxane, and aminoalkyl-containing polysiloxane have been widely used. Various organic polysiloxanes such as siloxanes. Among them, most of them use aminoalkyl-containing polysiloxanes that can impart particularly good flexibility to various fibers or fiber products. In particular, for the aminoalkyl _{group, it is a fiber treatment agent with organopolysiloxanes having -C 3} H ₆ NH ₂ groups, -C ₃ H ₆ NHCH ₂ CH ₂ NH ₂ groups, etc. as the main agent (Japanese Patent Publication 48-1480, JP 54-43614, JP 57-43673, JP 60-185879, JP 60-185880, JP 64-61576, etc. ) It is widely used because of its excellent flexibility.

Generally, fibers treated with a treatment agent with polysiloxane as the main component show water repellency. Even if the fiber originally has water absorption, it also shows hydrophobicity after being treated with polysiloxane. For example, when it is used in clothing, it also has the disadvantage of almost losing sweat absorption when sweating. Regarding this point, a review was conducted in order to impart both flexibility and water absorption to the fiber. For example, a technology has been proposed to contain an aminoalkyl group and a polyoxyalkylene group in the same polysiloxane molecule. Although the water absorption is improved by this, it contains the polyoxyalkylene group, so there is a disadvantage that the flexibility and smoothness are greatly reduced.

In order to improve the above-mentioned shortcomings, it has been proposed to modify the aminoalkyl group by reacting the aminoalkyl group-containing polysiloxane with the polyoxyalkylene glycol ether compound (Japanese Patent No. 3199609, JP 2014) -84398 Bulletin). In addition, block copolymers having siloxanes and polyoxyalkylenes alternately have also been used in this field (Japanese Patent No. 3859723, Japanese Patent Publication No. 2004-528412). However, although these silicone compounds can impart good softness and water absorption to the fibers, the silicone components will be removed after washing, which has the disadvantage of impairing the texture. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 48-1480 [Patent Document 2] Japanese Patent Publication No. 54-43614 [Patent Document 3] Japanese Patent Publication No. 57-43673 [Patent Document 4] Japanese Patent Application Laid-Open No. 60-185879 [Patent Document 5] Japanese Patent Application Laid-Open No. 60-185880 [Patent Document 6] Japanese Patent Laid-Open No. 64-61576 [Patent Document 7] Japanese Patent No. 3199609 [Patent Document 8] JP 2014-84398 A [Patent Document 9] Japanese Patent No. 3859723 [Patent Document 10] Japanese Special Publication No. 2004-528412

[The problem to be solved by the invention]

In view of the above-mentioned problems of the prior art, the present invention aims to provide a silicone composition that exhibits excellent flexibility and water absorption on the surface of the treated fiber. Furthermore, the object of the present invention is to provide a silicone composition that has excellent washing resistance and does not impair fiber flexibility after washing, and a fiber treatment agent containing the silicone composition. [Means to solve the problem]

The inventors of the present invention did not achieve the above objective and actively reviewed the results, and found that it contains (A) an organopolysiloxane with a specific group bonded to a silicon atom and a viscosity of 20 to 20,000 mPa·s at 25°C. And (B) a polysiloxane composition of a specific alkyl ether carboxylic acid or its salt, which can impart flexibility and water absorption to the fiber, thereby exhibiting high washing durability without impairing the softness of the fiber after washing. Complete the present invention.

(式中，R¹ 為碳數1~8之非取代或取代之2價烴基，a為0~4之數，R² 相互獨立地為氫原子或碳數1~10之非取代或取代之1價烴基)，及 (B)以下述式(2)表示之烷基醚羧酸或其鹽：相對於(A)100質量份，為10~200質量份

(式中，R³ 為碳數1~20之烷基，b為1~30之數，X為氫原子、鹼金屬、鹼土類金屬、銨或鹼性胺基酸)。 2. 如1之聚矽氧組成物，其中進而含有(C)以下述通式(3)表示之聚醚改質聚矽氧：相對於(A)100質量份，為1~50質量份

(式中，R⁴ 相互獨立地為苯基、碳數1~6之烷基、碳數1~6之烷氧基或羥基，R⁵ 相互獨立地為以式 -C_c H_2c O(C₂ H₄ O)_f (C₃ H₆ O)_g R⁷ 表示之有機基，R⁶ 相互獨立地為R⁴ 或R⁵ ，R⁷ 為氫原子、碳數1~6之烷基或碳數1~6之乙醯基，c為0~100之整數，d為0~100之整數，c+d為0~200，e為2~5之整數，f為1~40之整數，g為0~40之整數，但d=0時，R⁶ 中之至少一個為R⁵ )。 3. 如1或2之聚矽氧組成物，其中(B)成分中，上述式(2)中，X為氫原子或鹼金屬。 4. 如1至3中任一項之聚矽氧組成物，其中進而含有水。 5. 一種纖維處理劑，其係包含如1至4中任一項之聚矽氧組成物。 [發明效果]Therefore, the present invention provides the following silicone composition and fiber treatment agent. 1. A polysiloxane composition containing (A) organopolysilicon with a base bonded to silicon atoms represented by the following formula (1) and a viscosity of 20~20,000mPa·s at 25°C Oxyane: 100 parts by mass

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group with 1 to 8 carbons, a is a number from 0 to 4, and R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted with 1 to 10 carbons. Monovalent hydrocarbon group), and (B) alkyl ether carboxylic acid or salt thereof represented by the following formula (2): 10 to 200 parts by mass relative to 100 parts by mass of (A)

(In the formula, R ³ is an alkyl group with 1 to 20 carbon atoms, b is a number from 1 to 30, and X is a hydrogen atom, alkali metal, alkaline earth metal, ammonium or basic amino acid). 2. The polysiloxane composition as in 1, which further contains (C) polyether modified polysiloxane represented by the following general formula (3): 1-50 parts by mass relative to 100 parts by mass of (A)

(In the formula, R ^{4 is} independently of each other a phenyl group, an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6 or a hydroxyl group, and R ^{5 is} independently of each other in the formula -C _c H _2c O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R ⁷ represents an organic group, R ^{6 is} independently R ⁴ or R ⁵ , R ⁷ is a hydrogen atom, an alkyl group with 1 to 6 carbons or carbon number The acetyl group of 1~6, c is an integer of 0~100, d is an integer of 0~100, c+d is an integer of 0~200, e is an integer of 2~5, f is an integer of 1~40, and g is An integer of 0-40, but when d=0, at least one of R ^{6 is R 5} ). 3. The silicone composition of 1 or 2, wherein in the component (B), in the above formula (2), X is a hydrogen atom or an alkali metal. 4. The polysiloxane composition of any one of 1 to 3, which further contains water. 5. A fiber treatment agent, which contains the silicone composition of any one of 1 to 4. [Effects of the invention]

The composition of the present invention can impart excellent flexibility and water absorption to fibers. In addition, the composition of the present invention has excellent washing resistance, and the fibers treated with the composition of the present invention can maintain good flexibility after washing.

(式中，R¹ 為碳數1~8之非取代或取代之2價烴基，a為0~4之數，R² 相互獨立地為氫原子或碳數1~10之非取代或取代之1價烴基)。(A)成分可單獨使用1種亦可混合2種以上使用。The following is a detailed description of the present invention. [(A) Component] (A) is an organopolysiloxane with a silicon atom-bonded group represented by the following formula (1) and a viscosity of 20 to 20,000 mPa·s at 25°C,

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group with 1 to 8 carbons, a is a number from 0 to 4, and R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted with 1 to 10 carbons. Monovalent hydrocarbon group). (A) A component may be used individually by 1 type, and may mix and use 2 or more types.

The organopolysiloxane may have any of a linear structure, a branched structure, and a cyclic structure, but it is preferably a linear structure. In the organopolysiloxane, the group represented by the above formula (1) is bonded to the silicon atom of the polysiloxane skeleton, and it may exist at any one of the single end, both ends, and side chains of the molecular chain, or Only at one end, only at both ends, only at the side chain, and can also be bonded to each. The base molecule represented by the above formula (1) is at least one, preferably two or more.

In the above formula (1), R ¹ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms. For example, the divalent hydrocarbon group is exemplified by alkylene such as methylene, ethylene, propylene, and butylene, and among them, propylene is preferred. a is an integer of 0-4, preferably 1 or 2. R ^{2 is} independently a hydrogen atom or a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms. Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms include linear alkyl groups, branched chain alkyl groups, cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. The acetyl group having 1 to 10 carbon atoms is exemplified by acetyl group and the like. Preferably ^{, 33% or more of the groups represented by R 2} are hydrogen atoms, and more preferably 50% or more are hydrogen atoms.

(A) The viscosity of the component at 25°C is 20 to 20,000 mPa·s, preferably 40 to 15,000 mPa·s, and more preferably 40 to 10,000 mPa·s. In addition, the viscosity is a value measured with a BM type rotary viscometer.

[式中，R⁹ 相互獨立地為碳數1~12之非取代或取代之1價烴基，R¹⁰ 相互獨立地為-OY(Y為氫原子或碳數1~12之非取代或取代之1價烴基)，R⁸ 相互獨立地為R⁹ 或R¹⁰ 。R¹¹ 相互獨立地為以下述式(1)表示之基，

(式中，R¹ 為碳數1~8之非取代或取代之2價烴基，a為0~4之數，R² 相互獨立地為氫原子或碳數1~10之非取代或取代之1價烴基或醯基)。h為5~1,000之整數，j互相獨立地為0~3之整數，k互相獨立地為0或1，於各末端j+k為0~3。但式(4)及式(6)係選擇為於至少1個末端具有R¹¹ ]。The (A) component is exemplified by organopolysiloxanes represented by the following general formulas (4) to (6). Hereinafter, in the formula of polysiloxane, the bonding sequence of each siloxane unit is not limited to the following.

[In the formula, R ^{9 is} independently an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbons, and R ^{10 is} independently -OY (Y is a hydrogen atom or an unsubstituted or substituted with 1 to 12 carbons Monovalent hydrocarbon group), R ^{8 is R 9} or R ¹⁰ independently of each other. R ^{11 is} independently a group represented by the following formula (1),

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group with 1 to 8 carbons, a is a number from 0 to 4, and R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted with 1 to 10 carbons. Monovalent hydrocarbon group or acyl group). h is an integer of 5 to 1,000, j is an integer of 0 to 3 independently of each other, k is 0 or 1 independently of each other, and j+k is 0 to 3 at each end. However, formula (4) and formula (6) are selected to have R ¹¹ ] at at least one end.

The unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbons specified by R ⁸ , Y, and R ^{9 is} preferably an unsubstituted or substituted monovalent hydrocarbon group with 1 to 8 carbons. Examples are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl Alkyl groups such as eicosyl and eicosyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl groups; alkenyl groups such as vinyl and allyl groups and bonding of these groups Halogenated alkyl, halogenated alkenyl, etc. in which part or all of the hydrogen atoms in the carbon atoms are substituted by halogen atoms such as chlorine and fluorine. Among them, industrially preferred is a methyl group.

In the group represented by -OY defined by R ⁸ and R ¹⁰ , Y is a hydrogen atom or the above-mentioned unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms. Examples of the -Y group include hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and other alkyl groups. The -OY group is preferably a hydroxyl group or a methoxy group. , Ethoxy.

h is an integer of 5 to 1,000, preferably an integer of 10 to 800. If h is less than the above lower limit, the effect of imparting flexibility or smoothness to the fiber may become insufficient. In addition, when h exceeds the above upper limit, the organopolysiloxane becomes highly viscous, and it may be difficult to handle or emulsify.

j is an integer of 0~3 independently of each other, k is 0 or 1 independently of each other, and j+k in each end is 0~3. However, formula (4) and formula (6) are selected to have R ¹¹ at at least one end.

The organopolysiloxane represented by the above formulas (4) to (6) preferably has one or more R ¹⁰ in the molecule, j is preferably 1 or 2, more preferably 1, and j=1 at both ends Better. In formula (4), it is preferable that k at both ends is 1.

Examples of the organopolysiloxane represented by the above-mentioned formulas (4) to (6) include, for example, the following.

(式中，R⁹ 、R¹⁰ 、R¹¹ 、h及i如上述)。

(In the formula, R ⁹ , R ¹⁰ , R ¹¹ , h and i are as described above).

The organopolysiloxanes represented by the above formulas (4) to (6) can be easily obtained by conventional synthesis methods. For example, cyclic siloxanes such as octamethylcyclotetrasiloxane can be combined with 3-aminopropyl diethoxy in the presence of catalysts such as alkali metal hydroxides and tetramethylammonium hydroxide. Methyl silane or N-(2-aminoethyl)-3-aminopropyl dimethoxymethyl silane or its hydrolysate and other raw materials selected from compounds such as hexamethyldisiloxane Obtained by equilibrium reaction. In addition, dimethylpolysiloxane and 3-aminopropyl dimethoxymethyl siloxane can be blocked by both terminal hydroxyl groups in the absence of a catalyst or in the presence of a catalyst such as alkali metal hydroxide. Or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane is obtained by demethanolization reaction.

(式中，R³ 為碳數1~20之烷基，b為1~30之數，X為氫原子、鹼金屬、鹼土類金屬、銨或鹼性胺基酸)。(B)成分可單獨使用1種亦可混合2種以上使用。[Component (B)] The component (B) is an alkyl ether carboxylic acid or salt thereof represented by the following formula (2),

(In the formula, R ³ is an alkyl group with 1 to 20 carbon atoms, b is a number from 1 to 30, and X is a hydrogen atom, alkali metal, alkaline earth metal, ammonium or basic amino acid). (B) A component may be used individually by 1 type, and may mix and use 2 or more types.

In formula (2), R ³ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. In addition, ^{the alkyl chain of R 3} may be either a straight chain or a branched chain, and it may be one type or an alkyl group containing two or more types. b represents the number of added moles of ethylene oxide. b is a number of 1-30, preferably 3-20.

Examples of X include alkali metals such as hydrogen atoms, sodium and potassium, alkaline earth metals such as calcium and magnesium, ammonium, organic ammonium derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and L-arginine The basic amino acid and so on. X is preferably a hydrogen atom, an alkali metal, or an alkaline earth metal, and more preferably a hydrogen atom or an alkali metal.

As (B) alkyl ether carboxylic acid or its salt, for example, polyoxyethylene lauryl ether acetic acid, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether potassium acetate, polyoxyethylene lauryl ether calcium acetate, polyoxyethylene laurel Ether magnesium acetate, polyoxyethylene lauryl ether ammonium acetate, polyoxyethylene lauryl ether acetic acid, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene tridecyl ether acetic acid, polyoxyethylene tridecyl Sodium ether acetate and so on.

Commercial products can be used as (B) alkyl ether carboxylic acid or its salt. Examples of commercially available alkyl ether carboxylic acids or their salts are, for example, KAO AKYPO RLM-45, KAO AKYPO RLM-100, KAO AKYPO RLM-45NV (manufactured by Kao Chemical Company), VIEW LIGHT LCA-30D, VIEW LIGHT ECA (Sanyo Chemical company system) and so on.

The effect of the component (B) is not limited, but by using the component (A) and the component (B) together, it is considered that a polysiloxane composition with very high hydrophilicity can be obtained. If the polysiloxane composition of the present invention is effective In addition to the flexibility of silicone, it is believed that the cloth can be treated with excellent water absorption.

The blending amount of (B) component is 10 to 200 parts by mass relative to 100 parts by mass of (A) component, preferably 20 to 180 parts by mass, more preferably 30 to 150 parts by mass. When the blending amount of component (B) does not reach the above lower limit, the effect of imparting water absorption to the fiber is insufficient, and when the amount of component (B) exceeds the above upper limit, the effect of imparting flexibility to the fiber is insufficient.

(式中，R⁴ 相互獨立地為苯基、碳數1~6之烷基、碳數1~6之烷氧基或羥基，R⁵ 相互獨立地為以式 -C_c H_2c O(C₂ H₄ O)_f (C₃ H₆ O)_g R⁷ 表示之有機基，R⁶ 相互獨立地為R⁴ 或R⁵ ，R⁷ 為氫原子、碳數1~6之烷基或碳數1~6之乙醯基，c為0~100之整數，d為0~100之整數，c+d為0~200，e為2~5之整數，f為1~40之整數，g為0~40之整數，但d=0時，R⁶ 中之至少一個為R⁵ )。(C)成分可單獨使用1種亦可適當組合2種以上使用。[Component (C)] In the silicone composition of the present invention, it is preferable to blend the component (C) from the viewpoint of improving the flexibility after washing. (C) Component is polyether modified polysiloxane represented by the following general formula (3),

(In the formula, R ^{4 is} independently of each other a phenyl group, an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6 or a hydroxyl group, and R ^{5 is} independently of each other in the formula -C _c H _2c O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R ⁷ represents an organic group, R ^{6 is} independently R ⁴ or R ⁵ , R ⁷ is a hydrogen atom, an alkyl group with 1 to 6 carbons or carbon number The acetyl group of 1~6, c is an integer of 0~100, d is an integer of 0~100, c+d is an integer of 0~200, e is an integer of 2~5, f is an integer of 1~40, and g is An integer of 0-40, but when d=0, at least one of R ^{6 is R 5} ). (C) A component may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

As a specific example of (C)component, the following are illustrated.

(式中，c’、d’分別為1~100之整數，f為1~40之整數。g’為1~40之整數)。

(In the formula, c'and d'are integers from 1 to 100, and f is an integer from 1 to 40. g'is an integer from 1 to 40).

When compounding component (C), the compounding amount is preferably 1-50 parts by mass relative to 100 parts by mass of component (A), more preferably 2-30 parts by mass relative to 100 parts by mass of (A) component, and still more preferably It is 5-20 parts by mass.

In the silicone composition of the present invention, (D) water can also be blended. In the case of blending (D) water, the blending amount is preferably 10 to 10,000 parts by mass, and more preferably 20 to 6,000 parts by mass relative to 100 parts by mass of the above-mentioned silicone composition.

[Fiber Treatment Agent] The silicone composition of the present invention can be preferably used as a fiber treatment agent. When used as a fiber treatment agent, the above-mentioned polysiloxane composition is preferably dissolved in an organic solvent, dispersed in water, or emulsified by using emulsifiers such as nonionic, anionic, cationic, amphoteric surfactants, etc. Thinger.

Various solvents can be used for the fiber treatment agent of the present invention as needed. Examples of solvents include ether solvents such as dibutyl ether, dioxane, and THF, ketone solvents such as acetone and MEK, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2- Ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl- 1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol , 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol , 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3- Alcohol solvents such as propylene glycol, aromatic solvents such as toluene and xylene. These solvents may be used alone or in combination of two or more kinds.

The blending amount when blending the organic solvent is not particularly limited, but it is preferably 2,000 to 200,000 parts by mass, and more preferably 10,000 to 100,000 parts by mass relative to 100 parts by mass of the aforementioned polysiloxane composition.

The emulsifier used when the fiber treatment agent of the present invention is made into an emulsified product is not particularly limited. For example, nonionic (nonionic) surfactants include ethoxylated higher alcohols, ethoxylated alkylphenols, and polyphenol fatty acid esters. , Ethoxylated polyalkoxy fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid amides, sorbitol, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, sucrose fatty acid esters, etc. The HLB is preferably in the range of 5-20, more preferably in the range of 10-16.

Examples of anionic surfactants include higher alcohol sulfate ester salts, alkyl phenyl ether sulfate ester salts, alkylbenzene sulfonates, higher alcohol phosphate ester salts, ethoxylated higher alcohol sulfate ester salts, and ethoxylated alkyl groups. Phenyl ether sulfate, ethoxylated higher alcohol phosphate, etc. Examples of cationic surfactants include alkyl trimethyl ammonium chloride, alkyl amine hydrochloride, coconut amine acetate, alkyl amine acetate, alkyl xylylene dimethyl ammonium chloride, and the like. As amphoteric surfactants, for example, N-alkylamidopropyl-N,N-dimethylammonium betaines, N-amidopropyl-N,N'-dimethyl-N' -β-hydroxypropyl ammonium betaines, etc.

The blending amount when blending the emulsifier is preferably 0.5-50 parts by mass, more preferably 5-30 parts by mass relative to 100 parts by mass of the silicone composition. The amount of water used at the time of emulsification may be such that the (A) organopolysiloxane pure content concentration is 10 to 80% by mass, preferably 20 to 70% by mass.

Emulsions can be obtained by conventionally known methods, as long as the above-mentioned silicone composition is mixed with a surfactant, and it is mixed with a homomixer, homogenizer, colloid mill, line mixer, universal mixer (trade name), Emulsifiers such as ultra-micro mixer (trade name), planetary mixer (trade name), mixing kneader COMBIMIX (trade name), three-roll mixer, etc. can be used for emulsification.

In addition, in the fiber treatment agent of the present invention, within the range that does not impair the purpose of the present invention, it is also possible to add fiber agents such as anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents, antioxidants, and ultraviolet absorbers. Ingredients such as additives, pigments, metal powder pigments, rheology control agents, hardening accelerators, deodorants, antibacterial agents, etc.

In addition, when the fiber treatment agent of the present invention adheres to the fibers, it can be adhered to the fibers by dipping, spraying, roll coating, or the like. The adhesion amount varies according to the type of fiber and is not particularly limited, but as the total adhesion amount of the (A) component and (B) component in the silicone composition formulated in the fiber treatment agent, it is preferably 0.01-10 mass % Range. Secondly, it only needs to be dried with hot air blowing, heating furnace, etc. Although it differs depending on the type of fiber, the drying can be carried out only in the range of 100 to 180°C for 30 seconds to 5 minutes.

In addition, there are no particular restrictions on the fibers or fiber products that can be treated with the fiber treatment agent of the present invention. For natural fibers such as cotton, silk, hemp, wool, angora wool, and mohair, polyester, polyethylene, polypropylene, and nylon Synthetic fibers such as, acrylic, spandex, etc., all blended fibers of these combinations are effective. In addition, the form and shape are not limited, and are not limited to the shape of raw materials such as staple fiber, filament, fiber bundle, yarn, etc., and various processing forms such as woven fabric, knitted fabric, padding cotton, non-woven fabric, etc. can also be used in the present invention. The treatment object of fiber treatment agent.

In addition to fiber treatment applications, the silicone composition of the present invention can be used in various applications such as coatings, adhesives, caulking agents, inks, papers, etc., as well as impregnating agents for surface treatment or cosmetics. . At this time, additives may be used as needed. Examples of additives include anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents, and other fiber agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, hardening accelerators, deodorants, Antibacterial agents, etc. These additives can be used individually by 1 type or in combination of 2 or more types suitably. [Example]

Examples and comparative examples are shown below to specifically explain the present invention, but the present invention is not limited to the following examples. In addition, the bonding order of each siloxane unit in the formula is not limited to the following.

[Example 1] 100 parts by mass of organopolysiloxane represented by the following formula (A-1) (amine equivalent: 830 g/mol, viscosity 70 mPa·s) and KAO AKYPO RLM-45 (polyoxyethylene (4.5 ) Lauryl ether acetic acid, solid content 92% by mass, manufactured by Kao Corporation) 56 parts by mass (the pure content conversion amount is stated in the table, the same below), mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (1) .

[Example 2] 100 parts by mass of organopolysiloxane represented by the above formula (A-1) and 90 parts by mass of KAO AKYPO RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89% by mass, manufactured by Kao Corporation) Mix for 30 minutes at room temperature (25°C) to prepare a silicone composition (2).

[Example 3] 100 parts by mass of organopolysiloxane represented by the above formula (A-1) and KAO AKYPO RLM-100NV (sodium polyoxyethylene (10) lauryl ether acetate, solid content 24% by mass, manufactured by Kao Corporation) 330 parts by mass The mixture was mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (3).

[Example 4] 100 parts by mass of organopolysiloxane represented by the following formula (A-2) (amine equivalent: 2300 g/mol, viscosity 70 mPa·s) and KAO AKYPO RLM-100 (polyoxyethylene (10 ) Lauryl ether acetic acid, 89% by mass in solid content, manufactured by Kao Corporation) 180 parts by mass were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (4).

[Example 5] 100 parts by mass of organopolysiloxane represented by the following formula (A-3) (amine equivalent: 290 g/mol, viscosity 240 mPa·s) and KAO AKYPO RLM-100 (polyoxyethylene (10 ) Lauryl ether acetic acid, 89% by mass in solid content, manufactured by Kao Corporation) 130 parts by mass were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (5).

[Example 6] 100 parts by mass of organopolysiloxane represented by the following formula (A-4) (amine equivalent: 300g/mol, viscosity 420mPa·s) and KAO AKYPO RLM-100 (polyoxyethylene (10 ) Lauryl ether acetic acid, 89% by mass in solid content, manufactured by Kao Corporation) 130 parts by mass were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (6).

[Example 7] 100 parts by mass of organopolysiloxane represented by the above formula (A-1), KAO AKYPO RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, 89 mass% solid content, manufactured by Kao Corporation) ) 100 parts by mass and 20 parts by mass of polyether-modified silicone represented by the following formula (C-1) are mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (7).

[Example 8] 100 parts by mass of organopolysiloxane represented by the above formula (A-4), 100 parts by mass of KAO AKYPO RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content of 89% by mass, manufactured by Kao Corporation), and 20 parts by mass of the polyether-modified silicone represented by the above formula (C-1) were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (8).

[Example 9] 100 parts by mass of organopolysiloxane represented by the above formula (A-1), KAO AKYPO RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89 mass%, manufactured by Kao Corporation) ) 100 parts by mass and 20 parts by mass of polyether-modified silicone represented by the following formula (C-2) are mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (9).

[Comparative Example 1] Mix 5 parts by mass of organopolysiloxane represented by the above formula (A-1) and 245 parts by mass of IPA at room temperature (25°C) for 30 minutes to prepare the polysiloxane composition of the IPA dissolved product of (A-1)物(10).

[Comparative Example 2] 10 parts by mass of organopolysiloxane represented by the above formula (A-1) and 5 parts by mass of KAO AKYPO RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89% by mass, manufactured by Kao Corporation) The mixture was mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (11).

[Comparative Example 3] 100 parts by mass of organopolysiloxane represented by the following formula (A-5) (amine equivalent: 250g/mol, viscosity 8mPa·s) and KAO AKYPO RLM-100 (polyoxyethylene (10 ) Lauryl ether acetic acid, solid content of 89% by mass, manufactured by Kao Corporation) 130 parts by mass were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (12).

[Comparative Example 4] 100 parts by mass of organopolysiloxane (amine equivalent: 19,000 g/mol, viscosity 30,000 mPa·s) represented by the following formula (A-6) and KAO AKYPO RLM-100 (polyoxyethylene (10) Lauryl ether acetic acid, solid content of 89% by mass, manufactured by Kao Corporation) 130 parts by mass were mixed at room temperature (25°C) for 30 minutes to prepare a silicone composition (12).

[Comparative Example 5] Mix 100 parts by mass of the organopolysiloxane represented by the above formula (A-1) and 20 parts by mass of the polyether modified polysiloxane represented by the above formula (C-1) at room temperature (25°C) for 30 minutes , Preparation of polysiloxane composition (13).

[Evaluation Test] The evaluation test shown below was performed for each composition. The results are also recorded in Tables 1~3. 1. Softness Deionized water was added to the silicone composition and stirred, diluted to a solid content of 2% by mass, to prepare a test solution. After immersing polyester/cotton Broadcloth (65%/35%, manufactured by Guto Shinzo Co., Ltd.) in the test solution for 1 minute, twist it with a roller at a twist rate of 100% by mass, and dry it at 150°C for 2 minutes Then, it heat-processed at 150 degreeC for 2 minutes, and produced the processed cloth for softness evaluation. The treated cloth was touched with hands by three specialized sensory testers, and the softness was evaluated according to the following criteria. A and B are qualified. <Benchmark> A: The texture is very good to the touch B: Good texture and touch C: Poor tactile texture

2. Water absorption Deionized water was added to the silicone composition and stirred, diluted to a solid content of 2% by mass, to prepare a test solution. After immersing polyester/cotton Broadcloth (65%/35%, manufactured by Guto Store Co., Ltd.) in the test solution for 1 minute, twist it with a roller at a twist rate of 100%, and heat it at 150°C for 2 minutes . Subsequently, a drop (25 μL) of tap water was dropped on the treated cloth with a dropper, and the time (seconds) until the water drop was completely absorbed by the cloth (water absorption before washing) was measured. After that, the treated cloth was washed once in a washing machine in accordance with the method of JIS L0217 103. To the treated cloth after washing, drop a drop (25 μL) of tap water with a dropper, and measure the time (seconds) until the water drop is completely absorbed by the cloth (water absorption after washing). The evaluation is based on the following criteria. ◎ and ○ are qualified. <Benchmark> ◎: Those whose water droplets are absorbed within 3 seconds ○: more than 3 seconds and water droplets are absorbed within 20 seconds △: more than 20 seconds and water droplets are absorbed within 60 seconds ×: Even if it exceeds 60 seconds, the water droplets are not absorbed

3. Washing durability Deionized water was added to the silicone composition and diluted to a solid content of 2% by mass to prepare a test solution. After immersing the polyester/cotton Broadcloth (65%/35%, manufactured by Guto Shinyo Co., Ltd.) in the test solution for 10 seconds, it was twisted with a roller under the condition of a twist rate of 100%, and dried at 150°C for 2 minutes. Subsequently, the treated cloth was washed once in a washing machine in accordance with the method of JIS L0217 103. The residual amount of silicone on the fiber surface after washing once was measured with a fluorescent X-ray analyzer (manufactured by Rigaku), and the residual rate (mass%) was calculated by comparing it with the unwashed condition. The survival rate is more than 50% as qualified.

4. Softness after washing Deionized water was added to the silicone composition and diluted to a solid content of 2% by mass to prepare a test solution. After immersing the polyester/cotton Broadcloth (65%/35%, manufactured by Guto Shinyo Co., Ltd.) in the test solution for 10 seconds, it was twisted with a roller under the condition of a twist rate of 100%, and dried at 150°C for 2 minutes. Subsequently, the treated cloth was washed once in a washing machine in accordance with the method of JIS L0217 103. The washed cloth was touched by a human tester with hands, and the softness was evaluated according to the following criteria. A and B are qualified. <Benchmark> A: The texture is very good to the touch B: Good texture and touch C: Poor tactile texture

As shown in Tables 1 to 3, the silicone composition of the present invention can impart excellent water absorption and flexibility to fibers. In addition, the silicone composition of the present invention has excellent washing durability, and does not impair the flexibility of the fibers after washing.

Claims (5)

A polysiloxane composition containing (A) an organopolysiloxane with a base bonded to a silicon atom represented by the following formula (1) and a viscosity of 20 to 20,000 mPa·s at 25°C: 100 parts by mass

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group with 1 to 8 carbons, a is a number from 0 to 4, and R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted with 1 to 10 carbons. Monovalent hydrocarbon group or acyl group), and (B) alkyl ether carboxylic acid represented by the following formula (2) or its salt: 10 to 200 parts by mass relative to 100 parts by mass of (A)

(In the formula, R ³ is an alkyl group with 1 to 20 carbon atoms, b is a number from 1 to 30, and X is a hydrogen atom, alkali metal, alkaline earth metal, ammonium or basic amino acid). The polysiloxane composition of claim 1, which further contains (C) polyether modified polysiloxane represented by the following general formula (3): 1-50 parts by mass relative to 100 parts by mass of (A)

(In the formula, R ^{4 is} independently of each other a phenyl group, an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6 or a hydroxyl group, and R ^{5 is} independently of each other in the formula -C _c H _2c O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R ⁷ represents an organic group, R ^{6 is} independently R ⁴ or R ⁵ , R ⁷ is a hydrogen atom, an alkyl group with 1 to 6 carbons or carbon number The acetyl group of 1~6, c is an integer of 0~100, d is an integer of 0~100, c+d is an integer of 0~200, e is an integer of 2~5, f is an integer of 1~40, and g is An integer of 0-40, but when d=0, at least one of R ^{6 is R 5} ). Such as the silicone composition of claim 1 or 2, wherein in the component (B), in the above formula (2), X is a hydrogen atom or an alkali metal. For example, the silicone composition of claim 1 or 2, which further contains water. A fiber treatment agent comprising the silicone composition according to any one of claims 1 to 4.