JP7047804B2 - Silicone compositions and fiber treatment agents - Google Patents

Description

The present invention relates to a silicone composition. More specifically, the present invention relates to a silicone composition capable of imparting high flexibility and water absorption to fibers, and a fiber treatment agent containing the silicone composition.

Conventionally, various organopolysiloxanes such as dimethylpolysiloxane, epoxy group-containing polysiloxane, and aminoalkyl group-containing polysiloxane have been widely used as treatment agents for imparting flexibility and smoothness to various fibers or textile products. There is. Among them, aminoalkyl group-containing organopolysiloxanes that can impart particularly good flexibility to various fibers or textile products are often used. In particular, a fiber treatment agent mainly composed of an organopolysiloxane having -C ₃ H ₆ NH ₂ groups, -C ₃ H ₆ NHCH ₂ CH ₂ NH ₂ groups, etc. as aminoalkyl groups (Tokukosho 48-1480, Tokukousho). No. 54-43614, No. 57-43673, JP-A-60-185879, JP-A-60-185880, JP-A-64-61576, etc.) are widely used because of their excellent flexibility. ing.

In general, fibers treated with a treatment agent containing polysiloxane as a main component show water repellency. Even a fiber that originally has water absorbency exhibits hydrophobicity after being treated with polysiloxane, and when used for clothing, for example, it has a drawback that the sweat-absorbing action at the time of sweating is almost lost. In this regard, studies have been made to impart both flexibility and water absorption to the fibers. For example, a technique has been proposed in which an aminoalkyl group and a polyoxyalkylene group are contained in the same polysiloxane molecule. Although this improves the water absorption, there is a drawback that the flexibility and smoothness are significantly reduced by containing the polyoxyalkylene group.

In order to improve the above drawbacks, it has been proposed to modify an aminoalkyl group by reacting an aminoalkyl group-containing polysiloxane with a polyoxyalkylene glycidyl ether compound (Patent No. 3199609, JP-A-2014). No. 84398). Block copolymers having siloxanes and polyoxyalkylenes alternately are also used in the art (Patent No. 3859723, JP-A-2004-528412).
However, although these siloxane compounds can impart good flexibility and water absorption to the fibers, they have a drawback that the siloxane component is removed after washing and the texture is impaired.

Special Publication No. 48-1480 Special Publication No. 54-43614 Special Publication No. 57-43673 Japanese Unexamined Patent Publication No. 60-185879 Japanese Unexamined Patent Publication No. 60-185880 Japanese Unexamined Patent Publication No. 64-61576 Japanese Patent No. 3199609 Japanese Unexamined Patent Publication No. 2014-844398 Japanese Patent No. 3859723 Japanese Patent Publication No. 2004-528412

In view of the above problems of the prior art, it is an object of the present invention to provide a silicone composition exhibiting excellent flexibility and water absorption on the treated fiber surface. Further, an object of the present invention is to provide a silicone composition having excellent washing resistance and not impairing the flexibility of the fiber even after washing, and a fiber treatment agent containing the silicone composition.

As a result of diligent studies to achieve the above object, the present inventor has (A) an organopolysiloxane having a specific group bonded to a silicon atom and having a viscosity at 25 ° C. of 20 to 20,000 mPa · s. , (B) A silicone composition containing a specific alkyl ether carboxylic acid or a salt thereof can impart excellent flexibility and water absorption to the fiber, exhibit higher washing durability, and the fiber even after washing. It was found that the flexibility of the above was not impaired, and the present invention was reached.

（式中、Ｒ¹は炭素数１～８の非置換又は置換の２価炭化水素基であり、ａは０～４の数であり、Ｒ²は互いに独立に水素原子、又は炭素数１～１０の非置換又は置換の１価炭化水素基もしくはアシル基である。）
で表され、ケイ素原子に結合した基を有し、２５℃における粘度が、２０～２０，０００ｍＰａ・sであるオルガノポリシロキサン：１００質量部、及び
（Ｂ）下記式（２）

（式中、Ｒ³は炭素数１～２０のアルキル基であり、ｂは１～３０の数であり、Ｘは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は塩基性アミノ酸である。）
で表されるアルキルエーテルカルボン酸又はその塩：（Ａ）１００質量部に対し１０～２００質量部
を含有するシリコーン組成物。
２．さらに、（Ｃ）下記一般式（３）

（式中、Ｒ⁴は互いに独立にフェニル基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、又は水酸基であり、Ｒ⁵は互いに独立に式－Ｃ_eＨ_2eＯ（Ｃ₂Ｈ₄Ｏ）_f（Ｃ₃Ｈ₆Ｏ）_gＲ⁷で示される有機基であり、Ｒ⁶は互いに独立にＲ⁴又はＲ⁵であり、Ｒ⁷は水素原子、炭素数１～６のアルキル基、又は炭素数１～６のアセチル基であり、ｃは０～１００の整数、ｄは０～１００の整数で、ｃ＋ｄは０～２００であり、ｅは２～５の整数、ｆは１～４０の整数、ｇは０～４０の整数である。但し、ｄ＝０のとき、Ｒ⁶のうち少なくともひとつがＲ⁵である。）
で表されるポリエーテル変性シリコーン：（Ａ）成分１００質量部に対し１～５０質量部を含有する１記載のシリコーン組成物。
３．（Ｂ）成分において、上記式（２）中、Ｘは水素原子又はアルカリ金属である１又は２記載のシリコーン組成物。
４．さらに、水を含有する１～３のいずれかに記載のシリコーン組成物。
５．１～４のいずれかに記載のシリコーン組成物を含む繊維処理剤。 Therefore, the present invention provides the following silicone compositions and fiber treatment agents.
1. 1. (A) The following formula (1)

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, a is a number of 0 to 4, and R ² is a hydrogen atom or 1 to 1 carbon atoms independently of each other. 10 unsubstituted or substituted monovalent hydrocarbon group or acyl group.)
Organopolysiloxane, which has a group bonded to a silicon atom and has a viscosity at 25 ° C. of 20 to 20,000 mPa · s: 100 parts by mass, and (B) the following formula (2).

(In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, b is a number of 1 to 30, and X is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid.)
Alkyl ether carboxylic acid represented by (A) or a salt thereof: (A) A silicone composition containing 10 to 200 parts by mass with respect to 100 parts by mass.
2. 2. Further, (C) the following general formula (3)

(In the formula, R ⁴ is a phenyl group independently of each other, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and R ⁵ is an independent formula −C _e H _2e O ( C ₂ H ₄ O) _f (C ₃ H ₆ O) _g It is an organic group represented by R ⁷ , R ⁶ is R ⁴ or R ⁵ independently of each other, and R ⁷ is a hydrogen atom and has 1 to 6 carbon atoms. Is an alkyl group or an acetyl group having 1 to 6 carbon atoms, c is an integer of 0 to 100, d is an integer of 0 to 100, c + d is an integer of 0 to 200, e is an integer of 2 to 5, and f. Is an integer of 1 to 40, and g is an integer of 0 to 40. However, when d = 0, at least one of R ⁶ is R ^5. )
The silicone composition according to 1 which contains 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
3. 3. The silicone composition according to 1 or 2, wherein in the component (B), X is a hydrogen atom or an alkali metal in the above formula (2).
4. The silicone composition according to any one of 1 to 3 containing water.
A fiber treatment agent containing the silicone composition according to any one of 5.1 to 4.

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

（式中、Ｒ¹は炭素数１～８の非置換又は置換の２価炭化水素基であり、ａは０～４の数であり、Ｒ²は互いに独立に水素原子、又は炭素数１～１０の非置換又は置換の１価炭化水素基もしくはアシル基である。）
で表され、ケイ素原子に結合した基を有し、２５℃における粘度が、２０～２０，０００ｍＰａ・sであるオルガノポリシロキサンである。（Ａ）成分は１種単独でも２種以上を混合して使用してもよい。 Hereinafter, the present invention will be described in detail.
[(A) component]
(A) The following formula (1)

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, a is a number of 0 to 4, and R ² is a hydrogen atom or 1 to 1 carbon atoms independently of each other. 10 unsubstituted or substituted monovalent hydrocarbon group or acyl group.)
It is an organopolysiloxane represented by, having a group bonded to a silicon atom, and having a viscosity at 25 ° C. of 20 to 20,000 mPa · s. The component (A) may be used alone or in combination of two or more.

The organopolysiloxane may have a linear structure, a branched structure, or a cyclic structure, but is preferably linear. In the organopolysiloxane, the group represented by the above formula (1) is bonded to the silicon atom of the polysiloxane skeleton, and may be present at one end, both ends, or a side chain in the molecule, and one end may be present. Only, only both ends, only the side chains, or may be bound to each. The number of groups represented by the above formula (1) is at least one in the molecule, and it is preferable to have two or more groups.

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

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

[式中、Ｒ⁹は互いに独立に、炭素数１～１２の非置換又は置換の１価炭化水素基、Ｒ¹⁰は互いに独立に、－ＯＹ（Ｙは水素原子、又は炭素数１～１２の非置換又は置換の１価炭化水素基である。）、Ｒ⁸は互いに独立に、Ｒ⁹又はＲ¹⁰である。Ｒ¹¹は互いに独立に、下記式（１）

（式中、Ｒ¹は炭素数１～８の非置換又は置換の２価炭化水素基であり、ａは０～４の数であり、Ｒ²は互いに独立に水素原子、又は炭素数１～１０の非置換又は置換の１価炭化水素基もしくはアシル基である。）
で示される基である。ｈは５～１，０００の整数、ｊは互いに独立に０～３の整数であり、ｋは互いに独立に０又は１であり、各末端においてｊ＋ｋは０～３である。但し、式（４）及び式（６）は少なくとも１つの末端にＲ¹¹を有するように選択される。] Examples of the component (A) include organopolysiloxanes represented by the following general formulas (4) to (6).

[In the formula, R ⁹ is independent of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹⁰ is independent of each other, -OY (Y is a hydrogen atom, or 1 to 12 carbon atoms). It is an unsubstituted or substituted monovalent hydrocarbon group), R ⁸ is independent of each other, R ⁹ or R ¹⁰ . R ¹¹ is independent of each other and has the following equation (1).

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, a is a number of 0 to 4, and R ² is a hydrogen atom or 1 to 1 carbon atoms independently of each other. 10 unsubstituted or substituted monovalent hydrocarbon group or acyl group.)
It is a group indicated by. 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, equations (4) and (6) are selected to have R ¹¹ at at least one end. ]

The unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms specified in R ⁸ , Y, and R ⁹ is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. For example, alkyl such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group. Group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group and tolyl group; alkenyl group such as vinyl group and allyl group, and one of hydrogen atoms bonded to the carbon atom of these groups. Examples thereof include an alkyl halide group and an alkenyl halide group in which a part or the whole is substituted with a halogen atom such as chlorine or fluorine. Of these, the methyl group is industrially preferable.

Y in the group represented by —OY defined by R ⁸ and R ¹⁰ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the -Y group include an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, and examples of the -OY group include a hydroxyl group and a methoxy group. , Ethoxy group is preferred.

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 be insufficient. Further, when h exceeds the above upper limit value, the organopolysiloxane becomes highly viscous, which may make handling and emulsification difficult.

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, equations (4) and (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 ^10s in the molecule, j is preferably 1 or 2, more preferably 1 and j at both ends. The one with = 1 is preferable. In the formula (4), it is preferable that k at both ends is 1.

Examples of the organopolysiloxane represented by the above formulas (4) to (6) include the following.

（式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、ｈ及びｉは上述の通りである。）

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

The organopolysiloxane represented by the above formulas (4) to (6) can be easily obtained by a known synthetic method. For example, in the presence of a catalyst such as alkali metal hydroxide or tetramethylammonium hydroxide, cyclic siloxane such as octamethylcyclotetrasiloxane and 3-aminopropyldiethoxymethylsilane or N- (2-aminoethyl) -3. -It is obtained by an equilibrium reaction with aminopropyldimethoxymethylsilane, a hydrolyzate thereof, and a compound selected from hexamethyldisiloxane or the like as another raw material. Further, in the absence of a catalyst or in the presence of a catalyst such as an alkali metal hydroxide, both-terminal hydroxy group-blocking dimethylpolysiloxane and 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyldimethoxy It is obtained by demethanolizing with methylsilane.

（式中、Ｒ³は炭素数１～２０のアルキル基であり、ｂは１～３０の数であり、Ｘは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は塩基性アミノ酸である。）
で表されるアルキルエーテルカルボン酸又はその塩である。（Ｂ）成分は１種単独で又は２種以上を適宜組み合わせて用いることができる。 [(B) component]
The component (B) is the following formula (2).

(In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, b is a number of 1 to 30, and X is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid.)
It is an alkyl ether carboxylic acid represented by or a salt thereof. The component (B) may be used alone or in combination of two or more.

In the 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. Further, the alkyl chain of R ³ may be either a straight chain or a branched chain, and may contain one kind or two or more kinds of alkyl groups. b indicates the number of moles of ethylene oxide added. b is a number of 1 to 30, preferably 3 to 20.

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

Examples of the component (B) include polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether potassium acetate, polyoxyethylene lauryl ether calcium acetate, polyoxyethylene lauryl ether magnesium acetate, and polyoxy. Examples thereof include ethylene lauryl ether ammonium acetate, polyoxyethylene dodecyl ether acetate, polyooxyethylene dodecyl ether acetate sodium, polyoxyethylene tridecyl ether acetate, polyoxyethylene tridecyl ether acetate sodium acetate and the like.

As the alkyl ether carboxylic acid or a salt thereof, a commercially available product can be used. Examples of commercially available alkyl ether carboxylic acids or salts thereof include Kao Akipo RLM-45, Kao Akipo RLM-100, Kao Akipo RLM-45NV (manufactured by Kao Chemical Industries, Ltd.), Viewlite LCA-30D, Viewlite ECA, (Sanyo Chemical Industries, Ltd.). (Manufactured by the company) and the like.

The action and effect of the component (B) is not limited, but it is considered that the combined use of the component (A) and the component (B) results in a highly hydrophilic silicone composition. It is considered that when the silicone composition of the present invention is treated on a cloth, it is possible to impart very excellent water absorption to the cloth in addition to the flexibility of the silicone.

The blending amount of the component (B) is 10 to 200 parts by mass, preferably 20 to 180 parts by mass, and more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of the component (B) is less than the above lower limit value, the effect of imparting water absorption to the fiber is insufficient, and if the amount of the component (B) exceeds the above upper limit value, the effect of imparting flexibility to the fiber is insufficient. be.

（式中、Ｒ⁴は互いに独立にフェニル基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、又は水酸基であり、Ｒ⁵は互いに独立に式－Ｃ_eＨ_2eＯ（Ｃ₂Ｈ₄Ｏ）_f（Ｃ₃Ｈ₆Ｏ）_gＲ⁷で示される有機基であり、Ｒ⁶は互いに独立にＲ⁴又はＲ⁵であり、Ｒ⁷は水素原子、炭素数１～６のアルキル基、又は炭素数１～６のアセチル基であり、ｃは０～１００の整数、ｄは０～１００の整数で、ｃ＋ｄは０～２００であり、ｅは２～５の整数、ｆは１～４０の整数、ｇは０～４０の整数である。但し、ｄ＝０のとき、Ｒ⁶のうち少なくともひとつがＲ⁵である。）
で表されるポリエーテル変性シリコーンである。（Ｃ）成分は１種単独で又は２種以上を適宜組み合わせて用いることができる。 [(C) component]
The silicone composition of the present invention preferably contains the component (C) from the viewpoint of improving flexibility after washing. The component (C) is the following general formula (3).

(In the formula, R ⁴ is a phenyl group independently of each other, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and R ⁵ is an independent formula −C _e H _2e O ( C ₂ H ₄ O) _f (C ₃ H ₆ O) _g It is an organic group represented by R ⁷ , R ⁶ is R ⁴ or R ⁵ independently of each other, and R ⁷ is a hydrogen atom and has 1 to 6 carbon atoms. Is an alkyl group or an acetyl group having 1 to 6 carbon atoms, c is an integer of 0 to 100, d is an integer of 0 to 100, c + d is an integer of 0 to 200, e is an integer of 2 to 5, and f. Is an integer of 1 to 40, and g is an integer of 0 to 40. However, when d = 0, at least one of R ⁶ is R ^5. )
It is a polyether-modified silicone represented by. The component (C) may be used alone or in combination of two or more.

Specific examples of the component (C) include the following.

（式中、ｃ’，ｄ’はそれぞれ１～１００の整数であり、ｆは１～４０の整数である。ｇ’は１～４０の整数である。）

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

When the component (C) is blended, the blending amount thereof is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A), more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the component (A). Up to 20 parts by mass is more preferable.

(D) Water can be added to the silicone composition of the present invention. (D) When water is blended, the blending amount is preferably 10 to 10,000 parts by mass, more preferably 20 to 6,000 parts by mass, based on 100 parts by mass of the silicone composition.

[Fiber treatment agent]
The silicone composition of the present invention can be suitably used as a fiber treatment agent. When used as a fiber treatment agent, the above silicone composition is dissolved in an organic solvent, dispersed in water, or emulsified using an emulsifier such as a nonionic, anionic, cationic or amphoteric surfactant. It is preferable to use a product.

Various solvents can be used for the fiber treatment agent of the present invention, if necessary.
Examples of the solvent 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 and 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-butane Diol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propane Examples thereof include alcohol solvents such as diol, 2,2-diethyl-1,3-propanediol, and aromatic solvents such as toluene and xylene. These solvents may be used alone or in combination of two or more.

When the organic solvent is blended, the blending amount is not particularly limited, but is preferably 2,000 to 200,000 parts by mass, more preferably 10,000 to 100,000 parts by mass with respect to 100 parts by mass of the silicone composition. ..

The emulsifying agent for converting the fiber treatment agent of the present invention into an emulsion is not particularly limited, and for example, the nonionic (nonionic) surfactant includes ethoxylated higher alcohol, ethoxylated alkylphenol, and polyhydric alcohol fatty acid. Examples thereof include esters, ethoxylated polyhydric alcohol fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid amides, sorbitol, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, sucrose fatty acid esters and the like. The HLB is preferably in the range of 5 to 20, more preferably in the range of 10 to 16.

Examples of anionic surfactants include higher alcohol sulfates, alkylphenyl ether sulfates, alkylbenzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, and ethoxylated alkylphenyl ether sulfates. Examples thereof include salts and ethoxylated higher alcohol phosphates. Examples of cationic surfactants include alkyltrimethylammonium chloride, alkylamine hydrochloride, coconutamine acetate, alkylamine acetate, alkylbenzenedimethylammonium chloride and the like. Examples of the amphoteric surfactant include N-acylamide propyl-N, N-dimethylammoniobetaines, N-acylamide propyl-N, N'-dimethyl-N'-β-hydroxypropylammoniobetaines. Etc. are exemplified.

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

The emulsion can be obtained by a conventionally known method, and the above silicone composition is mixed with a surfactant, which is mixed with a homomixer, a homogenizer, a colloid mill, a line mixer, a universal mixer (trade name), and an ultramixer (trade name). It may be emulsified with an emulsifying machine such as a product name), a planetary mixer (product name), a combination mix (product name), or a three-roll mixer.

Further, the fiber treatment agent of the present invention includes wrinkle-proofing agents, flame-retardant agents, antistatic agents, heat-resistant agents and other textile agents, antioxidants, ultraviolet absorbers, and the like, as long as the object of the present invention is not impaired. Ingredients such as pigments, metal powder pigments, rhology control agents, curing accelerators, deodorants, and antibacterial agents can also be added.

Further, when the fiber treatment agent of the present invention is attached to the fiber, it can be attached to the fiber by dipping, spraying, roll coating or the like. The amount of adhesion varies depending on the type of fiber and is not particularly limited, but the total amount of adhesion of the component (A) and the component (B) in the silicone composition blended in the fiber treatment agent is in the range of 0.01 to 10% by mass. Is preferable. Then, it may be dried by blowing hot air, a heating furnace or the like. Although it depends on the type of fiber, drying may be performed at 100 to 180 ° C. for 30 seconds to 5 minutes.

Further, the fibers or textile products that can be treated with the fiber treatment agent of the present invention are not particularly limited, and natural fibers such as cotton, silk, linen, wool, angora and mohair, polyester, polyethylene, polypropylene, nylon, acrylic and spandex are not particularly limited. It is also effective for synthetic fibers such as, and blended fibers that combine these. Further, the form and shape are not limited, and the fiber of the present invention is not limited to the shape of raw materials such as staples, filaments, tows and threads, but also various processed forms such as woven fabrics, knitted fabrics, cotton stuffing and non-woven fabrics. It becomes a treatable target of the treatment agent.

The silicone composition of the present invention has various uses other than fiber treatment, such as paints, adhesives, sealants, inks, impregnants for paper, surface treatments, cosmetics, and the like. Can be used for. At this time, additives can be used if necessary.
Examples of additives include wrinkle-proofing agents, flame-retardant agents, antistatic agents, heat-resistant agents and other textile agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, and deodorants. Examples include agents and antibacterial agents. These additives may be used alone or in combination of two or more as appropriate.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The bonding order of each siloxane unit in the formula is not limited to the following.

[Example 1]
100 parts by mass of organopolysiloxane (amine equivalent: 830 g / mol, viscosity 70 mPa · s) represented by the following formula (A-1) and Kao Akipo RLM-45 (polyoxyethylene (4.5) lauryl ether acetic acid, solid content) A silicone composition (1) was prepared by mixing 56 parts by mass (92% by mass, manufactured by Kao Co., Ltd.) (the amount converted into pure content is shown in the table, the same applies hereinafter) at room temperature (25 ° C.) for 30 minutes.

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

[Example 3]
100 parts by mass of organopolysiloxane represented by the above formula (A-1) and 330 parts by mass of Kaoakipo RLM-100NV (polyoxyethylene (10) sodium lauryl ether acetate, solid content 24% by mass, manufactured by Kao Co., Ltd.) at room temperature. The silicone composition (3) was prepared by mixing at (25 ° C.) for 30 minutes.

[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 Akipo RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89 mass) %, Manufactured by Kao Co., Ltd.) 180 parts by mass was 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 Akipo RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89 mass) %, Manufactured by Kao Co., Ltd.) 130 parts by mass was 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: 300 g / mol, viscosity 420 mPa · s) and Kao Akipo RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89 mass) %, Manufactured by Kao Co., Ltd.) 130 parts by mass was 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), 100 parts by mass of Kaoakipo RLM-100 (polyoxyethylene (10) lauryl ether acetate, solid content 89% by mass, manufactured by Kao Co., Ltd.) and the following formula ( 20 parts by mass of the polyether-modified silicone shown in C-1) was 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 Kaoakipo RLM-100 (polyoxyethylene (10) lauryl ether acetate, solid content 89% by mass, manufactured by Kao Co., Ltd.) and the above formula ( 20 parts by mass of the polyether-modified silicone shown in C-1) was 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), 100 parts by mass of Kaoakipo RLM-100 (polyoxyethylene (10) lauryl ether acetate, solid content 89% by mass, manufactured by Kao Co., Ltd.) and the following formula (C). 20 parts by mass of the polyether-modified silicone shown in -2) was mixed at room temperature (25 ° C.) for 30 minutes to prepare a silicone composition (9).

[Comparative Example 1]
A silicone composition (10) which is an IPA-dissolved product of (A-1) is obtained by mixing 5 parts by mass of the organopolysiloxane represented by the above formula (A-1) and 245 parts by mass of IPA at room temperature (25 ° C.) for 30 minutes. ) Was prepared.

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

[Comparative Example 3]
100 parts by mass of organopolysiloxane (amine equivalent: 250 g / mol, viscosity 8 mPa · s) represented by the following formula (A-5) and Kao Akipo RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, solid content 89 mass) %, Manufactured by Kao Co., Ltd.) 130 parts by mass was 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 Akipo RLM-100 (polyoxyethylene (10) lauryl ether acetic acid, A silicone composition (12) was prepared by mixing 130 parts by mass of solid content (89% by mass, manufactured by Kao Co., Ltd.) at room temperature (25 ° C.) for 30 minutes.

[Comparative Example 5]
100 parts by mass of the organopolysiloxane represented by the above formula (A-1) 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. A silicone composition (13) was prepared.

[Evaluation test]
The following evaluation tests were performed on each composition. The results are also shown in Tables 1 to 3.
1. 1. Ion-exchanged water was added to the flexible silicone composition, and the mixture was stirred and diluted to a solid content of 2% by mass to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanito Shoten Co., Ltd.) was immersed in the test solution for 1 minute, squeezed using a roll under the condition of a drawing ratio of 100% by mass, dried at 150 ° C. for 2 minutes, and then dried. Further, heat treatment was performed at 150 ° C. for 2 minutes to prepare a treated cloth for evaluation of flexibility. The treated cloth was touched by three specialized panelists, and the flexibility was evaluated according to the following criteria. Pass A and B.
<standard>
A: Very good to the touch B: Good to the touch C: Poor to the touch

2. 2. Ion-exchanged water was added to the water-absorbent silicone composition, and the mixture was stirred and diluted to a solid content of 2% by mass to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanito Shoten Co., Ltd.) was immersed in the test solution for 1 minute, then squeezed using a roll under the condition of a drawing ratio of 100%, and heat-treated at 150 ° C. for 2 minutes. Then, one drop (25 μL) of tap water was dropped onto the treated cloth with a dropper, and the time (seconds) until the water drops were completely absorbed by the cloth was measured (water absorption before washing). After that, the treated cloth was washed once with a washing machine by a method based on JIS L0217 103. A drop (25 μL) of tap water was dropped onto the washed treated cloth with a dropper, and the time (seconds) until the water drops were completely absorbed by the cloth was measured (water absorption after washing). It was evaluated according to the following criteria. ◎ and ○ are accepted.
<standard>
⊚: Water droplets absorbed within 3 seconds 〇: Water droplets absorbed in more than 3 seconds and 20 seconds Δ: Water droplets absorbed in more than 20 seconds and 60 seconds ×: Even if more than 60 seconds , Water droplets were not absorbed

3. 3. Washing durability Ion-exchanged water was added to the silicone composition and diluted to a solid content of 2% by mass to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanito Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, squeezed using a roll under the condition of a drawing ratio of 100%, and dried at 150 ° C. for 2 minutes. After that, the treated cloth was washed once with a washing machine by a method based on JIS L0217 103. The residual amount of silicone on the fiber surface after one washing was measured with a fluorescent X-ray analyzer (manufactured by Rigaku), and the residual ratio (% by mass) was calculated by comparing with the case where no washing was performed. A passing rate of 50% or more is considered acceptable.

4. Post-washing flexibility Ion-exchanged water was added to the flexible silicone composition and diluted to a solid content of 2% by mass to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanito Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, squeezed using a roll under the condition of a drawing ratio of 100%, and dried at 150 ° C. for 2 minutes. After that, the treated cloth was washed once with a washing machine by a method based on JIS L0217 103. The cloth after washing was touched by a human paneler, and the flexibility was evaluated according to the following criteria. Pass A and B.
<standard>
A: Very good to the touch B: Good to the touch C: Poor to the touch

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

Claims (5)

(A) The following general formula ( 4 )

[In the formula, R ⁹ is independent of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹⁰ is independent of each other, -OY (Y is a hydrogen atom, or 1 to 12 carbon atoms). It is an unsubstituted or substituted monovalent hydrocarbon group), R ⁸ is independent of each other, R ⁹ or R ¹⁰ . R ¹¹ is independent of each other and has the following equation (1).

(In the formula, R ¹ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, a is a number of 0 to 4, and R ² is a hydrogen atom or 1 to 1 carbon atoms independently of each other. 10 unsubstituted or substituted monovalent hydrocarbon group or acyl group.)
It is a group indicated by. h is an integer of 5 to 1,000, j is 1 , k is 1 , and j + k is 2 at each end.
Organopolysiloxane having a viscosity at 25 ° C. of 20 to 20,000 mPa · s: 100 parts by mass,
(B) The following formula (2)

(In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, b is a number of 1 to 30, and X is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid.)
Alkyl ether carboxylic acid represented by (A) or a salt thereof: 10 to 200 parts by mass with respect to 100 parts by mass of (A), and (C) the following general formula (3).

(In the formula, R ⁴ is a phenyl group independently of each other, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and R ⁵ is an independent formula −C _e H _2e O ( C ₂ H ₄ O) _f (C ₃ H ₆ O) _g It is an organic group represented by R ⁷ , R ⁶ is R ⁴ or R ⁵ independently of each other, and R ⁷ is a hydrogen atom and has 1 to 6 carbon atoms. Is an alkyl group or an acetyl group having 1 to 6 carbon atoms, c is an integer of 0 to 100, d is an integer of 0 to 100, c + d is an integer of 0 to 200, e is an integer of 2 to 5, and f. Is an integer of 1 to 40, and g is an integer of 0 to 40. However, when d = 0, at least one of R ⁶ is R ^5. )
Polyether-modified silicone represented by: (A) A silicone composition containing 1 to 50 parts by mass with respect to 100 parts by mass of the component. The silicone composition according to claim 1, wherein the amount of the component (B) is 10 to 80 parts by mass with respect to 100 parts by mass of (A). The silicone composition according to claim 1 or 2, wherein in the component (B), X is a hydrogen atom or an alkali metal in the above formula (2). The silicone composition according to any one of claims 1 to 3, further comprising water. A fiber treatment agent containing the silicone composition according to any one of claims 1 to 4.