JP2018016909A - Film-forming silicone emulsion composition and fiber treatment agent - Google Patents

Abstract

The present invention provides a silicone emulsion composition whose fiber surface exhibits water absorbency after treatment, particularly a film-forming silicone emulsion composition which is excellent in durability and whose fiber surface maintains its water absorbency even after washing treatment, and a film-forming silicone emulsion composition whose fiber surface exhibits water absorption properties even after washing. Provided is a fiber treatment agent containing it as an active ingredient. [Solution] (A) an organopolysiloxane containing at least two hydroxy groups and/or alkoxy groups bonded to a silicon atom in one molecule, (B) a surfactant, (C) a polyester of the following formula (1). Ether modified silicone, (R1 is phenyl group, alkyl group or alkoxy group, R2 is -CxH2xO(C2H4O)y(C3H6O)zR4, R3 is R1 or R2, R4 is H, alkyl group or acetyl group, a, b are 0 ~100, a+b is 0-200, x is 2-5, y is 1-40, z is 0-40. However, when b = 0, at least one of R3 is R2.) (D) Contains water A film-forming silicone emulsion composition. [Selection diagram] None

Description

  The present invention relates to a film-forming silicone emulsion composition. More specifically, the present invention relates to a silicone emulsion composition that imparts high water absorption to fibers and a fiber treatment agent containing the composition as an active ingredient.

  Silicone emulsion compositions that form rubber films are conventionally known in various compositions, and are used as weather strip agents, air bag coating agents, and the like.

  For example, a silicone emulsion composition composed of hydroxylated diorganopolysiloxane, colloidal silica and an organic tin compound or an organic amine compound (Japanese Patent Laid-Open No. 56-16553: Patent Document 1), a dimethylsiloxane unit and a monophenylsiloxane unit A silicone latex composition comprising a siloxane block copolymer, water, a cationic surfactant, a filler and an aminosilane (US Pat. No. 3,817,894: Patent Document 2), a hydroxyl group-containing organopolysiloxane, Si— Silicone emulsion composition comprising H group-containing organopolysiloxane, colloidal silica, amide group and carboxyl group-containing silane, epoxy group-containing silane and curing catalyst (JP-A-8-85760: Patent Document 3), Group-containing organopolysiloxane, Si-H group-containing organopolysiloxane, colloidal silica, a reaction product of aminosilane and acid anhydride, epoxysilane, and a silicone emulsion composition comprising an addition reaction catalyst (Japanese Patent Laid-Open No. 9-208826: Patent Document 4), a silicone emulsion composition comprising hydrogen siloxane blocked with a hydroxyl group at the molecular end, an emulsifier, water and a curing catalyst (JP-A-9-208900: Patent Document 5), colloidal silica-silicone core shell body, Silicone emulsion composition comprising a curing catalyst, an emulsifier, and water (JP-A-9-208901, JP-A-9-208902, JP-A-9-208903: Patent Documents 6-8), hydroxyl group-containing organopolysiloxane , Colloidal silica, amide group And a silicone emulsion composition comprising a carboxyl group-containing silane, an epoxy group-containing silane, a curing catalyst and a photocatalytic oxide (JP 2002-363494 A: Patent Document 9), hydroxyl group-containing organopolysiloxane, colloidal silica, amide A silicone emulsion composition (Japanese Patent Laid-Open No. 2008-231276: Patent Document 10) composed of a group- and carboxyl group-containing silane and an epoxy group-containing silane has been proposed.

  Further, since dimethylpolysiloxane can impart flexibility and lubricity to various fibers or fiber products, a silicone emulsion composition of a type that forms a rubber film is also used as a fiber treatment agent. This silicone emulsion composition not only improves the texture of various fibers and fiber products, but also serves as a so-called binder for fixing functional agents such as deodorants, antibacterial agents, disperse pigments, and disperse dyes on fibers. Also plays a role. However, when a silicone emulsion composition of the type that forms the rubber film described above is processed into fibers, the fiber surface exhibits water repellency and the inherent water absorption of the fibers decreases. For example, since underwear and towels are required to absorb sweat and moisture, it is desirable that the fiber product has water absorption even after the fiber treatment agent is processed. Accordingly, even when the film-forming silicone emulsion composition is used as a binder, the fiber surface is required to exhibit water absorption.

JP 56-16553 A US Pat. No. 3,817,894 JP-A-8-85760 JP-A-9-208826 JP-A-9-208900 JP-A-9-208901 JP-A-9-208902 Japanese Patent Laid-Open No. 9-208903 JP 2002-363494 A JP 2008-231276 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and is a silicone emulsion composition in which the fiber surface after treatment exhibits water absorption, particularly excellent in durability, and the fiber surface maintains water absorption even after washing treatment. An object is to provide a film-forming silicone emulsion composition to be obtained, and a fiber treatment agent containing the composition as an active ingredient.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) an organopolysiloxane containing at least two hydroxy groups and / or alkoxy groups bonded to a silicon atom in one molecule, (B) an interface The film-forming silicone emulsion composition containing a specific amount of each of the activator, (C) polyether-modified silicone, and (D) water, the treated fiber surface exhibits water absorption, and exhibits excellent washing durability. The present inventors have found that the fiber surface after the washing treatment maintains high water absorption, and have made the present invention.

（式中、Ｒ¹は独立にフェニル基、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基であり、Ｒ²は独立に式−Ｃ_xＨ_2xＯ（Ｃ₂Ｈ₄Ｏ）_y（Ｃ₃Ｈ₆Ｏ）_zＲ⁴で示される有機基であり、Ｒ³は独立にＲ¹又はＲ²であり、Ｒ⁴は水素原子、炭素数１〜６のアルキル基又はアセチル基であり、ａは０〜１００の整数、ｂは０〜１００の整数で、ａ＋ｂは０〜２００であり、ｘは２〜５の整数、ｙは１〜４０の整数、ｚは０〜４０の整数である。但し、ｂ＝０のとき、Ｒ³のうち少なくともひとつがＲ²である。）
（Ｄ）水：５０〜１，０００質量部
を含有することを特徴とする皮膜形成性シリコーンエマルション組成物。
［２］．さらに、（Ｅ）コロイダルシリカを（Ａ）成分１００質量部に対して０．５〜５０質量部含有する［１］に記載の皮膜形成性シリコーンエマルション組成物。
［３］．さらに、（Ｆ）縮合触媒を（Ａ）成分１００質量部に対して０．１〜２０質量部含有する［１］又は［２］に記載の皮膜形成性シリコーンエマルション組成物。
［４］．さらに、（Ｇ）アミノ基含有オルガノアルコキシシラン及び／又はその部分加水分解物と酸無水物の反応生成物を（Ａ）成分１００質量部に対して０．１〜２０質量部含有する［１］〜［３］のいずれかに記載の皮膜形成性シリコーンエマルション組成物。
［５］．［１］〜［４］のいずれかに記載の皮膜形成性シリコーンエマルション組成物を有効成分として含有する繊維処理剤。 Accordingly, the present invention provides the following film-forming silicone emulsion composition and fiber treatment agent.
[1]. (A) Organopolysiloxane containing at least two hydroxy groups and / or alkoxy groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Surfactant: 0.1-50 parts by mass,
(C) Polyether-modified silicone represented by the following general formula (1): 0.1 to 50 parts by mass, and

(In the formula, R ¹ is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently represented by the formula —C _x H _2x O (C ₂ H ₄ O ) _Y (C ₃ H ₆ O) _z is an organic group represented by R ⁴ , R ³ is independently R ¹ or R ² , R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acetyl group A is an integer of 0-100, b is an integer of 0-100, a + b is 0-200, x is an integer of 2-5, y is an integer of 1-40, z is 0-40. (However, when b = 0, at least one of R ³ is R ^2. )
(D) Water: A film-forming silicone emulsion composition containing 50 to 1,000 parts by mass.
[2]. Furthermore, (E) The film-forming silicone emulsion composition as described in [1] which contains 0.5-50 mass parts colloidal silica with respect to 100 mass parts of (A) component.
[3]. The film-forming silicone emulsion composition according to [1] or [2], further comprising (F) 0.1 to 20 parts by mass of a condensation catalyst with respect to 100 parts by mass of component (A).
[4]. Further, (G) 0.1-20 parts by mass of the amino group-containing organoalkoxysilane and / or the reaction product of its partial hydrolyzate and acid anhydride is contained per 100 parts by mass of component (A) [1]. The film-forming silicone emulsion composition according to any one of to [3].
[5]. A fiber treatment agent containing the film-forming silicone emulsion composition according to any one of [1] to [4] as an active ingredient.

  According to the film-forming silicone emulsion composition of the present invention (hereinafter abbreviated as a silicone emulsion composition), the fiber is treated with various fibers or fiber products to give flexibility and lubricity, and fibers. Water absorption can be imparted to the surface. Furthermore, the fiber treatment agent containing the silicone emulsion composition of the present invention as an active ingredient is excellent in washing durability and can maintain good water absorption on the fiber surface even after washing treatment.

Hereinafter, the present invention will be described in detail.
[Component (A)]
Component (A) is an organopolysiloxane containing at least two hydroxy groups and / or alkoxy groups bonded to silicon atoms in one molecule. (A) A component can be used individually by 1 type or in combination of 2 or more types, Especially, what is shown by following General formula (2) is preferable.
_{X 3 SiO- (R 2 SiO)} c - (Y 2 SiO) d -SiX 3 (2)
(In the formula, R represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms. An aryl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group, Y is a group represented by X or — (O—X ₂ Si) _e —X, and R, X, and Y are Each may be the same or different, c is an integer of 100 to 10,000, d is an integer of 0 to 1,000, and e is an integer of 0 to 1,000, provided that X, Y, d, and e are selected so as to contain at least two hydroxy groups and / or alkoxy groups bonded to silicon atoms in one molecule.

  In the above formula (2), R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, or a butyl group. , Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group, Or the group etc. by which one part or all part of the hydrogen atom couple | bonded with these groups was substituted by the halogen atom, the amino group, the cyano group, etc. are mentioned. Of these, a methyl group is preferable.

  X is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group. Specifically, in addition to the hydroxy group, Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl Group: phenyl group, tolyl group, naphthyl group; methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group, or these groups Examples include groups in which some or all of the hydrogen atoms are substituted with halogen atoms, amino groups, cyano groups, etc. It is. Among these, X is preferably a methyl group, a hydroxy group, a methoxy group, or an ethoxy group.

Y is a group represented by X or — (O—X ₂ Si) _e —X.
R, X, and Y may be the same or different.

c is an integer of 100 to 10,000, preferably an integer of 500 to 5,000, more preferably an integer of 700 to 4,000. If c is less than 100, the silicone rubber film may have poor flexibility, and if it exceeds 10,000, the tear strength of the film may be reduced. d is an integer of 0 to 1,000, preferably an integer of 0 to 200, and more preferably an integer of 0 to 100. e is an integer of 0 to 1,000, preferably an integer of 0 to 200, and more preferably an integer of 0 to 100.
However, the above X, Y, d, and e are at least 2, preferably 2 to 40, more preferably 2 or more hydroxy groups and / or alkoxy groups bonded to a silicon atom in one molecule from the viewpoint of curability. It is necessary to have 2 or more and 20 or less.

The organopolysiloxane of component (A) preferably has a viscosity at 25 ° C. of 10,000 mPa · s or more, and more preferably has a viscosity at 25 ° C. of 100,000 mPa · s or more. Moreover, it is preferable that the viscosity in 25 degreeC is 10,000,000 mPa * s or less. In the present invention, the viscosity is a value measured with a rotational viscometer.
The organopolysiloxane of component (A) preferably has a polystyrene-equivalent weight average molecular weight of 50,000 to 5,000,000, particularly 100,000 to 3,000,000 by gel permeation chromatography (GPC). If the weight average molecular weight is too small, the durability when the composition is treated may decrease, and if it is too large, emulsification may be difficult when the composition is used.

  Specific examples of the organopolysiloxane of component (A) in the present invention include the following.

（式中、ｃ、ｄ及びｅは上記と同じ。）

(Wherein c, d and e are the same as above)

（式中、Ｍｅはメチル基、Ｅｔはエチル基であり、ｃ、ｄ及びｅは上記と同じ。）

(In the formula, Me is a methyl group, Et is an ethyl group, and c, d and e are the same as above.)

  The organopolysiloxane of component (A) in the present invention can be synthesized by a known method. For example, in the presence of a catalyst such as an alkali metal hydroxide, a cyclic siloxane such as octamethylcyclotetrasiloxane, or an α, ω-dihydroxysiloxane oligomer, an α, ω-dialkoxysiloxane oligomer, or an organoalkoxysilane. Obtained by equilibration reaction. It can also be obtained by subjecting α, ω-dihydroxydimethylpolysiloxane and organoalkoxysilane to dehydration and dealcoholization condensation in the presence of a catalyst such as an alkali metal hydroxide.

  The organopolysiloxane (A) is preferably used in the form of an oil-in-water emulsion. The emulsion may be formed by a known emulsion polymerization method. Accordingly, a cyclic siloxane, an α, ω-dihydroxysiloxane oligomer, an α, ω-dialkoxysiloxane oligomer, an organoalkoxysilane, or the like is previously used as an anionic surfactant or cationic. It can be easily synthesized by emulsifying and dispersing in water using a surfactant or a nonionic surfactant, and then performing an emulsion polymerization reaction by adding a catalyst such as an acid or an alkaline substance as necessary.

  Further, the organopolysiloxane as the component (A) and the surfactant described above are mixed and emulsified with an emulsifier such as a homomixer, a homogenizer, a colloid mill, or a line mixer, so that an emulsion can be obtained. .

[(B) component]
There is no restriction | limiting in particular as surfactant of (B) component, For example, a nonionic surfactant, anionic surfactant, a cationic surfactant, an amphoteric surfactant etc. can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, diethylene glycol and the like.

Among these, polyoxyalkylene alkyl ethers represented by the following general formula (3) are preferable.
R ⁵ O (EO) _n (PO) _m H (3)
(In the formula, R ⁵ is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, and n and m are each an integer of 0 to 50, preferably an integer of 0 to 25. N + m = 5 to 50. EO is a polyoxyethylene group and PO is a polyoxypropylene group.)

As the anionic surfactant, an alkyl sulfate represented by the following general formula (4) and an alkylbenzene sulfonate represented by the following general formula (5) are preferable.
R ⁶ -OSO ₃ M (4)
R ⁶ —C ₆ H ₄ —OS ₃ M (5)
(Wherein R ⁶ is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, and M is a hydrogen atom or a metal element, preferably a hydrogen atom, an alkali metal element or an alkali. It is an earth metal element.)

  Examples of the alkyl sulfate include sodium lauryl sulfate. Examples of the alkylbenzene sulfonate include salts of hexyl benzene sulfonic acid, octyl benzene sulfonic acid, decyl benzene sulfonic acid, dodecyl benzene sulfonic acid, cetyl benzene sulfonic acid, myristyl benzene sulfonic acid, and the like.

The anionic surfactant further includes higher fatty acids such as lauric acid, stearic acid, oleic acid and linolenic acid and salts thereof, polyoxyethylene monoalkyl ether sulfate represented by the following general formula (6), The polyoxyethylene alkylphenyl ether sulfate ester salt represented by General formula (7) is mentioned.
R ⁷ O (EO) _{n ′} (PO) _{m ′} SO ₃ M (6)
R ⁷ —C ₆ H ₄ —O (EO) _{n ′} (PO) _{m ′} SO ₃ M (7)
Wherein R ⁷ is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, and M is a hydrogen atom or a metal element, preferably a hydrogen atom, an alkali metal element or an alkali. It is an earth metal element, and n ′ and m ′ are each an integer of 0 to 30, preferably an integer of 0 to 20, and n ′ + m ′ = 5 to 50. EO is a polyoxyethylene group, PO is It is a polyoxypropylene group.)

  Examples of the cationic surfactant include anionic emulsifiers such as alkylbenzene sulfonates and alkyl phosphates, and cationic emulsifiers such as quaternary ammonium salts and alkylamine salts.

  Examples of amphoteric surfactants include alkyl betaines and alkyl imidazolines.

  (B) The compounding quantity of a component is 0.1-50 mass parts with respect to 100 mass parts of (A) component, 0.5-25 mass parts is preferable, and 2-10 mass parts is more preferable. When the component (B) is too small, emulsification is difficult, and when it is too large, the stability of the emulsion becomes insufficient.

（式中、Ｒ¹は独立にフェニル基、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基であり、Ｒ²は独立に式−Ｃ_xＨ_2xＯ（Ｃ₂Ｈ₄Ｏ）_y（Ｃ₃Ｈ₆Ｏ）_zＲ⁴で示される有機基であり、Ｒ³は独立にＲ¹又はＲ²であり、Ｒ⁴は水素原子、炭素数１〜６のアルキル基又はアセチル基であり、ａは０〜１００の整数、ｂは０〜１００の整数で、ａ＋ｂは０〜２００であり、ｘは２〜５の整数、ｙは１〜４０の整数、ｚは０〜４０の整数である。但し、ｂ＝０のとき、Ｒ³のうち少なくともひとつがＲ²である。） [Component (C)]
Component (C) is a polyether-modified silicone represented by the following general formula (1). These can be used singly or in appropriate combination of two or more.

(In the formula, R ¹ is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently represented by the formula —C _x H _2x O (C ₂ H ₄ O ) _Y (C ₃ H ₆ O) _z is an organic group represented by R ⁴ , R ³ is independently R ¹ or R ² , R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acetyl group A is an integer of 0-100, b is an integer of 0-100, a + b is 0-200, x is an integer of 2-5, y is an integer of 1-40, z is 0-40. (However, when b = 0, at least one of R ³ is R ^2. )

In Formula (1), R ¹ is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group, and a propyl group. Alkyl groups such as butyl group, pentyl group and hexyl group, alkoxy groups such as phenyl group, methoxy group, ethoxy group, propoxy group, butoxy group and hexyloxy group, preferably methyl group, ethyl group, phenyl group, A methoxy group and an ethoxy group.
R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acetyl group. Specific examples of R ⁴ include alkyl such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group or acetyl group.

a is an integer of 0 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. b is an integer of 0 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. a + b is 0-200, 1-100 are preferable, More preferably, it is 1-60.
X is an integer of 2 to 5, preferably an integer of 2 to 4, y is an integer of 1 to 40, preferably an integer of 1 to 20, and z is an integer of 0 to 40, preferably 0 to 20. It is an integer.

（式中、ａ’、ｂ’はそれぞれ１〜１００の整数であり、ｙは上記と同じである。ｚ’は１〜４０の整数である。） Specific examples of the component (C) include the following.

(In the formula, a ′ and b ′ are each an integer of 1 to 100, y is the same as above, and z ′ is an integer of 1 to 40.)

  (C) The compounding quantity of a component is 0.1-50 mass parts with respect to 100 mass parts of (A) component, 0.5-25 mass parts is preferable, and 2-20 mass parts is more preferable. When the amount of the component (C) is too small, the water absorption on the fiber surface is insufficient, and when the amount of the component (C) is too large, the stability of the emulsion is lowered.

  The present inventors consider the action mechanism of the component (C) as follows. By adding the component (C), the surface tension of the silicone emulsion composition can be reduced. Therefore, it is considered that the silicone emulsion composition penetrates more into the fiber by adding the component (C). Accordingly, it is possible to remain without being removed even after the washing process is performed. Moreover, (C) component contains the hydrophilic group in a molecule | numerator and can provide high water absorption with respect to a fiber.

[Component (D)]
In the silicone emulsion composition of the present invention, water is blended as the component (D). The compounding quantity of water is 50-1,000 mass parts with respect to 100 mass parts of (A) component, Preferably it is 50-500 mass parts.

[(E) component]
The silicone emulsion composition of the present invention may further contain (E) colloidal silica in addition to the components (A) to (D). The colloidal silica which is (E) component is added as a film reinforcing agent. In the present invention, colloidal silica can be used as an aqueous dispersion. As the aqueous dispersion of colloidal silica, a commercially available one may be used, and there is no limitation on the type thereof. For example, it may be one having an average particle size of 5 to 50 nm and stabilized with sodium, ammonium, aluminum or the like. Specifically, Snowtex (manufactured by Nissan Chemical Industries), Ludox (manufactured by Grace), silica doll (Japan) Chemical Industry Co., Ltd.), Adelite AT (manufactured by ADEKA), Cataloid S (manufactured by Catalytic Chemical Industry Co., Ltd.), COSMO S-40 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) and the like.

  (E) When mix | blending a component, 0.5-50 mass parts is preferable in conversion of the pure part of colloidal silica with respect to 100 mass parts of (A) component, and, as for the compounding quantity of (E) component, More preferably, 1- 30 parts by mass. By making the blending amount of colloidal silica 0.5 parts by mass or more, the effect of improving the strength and flame retardancy of the film is more exhibited, and when it exceeds 50 parts by mass, the film becomes hard and brittle, and elongation and flexibility May decrease.

[(F) component]
The silicone emulsion composition of the present invention may further contain (F) a condensation catalyst.
The condensation catalyst as component (F) is not particularly limited as long as the condensation reaction proceeds, but an organic tin compound, an organic zinc compound, an organic iron compound, an organic titanium compound, an organic bismuth compound, an organic zirconium compound, an organic aluminum compound, And organic metal compounds such as organic cerium compounds, organic indium compounds, and organic yttrium compounds. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin bisoleyl malate, tin octylate, zinc stearate, zinc octylate, zinc acetate, iron octylate, octylate Examples thereof include organic acid metal salts such as titanium, bismuth octylate, zirconium octylate, cerium octylate, indium octylate, and yttrium octylate. These condensation catalysts are preferably used in the form of an emulsion that has been previously emulsified and dispersed in water using a surfactant, except when water-soluble.

  (F) When mix | blending component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, as for the compounding quantity of (F) component, More preferably, 0.2-15 mass parts, Furthermore, Preferably it is 0.3-10 mass parts. If the amount is less than 0.1 parts by mass, the condensation reaction may not proceed, and if it is more than 20 parts by mass, it is uneconomical.

[(G) component]
The silicone emulsion composition of the present invention may further contain a reaction product of an amino group-containing organoalkoxysilane and / or a partial hydrolyzate thereof and an acid anhydride as the component (G). (G) A component is a component for improving the adhesiveness of a silicone rubber film and a base material.

  Examples of the amino group-containing organoalkoxysilane that is the starting material include γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- Examples include β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and the like. Moreover, these partial hydrolysates or mixtures thereof can also be used. Examples of the acid anhydride that is the other starting material include phthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, and the like.

(G) As a component, what is shown by a following formula and its oligomer are preferable.
_{(C 2 H 5 O) 3} SiC 3 H 6 -NHCO-CH = CHCOOH,
_{(C 2 H 5 O) 3} SiC 3 H 6 NH 3 + - OCOCH = CHCOOC 2 H 5

  The reaction of the amino group-containing organoalkoxysilane and / or its partial hydrolyzate with an acid anhydride is carried out at room temperature in a hydrophilic organic solvent for both the starting materials, for example, alcohols such as methanol, ethanol, and isopropanol. It can be easily carried out by stirring for ˜5 hours. Moreover, although it is preferable that those reaction molar ratios are equimolar, even if it uses either excessively, there is no problem.

  (G) When mix | blending a component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the compounding quantity of (G) component, More preferably, it is 0.5-10 mass parts. . If the amount is less than 0.1 parts by mass, the effect of improving the adhesion to the substrate may not be obtained, and if it exceeds 20 parts by mass, the stability of the composition may be reduced.

[(H) component]
The silicone emulsion composition of the present invention may further contain (H) an organoalkoxysilane that does not contain an amino group. The (H) component organoalkoxysilane is effective in improving the adhesion between the silicone rubber film and the substrate. As the organoalkoxysilane as the component (H), various known materials may be used as long as they are organoalkoxysilanes that do not contain an amino group. Examples of the (H) component organoalkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltri Examples include ethoxysilane, octyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane.

  When the component (H) is blended, the blending amount of the component (H) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). . If the amount is less than 0.1 parts by mass, the effect of improving the adhesion to the substrate may not be obtained, and if it exceeds 20 parts by mass, the stability of the composition may be reduced.

  In the silicone emulsion composition of the present invention, various thickeners, pigments, dyes, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, preservatives, as long as the effects of the present invention are not impaired. A water repellent, a crosslinking agent, an adhesion improver, other silicone oils, silicone resins, acrylic resins, urethane resins and the like can be appropriately blended.

The preparation method of the silicone emulsion composition of the present invention may follow a conventionally known emulsion polymerization method and phase inversion emulsification method. The emulsifier is not particularly limited, and for example, a homomixer, a homogenizer, a colloid mill, a universal mixing stirrer, a combination mix, a line mixer, and the like can be used. Moreover, after preparing an emulsion with (A) component and (B) component, you may mix | blend another component. Furthermore, when blending the component (F), prepare an emulsion with the component (A) and the component (B), prepare an emulsion with the component (F) and the component (B), and then blend other components. Also good.
10-70 mass% is preferable and, as for solid content concentration of a silicone emulsion composition, 20-60 mass% is more preferable.

  The silicone emulsion composition of the present invention is used by treating the surface of various base materials such as fiber, paper, metal, wood, rubber, plastic, glass, etc. Various conventionally known coating methods such as a roll coating method, a bar coating method, and a brush coating method are possible.

The coating amount of the silicone emulsion composition is not particularly limited, but is usually an amount that the coating amount as the emulsion composition 0.1 to 200 g / m ^2, especially 1 to 100 g / m ^2. After coating, the organopolysiloxane film can be obtained only by drying, and the drying may be performed under the condition that water is volatilized. It is 1 to 3 days at room temperature, and 100 to 180 ° C. when heated. It may be dried for about 1 to 30 minutes.

  The silicone emulsion composition of the present invention comprises a fiber treatment agent (for example, a fiber texture improving agent), an inorganic or organic binder (for example, a binder for a functional inorganic filler such as a photocatalyst), a paint, a release agent, and an adhesive sheet. It can be used for back surface treatment agents, surface coating agents for various substrates, release agents and slipperiness imparting agents on rubber articles, water repellents for paper and wood, etc. Absent.

Especially, since the fiber surface after a process has the outstanding water absorption, the silicone emulsion composition of this invention is useful as an active ingredient of a fiber processing agent. The silicone emulsion composition may be used as a fiber treatment agent as it is, or may be appropriately blended in the fiber treatment agent, for example, in the range of 0.01 to 99% by mass. Here, as other components in the fiber treatment agent, anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents and other fiber agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents , Curing accelerators, deodorants, antibacterial agents and the like.
When treating the fiber, the fiber treatment agent may be diluted and used, and the blending amount of the silicone emulsion composition in the fiber treatment agent diluent for treating the fiber is preferably 0.01 to 5% by mass as the solid content. 0.1 to 3% by mass is more preferable.

  The fiber treatment agent of the present invention is not only for natural fibers such as cotton, silk, hemp, wool, angora, mohair, but also for synthetic fibers such as polyester, nylon, acrylic, urethane, spandex, and textiles using these. All are valid. Also, there are no restrictions on the form and shape, and not only the shape of raw materials such as staples, filaments, tows and yarns, but also various processing forms such as woven fabrics, knitted fabrics, padded cotton, non-woven fabrics, paper, sheets, films, etc. Can also be treated by the fiber treatment agent of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition represents mass%.

[Production Example 1: (A-1)]
498 g of octamethylcyclotetrasiloxane, 2 g of triethoxyphenylsilane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous solution of dodecylbenzenesulfonic acid were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and then 400 g of water was added. Gradually added and diluted to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 24 hours, aged at 10 ° C. for 24 hours, and then with 10 g of 10% aqueous sodium carbonate solution. Neutralized. This emulsion had a non-volatile content of 45.4% after drying at 105 ° C. for 3 hours. The organopolysiloxane in the emulsion was subjected to instrumental analysis such as NMR, GPC, IR, etc.
[(HO) (CH ₃ ) ₂ SiO _1/2 ] ₃ [(CH ₃ ) ₂ SiO _2/2 ] ₉₀₀ [C ₆ H ₅ SiO _3/2 ] ₁
It was a soft gel-like thing blocked with a hydroxy group at the end represented by (A-1). The weight average molecular weight (Mw) by GPC of this organopolysiloxane was about 1,200,000. Thus, an emulsion containing the organopolysiloxane of component (A-1) was obtained.

[Production Example 2: (A-2)]
Charge 500 g of octamethylcyclotetrasiloxane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous solution of dodecylbenzenesulfonic acid into a 2 liter polyethylene beaker, uniformly emulsify with a homomixer, and gradually add 400 g of water to dilute. A uniform white emulsion was obtained. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 24 hours, aged at 10 ° C. for 24 hours, and then with 10 g of 10% aqueous sodium carbonate solution. Neutralized. This emulsion had a non-volatile content of 45.5% after drying at 105 ° C. for 3 hours. The organopolysiloxane in the emulsion was subjected to instrumental analysis such as NMR, GPC, IR, etc., and the average composition formula HO — [(CH ₃ ) ₂ SiO] ₃₀₀₀ -H
It was a raw rubber-like material having a viscosity of 2 million mPa · s (A-2). The weight average molecular weight (Mw) by GPC of this organopolysiloxane was about 300,000. Thus, an emulsion containing the organopolysiloxane of component (A-2) was obtained.

[Production Example 3: (A-3)]
300 g of organopolysiloxane (A-3) represented by an average composition formula HO — [(CH ₃ ) ₂ SiO] ₁₀₀₀ —H, 50 g of polyoxyethylene octylphenyl ether, 3 g of sodium polyoxyethylene nonylphenyl ether sulfate, Using a disper, the mixture was mixed at 1,000 rpm for 30 minutes and emulsified and dispersed in 10 g of water. Thereafter, the emulsion was diluted with 637 g of water to obtain an emulsion containing organopolysiloxane as component (A-3).

[Production Example 4: (F)]
Dioctyltin dilaurate (Neostan U-810, manufactured by Nitto Kasei Co., Ltd., active ingredient: 99%) 350 g and polyoxyethylene alkyl ether (Emulgen 1108, manufactured by Kao Co., Ltd.) 50 g were charged into a 2 liter polyethylene beaker. After uniformly mixing with a mixer, 600 g of water was gradually added to emulsify and disperse in water, and then passed twice through a high-pressure homogenizer at a pressure of 40 MPa to obtain a stable emulsion (F) containing an organotin compound. This emulsion had a non-volatile content of 39.5% after drying at 105 ° C. for 3 hours.

[Production Example 5: (G)]
After dissolving 154 g of maleic anhydride in 500 g of ethanol, 346 g of 3-aminopropyltriethoxysilane was added dropwise at room temperature for 1 hour, and further reacted at 80 ° C. under reflux of ethanol for 24 hours to obtain a pale yellow transparent (G) A solution “G” containing 50% of the components was obtained. This solution had a non-volatile content of 45.1% after drying at 105 ° C. for 3 hours, and the reaction product in the solution was subjected to instrumental analysis such as IR, GC, NMR, and GCMS, and about 60% A mixture of those represented by the formula below with the remaining about 40% being oligomers derived from them.
_{(C 2 H 5 O) 3} SiC 3 H 6 -NHCO-CH = CHCOOH
_{(C 2 H 5 O) 3} SiC 3 H 6 NH 3 + - OCOCH = CHCOOC 2 H 5

The following were used as the component (C).
(C-1) Polyether-modified silicone represented by the following formula (8)

(C-2) A polyether-modified silicone represented by the following formula (9)

(C-3) A polyether-modified silicone represented by the following formula (10)

  (E) As a component, colloidal silica (Snowtex C, manufactured by Nissan Chemical Industries, Ltd., active ingredient 20%)

[Examples 1 to 13, Comparative Examples 1 to 3]
Silicone emulsion compositions were obtained with the composition shown in Tables 1 and 2. Here, (B) component is the quantity contained in the emulsion obtained by the said manufacture examples 1-4, (D) component is the quantity contained in the emulsion etc. which were obtained by the said manufacture examples 1-4. . The following evaluation was performed about the obtained silicone emulsion composition. The results are also shown in Tables 1 and 2. In addition, when 20 g of the obtained silicone emulsion composition was weighed on a 15 cm × 10 cm PP tray, dried at 25 ° C. for 48 hours, and water was volatilized, in all of Examples 1 to 13 and Comparative Examples 1 to 3. A rubbery film was formed.

[Evaluation test]
1. Water-absorbing emulsion composition was added with ion-exchanged water and diluted to a solid content of 2% to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanigami Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, then squeezed with a roll under the condition of a squeezing rate of 100%, and dried at 130 ° C. for 2 minutes. Thereafter, a drop (25 μL) of tap water was dropped onto the treated cloth with a dropper, and the time (seconds) until the water drop was completely absorbed by the cloth was measured. Further, the residual amount of silicone on the fiber surface of the treated cloth was measured with a fluorescent X-ray analyzer (manufactured by Rigaku).

2. Washing durability Ion exchanged water was added to the emulsion composition and diluted to a solid content of 2% to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanigami Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, then squeezed with a roll under the condition of a squeezing rate of 100%, and dried at 130 ° C. for 2 minutes. Thereafter, the treated fabric was washed once by a washing machine by a method based on JIS L0217 103. Thereafter, one drop (25 μL) of tap water was dropped onto the treated cloth after one wash with a dropper, and the time (seconds) until the water drop was completely absorbed by the cloth was measured. Further, the residual amount of silicone on the fiber surface after one wash was measured with a fluorescent X-ray analyzer (manufactured by Rigaku). The residual ratio (%) was calculated by comparing with the amount of silicone remaining on the fiber surface when washing was not performed.

  By using the silicone emulsion composition of the present invention as a fiber treatment agent, good water absorption can be imparted to the fibers. Moreover, since the silicone emulsion composition of the present invention is excellent in washing durability, it can be used as a highly durable water-absorbing fiber treatment agent and binder.

Claims (5)

(A) Organopolysiloxane containing at least two hydroxy groups and / or alkoxy groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Surfactant: 0.1-50 parts by mass,
(C) Polyether-modified silicone represented by the following general formula (1): 0.1 to 50 parts by mass, and

(In the formula, R ¹ is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently represented by the formula —C _x H _2x O (C ₂ H ₄ O ) _Y (C ₃ H ₆ O) _z is an organic group represented by R ⁴ , R ³ is independently R ¹ or R ² , R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acetyl group A is an integer of 0-100, b is an integer of 0-100, a + b is 0-200, x is an integer of 2-5, y is an integer of 1-40, z is 0-40. (However, when b = 0, at least one of R ³ is R ^2. )
(D) Water: A film-forming silicone emulsion composition containing 50 to 1,000 parts by mass.   Furthermore, the film forming silicone emulsion composition of Claim 1 which contains 0.5-50 mass parts of (E) colloidal silica with respect to 100 mass parts of (A) component.   Furthermore, the film forming silicone emulsion composition of Claim 1 or 2 which contains 0.1-20 mass parts of (F) condensation catalysts with respect to 100 mass parts of (A) component.   Furthermore, 0.1-20 mass parts of (G) amino group containing organoalkoxysilane and / or the reaction product of its partial hydrolyzate and an acid anhydride are contained with respect to 100 mass parts of (A) component. The film-forming silicone emulsion composition according to any one of -3.   The fiber processing agent which contains the film formation silicone emulsion composition of any one of Claims 1-4 as an active ingredient.