JP2017197863A - Film formative silicone emulsion composition - Google Patents

Abstract

An object of the present invention is to provide a silicone emulsion composition in which the fiber surface after treatment exhibits water absorption. A film-forming silicone emulsion composition and a fiber treatment agent that are particularly excellent in durability and that can maintain water absorption on the fiber surface even after washing treatment are provided.
(A) Organopolysiloxane containing hydroxyl group and / or alkoxy group bonded to at least two silicon atoms in one molecule: 100 parts by mass (B) Surfactant: 0.1-50 mass Part (C) 0.1 to 50 parts by mass of polyoxyalkylene glycidyl ether, and (D) water: 50 to 1,000 parts by mass, a film-forming silicone emulsion composition.
[Selection figure] None

Description

  The present invention relates to a film-forming silicone emulsion. More specifically, the present invention relates to a silicone emulsion composition that forms a highly hydrophilic film and a fiber treatment agent comprising the composition.

  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 siloxane block copolymer, water, cationic surfactant, filler and aminosilane (US Pat. No. 3,817,894: Patent Document 2), hydroxyl group-containing organopolysiloxane, Si—H group Silicone emulsion composition comprising an organopolysiloxane containing colloidal silica, an amide group and a carboxyl group-containing silane, an epoxy group-containing silane, and a curing catalyst (JP-A-8-85760: Patent Document 3), an alkenyl group Silicone emulsion composition comprising organopolysiloxane having organic group, Si-H group-containing organopolysiloxane, colloidal silica, reaction product of aminosilane and acid anhydride, epoxysilane, and catalyst for addition reaction (Japanese Patent Laid-Open No. 9-208826: Patent Document) 4), a silicone emulsion composition comprising hydrogensiloxane having molecular ends blocked with a hydroxyl group, an emulsifier, water, and a curing catalyst (JP-A-9-208900: Patent Document 5), colloidal silica-silicone core shell body, curing catalyst , Emulsifier, and water-containing silicone emulsion composition (JP-A-9-208901, JP-A-9-208902, JP-A-9-208903: Patent Documents 6 to 8), hydroxyl group-containing organopolysiloxane, colloidal Silica, amide group and carbon Silicone emulsion composition (Japanese Unexamined Patent Publication No. 2002-363494: Patent Document 9) comprising a oxyl group-containing silane, an epoxy group-containing silane, a curing catalyst, and a photocatalytic oxide, hydroxyl group-containing organopolysiloxane, colloidal silica, amide group In addition, a silicone emulsion composition (Japanese Patent Laid-Open No. 2008-231276: Patent Document 10) comprising a 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 not only improves the texture of various fibers and textile 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. However, when a silicone emulsion 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 a film-forming silicone emulsion is used as a binder, the fiber surface is required to exhibit water absorption.

JP 56-16553 A U.S. 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

  An object of this invention is to provide the silicone emulsion composition in which the fiber surface after a process shows water absorption in view of the subject of the said prior art. An object of the present invention is to provide a film-forming silicone emulsion composition and a fiber treatment agent that are particularly excellent in durability and that can maintain water absorption on the fiber surface even after washing treatment.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) an organopolysiloxane containing a hydroxyl group and / or an alkoxy group bonded to at least two silicon atoms in one molecule, (B) A film-forming silicone emulsion composition containing a surfactant, (C) a specific polyoxyalkylene glycidyl ether, and (D) a specific amount of water, respectively. It has been found that the fiber surface after the washing treatment exhibits durability and maintains high water absorption, and has led to the present invention.

（式中、Ｚは水素原子、又は炭素数１〜２０の非置換又は置換の１価炭化水素基もしくは炭素数１〜２０のアシル基である。ａは２〜３０の整数、ｂは０〜３０の整数であり、オキシエチレン単位及びオキシプロピレン単位はブロック重合体を形成していてもよく、ランダム共重合体を形成していていもよい。）
（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]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]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]．繊維処理剤である、[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。 Accordingly, the present invention provides the following film-forming silicone emulsion composition.
[1]. (A) Organopolysiloxane containing hydroxyl group and / or alkoxy group bonded to at least two silicon atoms in one molecule: 100 parts by mass (B) Surfactant: 0.1-50 parts by mass (C) 0.1 to 50 parts by mass of a polyoxyalkylene glycidyl ether represented by the following formula (1), and

(In the formula, Z is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A is an integer of 2 to 30; (It is an integer of 30 and the oxyethylene unit and the oxypropylene unit may form a block polymer or a random copolymer.)
(D) Water: A film-forming silicone emulsion composition containing 50 to 1,000 parts by mass.
[2]. The film-forming silicone emulsion composition according to [1], further comprising 0.5 to 50 parts by mass of (E) colloidal silica with respect to 100 parts by mass of the component (A).
[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 reaction product of amino group-containing organoalkoxysilane and / or a partial hydrolyzate thereof and an 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]. The film-forming silicone emulsion composition according to any one of [1] to [4], which is a fiber treatment agent.

  The film-forming silicone emulsion composition of the present invention (hereinafter abbreviated as silicone emulsion composition) can impart water absorption to the fiber surface. Furthermore, the fiber treatment agent using the silicone emulsion composition of the present invention is excellent in washing durability and can maintain good water absorption on the fiber surface even after the washing treatment.

Hereinafter, the present invention will be described in detail.
The component (A) is an organopolysiloxane containing a hydroxyl group and / or an alkoxy group bonded to at least two 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 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 hydroxyl group, Y is a group represented by X or — (O—X ₂ Si) _e —X, and R, X, and Y 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 hydroxyl groups bonded to silicon atoms in one molecule.)

  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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, Bonds to heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl, or these groups Examples include a group in which part or all of the hydrogen atoms are substituted with a halogen atom, an amino group, a cyano group, or the like. 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 hydroxyl group. Specifically, in addition to the hydroxyl group, 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; cyclopentyl group, cyclohexyl group, 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 hydrogen bonded to these groups Groups in which some or all of the atoms are substituted with halogen atoms, amino groups, cyano groups, etc. It is.

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 1,000 to 5,000. 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. e is an integer of 0 to 1,000, preferably an integer of 0 to 200. However, X, Y, d, and e are those having at least 2, preferably 2 to 3, more preferably 3 or more hydroxyl groups bonded to a silicon atom in one molecule from the viewpoint of curability. It is necessary to have a group and / or an alkoxy group.

  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 prepared by a known emulsion polymerization method. Accordingly, an anionic surfactant or a cationic system is used in advance, such as cyclic siloxane, α, ω-dihydroxysiloxane oligomer, α, ω-dialkoxysiloxane oligomer, or organoalkoxysilane. 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.

  Moreover, it can be set as the form of an emulsion by mixing organopolysiloxane of (A) component and surfactant, and emulsifying this with emulsifiers, such as a homomixer, a homogenizer, a colloid mill, a line mixer.

  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 ¹ O (EO) _n (PO) _m H (3)
(In the formula, R ¹ is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, n and m are 0 to 50, preferably 0 to 25, and n + m = 5 to 5. (20 is 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 ² -OSO ₃ M (4)
In R ² —C ₆ H ₄ —OS ₃ M (5)
Wherein R ² 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 alkaline earth. It is a similar 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.

Examples of the anionic surfactant include 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), and the following general formula The polyoxyethylene alkylphenyl ether sulfate ester salt represented by (7) is mentioned.
R ³ O (EO) _n (PO) _m SO ₃ M (6)
R ³ —C ₆ H ₄ —O (EO) _{n ′} (PO) _{m ′} SO ₃ M (7)
(In the formula, R ³ is a linear or branched alkyl group having 8 to 30 carbon atoms, M is a hydrogen atom or a metal element, n ′ and m ′ are 0 to 30, and n ′ + m ′ is 5 to 20. EO is a polyoxyethylene group and PO 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.

（式中、Ｚは水素原子、又は炭素数１〜２０の非置換又は置換の１価炭化水素基もしくは炭素数１〜２０のアシル基である。ａは２〜３０の整数、ｂは０〜３０の整数であり、オキシエチレン単位及びオキシプロピレン単位はブロック重合体を形成していてもよく、ランダム共重合体を形成していていもよい。） The component (C) is a polyoxyalkylene glycidyl ether represented by the following formula (1). These can be used singly or in appropriate combination of two or more.

(In the formula, Z is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A is an integer of 2 to 30, and b is 0 to 0. (It is an integer of 30 and the oxyethylene unit and the oxypropylene unit may form a block polymer or a random copolymer.)

  Z is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, or 1 to 20 carbon atoms, preferably carbon atoms. An acyl group having 1 to 12, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. Examples of the monovalent hydrocarbon group include 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 alkyl groups such as eicosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; and carbon atoms of these groups And a halogenated alkyl group or a halogenated alkenyl group in which a part or all of the hydrogen atoms bonded to is substituted with a halogen atom such as chlorine or fluorine. Among them, Z is preferably a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an acyl group such as an acetyl group and a benzoyl group, particularly a methyl group, a butyl group, And an acetyl group is preferred.

  In formula, a is an integer of 2-30, Preferably it is an integer of 2-20. When a is smaller than the above lower limit, the effect of imparting hydrophilicity (water absorption) to the fiber becomes insufficient, and when a is larger than the upper limit, flexibility is insufficient, which is not preferable. b is an integer of 0-30, preferably an integer of 0-20, more preferably an integer of 0-10. When b is larger than the above upper limit, the hydrophilicity (water absorption) of the fiber becomes insufficient.

Examples of the polyoxyalkylene glycidyl ether represented by the above formula (1) include the following. a and b are the same as above.

  (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 2-10 mass parts is more preferable. When the amount of component (C) is too small, the water absorption on the fiber surface is insufficient, and when the amount of component (C) is too large, the flexibility of the fiber is insufficient.

  The present inventors consider the action mechanism of the component (C) as follows. The hydroxyl group contained in the component (A) can react with the glycidyl group of the component (C). Moreover, since the alkoxy group contained in (A) component is hydrolyzed in water and becomes a hydroxyl group, it can react with the glycidyl group of (C) component. The hydroxyl group and / or alkoxy group of component (A) is crosslinked by a condensation reaction, and forms a film after drying. At this time, the (A) component and the (C) component react with each other, and a polyoxyalkylene moiety derived from the (C) component is contained in the formed film. Since the polyoxyalkylene group is a hydrophilic group, it is considered that the fiber surface can be made water-absorbing when processed into a fiber. Moreover, since the hydrophilic group is contained in the film, it remains without being removed even when the washing treatment is performed, and it is possible to maintain water absorption.

  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.

  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 Catalyst Kasei Kogyo 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.

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.

In the silicone emulsion composition of the present invention, the reaction product of the amino group-containing organoalkoxysilane and / or its partial hydrolyzate and acid anhydride, which is the component (G), is a combination of the silicone rubber film and the substrate. It is a component for improving adhesiveness. 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 between the amino group-containing organoalkoxysilane and / or its partial hydrolyzate and acid anhydride is carried out at a room temperature in a parent solvent for both starting materials, for example, alcohols such as methanol, ethanol, isopropanol, etc. It can be easily performed by stirring for a period of time. 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 it is less than 0.1 part by mass, there is no effect of improving the adhesion to the substrate, and if it exceeds 20 parts by mass, the stability of the composition is lowered.

  The silicone emulsion composition of the present invention may 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 it is less than 0.1 part by mass, there is no effect of improving the adhesion to the substrate, and if it exceeds 20 parts by mass, the stability of the composition is lowered.

  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 composition by (A) component and (B) component, you may mix | blend another component. 10-80 mass% is preferable and, as for the solid content density | concentration of a silicone emulsion composition, 20-70 mass% is more preferable.

  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. Water repellents, crosslinking agents, adhesion improvers, other silicone oils, silicone resins, acrylic resins, urethane resins, and the like can be appropriately blended. 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 is 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 a fiber processing agent. Even if it uses a silicone emulsion composition as a fiber processing agent as it is, you may mix | blend suitably in a fiber processing agent, for example in 0.01-99 mass%. 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 1% by mass is more preferable.

  The fiber treatment agent of the present invention is effective not only for natural fibers such as cotton, silk, hemp, wool, angora, and mohair, but also for synthetic fibers such as polyester, nylon, acrylic, and spandex, and fiber products using these. It is. 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, stuffed 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. The 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., and the average composition formula HO — [(CH _{3) 2 SiO] 3000 - [} C 6 H 5 (OH ((CH 3) 2 OSi) 100) OSiO] 4 -Si (CH 3) 2 -OH
It was a soft gel-like thing blocked with a hydroxyl 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. The weight average molecular weight (Mw) by GPC of this organopolysiloxane was about 300,000 (A-2). Thus, an emulsion containing the organopolysiloxane of component (A-2) was obtained.

[Production Example 3: (F)]
Dioctyltin dilaurate (Neostan U-810, manufactured by Nitto Kasei Co., Ltd., active ingredient: 99% by mass) and 50 g of polyoxyethylene alkyl ether (Emulgen 1108, Kao Co., Ltd.) were charged into a 2-liter polyethylene beaker and homo After uniformly mixing with a mixer, 600 g of water was gradually added and emulsified and dispersed 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 4: (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) Polyoxyethylene glycol butyl glycidyl ether (the following formula (8), manufactured by Nippon Emulsifier Co., Ltd.)
(C-2) Polyoxyethylene polyoxypropylene glycol butyl glycidyl ether unilube 50MOE-100 (the following formula (9), manufactured by NOF Corporation)

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

[Examples 1-9, Comparative Examples 1-3]
Silicone emulsion compositions (non-volatile content 40%) were obtained with the blending compositions shown in Tables 1 and 2. The component (B) is an amount contained in the component (A-1) and the component (E) is an amount contained in the component (A-1). The following evaluation was performed about the obtained silicone emulsion composition. The results are also shown in the table. In addition, when 20 g of the obtained silicone emulsion composition was weighed on a 15 cm × 10 cm PP tray and dried at 25 ° C. for 48 hours to evaporate water, rubber in all of Examples 1 to 9 and Comparative Examples 1 to 3 was used. A 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.

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. The amount of silicone remaining on the fiber surface after one wash was measured with a fluorescent X-ray analyzer (manufactured by Rigaku). The residual rate (%) was calculated in comparison with the case where 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 fiber. Moreover, it is excellent in washing durability and can be used as a highly durable water-absorbing fiber treatment agent and binder.

Claims (5)

(A) Organopolysiloxane containing hydroxyl group and / or alkoxy group bonded to at least two silicon atoms in one molecule: 100 parts by mass (B) Surfactant: 0.1-50 parts by mass (C) 0.1 to 50 parts by mass of a polyoxyalkylene glycidyl ether represented by the following formula (1), and

(In the formula, Z is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A is an integer of 2 to 30, and b is 0 to 0. (It is an integer of 30 and the oxyethylene unit and the oxypropylene unit may form a block polymer or a random copolymer.)
(D) Water: A film-forming silicone emulsion composition containing 50 to 1,000 parts by mass.   The film-forming silicone emulsion composition according to claim 1, further comprising 0.5 to 50 parts by mass of (E) colloidal silica with respect to 100 parts by mass of component (A).   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 of any one of -3.   The film-forming silicone emulsion composition according to any one of claims 1 to 4, which is a fiber treatment agent.