JP2008095002A - Emulsion composition for coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsion composition for coating excellent in the uniformity of coating. <P>SOLUTION: The invention relates to the emulsion composition for coating prepared by emulsifying a mixture in the presence of a surfactant, wherein the mixture comprises (A) 100 pts.mass of an organopolysiloxane having at least two hydroxyl groups bonding to silicon atom in a molecule, (B) 0.5-20 pts.mass of a reaction product of an organoalkoxysilane containing an amino group, with a dicarboxylic acid anhydride, (C) 0-20 pts.mass of an organoalkoxysilane containing an epoxy group and/or a product of its partial hydrolysis, (D) 0-50 pts.mass of a colloidal silica and/or polysilsesquisiloxane, (E) 0-10 pts.mass of a hardening catalyst and (F) 0.5-20 pts.mass of an organopolysiloxane containing a long chain alkyl group and an aloxyl group and not containing a hydroxyl group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coating emulsion composition excellent in uniform coatability.

  Various crosslinkable silicone emulsion compositions that cure to form a rubber film have been proposed (Japanese Patent Application Laid-Open No. 5-98579 (Patent Document 1), Japanese Patent Application Laid-Open No. 8-85760 (Patent Document 2), and 9-208826 (Patent Document 3), JP-A 2000-34410 (Patent Document 4), JP-A 2001-55510 (Patent Document 5)). In the case of a substrate having an uneven surface such as fiber or building material, these could be applied without any problem. However, when an attempt was made to process a thin film on a substrate with little unevenness such as a film or paper, coating unevenness occurred during coating, and a coating film having a uniform film thickness could not be obtained.

Japanese Patent Laid-Open No. 5-98579 JP-A-8-85760 JP-A-9-208826 JP 2000-34410 A JP 2001-55510 A

  An object of this invention is to provide the emulsion composition for coating excellent in uniform coating property.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a coating emulsion composition in which the following components (A) to (F) are emulsified and dispersed in water in the presence of a surfactant. As a result, the present invention has been found.

That is, the present invention provides an emulsion composition for coating that solves the above problems.
(A) 100 parts by mass of an organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule;
(B) 0.5-20 parts by mass of a reaction product of an amino group-containing organoalkoxysilane and a dicarboxylic acid anhydride,
(C) 0-20 parts by mass of an epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof,
(D) 0-50 parts by mass of colloidal silica and / or polysilsesquioxane,
(E) Curing catalyst 0 to 10 parts by mass, and (F) 0.5 to 20 parts by mass of an organopolysiloxane not containing a hydroxyl group and containing a long-chain alkyl group and an alkoxy group in the presence of a surfactant in water An emulsion composition for coating is provided which is emulsified and dispersed.

  The coating film obtained from the emulsion composition for coating of the present invention is uniform and has excellent adhesion to the substrate, so that it is water repellent and waterproof when treated with fibers, paper, film, leather, building materials, etc. And releasability can be imparted, and is particularly effective for coating the surface of a substrate with little unevenness. It can also be used as a binder material for functional inorganic fillers such as photocatalysts.

  By coating with the composition of the present invention, a uniform coating film without unevenness can be obtained.

［式中、Ｒは同一又は異種の炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基、Ｘは同一又は異種の炭素数１〜２０のアルコキシ基又はヒドロキシル基（但し、Ｘの２個以上はヒドロキシル基）、ａは０又は０＜ａ≦１，０００の正数、ｂは１００≦ｂ≦１０，０００の正数、ｃは０又は０＜ｃ≦１，０００の正数であり、１００≦ａ×ｃ＋ｂ≦１００，０００、ｒは１、２又は３である。］
で示されるオルガノポリシロキサンを挙げることができる。 Hereinafter, each component used in the emulsion composition for coating of the present invention will be described in detail.
The organopolysiloxane in the component (A) contains at least two hydroxyl groups bonded to silicon atoms in one molecule. For example, the following average composition formula (1):

[Wherein, R is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, X is the same or different alkoxy group having 1 to 20 carbon atoms or hydroxyl group (provided that X 2 or more are hydroxyl groups), a is 0 or a positive number of 0 <a ≦ 1,000, b is a positive number of 100 ≦ b ≦ 10,000, c is a positive number of 0 or 0 <c ≦ 1,000 100 ≦ a × c + b ≦ 100,000, and r is 1, 2 or 3. ]
Can be mentioned.

  Here, R is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Chain alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, phenyl group, tolyl Group, an aryl group such as a naphthyl group, and the like, and a methyl group is preferable. X is the same or different alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, or hydroxyl group. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and the like. It is done.

  If a is greater than 1,000, the strength of the resulting film will be insufficient, so 0 or a positive number from 0 to 1,000, preferably a positive number from 0 to 200. Flexibility is poor, and if it is greater than 10,000, the tear strength decreases, so a positive number of 100 to 10,000, preferably a positive number of 1,000 to 5,000 is set. Further, c is preferably a positive number from 1 to 1,000. In addition, (A) component needs to have a hydroxyl group couple | bonded with at least 2 silicon atom in 1 molecule from a crosslinkable surface.

ここで、Ｍｅはメチル基、Ｐｈはフェニル基を示す。また、ｍは０又は０＜ｍ≦１，０００、好ましくは０＜ｍ≦２００、ｎは１００≦ｎ≦１０，０００、好ましくは１，０００≦ｎ≦５，０００、ｐは０又は０＜ｐ≦１，０００、好ましくは１≦ｐ≦１，０００である。 Specific examples of such organopolysiloxanes include the following.

Here, Me represents a methyl group, and Ph represents a phenyl group. M is 0 or 0 <m ≦ 1,000, preferably 0 <m ≦ 200, n is 100 ≦ n ≦ 10,000, preferably 1,000 ≦ n ≦ 5,000, and p is 0 or 0 <. p ≦ 1,000, preferably 1 ≦ p ≦ 1,000.

  Such an organopolysiloxane can be produced by a known method. For example, it can be obtained by carrying out an equilibration reaction between a cyclic siloxane such as octamethylcyclotetrasiloxane and an α, ω-dihydroxysiloxane oligomer in the presence of a catalyst such as a metal hydroxide. In addition, since the component (A) is preferably used in the form of an emulsion, the component (A) may be used as an emulsion by a known emulsion polymerization method, and the component (A) is a cyclic siloxane, α, After emulsifying and dispersing ω-dihydroxysiloxane oligomer, α, ω-dialkoxysiloxane oligomer, alkoxysilane, etc. in water using an anionic surfactant or cationic surfactant, acid, alkaline substance, etc. as necessary It can manufacture easily by adding the catalyst of and performing a polymerization reaction.

  The above emulsion is obtained by emulsifying and dispersing an organopolysiloxane as described above in an aqueous medium in the presence of at least one anionic surfactant selected from organic sulfonic acid, organic sulfate and organic sulfonate. It is preferable to prepare an initial emulsion, polymerize it, and further neutralize it. The average particle size of the emulsion is preferably 500 nm or less, and preferably 400 nm or less. If the average particle size is greater than 500 nm, the stability of the emulsion is deteriorated, the polymerization reaction is slowed, and the process time may be long. Because there is.

  The polymerization temperature for polymerizing the above-mentioned emulsion is preferably 0 to 90 ° C, more preferably 5 to 80 ° C. When the polymerization temperature is lower than 0 ° C., the polymerization reaction is slow, and when it is higher than 90 ° C., the stability of the emulsion may be lowered during the polymerization reaction. The time for the polymerization reaction is preferably 1 to 200 hours, more preferably 5 to 100 hours, and it is preferable to perform the reaction under standing or gentle stirring.

  After this polymerization reaction, it is preferably neutralized to pH 4-9 by adding an alkaline substance. Even if this pH is less than 4 or greater than 9, the long-term stability of the resulting organopolysiloxane emulsion may be lowered, so that it is preferably 4 to 9, and more preferably 5 to 8. In this case, the alkaline substance to be added includes inorganic alkali compounds such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, and organic alkali compounds such as ammonia and organic amines. Is mentioned.

  Furthermore, in order to improve the stability of the organopolysiloxane emulsion of component (A) obtained by emulsion polymerization, other anionic surfactants, nonionic surfactants or amphoteric surfactants are not impaired. You may add in the range before emulsion polymerization, after emulsion polymerization, or after neutralization. Examples of the anionic surfactant include salts of higher alkyl sulfates, salts of alkyl phenyl ether sulfates, alkylbenzene sulfonates, salts of higher alkyl phosphates, salts of ethoxylated higher alkyl sulfates, salts of ethoxylated alkyl phenyl ether sulfates, Examples of the nonionic surfactant include ethoxylated higher alcohol, ethoxylated alkylphenol, polyhydric alcohol fatty acid ester, ethoxylated polyhydric alcohol fatty acid ester, ethoxylated fatty acid, and ethoxylated fatty acid. Amide, sorbitol, sorbitan fatty acid ester, ethoxylated sorbitan fatty acid ester, sucrose fatty acid ester and the like are listed. Examples of amphoteric surfactants include amino acid type Those of betaine type and the like.

The reaction product of (B) component amino group-containing organoalkoxysilane and dicarboxylic acid anhydride is a component for improving the adhesion between the silicone film (coating film) and the substrate. Silane and dicarboxylic acid anhydride are reacted. The amino group-containing alkoxysilane as a raw material has a general formula: A (R) _g Si (OR) _{3 -g} [wherein R is the same as defined above, and A is —R ³ (NHR ³ ) _h NHR ⁴ (where R ³ is the same or different divalent hydrocarbon group having 1 to 6 carbon atoms, R ⁴ is R or a hydrogen atom, h is an integer of 0 to 6), g is 0, 1 or unsubstituted amino group represented by 2 (i.e., -NH ₂₎ or a substituted amino group (i.e., -NHR ⁴⁾ an organoalkoxysilane containing, specifically include the following.

(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂
(C ₂ H ₅ O) ₂ (CH ₃ ) SiC ₃ H ₆ NH ₂
(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂
(CH ₃ O) ₂ (CH ₃ ) SiC ₃ H ₆ NH ₂
(CH ₃ O) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH ₂
(CH ₃ O) ₂ (CH ₃ ) SiC ₃ H ₆ NHC ₂ H ₄ NH ₂

  Examples of the dicarboxylic anhydride for reacting with the amino group-containing alkoxysilane include maleic anhydride, phthalic anhydride, succinic anhydride, methyl succinic anhydride, glutaric anhydride, itaconic anhydride, and the like. Can be mentioned. Of these, maleic anhydride is preferred. The reaction between the amino group-containing organoalkoxysilane and the dicarboxylic acid anhydride is carried out according to the blending ratio of both of the above so that the amino group / acid anhydride (molar ratio) is 0.5 to 2, and a hydrophilic organic as required. It can be easily carried out by mixing in a solvent at room temperature or under heating. Examples of the hydrophilic organic solvent at this time include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, acetonitrile and tetrahydrofuran.

  (B) The compounding quantity of a component is 0.5-20 mass parts with respect to 100 mass parts of (A) component, and when less than 0.5 mass part, the adhesive effect with a base material becomes weak, When it is more than 20 parts by mass, the film becomes hard and brittle. More preferably, it is 1-10 mass parts.

  The (C) component epoxy group-containing organoalkoxysilane and / or its partial hydrolyzate is a component for improving the adhesion between the silicone film and the substrate, specifically γ-glycidoxypropyl. Examples include trimethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, and the like. (C) The compounding quantity of a component is 0-20 mass parts with respect to 100 mass parts of (A) component, and when it exceeds 20 mass parts, a film | membrane will become hard and brittle. Preferably, it is 1-10 mass parts.

  The component (D), colloidal silica and / or polysilsesquioxane, is added as a film reinforcing agent, specifically, polymethylsilsesquiol which is a hydrolysis condensate of colloidal silica and trimethoxymethylsilane. Oxane and the like. As the colloidal silica, commercially available ones can be used, and there is no limitation on the kind thereof. For example, the colloidal silica may be one having a particle diameter of 5 to 50 nm and stabilized with sodium, ammonia, aluminum or the like. Examples include Tex (manufactured by Nissan Chemical Co., Ltd.), Ludox (manufactured by Grace Co., Ltd.), silica doll (manufactured by Nippon Chemical Industry Co., Ltd.), Adelite AT (manufactured by Asahi Denka Kogyo Co., Ltd.), Cataloid S (manufactured by Catalytic Chemical Industry Co., Ltd.)

  Polymethylsilsesquioxane is prepared by adding an acid such as sulfuric acid or an alkali compound such as potassium hydroxide as a condensation catalyst to an aqueous surfactant solution, adding trimethoxymethylsilane dropwise, stirring and emulsifying. An emulsion containing silsesquioxane is obtained. At this time, alkoxytrialkylsilane, dialkoxydialkylsilane, tetraalkoxysilane or the like may be added to adjust the degree of crosslinking of the polysilsesquioxane. Also, vinyl silane, epoxy silane, acryl silane, methacryl silane or the like may be added to increase the reactivity of polysilsesquioxane. In addition, the compounding quantity of (D) component is 0-50 mass parts with respect to 100 mass parts of (A) component, and when it is more than 50 mass parts, a silicone film will become hard and brittle. Preferably it is 1-30 mass parts, More preferably, it is 2-25 mass parts. The average particle size of the component (D) is preferably 2 to 200 nm.

  The curing catalyst as component (E) is blended for crosslinking and curing the components of the composition of the present invention by a condensation reaction. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin. Organic acid metal salts such as diversate, dioctyltin diacetate, dibutyltin bisoleyl malate, tin octylate, zinc stearate, zinc octylate, zinc acetate, iron octylate, and amine compounds such as n-hexylamine and guanidine And so on. These curing catalysts are preferably in the form of an emulsion emulsified and dispersed in water using a surfactant in advance, except when water-soluble. The compounding quantity of this (E) component is 0-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0-5 mass parts. When the amount exceeds 10 parts by mass, the catalyst component remaining in the film as a non-volatile component inhibits the film characteristics. Even in the case of 0 parts by mass, since the reaction product of the amino group-containing organoalkoxysilane and the dicarboxylic acid anhydride as component (B) acts as a cocatalyst, the crosslinking reaction proceeds, but component (E) It is also possible to adjust the curing rate and the properties of the resulting film by adding at 10 parts by mass or less, preferably 5 parts by mass or less.

［式中、Ｒ¹は同一又は異種の炭素数１〜３のアルキル基又はフェニル基、Ｑは同一又は異種の炭素数４〜２０のアルキル基、Ｚは同一又は異種の−ＯＲ²、−Ｃ₂Ｈ₄−Ｓｉ（ＯＲ²）₃又は−Ｃ₃Ｈ₆−Ｓｉ（ＯＲ²）₃で示される基（Ｒ²は炭素数１〜６のアルキル基）、ｄは１〜１００の正数、ｅは１〜１００の正数、ｆは０．１〜３０の正数、ｑは０、１、２又は３である。］ (F) The organopolysiloxane which does not contain a hydroxyl group as a component and contains a long chain (preferably having 4 to 20 carbon atoms) alkyl group and an alkoxy group is intended to improve uniform coatability during coating treatment. What is mix | blended and shown by the following average composition formula (2) is suitable.

[Wherein, R ¹ is the same or different alkyl group having 1 to 3 carbon atoms or phenyl group, Q is the same or different alkyl group having 4 to 20 carbon atoms, Z is the same or different —OR ² , —C _{A group represented by 2} H ₄ —Si (OR ² ) ₃ or —C ₃ H ₆ —Si (OR ² ) ₃ (R ² is an alkyl group having 1 to 6 carbon atoms), d is a positive number from 1 to 100, e is a positive number from 1 to 100, f is a positive number from 0.1 to 30, and q is 0, 1, 2, or 3. ]

Here, R ¹ is the same or different alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. Q is the same or different alkyl group having 4 to 20 carbon atoms, specifically, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group And octadecyl group. A hexyl group, an octyl group, a decyl group, and a dodecyl group are preferable. Z is the same or different group represented by —OR ² , —C ₂ H ₄ —Si (OR ² ) ₃ or —C ₃ H ₆ —Si (OR ² ) ₃ (R ² is alkyl having 1 to 6 carbon atoms) a group), specifically, methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentyloxy group, hexyloxy _{group, -C 2 H 4 -Si (OCH} 3) 3, -C 2 H 4 -Si ( _{OC 2 H 5) 3, -C} 3 H 6 -Si (OCH 3) 3, etc. _{-C 3 H 6 -Si (OC 2} H 5) 3 and the like. Preferably, methoxy, _{ethoxy, -C 2 H 4 -Si (OCH} 3) _3.

［式中、Ｑはヘキシル基、オクチル基、デシル基、ドデシル基の中から選ばれる同一又は異種の基、Ｚはメトキシ基、エトキシ基、−Ｃ₂Ｈ₄−Ｓｉ（ＯＣＨ₃）₃の中から選ばれる同一又は異種の基、ｄは１〜１００の正数、ｅは１〜１００の正数、ｆは０．１〜３０の正数である。］ Among those represented by the above average composition formula (2), those represented by the following average composition formula (3) are particularly suitable.

[In the formula, Q is the same or different group selected from hexyl, octyl, decyl and dodecyl groups, Z is a methoxy group, an ethoxy group, and —C ₂ H ₄ —Si (OCH ₃ ) ₃ . The same or different groups selected from: d is a positive number of 1 to 100, e is a positive number of 1 to 100, and f is a positive number of 0.1 to 30. ]

  Moreover, in order to provide uniform coatability, d must be a positive number of 1 to 100, e must be a positive number of 1 to 100, and f must be a positive number of 0.1 to 30, especially d. Is preferably a positive number of 2 to 90, e is a positive number of 2 to 90, and f is a positive number of 0.1 to 20. The compounding quantity of this (F) component is 0.5-20 mass parts with respect to 100 mass parts of (A) component. When the amount is less than 0.5 parts by mass, there is no effect of imparting uniform coatability, and when it exceeds 20 parts by mass, the curability of the film is lowered and the film properties are impaired. A preferable range is 1 to 15 parts by mass, and a more preferable range is 1 to 10 parts by mass.

  There are no particular restrictions on the surfactant used to make each of the above components into an emulsion form, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates, polyoxyethylene alkyl ethers, Nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene fatty acid esters, cationic surfactants such as quaternary ammonium salts and alkylamine acetates, amphoteric surfactants such as alkylbetaines and alkylimidazolines, Examples thereof include water-soluble polymer compounds such as polyvinyl alcohol.

  The coating emulsion composition of the present invention can be produced by emulsifying and dispersing the above components (A) to (F) in water in the presence of a surfactant. The emulsification and dispersion for obtaining the emulsion composition is preferably performed under a high shear pressure of 10 MPa or more using a high-pressure emulsifier such as a homogenizer. If this pressure is lower than 10 MPa, it is difficult to make the average particle size of the emulsion 500 nm or less. In addition, even if higher than 200 MPa, the effect of reducing the average particle size cannot be expected any more, and it is inefficient. Therefore, it is more preferably 15 to 150 MPa, particularly 20 to 100 MPa. Before this high-pressure emulsification, rough emulsification using a homomixer, azimuhomomixer (trade name), combimix (trade name), Supraton (trade name), Claremix (trade name), colloid mill, etc. is optional. It is. Note that the same emulsification dispersion method can also be applied when the components (A) to (F) are blended individually as emulsions.

  There are no particular restrictions on the method of coating the substrate using the coating emulsion composition of the present invention, but known methods such as brush coating, roll coating, gravure coating, bar coating, spray coating, knife coating, dip coating, etc. The coating emulsion composition is applied to the substrate by the method, and then the moisture is removed by drying to form a silicone film. In addition, in order to improve workability during the coating process, it is possible to adjust the liquid viscosity by adding a thickener or the like. Examples of the thickening agent include carboxymethyl cellulose, sodium polyacrylate, starch, casein, cellulose acetate, hydroxyethyl cellulose, and polyvinyl alcohol.

  Examples of application of the emulsion composition of the present invention include, but are not limited to, use as water repellents such as films and papers, water absorption inhibitors, mold release agents, antifouling agents, and the like.

  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 addition, a part shows a mass part by the following example.

[Synthesis Example 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 in a 2 liter polyethylene beaker and uniformly emulsified with a homomixer. The mixture was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 30 MPa 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 to pH 6.2. This emulsion has a non-volatile content of 45.4% after drying at 105 ° C. for 3 hours, the organopolysiloxane in the emulsion is a non-flowable soft gel, and has an average composition represented by the following formula: The hydroxyl group was blocked. In this way, an emulsion (A-1) containing 44.4% of the component (A) was obtained.

ここで、Ｍｅはメチル基、Ｐｈはフェニル基を示す。また、ｍ＝１、ｎ＋ｐ＝１，０００である。

Here, Me represents a methyl group, and Ph represents a phenyl group. Further, m = 1 and n + p = 1,000.

[Synthesis Example 2]
500 g of octamethylcyclotetrasiloxane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous dodecylbenzenesulfonic acid solution were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and then gradually diluted with 400 g of water. And passed through a high-pressure homogenizer twice at a pressure of 30 MPa 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 to pH 6.2. This emulsion has a non-volatile content of 45.5% after drying at 105 ° C. for 3 hours, and the organopolysiloxane in the emulsion has a viscosity of 1,000 Pa · s or more represented by HO — [(CH ₃ ) ₂ SiO] _n —H. It was like a raw rubber. In this way, an emulsion (A-2) containing 44.5% of the component (A) was obtained.

[Synthesis Example 3]
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 (B) A solution (B-1) 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, GCMS, and about 60% was as follows. formula _{(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 ⁺ C ₂ H ₅ OCOCH═CHCOO ⁻
And the remaining approximately 40% were oligomers derived from them.

[Synthesis Example 4]
300 g of dioctyltin dilaurate and 50 g of polyoxyethylene nonylphenyl ether (EO 10 mol adduct) were charged into a 2 liter polyethylene beaker and mixed uniformly with a homomixer, and then 650 g of water was gradually added and emulsified and dispersed in water. An emulsion (E-1) containing 30% of the component (E) was obtained by passing twice through a high-pressure homogenizer at a pressure of 30 MPa.

で示される動粘度３７ｍｍ²／ｓの、長鎖アルキル基、及びアルコキシ基を含有するオルガノポリシロキサン５００ｇとポリオキシエチレンデシルエーテル（ＥＯ４モル付加物）２０ｇ、スルホコハク酸ナトリウム５ｇを２リットルポリエチレン製ビーカーに仕込み、ホモミキサーで均一に混合した後、水４７５ｇを徐々に加えて水中に乳化分散させ、次いで圧力３０ＭＰａで高圧ホモジナイザーに２回通し、（Ｆ）成分を５０％含有するエマルジョン（Ｆ−１）を得た。 [Synthesis Example 5]
The following average composition formula

A 2-liter polyethylene beaker containing 500 g of an organopolysiloxane containing a long chain alkyl group and an alkoxy group, 20 g of polyoxyethylene decyl ether (EO 4 mol adduct), and 5 g of sodium sulfosuccinate having a kinematic viscosity of 37 mm ² / s. After mixing uniformly with a homomixer, 475 g of water is gradually added and emulsified and dispersed in water, then passed twice through a high-pressure homogenizer at a pressure of 30 MPa, and an emulsion containing 50% of the component (F-1) (F-1 )

[Examples 1-4, Comparative Examples 1-3]
(C) γ-glycidoxypropyltrimethoxysilane “C-1” is used as the component, and colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd .: 20% active ingredient) “D-1” is used as the component (D). Each silicone emulsion composition was obtained by mixing components A) to (F) in the pure equivalent composition shown in Table 1. The silicone emulsion composition was coated so that the net amount 2 g / m ² using a wire bar to white paperboard was evaluated surface coating state (coating state) visually. Furthermore, the surface tack feeling of the coating film after drying at 80 ° C. for 1 minute and the adhesion to the substrate were evaluated by touch, and further, cellophane adhesive tape was applied to the coated surface, the release property was evaluated, and the results are shown. It was shown in 1.

（＊１）○：均一、×：ムラあり
（＊２）○：タック感なし、×：タック感あり
（＊３）○：指で擦っても皮膜脱離なし、×：指で擦ると皮膜脱離する
（＊４）○：軽く剥がれる、×：一部基材と接着して剥がれにくい

(* 1) ○: Uniform, ×: Uneven (* 2) ○: No tackiness, ×: Tackiness (* 3) ○: No film detachment even when rubbed with a finger, X: Film when rubbed with a finger Detach (* 4) ○: lightly peels off, ×: adheres to a part of the base material and is difficult to peel off

Claims (3)

(A) 100 parts by mass of an organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule;
(B) 0.5-20 parts by mass of a reaction product of an amino group-containing organoalkoxysilane and a dicarboxylic acid anhydride,
(C) 0-20 parts by mass of an epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof,
(D) 0-50 parts by mass of colloidal silica and / or polysilsesquioxane,
(E) Curing catalyst 0 to 10 parts by mass, and (F) 0.5 to 20 parts by mass of an organopolysiloxane not containing a hydroxyl group and containing a long-chain alkyl group and an alkoxy group in the presence of a surfactant in water An emulsion composition for coating, which is emulsified and dispersed. Component (F) has the following average composition formula (2):

[Wherein, R ¹ is the same or different alkyl group having 1 to 3 carbon atoms or phenyl group, Q is the same or different alkyl group having 4 to 20 carbon atoms, Z is the same or different —OR ² , —C _{A group represented by 2} H ₄ —Si (OR ² ) ₃ or —C ₃ H ₆ —Si (OR ² ) ₃ (R ² is an alkyl group having 1 to 6 carbon atoms), d is a positive number from 1 to 100, e is a positive number from 1 to 100, f is a positive number from 0.1 to 30, and q is 0, 1, 2, or 3. ]
The emulsion composition for coating of Claim 1 shown by these. Component (F) has the following average composition formula (3):

[In the formula, Q is the same or different group selected from hexyl, octyl, decyl and dodecyl groups, Z is a methoxy group, an ethoxy group, and —C ₂ H ₄ —Si (OCH ₃ ) ₃ . The same or different groups selected from: d is a positive number of 1 to 100, e is a positive number of 1 to 100, and f is a positive number of 0.1 to 30. ]
The emulsion composition for coating of Claim 1 shown by these.