JP2008138059A - Organosilicone resin emulsion composition and article with coated film of the composition formed thereon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organosilicone resin emulsion composition free from environmental problem, having good stability, and exhibiting excellent adhesion to a base material, and to provide an article with a coated film of the composition. <P>SOLUTION: The organosilicone resin emulsion composition comprises (A) 100 pts.mass of an organosilicone resin represented by the composition formula: [XSiO<SB>3/2</SB>]<SB>h</SB>[R(X)SiO]<SB>k</SB>[RSiO<SB>3/2</SB>]<SB>m</SB>[R<SB>2</SB>SiO]<SB>n</SB>(Rs are the same or different kinds of 1-20C monovalent hydrocarbon groups; X is a 1-20C monovalent hydrocarbon group; X is a 1-20C monovalent reactive organic group; h, k, m and n are 0-0.5, 0-0.5, 0.2-0.99 and 0-0.8 respectively, and each a positive number satisfying h+k+m+n≤1.0 and 0<h+k≤0.5), (B) 2-50 pts.mass of water-miscible organic solvent having 8.0-11.0 SP (solubility parameter) value, (C) 1-50 pts.mass of an emulsifier and (D) 25-2,000 pts.mass of water, and is substantially free from an organic solvent except the component (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an emulsion composition of a silicone resin that is suitably used as a protective coating agent for various substrates, a coating material for exteriors such as structures and building materials, and an article having the coating.

  In recent years, from the viewpoint of environmental pollution and ensuring a safe working environment, in the field of paints or coating agents, it is required to change the dispersion medium from an organic solvent to an aqueous system. Based on this requirement, emulsion paints obtained by emulsion polymerization of radically polymerizable vinyl monomers typified by acrylic resins have been widely used as basic materials for coating agents because of their excellent film-forming properties and good chemical resistance. However, this type of coating has the disadvantage that it is inherently inferior in water resistance and weather resistance.

On the other hand, silicone resins obtained by hydrolyzing and condensing silane compounds are attracting attention as coating agents because of their high hardness and ability to form films with excellent weather resistance, water resistance, heat resistance, and water repellency. . However, an emulsion polymerization method for polymerizing a silicone resin from a monomer in an emulsion has not been established. For this reason, a general method is to emulsify a silicone resin solution produced in an organic solvent system such as toluene or xylene as it is.
However, such an organic solvent-containing silicone resin emulsion has a problem of poor stability. Furthermore, it is necessary to suppress the use of organic solvents such as toluene and xylene due to environmental problems.

  The present inventor has proposed a silicone resin emulsion composition containing substantially no organic solvent by using a small amount of a specific water-miscible organic solvent (Japanese Patent Laid-Open No. 2006-225629: Patent Document 1). However, even such a silicone resin emulsion composition may have insufficient adhesion to the substrate depending on the type of the substrate.

  In addition, an epoxy group-containing silicone resin has been proposed as a reactive silicone resin (JP-A-6-298940, JP-A-2003-12767, JP-A-2003-327664, JP-A-2006-188593). : Patent Documents 2 to 5) do not describe the emulsion composition.

JP 2006-225629 A JP-A-6-298940 JP 2003-12767 A JP 2003-327664 A JP 2006-188593 A

  The present invention has been made in view of the above circumstances, and has an organosilicone resin emulsion composition having no environmental problems, good stability, and excellent adhesion to a substrate, and a coating film of the composition The purpose is to provide goods.

As a result of intensive studies to achieve the above object, the present inventor has (A) composition formula: [XSiO _3/2 ] _h [R (X) SiO] _k [RSiO _3/2 ] _m [R ₂ SiO ] _n (wherein, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms the same or different, X is a monovalent reactive organic group having 1 to 20 carbon atoms, h is 0 to 0.5, k Is 0 to 0.5, m is 0.2 to 0.99, n is 0 to 0.8, and is a positive number satisfying h + k + m + n ≦ 1.0 and 0 <h + k ≦ 0.5. Organosilicone Resin: 100 parts by mass, (B) Water miscible organic solvent having an SP value of 8.0-11.0: 2-50 parts by mass, (C) Emulsifier: 1-50 parts by mass and (D) Water: Organosilicone resin emulsion composition containing 25 to 2,000 parts by mass and containing substantially no organic solvent other than component (B) However, it was found that there was no environmental problem and the stability was good, and that an article having a coating film of this composition had good adhesion to the substrate, which led to the present invention.

Therefore, the present invention
(A) The following composition formula:
[XSiO _3/2 ] _h [R (X) SiO] _k [RSiO _3/2 ] _m [R ₂ SiO] _n
(In the formula, R is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a monovalent reactive organic group having 1 to 20 carbon atoms, h is 0 to 0.5, and k is 0. -0.5, m is 0.2-0.99, n is 0-0.8, and is a positive number satisfying h + k + m + n ≦ 1.0 and 0 <h + k ≦ 0.5.)
An organosilicone resin represented by: 100 parts by mass,
(B) Water-miscible organic solvent having an SP value of 8.0 to 11.0: 2 to 50 parts by mass
(C) Emulsifier: 1 to 50 parts by mass,
(D) Water: An organosilicone resin emulsion composition characterized by containing 25 to 2,000 parts by mass and containing substantially no organic solvent other than the component (B), and the surface of the substrate. An article having a coating of an organosilicone resin emulsion composition formed thereon is provided.

  In the present invention, “substantially free of an organic solvent other than the component (B)” means that the organic solvent other than the component (B) is not contained at all, and the component (B) is substantially included. In the case where no other organic solvent is contained, that is, the case where a small amount of the organic solvent other than the component (B) is included so as not to affect the stability and has no environmental problems is also included. Specifically, the organic solvent other than the component (B) may be contained in the total organic solvent in an amount of 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less of the entire composition. .

  ADVANTAGE OF THE INVENTION According to this invention, the stable emulsion composition of the silicone resin which has a high-hardness film | membrane with favorable adhesiveness can be obtained.

The organosilicone resin emulsion composition of the present invention is
(A) The following composition formula:
[XSiO _3/2 ] _h [R (X) SiO] _k [RSiO _3/2 ] _m [R ₂ SiO] _n
An organosilicone resin represented by
(B) a water-miscible organic solvent having an SP value of 8.0 to 11.0,
(C) an emulsifier,
(D) It contains water and does not substantially contain an organic solvent other than the component (B).

The organosilicone resin as component (A) has the following composition formula:
[XSiO _3/2 ] _h [R (X) SiO] _k [RSiO _3/2 ] _m [R ₂ SiO] _n
(In the formula, R is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a monovalent reactive organic group having 1 to 20 carbon atoms, h is 0 to 0.5, and k is 0. -0.5, m is 0.2-0.99, n is 0-0.8, and is a positive number satisfying h + k + m + n ≦ 1.0 and 0 <h + k ≦ 0.5.)
It is shown by.

  Here, R is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Examples thereof include alkyl groups such as tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl and naphthyl, and alkenyl groups such as vinyl and allyl. In the present invention, it is desirable that 30 mol% or more of R is a methyl group.

  X is a monovalent reactive organic group having 1 to 20 carbon atoms, and has a function of imparting adhesion and reactivity with a base material and a combination resin. Examples of the reactive organic group include an epoxy group, a mercapto group, a methacryl group, an acrylic group, a carboxyl group, and a monovalent organic group containing an amino group. Specifically, 3-glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3-mercaptopropyl, 3-methacryloxypropyl, 3-acryloxypropyl, 3-aminopropyl, N- (2 -Aminoethyl) -3-aminopropyl, N- (1,3-dimethylbutylidene) -3-aminopropyl, N-phenyl-3-aminopropyl, 3-ureidopropyl, 3-chloropropyl, 10-carboxydecyl , 2-carboxyethyl, 3- (2-hydroxyethoxy) propyl and the like. Among these, the reactive organic group is preferably a monovalent organic group containing an epoxy group, a mercapto group, a methacryl group, or an acrylic group.

The molar ratio (h) of [XSiO _3/2 ] units in the silicone resin is from 0 to 0.5, preferably from 0 to 0.3, more preferably from 0 to 0.2. If it is larger than 0.5, the stability during emulsification is lowered. Moreover, the molar ratio (k) of the [R (X) SiO] unit in the silicone resin is 0 to 0.5, preferably 0 to 0.3, and more preferably 0 to 0.2. If it is larger than 0.5, the stability during emulsification is lowered. It should be noted that 0 <h + k ≦ 0.5 from the necessity of containing a reactive organic group in the silicone resin, preferably 0 <h + k ≦ 0.3, more preferably 0 <h + k ≦ 0.2. is there.

Next, the molar ratio (m) of [RSiO _3/2 ] units in the silicone resin is 0.2 to 0.99, preferably 0.3 to 0.99, and more preferably 0.4 to 0.99. 0.99. If it is less than 0.2, the film hardness becomes soft and the durability is lowered. The molar ratio of [R ₂ SiO] units in the silicone resin (n) is from 0 to 0.8, preferably from 0 to 0.7, more preferably from 0 to 0.6. When it is larger than 0.8, the coating hardness becomes soft and the durability is lowered. Note that h + k + m + n ≦ 1.0.

Such an organosilicone resin can be produced by a known method. For example, it can be obtained by subjecting chlorosilane or alkoxysilane of the corresponding unit to hydrolysis and condensation reaction. These organosilicone resins are solid when the content of [XSiO _3/2 ] units or [RSiO _3/2 ] units is high, and easily gelled when the condensation reactivity is high. From the present invention, it is usually handled in a state diluted with an organic solvent such as toluene or xylene. In the present invention, such an organic solvent is replaced with a water-miscible organic solvent solution as component (B) or used. It is necessary to use it as a solvent when producing an organosilicone resin.

Further, the component (A) of the present invention may contain a small amount of [Q ₃ SiO _1/2 ] units (Q is R or X described above) and / or [SiO ₂ ] units within a range not impairing the curability. Absent. In this case, h + k + m + n is preferably 0.8 to 1.0, particularly 0.9 to 1.0. When h + k + m + n ≦ 1.0 is not satisfied, the balance is [Q ₃ SiO _1/2 ], [SiO ₂ ]. It is a unit and the total of them is 1.0.

  The water miscible organic solvent having an SP value of 8.0 to 11.0 as the component (B) is used for imparting fluidity when emulsifying the organosilicone resin as the component (A). And the SP value (solubility parameter) is 8.0 to 11.0 and must be water miscible.

  When the SP value is less than 8.0, the organosilicone resin cannot be uniformly dissolved. When the SP value is greater than 11.0, the stability of the emulsion when emulsified is lowered. Must be ~ 11.0. Preferably it is 8.5-10.5.

  Further, the organic solvent needs to be miscible with water, and if it is not miscible with water, the stability of the emulsion when emulsified is lowered. As the water miscibility, the solubility in 100 g of water at 20 ° C. is 1 g or more, preferably 3 g or more.

  Examples of such water-miscible organic solvents include alcohol compounds, ketone compounds, ester compounds, ether compounds, and the like. Among these, compounds having an alkylene oxide unit are preferable. Specifically, cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether methyl carbitol, carbitol, propyl carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, propylene glycol Examples thereof include monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate. Of these, butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like, which are usually used as a film-forming auxiliary for paints, are preferable.

  Component (B) is added in an amount of 2 to 50 parts by mass with respect to 100 parts by mass of component (A), but if it is less than 2 parts by mass, the viscosity of the organosilicone resin solution is high and emulsification is difficult. If the amount is more than 50 parts by mass, there is no problem in characteristics, but it is not preferable that the amount is too large in consideration of volatilization into the environment during use. Preferably it is 3-40 mass parts, More preferably, it is 5-30 mass parts.

  The viscosity of the organosilicone resin solution diluted with the water-miscible organic solvent is preferably 500 to 200,000 mPa · s, particularly 1,000 to 100,000 mPa · s at 25 ° C. The viscosity can be measured with a rotational viscometer.

  The emulsifier as component (C) is not particularly limited as long as it is for emulsifying and dispersing a water-miscible organic solvent solution of an organosilicone resin in water. For example, polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl Nonionic surfactants such as ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxy Examples include anionic surfactants such as ethylene alkylphenyl ether sulfates, cationic surfactants such as quaternary ammonium salts and alkylamine acetates, and amphoteric surfactants such as alkylbetaines and alkylimidazolines. Kill.

Among these, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, and polyoxyethylene alkylphenyl ether are preferable from the viewpoint of stability.
Specific examples thereof include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene tridecyl Ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styrenated phenyl ether, etc. Is mentioned. These emulsifiers can be used alone or in combination of two or more.

  (C) As addition amount of a component, it is necessary to be 1-50 mass parts with respect to 100 mass parts of (A) component, but when it is less than 1 mass part, emulsification is difficult and it is more than 50 mass parts And the hardness and transparency of the coating and the adhesion to the substrate will be reduced. Preferably it is 2-30 mass parts, More preferably, it is 3-20 mass parts.

  The organosilicone resin emulsion composition of the present invention contains water as the component (D), mixes the above-described water-miscible organic solvent solution of the organosilicone resin, an emulsifier and water, and emulsifies and disperses it according to a conventional method. Can be prepared.

  In this case, the water content of the component (D) is 25 to 2,000 parts by mass and preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the component (A). If the amount of water is too small, the viscosity is high and the workability is poor, and if it is too large, the stability of the emulsion decreases.

  Moreover, it is preferable that the non volatile matter (solid content) of the obtained emulsion composition is 5-80 mass%, especially 10-70 mass%.

  Furthermore, the average particle size of the obtained emulsion is preferably 50 to 1,000 nm, particularly preferably 100 to 800 nm. In the present invention, the average particle size can be measured by a particle size distribution measuring device N4Plus manufactured by Coulter.

  The organosilicone resin emulsion composition of the present invention can be crosslinked and cured by heating when the hydroxyl groups and alkoxy groups remaining in the organosilicone resin remove water and the solvent of the component (B), but the curing rate is accelerated. If necessary, a condensation catalyst may be added at the time of use for the purpose of enabling curing at a lower temperature. Examples of the condensation catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium acetate, potassium acetate, sodium methylate, potassium methylate, n-hexylamine, tributylamine and the like. The addition amount of these condensation catalysts is preferably 0.01 to 5 parts by mass, particularly 0.1 to 3 parts by mass with respect to 100 parts by mass of component (A).

  In the present invention, the organosilicone resin emulsion composition can be used in combination with an acrylic resin emulsion, a urethane resin emulsion, or the like. In this case, it is preferable to mix | blend so that the (A) component in the said organosilicone resin emulsion composition may become a ratio of 10-90 mass% in a mixture. In addition, it is also possible to improve the characteristics of the coating film by crosslinking reaction with a resin having a functional group capable of reacting with the reactive organic group of the present invention.

  The organosilicone resin emulsion composition of the present invention is applied to the surface of a transparent or opaque base material such as metal, ceramic inorganic material, glass, wood, paper product, plastic, rubber, etc., and cured by room temperature or heating. Thus, a cured protective film can be formed. This cured protective coating is high in hardness, rich in flexibility, has good adhesion and weather resistance, and can also impart water repellency, so that the base treatment agent for exterior building materials such as metal, ceramic, and wood, It is suitable for paints such as topcoat agents, protective coating agents for metal surfaces such as precoat metals, charge control coating agents for electrophotographic carriers, or adhesives.

  When the base material is metal, it is used for surface treatment of iron, stainless steel building structure materials, aluminum sash building materials, etc., surface treatment such as anticorrosion treatment coating, electrodeposition coating for automobiles or electrical appliances, or electrophotographic carrier It can be suitably used for the surface protective coating of magnetic powder. When the substrate is a plastic, it can be suitably used as a plastic plate, a magnetic or heat-sensitive recording film, a packaging film, a surface protective coating such as vinyl cloth, or a function-imparting binder. When the substrate is a wood or paper product, it can be applied to a surface protective coating for plywood, a surface protection for thermal recording, a water-resistant coating for treating the printed surface, and the like. Moreover, since it also has water repellency, it can also be applied as a surface protective coating for synthetic leather or the like. It can also be applied as a water-soluble binder for water-resistant printing inks. When the base material is inorganic material, mortar, concrete or cement exterior wall material or ceramic panel, ALC plate, sizing board, gypsum board, brick, glass, ceramics, artificial marble surface protection coating, surface treatment It can be applied as a paint. It can also be used as a base polymer for adhesives, and by adding other organic resins or silane coupling agents, it is possible to obtain an adhesive effective for adhesion between different kinds of substrates.

  As a method for applying the organosilicone resin emulsion composition of the present invention to a substrate, various conventionally known coating methods such as dipping, spraying, roll coating, and brushing can be used. The coating amount of the organosilicone resin emulsion composition is not particularly limited, but is usually an amount such that the film thickness after drying is 0.1 to 1,000 μm, particularly 1 to 100 μm.

  When it is used as a protective film without being cured, it is only necessary to leave the substrate after coating at room temperature to volatilize moisture and the solvent of component (B). When cross-linking is promoted by curing at room temperature to obtain a high-hardness film, a good cured film can be obtained by leaving the substrate coated with the emulsion composition to which the condensation catalyst is added at room temperature for 0.1 to 30 days. . In addition, when crosslinking is promoted by heat curing to obtain a high-hardness film, a substrate coated with an emulsion composition to which no catalyst or a condensation catalyst is added is placed in a temperature range of 50 to 300 ° C. for 0.5 minutes to 200 hours. Achieved by maintaining.

  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,% indicates mass%, and the viscosity is a value at 25 ° C. measured with a BM type rotational viscometer.

[Example 1]
740 g of a partial hydrolyzate of trimethoxymethylsilane represented by an average structural formula: CH ₃ O— [CH ₃ (CH ₃ O) SiO] ₂ —CH ₃ in a ₃ L Separa flask with a condenser, average structural formula: CH ₃ O _{- [C 6 H 5 (CH} 3 O) SiO] g of ₂ -CH ₃ partial hydrolyzate of trimethoxyphenyl silane represented by 600 g, 3- mercaptopropyltrimethoxysilane 102 g, further toluene 465 g, isopropanol 87 g, methane 28 g of sulfonic acid was added and the temperature was raised to 50 ° C. with stirring. Thereafter, 271 g of ion-exchanged water was dropped in about 30 minutes using a dropping funnel to perform a hydrolysis reaction. Furthermore, stirring was continued for 2 hours while adjusting the temperature to 70 ° C., a condensation reaction was performed, and the mixture was cooled to 30 ° C. and then neutralized with 29 g of sodium bicarbonate. After adding 500 g of toluene, washing with water, taking out the toluene layer, adding 188 g of water miscible organic solvent butyl cellosolve acetate (SP value 8.9) and performing a vacuum strip at 60 ° C., completely removing only toluene. Distilled off to obtain a butyl cellosolve acetate solution of mercapto group-containing silicone resin. This solution had a nonvolatile content of 84.9% at 150 ° C./3 hours, a viscosity of 61,000 mPa · s, and a molecular weight by GPC of 2,500. As a result of gas chromatography measurement, the butyl cellosolve acetate content was 14.3% and the xylene content was 0.1%. The obtained silicone resin, the measurement of NMR, it is of _{[CH 3 SiO 3/2] 0.62 [} C 6 H 5 SiO 3/2] 0.33 [HSC 3 H 6 SiO 3/2] 0.05 Was confirmed.

  500 g of this mercapto group-containing silicone resin in butyl cellosolve acetate solution (silicone resin / butyl cellosolve acetate = 85.6 / 14.3 mass ratio), 25 g Neugen XL40 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB10.5) as an emulsifier , Neugen XL400 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB18.4) 25 g, New Coal 291M (Japan emulsifier: 75% sodium alkylsulfosuccinate solution) and 445 g of ion-exchanged water were emulsified using a homodisper. And a pale white emulsion A was obtained. The average particle size of this product was 190 nm as measured with a particle size distribution analyzer N4Plus manufactured by Coulter, and no separation or thickening was observed even after 1 month at room temperature.

のものであることが確認できた。 [Example 2]
A 3 L Separa flask equipped with a condenser was charged with 1,020 g of trimethoxymethylsilane, 240 g of dimethoxydimethylsilane, 118 g of 3-glycidoxypropyltrimethoxysilane, and 380 g of isobutanol. 3 g of the mixed solution was dropped in about 1 hour using a dropping funnel to perform a hydrolysis reaction. Furthermore, stirring was continued for 6 hours while adjusting the temperature to 40 ° C., and a condensation reaction was performed. Thereafter, 800 g of toluene was added and washed with water, the toluene layer was taken out, 52 g of butyl cellosolve acetate (SP value 8.9), which is a water-miscible organic solvent, was added, and vacuum stripping was performed at 60 ° C. to completely remove toluene. To obtain a butyl cellosolve acetate solution of an epoxy group-containing silicone resin. This solution had a non-volatile content of 89.3% at 150 ° C./3 hours, a viscosity of 8,900 mPa · s, and a molecular weight by GPC of 4,300. As a result of gas chromatography measurement, the butyl cellosolve acetate content was 8.3% and the toluene content was less than 0.1%. Moreover, the obtained silicone resin was measured by NMR,

It was confirmed that

  500 g of a butyl cellosolve acetate solution of this epoxy group-containing silicone resin (silicone resin / butyl cellosolve acetate = 91.7 / 8.3 mass ratio), 25 g of Neugen XL40 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB10.5) as an emulsifier , Neugen XL400 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB18.4) 25 g, New Coal 291M (Japan emulsifier: 75% sodium alkylsulfosuccinate solution) and 445 g of ion-exchanged water were emulsified using a homodisper. And a pale white emulsion B was obtained. The average particle size of this product was 200 nm when measured with a particle size distribution measuring device N4Plus manufactured by Coulter, and no separation or thickening was observed even after one month at room temperature.

のものであることが確認できた。 [Example 3]
740 g of partial hydrolyzate of trimethoxymethylsilane represented by an average structural formula: CH ₃ O— [CH ₃ (CH ₃ O) SiO] ₂ —CH ₃ in a ₃ L Separa flask with a condenser, average structural formula: CH ₃ O _{- [C 6 H 5 (CH} 3 O) SiO] 2 -CH 3 partial hydrolyzate of trimethoxyphenyl silane represented by 600 g, 3- methacryloxypropyl g of trimethoxysilane 129 g, further toluene 465 g, isopropanol 87 g, 28 g of methanesulfonic acid was added and the temperature was raised to 50 ° C. with stirring. Thereafter, 271 g of ion-exchanged water was dropped in about 30 minutes using a dropping funnel to perform a hydrolysis reaction. Furthermore, stirring was continued for 2 hours while adjusting the temperature to 70 ° C., a condensation reaction was carried out, the mixture was cooled to 30 ° C., and then neutralized with 29 g of sodium bicarbonate. After adding 500 g of toluene, washing with water, taking out the toluene layer, adding 188 g of water miscible organic solvent butyl cellosolve acetate (SP value 8.9) and performing a vacuum strip at 60 ° C., completely removing only toluene. Distilled off to obtain a butyl cellosolve acetate solution of a methacryloxy group-containing silicone resin. This solution had a nonvolatile content of 82.0% at 150 ° C./3 hours, a viscosity of 38,000 mPa · s, and a molecular weight by GPC of 2,800. As a result of gas chromatography measurement, the butyl cellosolve acetate content was 15.6%, and the toluene content was less than 0.1%. Moreover, the obtained silicone resin was measured by NMR,

It was confirmed that

  500 g of butyl cellosolve acetate solution (silicone resin / butyl cellosolve acetate = 84.4 / 15.6 mass ratio) of this methacryloxy group-containing silicone resin, 25 g of Neugen XL40 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB10.5) as an emulsifier , Neugen XL400 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB18.4) 25 g, New Coal 291M (Japan emulsifier: 75% sodium alkylsulfosuccinate solution) and 445 g of ion-exchanged water were emulsified using a homodisper. And a pale white emulsion C was obtained. The average particle size of this product was 220 nm when measured with a particle size distribution measuring device N4Plus manufactured by Coulter, and no separation or thickening was observed even after 1 month at room temperature.

[Examples 4 and 5]
The adhesion of the cured coatings of Emulsion A and Emulsion B obtained in Examples 1 and 2 was evaluated by the following procedure. A compound having the composition shown in Table 1 was applied to a urethane rubber sheet having a clean surface so that the film thickness after curing was about 20 μm, and was cured at 80 ° C./1 hour. Thereafter, the treated rubber sheet was immersed in warm water at 40 ° C. for 24 hours, and the surface coating state was visually observed. The results are shown in Table 1.

[Example 6]
The adhesion of the cured coating film of Emulsion C obtained in Example 3 was evaluated according to the following procedure. A compound having the composition shown in Table 1 was applied to an EPDM rubber sheet having a clean surface so that the film thickness after curing was about 20 μm, and was cured at 80 ° C./1 hour. Thereafter, the treated rubber sheet was immersed in warm water at 40 ° C. for 24 hours, and the surface coating state was visually observed. The results are shown in Table 1.

[Comparative Examples 1 and 2]
In a distillation apparatus equipped with a decompressor, 1 kg of a 50% xylene solution of an organosilicone resin represented by [(CH ₃ ) SiO _3/2 ] _0.65 [(C ₆ H ₅ ) SiO _3/2 ] _0.35 , and butyl cellosolve acetate (SP value 8) .9) 125 g was added and vacuum stripping was performed at 70 ° C., and only xylene was completely distilled off to obtain a butyl cellosolve acetate solution of silicone resin. This solution had a non-volatile content of 84.1% at 150 ° C./3 hours, a viscosity of 41,000 mPa · s, and a molecular weight by GPC of 3,100. As a result of gas chromatography measurement, the butyl cellosolve acetate content was 15.3%.

  500 g of this silicone resin butyl cellosolve acetate solution (silicone resin / butyl cellosolve acetate = 84.7 / 15.3 mass ratio), Neugen XL40 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB10.5) as an emulsifier, Neugen XL400 (Daiichi Kogyo Seiyaku: polyoxyalkylene decyl ether, HLB18.4) 25 g, New Coal 291M (Japan emulsifier: alkylsulfosuccinic acid sodium 75% solution) 5 g and ion-exchanged water 445 g are emulsified using a homodisper, A pale white emulsion D was obtained. The average particle size of this product was 210 nm as measured with a particle size distribution analyzer N4Plus manufactured by Coulter.

  The adhesion of the cured film of this emulsion D was evaluated by the following procedure. A composition having the composition shown in Table 1 was applied to a urethane rubber sheet and an EPDM rubber sheet having a clean surface so that the film thickness after curing was about 20 μm, and was cured at 80 ° C./1 hour. Thereafter, the treated rubber sheet was immersed in warm water at 40 ° C. for 24 hours, and the surface coating state was visually observed. The results are shown in Table 1.

（密着性の評価基準）○：フクレによる剥離なし、×：部分的にフクレによる剥離あり

(Evaluation criteria for adhesion) ○: No peeling due to swelling, ×: Partial peeling due to swelling

Claims (6)

(A) The following composition formula:
[XSiO _3/2 ] _h [R (X) SiO] _k [RSiO _3/2 ] _m [R ₂ SiO] _n
(In the formula, R is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a monovalent reactive organic group having 1 to 20 carbon atoms, h is 0 to 0.5, and k is 0. -0.5, m is 0.2-0.99, n is 0-0.8, and is a positive number satisfying h + k + m + n ≦ 1.0 and 0 <h + k ≦ 0.5.)
An organosilicone resin represented by: 100 parts by mass,
(B) Water-miscible organic solvent having an SP value of 8.0 to 11.0: 2 to 50 parts by mass
(C) Emulsifier: 1 to 50 parts by mass,
(D) Water: An organosilicone resin emulsion composition characterized by containing 25 to 2,000 parts by mass and containing substantially no organic solvent other than the component (B).   2. The organosilicone resin emulsion according to claim 1, wherein the monovalent reactive organic group of component (A) is selected from an epoxy group, a mercapto group, a methacryl group, an acrylic group, a carboxyl group, and an amino group-containing monovalent organic group. Composition.   The organosilicone resin emulsion composition according to claim 2, wherein the monovalent reactive organic group of the component (A) is an epoxy group-containing monovalent organic group.   The organosilicone resin emulsion composition according to claim 2, wherein the monovalent reactive organic group of the component (A) is a mercapto group-containing monovalent organic group.   The organosilicone resin emulsion composition according to claim 2, wherein the monovalent reactive organic group of the component (A) is a methacrylic group or an acrylic group-containing monovalent organic group.   An article in which a coating of the organosilicone resin emulsion composition according to any one of claims 1 to 5 is formed on a substrate surface.