JP2003155411A - Aqueous silicone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous silicone composition having more improved abrasion resistance and surface smoothness of a coating film than the conventional product. SOLUTION: This aqueous silicone composition comprises (A) a terminal hydroxyl group-blocked organopolysiloxane having a complex viscosity coefficient at 25 deg.C of >=1×10<4> mPa.s, (B) an organotrialkoxysilane which does not contain amide group, carboxyl group, and epoxy group and/or its partial hydrolysis condensate, (C) an organoalkoxysilane containing amide group and carboxyl group and/or its partial hydrolysis condensate, (D) an organoalkoxysilane containing epoxy group and/or its partial hydrolysis condensate, (E) a curing catalyst, (F) spherical silicone rubber fine particles having an average particle diameter of 0.5-50 μm, and (G) silica based fine particles and/or hydrophobic fine particles obtained by trialkylsilylating the surfaces of polyorganosilsesquioxane based fine particles as the major components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to adhesion to a substrate,
The present invention relates to an aqueous silicone composition useful for the surface coating of rubber materials and fiber materials having excellent wear resistance and surface smoothness.

[0002]

2. Description of the Related Art Conventionally, in order to impart smoothness and abrasion resistance to the surface of various rubbers, a method of coating the surface with a silicone composition has been carried out. Examples of the silicone composition include a composition comprising an epoxy group-containing organopolysiloxane and an amino group-containing alkoxysilane (see JP-A-54-43891), a hydroxyl group-containing organopolysiloxane, an organohydrogenpolysiloxane and an epoxy group. A composition comprising a containing organopolysiloxane and an amino group-containing alkoxysilane (JP-A-54-4)
5361, JP-A-54-90369, JP-A-54-
No. 90375, see each publication), a composition comprising a hydrolyzed condensate of a hydroxyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and an amino group-containing dialkoxysilane (JP-A-7-109440 and JP-A 7-1).
No. 26417, each publication), a composition comprising a hydroxyl group- or vinyl group-containing organopolysiloxane, an organohydrogenpolysiloxane and dimethylpolysiloxane (see JP-A-62-215667), a hydrolyzable group-containing organo. A composition comprising a polysiloxane and epoxy or an organopolysiloxane containing an amino group and a hydrolyzable group and a hydrolyzable silane containing an epoxy group or an amino group (see JP-A-7-196984),
A composition comprising a polyorganosiloxane containing a hydroxyl group and an epoxy group, an alkoxysilane containing an amino group and an alkoxysilane containing a mercapto group (see JP-A-5-5082) has been proposed.

However, the coating film of these silicone resin compositions is particularly poor in abrasion resistance and surface smoothness, and therefore, silicone resin compositions containing fine powders of polymethylsilsesquioxane have been proposed. For example, a composition comprising a hydroxyl group-containing polyorganosiloxane, an epoxy group-containing polyorganosiloxane, an amino group-containing alkoxysilane, and polymethylsilsesquioxane powder (JP-A-61-159427, JP-A-2-2337).
No. 63, each publication), a composition comprising silanol group-containing dimethylpolysiloxane, amino group-containing diorganopolysiloxane, γ-glycidoxypropyltrimethoxysilane and polymethylsilsesquioxane fine powder (JP-A-7- 251124).

A silicone resin composition containing a fine powder of silicone rubber has also been proposed. For example, a composition comprising a hydrolyzed condensate of a non-fluidic branched organopolysiloxane and an epoxy group-containing dialkoxysilane, a hydrolyzed condensate of an amino group-containing dialkoxysilane, and a silicone rubber fine powder (JP-A-7-233351). (See Japanese Patent Application Laid-Open No. 2003-242,), a hydrolyzed condensate of a non-fluidic branched organopolysiloxane, an amino group-containing diorganopolysiloxane and an epoxy group-containing dialkoxysilane, and a hydrolysis condensate of an amino group-containing dialkoxysilane (meth) A composition comprising a trialkoxysilane containing an acrylic group or an amino group and a silicone rubber fine powder (see JP-A-7-310051), a hydrolyzed condensate of a hydroxyl group-containing organopolysiloxane and an epoxy group-containing dialkoxysilane, and a water-soluble amino. Composition consisting of compound and silicone rubber fine powder Rights see JP 9-53047) and the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous silicone composition in which the coating film has improved abrasion resistance and surface smoothness over conventional products.

[0006]

The aqueous silicone composition of the present invention is represented by (A) a unit represented by the general formula [R ¹ ₂ SiO _2/2 ] and a unit represented by the general formula [R ² SiO _3/2 ]. Unit (here R ¹
And R ² is 1 or 2 or more 1 having 1 to 20 carbon atoms.
Becomes valence hydrocarbon group) as a constituent unit, the molar ratio of [R ¹ ₂ SiO _2/2] / [R ² SiO _3/2] = 1 / (0 to 0.0
1) and the complex viscosity at 25 ° C. is 1 × 10 ⁴ m
100 parts by weight of organopolysiloxane end-capped with a hydroxyl group of Pa · s or more, (B) General formula R ³ Si (OR ⁴ ) ₃ (R ³ is a monovalent organic group having 1 to 20 carbon atoms, and R ⁴ is 1 to 1 carbon atoms. 6 monovalent hydrocarbon group) and does not contain an amide group, a carboxyl group or an epoxy group, and / or a partially hydrolyzed condensate thereof.
1 to 10 parts by weight of (C) amide group- and carboxyl group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof, (D) Epoxy group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to
10 parts by weight, (E) curing catalyst 0.01 to 10 parts by weight,
(F) an average particle size of 10 to 100 parts by weight spherical silicone rubber microparticles is 0.5 to 50 [mu] m, the unit and / or the general formula represented by (G) formula [SiO _4/2] [R ⁶ SiO _3/2 ] (Wherein R ⁶ is one or more monovalent organic groups having 1 to 20 carbon atoms) as a constitutional unit, the surface of the fine particles is trialkylsilylated, Hydrophobic fine particles 20-200 having an average particle diameter of 5-1,000 nm
It is an aqueous silicone composition whose main component is parts by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. (A) in the aqueous silicone composition of the present invention
The component comprises a unit represented by the general formula [R ¹ ₂ SiO _2/2 ] and a unit represented by the general formula [R ² SiO _3/2 ] as a constitutional unit, and its molar ratio is [R ¹ ₂ SiO _{2 / 2} ] / [R ² SiO _3/2 ]
= 1 / (0 to 0.01), which is an organopolysiloxane endblocked by a hydroxyl group having a complex viscosity at 25 ° C. of 1 × 10 ⁴ mPa · s or more. R ¹ and R ² in the formula are one or two or more monovalent hydrocarbon groups having 1 to 20 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Alkyl groups such as hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group; cyclohexyl group etc. Examples thereof include alkyl groups and groups in which a part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, such as a 3,3,3-trifluoropropyl group, and a methyl group is particularly preferable.

[R ¹ ₂ SiO _2/2 ] units [R ^{1
When the} content of ² SiO _3/2 ] is more than 0.01 mol, the surface smoothness becomes low and the wear resistance becomes poor.
The molar ratio of the structural units is [R ¹ ₂ SiO _2/2 ] / [R ² SiO _3/2 ]
= 1 / (0-0.01), more preferably [R ¹ ₂ S
iO _2/2 ] / [R ² SiO _3/2 ] = 1 / (0 to 0.005). If the complex viscosity at 25 ° C. of this organopolysiloxane is less than 1 × 10 ⁴ mPa · s, the resulting coating does not exhibit sufficient adhesion to the substrate and surface smoothness, so that the organopolysiloxane of The complex viscosity at 25 ° C. needs to be 1 × 10 ⁴ mPa · s or more, preferably 1 × 10 ⁵ mPa · s or more. Here, the complex viscosity is easily measured by a commercially available general measuring device. For example, using a "controlled stress rheometer CS type" (manufactured by Bolin), "Ares viscoelasticity measuring system (for fluid measurement)" (manufactured by Rheometric Scientific), etc., a low fixed frequency, For example, it may be measured at 0.1 rad / s.

Organopoly (A) component of the present invention
Siloxane can be synthesized by known methods.
The presence of a catalyst such as an alkali metal hydroxide
Below, the general formula [R¹ ₂SiO]_m(m is a number from 3 to 7)
Cyclopolysiloxane, general formula R²Si (OR⁸)₃(here
And R⁸Is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
The equilibration reaction of ganotrialkoxysilane and water
The present invention provides an aqueous silicone composition
Yes, for that purpose, the organopolys that are the (A) component
Roxan should be an aqueous emulsion,
A stable emulsion can be obtained when the viscosity of the siloxane is high.
Since it is difficult to produce it, use a known emulsion polymerization method.
Is preferred. That is, the general formula [R¹ ₂SiO]_m(m is 3 to 7
The number) of cyclopolysiloxane and / or general
Formula R⁹O [R¹ ₂SiO]_nR⁹(Where R ⁹Is a hydrogen atom or
It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 1,000.
Of the organopolysiloxane represented by the general formula R²
Si (OR⁸)₃(R⁸Is the same as above)
Xysilane ([R¹ ₂SiO_2/2] / [R²SiO_3/2] = 1 /
If it is a constitutional unit of 0, do not mix this)
Disperse in water using an emulsifier and use it as a catalyst for acid, alkali, etc.
The polymerization reaction is carried out using
It can be easily obtained by activating.

In the aqueous silicone composition of the present invention
The component (B) functions as a cross-linking agent for the organopolysiloxane which is the component (A), and is an organotrioxy compound having no amide group, carboxyl group or epoxy group represented by the general formula R ³ Si (OR ⁴ ) _3. It is an alkoxysilane and / or a partial hydrolysis-condensation product thereof. R ³ in the formula has 1 to 1 carbon atoms.
20 monovalent hydrocarbon groups, specifically, a methyl group,
Alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, etc .;
Alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; cycloalkyl groups such as cyclohexyl groups and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms or mercapto groups. A group substituted with an organic group containing an acryloxy group or the like,
For example, 3,3,3-trifluoropropyl group, γ-methacryloxypropyl group, γ-acryloxypropyl group, γ
-A mercaptopropyl group etc. are mentioned. R in the formula
⁴ is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group and an ethyl group are particularly preferable.

Specific examples of the organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane and propyl. Triethoxysilane, butoxytrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, octadecyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mel Examples thereof include captopropyltrimethoxysilane, 3,3,3, -trifluoropropyltrimethoxysilane and the like.

If the amount of the component (B) is less than 0.01 parts by weight per 100 parts by weight of the component (A), the film obtained is not sufficiently cured, and if it exceeds 10 parts by weight, the base material is Since it does not exhibit adhesion with the component (A), it is preferably 0.01 to 10 parts by weight, more preferably 0.00
1 to 5 parts by weight.

In the aqueous silicone composition of the present invention
The component (C) is a component for improving the adhesion between the film of the aqueous silicone composition and the substrate, and is an amide group- and carboxyl group-containing organoalkoxysilane and / or its partial hydrolysis-condensation product. The amide group- and carboxyl group-containing organoalkoxysilane is obtained by reacting an amino group-containing alkoxysilane with a dicarboxylic acid anhydride. Specific examples of the amino group-containing alkoxysilane as a raw material for obtaining the amide group- and carboxyl group-containing organoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropylmethyldimethoxy. Silane, γ-aminopropylmethyldiethoxysilane, γ- (N-β-aminoethyl) aminopropyltrimethoxysilane, γ- (N-β-aminoethyl) aminopropyltriethoxysilane, γ- (N-β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ- (N-β-aminoethyl) aminopropylmethyldiethoxysilane, and the like. Specific examples of the dicarboxylic acid anhydride include phthalic acid anhydride and succinic acid anhydride. ,
Examples thereof include methylsuccinic anhydride, maleic anhydride, glutaric anhydride, and itaconic anhydride.

The component (C) can be easily obtained by mixing the amino group-containing alkoxysilane and the dicarboxylic acid anhydride in a parent solvent for the above raw materials, for example, alcohol at room temperature. In this case, since one molecule of the reaction product must contain at least one amide group and carboxyl group, it is present in one molecule of the amino group-containing alkoxysilane or its partially hydrolyzed condensate. It is necessary to react at least one molecule of dicarboxylic acid anhydride with one NH group. When the amount of the component (C) is less than 1 part by weight per 100 parts by weight of the component (A), the resulting coating does not exhibit adhesion to the substrate, and 10
When the amount is more than 10 parts by weight, the base material does not follow the base material and has no elongation. Therefore, it is preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight, relative to 100 parts by weight of the component (A).

In the aqueous silicone composition of the present invention
The component (D) is a component for improving the adhesion between the film of the silicone composition and the base material, and is an epoxy group-containing organoalkoxysilane and / or its partial hydrolysis-condensation product. Specific examples of the epoxy group-containing organoalkoxysilane include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ.
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4
Examples include -epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane. The amount of component (D) is
When the amount is less than 1 part by weight per 100 parts by weight of the component (A),
The obtained film does not exhibit adhesion to the base material, and if it exceeds 10 parts by weight, the film does not follow the base material and does not extend. Therefore, 1 to 10 parts by weight relative to 100 parts by weight of the component (A). Parts are preferred, and more preferably 3 to 7 parts by weight.

In the aqueous silicone composition of the present invention
The component (E) is a curing catalyst for crosslinking and curing the components of the composition of the present invention, and specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, tin octylate. Organozin compounds such as; zinc laurate, zinc acetate, zinc stearate, zinc octylate, and other organic zinc compounds; tetrapropyl titanate and its partially hydrolyzed condensate; tetrabutyl titanate and its partially hydrolyzed condensate; bisdi Examples include organic titanium compounds such as propoxy titanium, bis (acetylacetonate) titanium oxide, titanium lactate, and ammonium titanium lactate. When the curing catalyst is insoluble in water, it is preferable to emulsify and disperse the catalyst in water using an emulsifier in advance to prepare an aqueous emulsion. If the amount of the component (E) compounded is less than 0.01 parts by weight per 100 parts by weight of the component (A), the resulting coating will be insufficiently cured, and even if it exceeds 10 parts by weight, the effect will not be obtained. Since it does not change and becomes uneconomical, the amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the component (A).

In the aqueous silicone composition of the present invention
The component (F) is a component that improves the surface smoothness of the film of the aqueous silicone composition, and is spherical silicone rubber fine particles. This spherical silicone rubber has an average particle size of 0.5μ.
If it is less than m, the surface smoothness of the obtained film is deteriorated,
When the thickness exceeds μm, the film strength decreases and the wear resistance deteriorates. Therefore, the average particle size is preferably 0.5 to 50 μm, more preferably 1 to 20 μm. The component (F) can be produced by a known method. For example, when a curable silicone is emulsified and dispersed in water using a surfactant and then cured, an aqueous emulsion of spherical silicone rubber fine particles is obtained. . Since the present invention is an aqueous composition, the component (F) may be blended as this aqueous dispersion.

The above-mentioned curable silicone may be cured by any method such as addition reaction, condensation reaction curing, and ultraviolet curing. If the curable silicone is a solid substance having rubber elasticity upon curing, it may be a silicon atom. There is no particular limitation on the organic group or molecular structure bonded to the. When this curing is carried out by an addition reaction, the raw material curable silicone has an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and a silicon atom bonded in one molecule. Any mixed solution of an organohydrogenpolysiloxane having at least two hydrogen atoms may be used, and a platinum catalyst may be used for the addition reaction. Further, by preliminarily blending with the curable silicone as a raw material, the component (F) can contain silicone oil, silane, organic powder, inorganic fine powder and the like. Complex viscosity is 1 × 10 ² ~
It is also one of the preferred embodiments to add and mix 1 × 10 ⁸ mPa · s of trialkylsiloxy-blocked dialkylpolysiloxane at both ends to the component (F). The shape of the component (F) does not have to be a true sphere, but includes a case where the cross section has a shape approximate to a circle such as an ellipse. The blending amount of the component (F) is 10 for the component (A)
If the amount is less than 5 parts by weight relative to 0 parts by weight, the resulting coating has poor surface smoothness and poor wear resistance, and 1
When the amount is more than 00 parts by weight, the film strength is lowered and the wear resistance is deteriorated.
It is preferably part by weight, more preferably 10 to 70 parts by weight.

In the aqueous silicone composition of the present invention
The component (G) is a component that improves the surface smoothness and abrasion resistance of the film of the aqueous silicone composition formed on the substrate, and is the particle surface of silica-based and / or polyorganosilsesquioxane-based particles. Is a hydrophobic fine particle silylated with a trialkylalkoxysilane or a trialkylsilanol. The silica-based and / or polyorganosilsesquioxane-based fine particles include silica-based fine particles having a unit represented by the formula [SiO _4/2 ] as a constitutional unit, a unit represented by the formula [SiO _4/2 ] and a general formula. [R ⁶ Si
O _3/2 ], a fine particle having a unit represented by a unit of
It is any of polyorganosilsesquioxane-based fine particles having a unit represented by the general formula [R ⁶ SiO _3/2 ] as a constitutional unit. The fine particles [SiO _4/2] and [R ⁶ SiO
_3/2 ], the ratio of the two is arbitrary. In addition, a unit represented by the general formula [R ¹⁰ ₂ SiO _2/2 ] (wherein R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms),
A unit represented by the general formula [R ¹¹ ₃ SiO _1/2 ] (here, R ^{1 1}
May have a C1-20 monovalent hydrocarbon group) as a constituent unit, but if the content of these units is high, the fine particles become soft and the strength of the resulting coating film decreases, resulting in abrasion resistance. Becomes worse. Therefore, in order to avoid this [Si
O _4/2 ] and / or [R ⁶ SiO _3/2 ] unit content is 7
It is necessary to be 0 mol% or more, preferably 90 mol% or more.

R ⁶ in the constituent unit of the component (G) in the present invention is one or more monovalent organic groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, Alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl; alkenyl groups such as vinyl, allyl; phenyl group, tolyl group Aryl groups such as; aralkyl groups such as β-phenylpropyl, and trifluoropropyl in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced with halogen atoms, β- (perfluorobutyl) ethyl, β- (perfluoro) Halogenated hydrocarbon groups such as octyl) ethyl and the like Selected from organic groups in which some or all of the hydrogen atoms of the hydrocarbon groups are substituted with functional groups such as amino, epoxy, acryloxy, methacryloxy, mercapto, cyano. Of these, a methyl group and / or a vinyl group is most preferable.

The hydrophobic fine particles of the component (G) in the present invention have the particle surface of the silica-based and / or polyorganosilsesquioxane-based fine particles represented by the general formula [R ⁵ ₃ SiO _1/2 ].
It is silylated with the unit shown by. R ⁵ is one or more monovalent organic groups having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, Alkyl groups such as tetradecyl, hexadecyl, octadecyl, eicosyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl; alkenyl groups such as vinyl, allyl; aryl groups such as phenyl group, tolyl group; aralkyl groups such as β-phenylpropyl and Trifluoropropyl in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced with halogen atoms, β- (perfluorobutyl) ethyl, β-
Halogenated hydrocarbon groups such as (perfluorooctyl) ethyl and some or all of the hydrogen atoms of these hydrocarbon groups are amino, epoxy, acryloxy, methacryloxy,
It is selected from organic groups substituted with functional groups such as mercapto and cyano. Of these, a methyl group is most preferred.

Hydrophobic fine particles of component (G) in the present invention
Is the skin obtained when the average particle size is larger than 1,000 nm.
The film has low strength and poor wear resistance, and the average particle size is 5n.
Since it is practically difficult to obtain a product having a size of less than m,
The average particle size is 5 nm to 1,000 nm, preferably
10 nm to 500 nm, more preferably 10 nm to 10 nm
It is in the range of 0 nm. The component (G) of the present invention is anionic
Silica system containing surfactant and acidic catalyst and / or
Aqueous dispersion of polyorganosilsesquioxane fine particles
To the general formula R ^Five ₃SiOR¹²(R^FiveIs the same as above, R¹²Is charcoal
Trialkyl represented by a monovalent hydrocarbon group having a prime number of 1 to 6)
Alkoxysilane or general formula R^Five ₃SiO (R^FiveIs the above
The same) as the trialkylsilanol
Or react with a cationic surfactant and an alcohol.
Silica-based and / or polyorgano containing potassium catalyst
Trilucidation in an aqueous dispersion of silsesquioxane-based particles
Addition of lualkoxysilane or trialkylsilanol
It is obtained by a condensation reaction. Book
Since the invention is an aqueous composition, the component (G) is
It may be blended as a dispersion.

Silica-based and / or used in the present invention
Alternatively, the aqueous dispersion of polyorganosilsesquioxane-based fine particles is not particularly limited, for example, water glass as a starting material, the alkali is extracted by an ion exchange method,
Obtained by growing the nuclei of the particles until they become silica sol,
So-called colloidal silica slurry can be used. Further, an aqueous dispersion obtained by blending an anionic surfactant or a cationic surfactant with this colloidal silica slurry, adding organotrialkoxysilane under acidic or alkaline conditions, and hydrolyzing and condensing it can be used. As described in JP-B-52-1219, an aqueous dispersion of fine particles of polyorganosilsesquioxane, that is,
Organotrialkoxysilane or a partial hydrolyzed condensate thereof is added to water containing an anionic surfactant and an acidic catalyst or water containing a cationic surfactant and an alkaline catalyst to carry out a hydrolytic condensation reaction. Aqueous dispersions obtained by the method can be used.

In the present invention, when an aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based fine particles is produced using a large amount of organotrialkoxysilane, the amount of alcohol as a by-product increases, Since the storage stability of the aqueous silicone composition of the present invention obtained using this as a raw material is poor, a colloidal silica slurry or an aqueous dispersion obtained by adding an organotrialkoxysilane to the colloidal silica slurry and hydrolyzing and condensing the same is used. Preference is given to using. When a colloidal silica slurry is used as an aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based fine particles,
Since it contains no surfactant, it is necessary to add an anionic surfactant or a cationic surfactant. If an aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based fine particles, which already contains an anionic surfactant or a cationic surfactant, is used, the anionic surfactant may be added as necessary. Alternatively, a cationic surfactant is added. Furthermore, a small amount of a nonionic surfactant and / or an amphoteric surfactant may be used in combination.

In the present invention, when the surfactant mixed in the aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based fine particles is an anionic surfactant, an acidic catalyst is added. The acidic catalyst is not particularly limited as long as it is an acidic substance, but a strong acid having a low pH value in a small amount is preferable, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, alkyl sulfuric acid, alkylbenzene sulfonic acid, and polyoxyethylene alkyl ether sulfuric acid. Can be mentioned. When alkyl sulfuric acid, alkyl benzene sulfonic acid, or polyoxyethylene alkyl ether sulfuric acid is used, it can have both surface activity and acid catalysis. If the pH of the aqueous dispersion is higher than 4.0, the reaction rate of the trialkylalkoxysilane or trialkylsilanol will be poor, and even if the pH is less than 1.0, Since no improvement can be expected, p of the aqueous dispersion is
The amount of H is required to be in the range of 1.0 to 4.0, and preferably the amount of pH is 1.5 to 3.0.

In the present invention, when the surfactant mixed in the aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based fine particles is a cationic surfactant, an alkaline catalyst is added. The alkaline catalyst is not particularly limited as long as it is an alkaline substance, and examples thereof include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. Alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia,
Tetraammonium oxide or monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentaamine, dimethylamine, diethylamine, trimethylamine, triethanolamine,
Amines such as ethylenediamine can be used.
When the pH of the aqueous dispersion is less than 9.0, the reaction rate of the trialkylalkoxysilane or the trialkylsilanol becomes poor, and the amount of the alkaline catalyst to be added is p.
Since an improvement in the reaction rate cannot be expected even if H is higher than 13.0, the amount of the aqueous dispersion is required to be in the range of 9.0 to 13.0, preferably the pH is 10.0. 12.0
Is the amount.

The trialkylalkoxysilane which is a hydrophobizing agent for the surface of silica-based and / or polyorganosilsesquioxane-based fine particles used in the production of the hydrophobic fine particles of the component (G) in the present invention is trialkylmethoxysilane. Examples include silane, trialkylethoxysilane, trialkylpropoxysilane, trialkylbutoxysilane, trialkylpentoxysilane, and trialkylhexoxysilane, but from the viewpoint of good reactivity, trimethylmethoxysilane or trimethylethoxysilane is preferable. preferable.

The hydrophobic fine particles of the component (G) in the present invention are trialkylalkoxy with stirring in an aqueous dispersion of silica-based and / or polyorganosilsesquioxane-based particles containing a surfactant and a catalyst. It is produced by adding silane or trialkylsilanol. If the amount of the trialkylalkoxysilane or trialkylsilanol to be added is less than 0.1 part by weight based on 100 parts by weight of the silica-based and / or polyorganosilsesquioxane-based fine particles, the surface treatment is not sufficiently performed, and Since the amount of surface treatment does not increase even if the amount is more than 0.5 parts by weight, 0.1 to 20 parts by weight is necessary, preferably 0.5 to
It is in the range of 10 parts by weight. The temperature at which the trialkylalkoxysilane or the trialkylsilanol is charged may be between the freezing point and the boiling point of the aqueous dispersion. In order to complete the reaction, it is preferable to continue stirring for a while after the addition. Then, if necessary, it is neutralized with an acidic substance or an alkaline substance.

In the aqueous silicone composition of the present invention,
The amount of component (G) is 20 per 100 parts by weight of component (A).
When the amount is less than 100 parts by weight, the resulting film has low strength and poor wear resistance, and when the amount exceeds 200 parts by weight, the film does not follow the base material and has no elongation. Therefore, 100 parts by weight of the component (A) is used. It is preferably 20 to 200 parts by weight, more preferably 40 to 150 parts by weight.

The aqueous silicone composition of the present invention comprises (A)
It can be obtained by mixing the components of (G), and the mixing method may be carried out by using a conventionally known stirring mixer equipped with stirring blades such as paddle type and anchor type, and (B) and (C). Although the components (D) and (D) can be mixed as they are, the components (A), (F) and (G) are emulsified and dispersed in water using a surfactant as described above. When the component (E) is not water-soluble, it is desirable that the component (E) be emulsified and dispersed in water by using a surfactant in advance and be blended as an aqueous emulsion. Then dilute with water if necessary.

The aqueous silicone composition of the present invention contains carbon black, fluororesin powder, melamine resin powder, acrylic resin powder, polycarbonate resin powder, nylon resin, if necessary, within a range that does not impair the effects of the present invention. Powder, paraffin wax, polyethylene wax,
It is optional to add silicone oil, various organic or inorganic pigments, thickeners, defoamers, preservatives and the like.

When the aqueous silicone composition of the present invention is used for the surface coating of a rubber article, it has excellent adhesion of the film to the base material, abrasion resistance of the film, and surface smoothness of the film as compared with conventional products. Becomes Examples of the rubber material which can be surface coated with the aqueous silicone composition of the present invention include natural rubber, EPDM, SBR, chloroprene rubber,
Examples thereof include isoprene-isobutylene rubber and nitrile rubber, and the rubber article made of these rubber materials may be in the form of sponge or solid. Also,
Examples of the fiber material which can be surface-coated with the aqueous silicone composition of the present invention are synthetic fibers such as nylon, polyester, acrylic, vinylon and acetate, or natural fiber materials such as cotton, silk and wool. As the surface coating method of each of the above materials, after coating the aqueous silicone composition by a method such as brush coating, spray coating, roll coating, dip coating, or knife coating,
The coating may be cured at room temperature or by heating and drying. At this time, the thickness of the cured film is 0.1 to 20 μm.
The range of m is preferably 0.5 to 10 μm, and in particular, the rubber article thus treated has a coating surface excellent in abrasion resistance and surface smoothness. It is useful as a strip material, an O-ring, a gasket, a sealing material such as various packings, and a rubber hose material.

[0033]

EXAMPLES Next, the components (A), (C) and (F) of the present invention
The present invention will be described in more detail with reference to Preparation Examples, Examples and Comparative Examples of the component and the component (G), but the present invention is not limited thereto. The complex viscosity in the examples and the surface smoothness and wear resistance of rubber articles were evaluated according to the following methods.

(Measurement Method of Complex Viscosity) Controlled
Using a stress rheometer CS type (manufactured by Borin Co.), a 20 mmφ cone plate was used as a fixture, and the complex viscosity at a fixed frequency of 0.1 rad / sec was measured at 25 ° C. (Evaluation method of surface smoothness) Two solid rubbers (10 mm x 50 mm, thickness 2 mm) made of EPDM were attached to glass plates (5
0 mm × 50 mm) as shown in FIG. 1, and using the dynamic friction coefficient measuring device shown in FIG. 2, load 1 kg.
The coefficient of kinetic friction with the glass plate was measured under conditions of a pulling speed of 100 mm / min.

(Evaluation Method of Abrasion Resistance) Solid rubber (50 mm × 50 mm, thickness 2 mm) made of EPDM whose surface is coated with the aqueous silicone composition of the present invention is strongly rubbed twice with a thumb to remove the coating film. I observed whether or not. Furthermore, a sponge rubber made of EPDM [15 mm] having a coating film coated on the surface with a small amount of dropout and an aqueous silicone composition which did not drop off [15 mm
× 150mm, thickness 2mm, hardness (according to JIS A) 3
6, specific gravity of 0.63], using a paper file AA80 in a wear resistance tester shown in FIG. 3, using a surface-polished glass cell (line contact, line width 5 mm), thrust load 3
The number of reciprocating rubs until the rubber surface was abraded was measured when the reciprocating rub was carried out under the conditions of a friction speed of 60 reciprocations / min and a friction stroke of 70 mm over 50 g.

[Preparation example 1 of component (A)] 350 g of octamethylcyclotetrasiloxane and 7 g of a 10% aqueous solution of dodecylbenzenesulfonic acid were charged into a 1 liter glass beaker and stirred at 6,000 rpm using a homomixer. Phase inversion occurs from W / O type to O / W type,
Although thickening was observed, stirring was continued for 10 minutes.
Then, with stirring at 2,000 rpm, 343 g of water
Was added, and the mixture was passed through a high-pressure homogenizer twice at a pressure of 30 MPa, and a stable emulsion was obtained. Next,
This emulsion was transferred to a glass flask having a volume of 1 liter equipped with a stirrer, a thermometer and a reflux condenser, reacted at 70 ° C. for 6 hours, aged at 15 ° C. for 12 hours, and then 13 g of 10% sodium carbonate aqueous solution. And pH
The mixture was neutralized to 6.6 to obtain a uniform white turbid aqueous emulsion (aqueous emulsion A-1). When several g of this aqueous emulsion A-1 was weighed and dried in a hot air circulation type constant temperature bath set at 105 ° C. for 3 hours, the amount of dry residue was measured and the residual rate was calculated.
It was 46.0%. Isopropyl alcohol was added to this aqueous emulsion to break the emulsion, and then siloxane was extracted and dried at 105 ° C. for 24 hours, and the complex viscosity was measured and found to be 2.3 × 10 ⁶ mPa · s. It was

[Preparation example 2 of component (A)] 350 g of octamethylcyclotetrasiloxane, 1.3 g of phenyltriethoxysilane and 7 g of a 10% aqueous solution of dodecylbenzenesulfonic acid were placed in a 1 liter glass beaker and a homomixer was used. After stirring at 6,000 rpm,
Although phase inversion from the W / O type to the O / W type occurred and thickening was observed, stirring was continued for 10 minutes. Then 2,000
While stirring at 0 rpm, 343 g of water was added, and the pressure was 30
After passing twice through a high pressure homogenizer at MPa, a stable emulsion was obtained. Next, this emulsion was transferred to a glass flask having a volume of 1 liter equipped with a stirrer, a thermometer, and a reflux condenser, reacted at 70 ° C. for 6 hours, aged at 15 ° C. for 24 hours, and then 10% carbonic acid. 13 g of an aqueous sodium solution was added and neutralized to pH 6.4 to obtain a uniform white turbid aqueous emulsion (aqueous emulsion A-2).
A few g of this aqueous emulsion A-2 was weighed and dried for 3 hours in a hot air circulation type constant temperature bath set at 105 ° C., and the amount of dried residue was measured, and the residual rate was calculated to be 46.2. %Met. Isopropyl alcohol was added to this aqueous emulsion to break the emulsion, and the siloxane was extracted to
When it was dried at 05 ° C for 24 hours and the complex viscosity was measured,
This showed 2.8 × 10 ⁷ mPa · s.

[Preparation example 3 of component (A)] 350 g of octamethylcyclotetrasiloxane and 7 g of a 10% aqueous solution of dodecylbenzenesulfonic acid were placed in a 1 liter glass beaker and stirred at 6,000 rpm using a homomixer. Phase inversion occurs from W / O type to O / W type,
Although thickening was observed, stirring was continued for 10 minutes.
Then, with stirring at 2,000 rpm, 343 g of water
Was added, and the mixture was passed through a high-pressure homogenizer twice at a pressure of 30 MPa, and a stable emulsion was obtained. Next,
This emulsion was transferred to a glass flask having a volume of 1 liter equipped with a stirrer, a thermometer, and a reflux condenser, reacted at 85 ° C. for 16 hours, and then a 10% sodium carbonate aqueous solution 1
3 g was added and neutralized to pH 6.4 to obtain a uniform white turbid aqueous emulsion (aqueous emulsion A-3). A few g of this aqueous emulsion A-3 was weighed and dried for 3 hours in a hot air circulation type constant temperature bath set at 105 ° C., and the amount of the dry residue was measured, and the residual ratio was calculated to be 46.2. %Met. Isopropyl alcohol was added to this aqueous emulsion A-3 to break the emulsion, and then siloxane was extracted and the temperature was adjusted to 105 ° C.
It was dried for 24 hours and the complex viscosity was measured.
It was × 10 ³ mPa · s.

[Preparation Example of Component C] A glass flask having a capacity of 1 liter equipped with a stirrer, a thermometer, and a reflux condenser was charged with 108 g of maleic anhydride and 350 g of ethanol and uniformly dissolved, and then γ-aminopropyl 242 g of triethoxysilane was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the reaction was further continued by stirring for 1 hour to obtain a pale yellow transparent solution (solution C). A few g of this solution C was weighed and dried for 3 hours in a hot air circulation type constant temperature bath set at 105 ° C., and the amount of dried residue was measured, and the residual rate was calculated to be 49.5%. When the reaction product in this solution was subjected to instrumental analysis such as GPC, IR, and NMR, the components shown below were the main components. HOOCCH = CHCONHC ₃ H ₆ Si (OC ₂ H ₅ ) ₃

[Preparation Example 1 of Component (F)] [Formula 1]
In a glass beaker having a capacity of 1 liter, 294 g of methylvinylsiloxane having a complex viscosity of 10 mPa · s and 79 g of methylhydrogenpolysiloxane having a complex viscosity of 200 mPa · s represented by the following formula [Chem. Then, it was dissolved by stirring with a homomixer at 2,000 rpm. Then, 1.4 g of polyoxyethylene (additional mol number: 9 mol) lauryl ether and 28 g of water were added, and the mixture was stirred at 6,000 rpm using a homomixer. As a result, phase inversion from W / O type to O / W type occurred. A thickening was observed, and stirring was continued for 15 minutes. Then 2,000
When 298 g of water was added while stirring at 0 rpm,
A uniform white emulsion was obtained. This emulsion was transferred to a 1-liter glass flask equipped with a stirrer and stirred at room temperature with 1.1 g of a toluene solution of chloroplatinic acid-olefin complex (platinum content: 0.5%) and polyoxyethylene (additional mole). Number 9 mol) 0.7 g of lauryl ether
The mixture was added and stirred for 12 hours to obtain an aqueous emulsion (aqueous emulsion F-1). The average particle size of this aqueous emulsion F-1 was measured using Multisizer II (trade name, manufactured by Coulter Co.), and it was 4 μm. Count this aqueous emulsion
g Weigh and 3 in a hot air circulation type thermostat set at 105 ° C
After drying for an hour, the amount of dry residue was measured, and the residual rate was calculated to be 46.2%. The dry residue was a white rubber powder.

[0041]

[Chemical 1]

[0042]

[Chemical 2]

[Preparation Example 2 of Component (F)] 350 g of methylvinylsiloxane having a complex viscosity of 10 mPa · s represented by the above-mentioned formula [Chemical formula 1] and the complex viscosity represented by the above-mentioned formula [Chemical formula 2] 100 g of 200 mPa · s methylhydrogenpolysiloxane and 50 g of dimethylpolysiloxane having a complex viscosity of 5.8 × 10 ⁶ mPa · s represented by the following formula [Chemical Formula 3] and a glass of 1 liter in volume equipped with a stirrer The mixture was placed in a flask and stirred at room temperature for 8 hours to uniformly dissolve it. Next, 350 g of this melt was transferred to a glass beaker having a capacity of 1 liter, and polyoxyethylene (addition mole number 9
(Mol) lauryl ether (2.8 g) and water (35 g) were added, and the mixture was stirred at 6,000 rpm using a homomixer.
Phase inversion occurred from W / O type to O / W type, thickening was observed,
Furthermore, stirring was continued for 15 minutes. Then 2,000r
When 307 g of water was added while stirring at pm,
A uniform white emulsion was obtained. This emulsion was transferred to a 1-liter glass flask equipped with a stirrer and stirred at room temperature with 1.1 g of a toluene solution of chloroplatinic acid-olefin complex (platinum content: 0.5%) and polyoxyethylene (additional mole). Number 9 mol) 4.2 g of lauryl ether
And the mixture is stirred for 12 hours, and the aqueous emulsion F is added.
-2 was obtained. The average particle size of this aqueous emulsion F-2 was measured using Multisizer II (trade name, manufactured by Coulter Co.), and it was 4 μm. Weigh several g of this aqueous emulsion,
After drying for 3 hours in a hot air circulation type thermostat set at 105 ° C, the amount of dry residue was measured and the residual rate was calculated.
It was 50.9%, and the dry residue was white rubber powder.

[0044]

[Chemical 3]

[Preparation Example 1 of component (G)] Snowtex O [Colloidal silica slurry manufactured by Nissan Chemical Industries, Ltd., trade name, concentration 20] in a 1 liter glass flask.
%, Particle size 10 to 20 nm] 986 g and dodecylbenzene sulfonic acid 2 g were charged, mixed and dissolved, and the temperature of the aqueous solution was set to 20 ° C., and pH was 2.0. While stirring, 10 g of trimethylsilanol was added, and the mixture was stirred for 1 hour while maintaining the liquid temperature at 15 to 25 ° C. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then 1.9 g of triethanolamine was added for neutralization to obtain an aqueous dispersion of silica fine particles whose surface had been trimethylsilylated (fine particle dispersion G- 1) was obtained. A few g of this fine particle dispersion G-1 was weighed and dried in a hot air circulation type constant temperature bath set at 105 ° C. for 3 hours, and then the dry residue was measured, and the residual ratio was calculated to be 21.1%. The average particle size was 22 nm when measured using a particle size analyzer N4Plus (trade name, manufactured by Coulter Co.).

[Preparation example 2 of component (G)] A 1 liter glass flask was charged with 974 g of colloidal silica slurry Snowtex O (described above) and 2 g of dodecylbenzenesulfonic acid, mixed and dissolved, and the temperature of the aqueous solution was adjusted to 20. ℃
As a result, the pH was 2.0. Liquid temperature 15 to 2
While maintaining the temperature at 5 ° C., 20 g of vinyltrimethoxysilane was added dropwise over 20 minutes while stirring, and then 2 g of trimethylsilanol was added and stirred for 1 hour. In addition, increase the liquid temperature to 50
While stirring at -60 ° C for 1 hour, triethanolamine (1.9 g) was added for neutralization, and an aqueous dispersion of fine particles of silica-polyvinylsilsesquioxane polymer whose surface was trimethylsilylated (fine particle dispersion) G-2) was obtained. Several g of this fine particle dispersion G-2 is weighed and the temperature is 105 ° C.
After drying for 3 hours in the hot air circulation type thermostat set to 1, the dry residue was measured and the residual rate was calculated to be 21.6.
%Met. It was 21 nm when the average particle diameter was measured using the particle diameter measuring device N4Plus.

[Preparation example 3 of component (G)] A 1-liter glass flask was charged with 847 g of ion-exchanged water and 2 g of dodecylbenzenesulfonic acid and mixed and dissolved. When the temperature of the aqueous solution was 20 ° C., the pH was 2 It was 1. While stirring at a liquid temperature of 15 to 25 ° C., 148 g of methyltrimethoxysilane was added dropwise over 4 hours, 2 g of trimethylsilanol was then added, and the mixture was stirred for 1 hour. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then 1 g of triethanolamine was added to neutralize the solution, and an aqueous dispersion of fine particles of polymethylsilsesquioxane having trimethylsilylated particle surfaces (fine particle dispersion). Liquid G-3) was obtained. A few g of this fine particle dispersion G-3 was weighed and dried in a hot air circulation type constant temperature bath set at 105 ° C. for 3 hours, and the dry residue was measured, and the residual ratio was calculated to be 8.0%. Met. The average particle size was 26 nm when measured using a particle size analyzer N4Plus.

[Preparation Example 4 of Component (G)] A 1-liter glass flask was charged with 958 g of colloidal silica slurry Snowtex O (described above) and 2 g of dodecylbenzenesulfonic acid, mixed and dissolved, and the temperature of the aqueous solution was adjusted to 20. ℃
As a result, the pH was 2.0. Liquid temperature 15 to 2
While stirring at 5 ° C., 20 g of vinyltrimethoxysilane was added dropwise over 20 minutes, and the mixture was stirred for 1 hour. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then 1.9 g of triethanolamine was added for neutralization to obtain an aqueous dispersion of silica-polyvinylsilsesquioxane polymer fine particles (fine particle dispersion G -4) was obtained. A few g of this fine particle dispersion G-4 was weighed and dried for 3 hours in a hot-air circulation type constant temperature bath set at 105 ° C., and the dry residue was measured, and the residual ratio was calculated to be 21.3%. Met. When the average particle size was measured using a particle size measuring device N4Plus, 2
It was 1 nm.

[Preparation example 5 of component (G)] A 1-liter glass flask was charged with 847 g of ion-exchanged water and 2 g of dodecylbenzenesulfonic acid and mixed and dissolved. The temperature of the aqueous solution was 20 ° C. It was 1. While maintaining the liquid temperature at 15 to 25 ° C. and stirring, 150 g of methyltrimethoxysilane was added dropwise over 4 hours, and the mixture was stirred for 1 hour. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then 1 g of triethanolamine was added for neutralization to obtain an aqueous dispersion of fine particles of polymethylsilsesquioxane (fine particle dispersion G-5). . This fine particle dispersion G
A few g of -5 was weighed and dried for 3 hours in a hot air circulation type constant temperature bath set at 105 ° C., and the amount of dried residue was measured, and the residual rate was calculated to be 8.1%. When the average particle size was measured using a particle size measuring device N4Plus, it was 26 nm.
Met.

[Preparation example 6 of component (G)] Fine particle dispersion G
As -6, Snowtex O (mentioned above) was used as it was.

Examples 1 to 6 Component (A), component (C), component (F), component (G) obtained in each of the above preparation examples and the following
The component (B), the component (D) and the component (E) are mixed in the composition shown in Table 1 to prepare an aqueous silicone composition as a surface treatment composition. 2 mm) and EPDM sponge rubber [thickness 2 m
m, hardness 36 (value measured by JIS A), specific gravity of 0.
63] on the surface with a brush, and left for 2 minutes in a hot air circulation type constant temperature bath adjusted to 105 ° C to perform coating,
Evaluate the surface smoothness and wear resistance according to the above method,
The results are shown in Table 1.

Component (B) Silane B-1: Phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), Silane B-2: Methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), (D) Component silane D: γ-glycidoxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd.], (E) component aqueous emulsion E: 30% dibutyltin dilaurate emulsion.

[0053]

[Table 1]

Comparative Examples 1 to 11 Component (A), Component (C), Component (F), Component (G) obtained in the above Preparation Example and the above
Component (B), component (D), and component (E) were mixed in the composition shown in Table 2 to prepare an aqueous silicone composition, and the EPDM rubber was surface-treated by using these in the same manner as in the example. The surface smoothness and abrasion resistance were evaluated according to the above-mentioned method, and the results are shown in Table 2.

[0055]

[Table 2]

(Summary of Examples) The aqueous silicone compositions used in Examples 1 to 6 all had the requirements described in the claims of the present invention, and the surface smoothness of the obtained coatings was The abrasion resistance proved to be excellent.

(Summary of Comparative Example) As in Comparative Example 1 (A)
When the complex viscosity of the component organopolysiloxane is low, the surface smoothness and wear resistance are poor. When the organotrialkoxysilane of the component (B) is not blended as in Comparative Example 2, The film is not sufficiently cured, and the alkenylalkoxysilane containing the amide group and the carboxyl group of the component (C) and the organoalkoxysilane containing the epoxy group of the component (D) are not added as in Comparative Example 3. In this case, the surface smoothness and abrasion resistance are poor, and as in Comparative Example 4, (C) component-containing organoalkoxysilane and (D) component-epoxy group-containing organoalkoxysilane. If the amount of silane added is too large, the abrasion resistance becomes poor, and as in Comparative Example 5, the silicone rubber fine particles of component (F) are mixed. If not, surface smoothness, it becomes poor abrasion resistance, as in Comparative Example 6
If the amount of the silicone rubber fine particles as the component (F) added is too large, the abrasion resistance becomes poor. When the hydrophobic fine particles of the component (G) are not blended as in Comparative Example 7, the abrasion resistance is poor, and as in Comparative Example 8.
When the addition amount of the hydrophobic fine particles as the component (G) is too large,
When the component (G) is fine particles which are not hydrophobized with a trialkylsilyl group as in Comparative Examples 9, 10 and 11, the abrasion resistance becomes poor and the surface smoothness and abrasion resistance are reduced. It becomes poor in sex.

[0058]

The abrasion resistance and surface smoothness of the film of rubber material or fiber material coated with the aqueous silicone composition of the present invention are more excellent than those of conventional products.

[Brief description of drawings]

FIG. 1 is a sketch of a sample for measuring a dynamic friction coefficient used in an example.

FIG. 2 is a schematic vertical cross-sectional view of the dynamic friction coefficient measuring device used in the examples.

FIG. 3 is a schematic perspective view of an abrasion resistance test device used in Examples.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/08 C09D 183/08 // (C08L 83/04 C08L 83:08 83:08 83:06 83: 06) F-term (reference) 4J002 CP031 CP053 CP092 DJ017 EZ006 FB097 FB267 FD017 FD146 4J038 DL021 DL022 DL031 DL032 DL052 DL082 DL111 JC38 JC39 KA04 KA09 MA08 MA10 NA01 NA11 PC07 PC10 PC10

Claims (8)

[Claims] 1. A unit represented by the general formula [R ¹ ₂ SiO _2/2 ] and a unit represented by the general formula [R ² SiO _3/2 ] (wherein R ¹ and R ² have 1 carbon atoms). To 20 of one or more monovalent hydrocarbon groups) as a constitutional unit, and the molar ratio thereof is [R ¹ ₂ SiO _2/2 ] / [R ² SiO _3/2 ] = 1 / (0 0.0
1) and the complex viscosity at 25 ° C. is 1 × 10 ⁴ m
100 parts by weight of organopolysiloxane with a terminal hydroxyl group of Pa · s or more, (B) General formula R ³ Si (OR ⁴ ) ₃ (wherein R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a carbon atom). (1 to 6 monovalent hydrocarbon group) and does not contain an amide group, a carboxyl group and an epoxy group and / or an organotrialkoxysilane and / or a partial hydrolysis condensate thereof 0.01 to 10 parts by weight, C) Amido group- and carboxyl group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight, (D) Epoxy group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight Part, (E) curing catalyst 0.01 to 10 parts by weight, (F) spherical silicone rubber fine particles having an average particle size of 0.5 to 50 μm 10 to 100 parts by weight, (G) formula [SiO _4/2 ] Indicated by Unit (here represented by the surface general formula of the silica-based fine particles as constituent units [R ⁵ ₃ SiO _1/2], R ⁵ is from 1 to 20 carbon atoms, one or two or more monovalent organic An aqueous silicone composition comprising 20 to 200 parts by weight of hydrophobic fine particles having an average particle diameter of 5 to 1,000 nm, which are silylated with a base group. 2. A unit represented by the general formula [R ¹ ₂ SiO _2/2 ] and a unit represented by the general formula [R ² SiO _3/2 ] (wherein R ¹ and R ² have 1 carbon atoms). To 20 of one or more monovalent hydrocarbon groups) as a constitutional unit, and the molar ratio thereof is [R ¹ ₂ SiO _2/2 ] / [R ² SiO _3/2 ] = 1 / (0 0.0
1) and the complex viscosity at 25 ° C. is 1 × 10 ⁴ m
100 parts by weight of organopolysiloxane with a terminal hydroxyl group of Pa · s or more, (B) General formula R ³ Si (OR ⁴ ) ₃ (wherein R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a carbon atom). (1 to 6 monovalent hydrocarbon group) and does not contain an amide group, a carboxyl group and an epoxy group and / or an organotrialkoxysilane and / or a partial hydrolysis condensate thereof 0.01 to 10 parts by weight, C) Amido group- and carboxyl group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight, (D) Epoxy group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight Parts, (E) curing catalyst 0.01 to 10 parts by weight, (F) 10 to 100 parts by weight of spherical silicone rubber fine particles having an average particle size of 0.5 to 50 μm, (G) formula [SiO _4/2 ] Unit indicated by Fine the general formula [R ⁶ Si
O _3/2 ] (wherein R ⁶ is one or more monovalent organic groups having 1 to 20 carbon atoms) and the surface of fine particles having a unit as a constitutional unit is represented by the general formula [ R ⁵ ₃ SiO _1/2 ]
(Here, R ⁵ is one or two or more monovalent organic groups having 1 to 20 carbon atoms.) Silylated hydrophobic units having an average particle size of 5 to 1,000 nm Aqueous silicone composition containing 20 to 200 parts by weight of hydrophilic fine particles as a main component. 3. A unit represented by the general formula [R ¹ ₂ SiO _2/2 ] and a unit represented by the general formula [R ² SiO _3/2 ] (wherein R ¹ and R ² have 1 carbon atoms). To 20 of one or more monovalent hydrocarbon groups) as a constitutional unit, and the molar ratio thereof is [R ¹ ₂ SiO _2/2 ] / [R ² SiO _3/2 ] = 1 / (0 0.0
1) and the complex viscosity at 25 ° C. is 1 × 10 ⁴ m
100 parts by weight of organopolysiloxane with a terminal hydroxyl group of Pa · s or more, (B) General formula R ³ Si (OR ⁴ ) ₃ (wherein R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a carbon atom). (1 to 6 monovalent hydrocarbon group) and does not contain an amide group, a carboxyl group and an epoxy group and / or an organotrialkoxysilane and / or a partial hydrolysis condensate thereof 0.01 to 10 parts by weight, C) Amido group- and carboxyl group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight, (D) Epoxy group-containing organoalkoxysilane and / or partial hydrolysis condensate thereof 1 to 10 parts by weight Parts, (E) curing catalyst 0.01 to 10 parts by weight, (F) 10 to 100 parts by weight of spherical silicone rubber fine particles having an average particle size of 0.5 to 50 μm, (G) general formula [R ⁶ SiO _{3 / 2]} (here , R ⁶ is from 1 to 20 carbon atoms, one or two or more monovalent organic group.) The surface of polyorganosilsesquioxane particles as constituent units unit represented by the general formula [R ⁵ ₃ Si
O _1/2 ] (wherein R ⁵ is one or more monovalent organic groups having 1 to 20 carbon atoms) and silylated with an average particle size of 5 to 5. An aqueous silicone composition comprising 20 to 200 parts by weight of 1,000 nm hydrophobic fine particles as a main component. 4. The hydrophobic fine particles of (G) have the formula [SiO _4/2 ].
And a unit represented by the general formula [R ⁷ SiO _3/2 ] (where:
R ⁷ is a methyl group and / or a vinyl group. 4. The aqueous silicone composition according to claim 2, wherein the surface of fine particles having a unit represented by the formula (1) as a constituent unit is silylated. 5. The hydrophobic fine particles of (G) have the general formula [R ⁷ Si
O _3/2 ] (wherein R ⁷ is a methyl group and / or a vinyl group.) The surface of the polyorganosilsesquioxane fine particles having the unit shown as a constituent unit is silylated. The aqueous silicone composition according to claim 3, characterized in that 6. The hydrophobic fine particles of (G) have the formula [(CH ₃ ) ₃
The aqueous silicone composition according to any one of claims 1 to 5, which is silylated with a unit represented by SiO _1/2 ]. 7. A hydrophobic fine particle comprises a trialkylalkoxysilane or a trialkylsilanol added to an aqueous dispersion of silica fine particles and / or polyorganosilsesquioxane fine particles containing an anionic surfactant and an acidic catalyst. 7. The method according to claim 1, wherein the fine particles are obtained by a method of silylating the surface of the fine particles.
The aqueous silicone composition according to the item. 8. A hydrophobic fine particle is an aqueous dispersion of silica-based fine particles and / or polyorganosilsesquioxane-based fine particles containing a cationic surfactant and an alkaline catalyst, to which trialkylalkoxysilane or trialkylsilanol is added. The aqueous silicone composition according to any one of claims 1 to 6, which is obtained by a method of silylating the surface of the fine particles.