JPH1149955A - Aqueous silicone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film having good adhesion to a rubber material or a fiber material, excellent abrasion resistance and surface smoothness, and giving a good appearance without whitening due to a bending operation. An aqueous silicone composition that forms SOLUTION: 100 parts by weight of a linear organopolysiloxane, 0.01 to 10 parts by weight of an organotrialkoxysilane and / or a partially hydrolyzed condensate thereof, an organoalkoxysilane containing an amide group and a carboxyl group and / or
Or 1 to 10 parts by weight of a partially hydrolyzed condensate thereof, an organoalkoxysilane containing an epoxy group and / or 1 to 10 parts by weight of a partially hydrolyzed condensate thereof, and (E) a catalyst for curing.
Aqueous silicone compositions comprising from 0.01 to 10 parts by weight as main components or from 1 to 100 parts by weight of spherical silicone rubber cured particles having an average particle size of from 0.1 to 100 μm to these components are added as main components. Aqueous silicone rubber composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is useful as a surface coating agent for aqueous silicone compositions, particularly rubber materials and fiber materials.
The present invention relates to an aqueous silicone composition having excellent abrasion resistance and surface smoothness on the surface of a coating layer.

[0002]

2. Description of the Related Art Conventionally, it has been general to apply a solvent-based composition to the surface of various rubbers in order to impart smoothness and abrasion resistance. However, an aqueous system is required due to safety and environmental problems. Therefore, a method of performing a surface treatment with a silicone resin composition has been proposed. For example,
A method of surface-treating a composition comprising a hydrolyzed condensate of a hydroxyl group-containing organopolysiloxane, an organohydrogenpolysiloxane and an amino group-containing dialkoxysilane (see JP-A-7-109440); A method has been proposed in which a surface treatment is carried out with a composition comprising a polysiloxane and an epoxy or amino group-containing organopolysiloxane containing a hydrolyzable group and an epoxy group or an amino group-containing hydrolyzable silane (see JP-A-7-196984). However, these methods are insufficient in adhesion, abrasion resistance, and surface smoothness of the silicone composition to a substrate. Therefore, the present inventors have proposed a method of surface-treating a composition comprising a hydrolysis condensate of a hydroxyl group-containing organopolysiloxane and an epoxy group-containing dialkoxysilane, a hydrolysis condensate of an amino group-containing dialkoxysilane, and a silicone rubber fine powder ( JP-A-7-233351, JP-A-8-120572 and JP-A-8-245882), a hydrolyzed condensate of a hydroxyl-containing organopolysiloxane and an epoxy-containing dialkoxysilane, an aqueous amino compound and a silicone rubber Method for surface treatment with a composition comprising fine powder (Japanese Patent Laid-Open No. 9-5304)
No. 7). Although some improvement in characteristics was recognized by these, it was still insufficient.

[0003]

A coating film which has good adhesion to rubber materials and fiber materials, has excellent wear resistance and surface smoothness, and provides good appearance without being whitened by a bending operation. The present invention provides an aqueous silicone composition that forms

[0004]

SUMMARY OF THE INVENTION The present invention relates to an aqueous silicone composition which solves these problems.
This is represented by the following general formula (A):

Embedded image (Where R ¹ is one or more substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, p Is a number of 800 to 20,000), and 100 parts by weight of a linear organopolysiloxane having a complex viscosity of 1 × 10 ⁴ to 1 × 10 ⁸ centipoise at 25 ° C., (B) the following general formula ( Chemical 4)

Embedded image (Where R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms) and / or 0.01 to 10 parts by weight of the partially hydrolyzed condensate, (C) 1 to 10 parts by weight of an organoalkoxysilane containing an amide group and a carboxyl group and / or (D) organoalkoxysilane containing an epoxy group And / or (A) an aqueous silicone composition comprising 1 to 10 parts by weight of a partially hydrolyzed condensate thereof and (E) 0.01 to 10 parts by weight of a curing catalyst.
An aqueous silicone rubber composition comprising, as a main component, (F) a component obtained by further adding (F) 1 to 100 parts by weight of a spherical silicone rubber cured product particle having an average particle size of 0.1 to 100 μm.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The component (A) of the aqueous silicone composition of the present invention is a linear organopolysiloxane represented by the general formula (Chemical Formula 1) having a complex viscosity of 1 × 10 ⁴ to 1 × 10 ⁸ centipoise at 25 ° C. Here, the complex viscosity is easily measured by a commercially available general measuring device. For example, "Controlled stress rheometer CS type" (Borin), "Ares viscoelasticity measurement system (for fluid measurement)"
(Manufactured by Rheometric Scientific) or the like, and the measurement may be performed at a low fixed frequency, for example, 0.1 rad / s. R ^{1 in} the formula (Chem. 1) is one or two or more substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms;
Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl; vinyl, allyl Alkenyl groups such as phenyl group and tolyl group; cycloalkyl groups such as cyclohexyl group; and groups in which part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, for example, 3, Examples include a 3,3-trifluoropropyl group, and a methyl group is particularly preferable. R
² is a hydrogen atom or a methyl group, an ethyl group, a propyl group,
C 1-6 such as butyl group, pentyl group, hexyl group
And particularly preferably a hydrogen atom.

When the complex viscosity at 25 ° C. of the organopolysiloxane is less than 1 × 10 ⁴ centipoise,
The resulting film does not adhere sufficiently to the substrate and does not show slipperiness. If the viscosity exceeds 1 × 10 ⁸ centipoise, the resulting film does not show sufficient slipperiness. Therefore, the complex viscosity of this organopolysiloxane at 25 ° C. is 1 × 10 ⁴ to 1 × 10 ^4.
It must be ⁸ centipoise. Preferably, it is 1 × 10 ⁵ to 1 × 10 ⁷ centipoise.

[0007] Such organopolysiloxanes are publicly available.
Can be synthesized by known methods, such as alkali
In the presence of a catalyst such as a metal hydroxide, [R¹ ₂SiO]_m
(Where m = 3 to 7) a cyclopolysiloxane represented by
And water or R²O [R¹ ₂SiO] _nR²(Where n = 1 to 1,0
Equilibration reaction of organopolysiloxane represented by (00)
To be obtained. The present invention is an aqueous composition.
Therefore, the organopolysiloxane of the component (A) is
It must be a suspension, but the organopolysiloxane viscosity
Is high, it is difficult to obtain a stable emulsion,
It is preferable to produce by a known emulsion polymerization method. That is, [R
¹ ₂SiO]_m(Where m = 3 to 7)
Siloxane or optionally R²O [R¹ ₂SiO]_nR
²(Where n = 1 to 1,000)
Loxane is dispersed in water using an emulsifier,
The polymerization reaction is carried out using a catalyst such as rukari, and neutralization after polymerization, etc.
If the catalyst is deactivated by the component (A) of the present invention,
Aqueous emulsions of organopolysiloxanes
Wear.

[0008] The component (B) in the aqueous silicone composition of the present invention functions as a crosslinking agent for the organopolysiloxane of the component (A), and comprises an organotrialkoxysilane represented by the above general formula (Chemical Formula 2) and / or Or a partially hydrolyzed condensate thereof. R ³ in the formula has 1 carbon atom
~ 20 substituted or unsubstituted monovalent hydrocarbon groups, specifically, methyl, ethyl, propyl, butyl,
Alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; cyclohexyl group Or a group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms or organic groups containing a mercapto group, an acryl group, etc. Examples thereof include a fluoropropyl group, a γ-methacryloxypropyl group, a γ-acryloxypropyl group, and a γ-mercaptopropyl group.

R ⁴ in the formula 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 preferred.

Specific examples of the organotrialkoxysilane as the component (B) in the aqueous silicone composition of the present invention include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane. , Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butoxytrimethoxysilane,
Pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane and the like.

In the aqueous silicone composition of the present invention, the amount of the component (B) is 0.1% based on 100 parts by weight of the component (A).
If the amount is less than 01 parts by weight, the obtained film is not sufficiently cured, and if it exceeds 10 parts by weight, it does not show adhesion to the substrate, so that 0.01 to 10 parts by weight based on 100 parts by weight of the component (A) Parts by weight, more preferably 0.1 to 5 parts by weight.

The component (C) in the aqueous silicone composition of the present invention is a component for improving the adhesion to a substrate, and comprises an amide group and a carboxyl group-containing organoalkoxysilane and / or a partial hydrolytic condensation thereof. Things. The organoalkoxysilane containing an amide group and a carboxyl group can be obtained by reacting an alkoxysilane containing an amino group with a dicarboxylic anhydride. Specific examples of the amino group-containing alkoxysilane as a starting material for obtaining the amide group and carboxyl group-containing organoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Propylmethyldimethoxysilane, 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 dicarboxylic anhydrides include phthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and glutaric anhydride. Acid anhydride,
Examples include itaconic anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, azelaic anhydride, sebacic anhydride, fumaric anhydride and the like. And
The chemical formulas of specific examples of the organoalkoxysilane containing an amide group and a carboxyl group are shown as the following (Chemical Formulas 5 to 10).

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[0013] The component (C) in the aqueous silicone composition of the present invention is a solvent which is a parent solvent for the above-mentioned starting material;
For example, it can be easily obtained by mixing the above two components at room temperature in alcohol. 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 partial hydrolysis condensate. It is necessary to react so that at least one molecule of dicarboxylic anhydride can correspond to one NH group.

The amount of component (C) in the aqueous silicone composition of the present invention is 1 to 100 parts by weight of component (A).
When the amount is less than 10 parts by weight, the obtained film does not show adhesion to the substrate, and when the amount exceeds 10 parts by weight, the film has no elongation and does not follow the substrate. 1 to 1
It is preferably 0 parts by weight, more preferably 3 to 7 parts by weight.

The component (D) in the aqueous silicone composition of the present invention is also a component for improving the adhesion to the substrate, and is an epoxy group-containing organoalkoxysilane and / or a partially hydrolyzed condensate thereof. Specific examples of the epoxy group-containing organoalkoxysilane include β-glycidoxyethyltrimethoxysilane and β-glycidoxyethyltrimethoxysilane.
Glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltriethoxysilane and the like.

The amount of the component (D) in the aqueous silicone composition of the present invention is 1 to 100 parts by weight of the component (A).
If the amount is less than 10 parts by weight, the resulting film does not show adhesion to the substrate, and if the amount exceeds 10 parts by weight, the film has no elongation and does not follow the substrate. 1 for
It is preferably from 10 to 10 parts by weight, more preferably from 3 to 7 parts by weight.

The component (F) of the aqueous silicone composition according to claim 2 of the present invention is a cured spherical silicone rubber particle having an average particle size of 0.1 to 100 μm. By further adding the component (F) to the aqueous silicone composition according to claim 1 of the present invention,
The sliding properties and abrasion resistance of the resulting film are further improved. When the average particle size of the component (F) is less than 0.1 μm, the obtained film does not show sufficient slipperiness. When the average particle size exceeds 100 μm, the obtained film has poor abrasion resistance. However, it is preferably 1 to 20 μm. In a preferred embodiment of the component (F), since the present composition is aqueous, it is preferable to mix the component (F) in the form of an aqueous dispersion. In order to obtain the aqueous dispersion of the component (F), a conventionally known method in which the curable organopolysiloxane is dispersed in water and then cured is performed. The form of the curing reaction may be any of addition and condensation, but the addition reaction is particularly preferred. For example, one molecule contains at least two alkenyl groups bonded to silicon atoms.
After dispersing in water using a surfactant, an organopolysiloxane mixture consisting of an organopolysiloxane having two hydrogen atoms and at least two hydrogen atoms bonded to a silicon atom in one molecule. The addition reaction may be performed using a platinum catalyst. Further, in the organopolysiloxane mixture,
It is also one of the preferred embodiment further complex sticky rate is added to and blended both ends trialkylsiloxy blocked dialkyl polysiloxanes of 1 × 10 ² ~1 × 10 ⁸ centipoise. If the amount of the component (F) is less than 1 part by weight per 100 parts by weight of the component (A), the obtained film does not show sufficient slipperiness, and if it exceeds 100 parts by weight, the obtained film has abrasion resistance. Is insufficient, so 100 parts by weight of component (A)
To 100 parts by weight, more preferably 10 to 50 parts by weight.

The component (E) in the aqueous silicone composition of the present invention is a curing catalyst for crosslinking and curing the components of the composition of the present invention. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin Organic tin compounds such as dilaurate, dioctyltin diacetate, and tin octylate; zinc laurate, zinc acetate, zinc stearate, and organic zinc compounds such as zinc octylate; tetrapropyl titanate and its partially hydrolyzed condensate; tetrabutyl titanate And its partially hydrolyzed condensates, bisdipropoxytitanium, bis (acetylacetonate)
Organic titanium compounds such as titanium oxide, titanium lactate, and ammonium titanium lactate are exemplified. When the curing catalyst is not water-soluble, it is desirable to emulsify and disperse in water using an emulsifier in advance and use it as an aqueous emulsion. The amount of the component (E) in the aqueous silicone composition of the present invention is 0.1% based on 100 parts by weight of the component (A).
If the amount is less than 01 parts by weight, the resulting film is not sufficiently cured, and if the amount exceeds 10 parts by weight, the effect is not changed and uneconomical. Ten
Part by weight is preferred, more preferably 0.1 to 2 parts by weight.

The aqueous silicone composition of the present invention comprises (A)
(E) or (A) to (F) may be obtained by mixing the components, and may be performed using a conventionally known mixing stirrer having a paddle type, anchor type, or other stirring blade. The components (B), (C) and (D) can be mixed as they are, but as described above, the component (A) must be emulsified and dispersed in water using an emulsifier in advance to form an aqueous emulsion. When the component (F) is not water-soluble, it is also desirable to emulsify and disperse in water using an emulsifier in advance and use it as an aqueous emulsion. And it is good to dilute with water as needed.

The aqueous silicone composition of the present invention may contain carbon black, fluororesin powder, melamine resin powder, acryl resin powder, polycarbonate resin powder, silicone resin powder, or the like, as long as the effects of the present invention are not impaired. Nylon resin powder, paraffin wax,
It is optional to incorporate polyethylene wax, silicone oil, various organic or inorganic pigments, thickeners, defoamers, preservatives, and the like.

The aqueous silicone composition of the present invention is useful as a surface coating agent for rubber materials having excellent adhesion to a substrate, abrasion resistance and surface smoothness. As a rubber material to be surface-coated with this aqueous silicone composition,
Examples include natural rubber, FPDM, SBR, chloroprene rubber, isoprene-isobutylene rubber, nitrile rubber, and the like. The rubber product made of these rubber materials may be in any form such as sponge or solid. Examples of the fiber material include synthetic fibers such as nylon, polyester, acrylic, vinylon, and acetate, and natural fiber materials such as cotton, silk, and wool.

In order to improve the adhesion to the substrate, the substrate may be coated with a primer such as a silane coupling agent before coating the aqueous silicone composition of the present invention. As a method of treating the surface coating agent on these materials, the aqueous silicone composition is brushed,
After coating by a method such as spray coating, roll coating, dip coating, or knife coating, the coating may be cured by drying at room temperature or by heating. The thickness of the cured coating is preferably 0.1 to 20 μm, more preferably 0.5 to 20 μm. ~Ten
μm. The rubber product treated in this way has excellent abrasion resistance and surface smoothness. Therefore, weatherstrip materials for automobiles, O-rings, gaskets,
It is useful as a seal material for various packings and a rubber hose material.

[0023]

Now, the present invention will be described in further detail with reference to Synthesis Examples, Examples and Comparative Examples of the components (A), (C) and (F) of the present invention. It is not limited. The complex viscosity in the examples was measured by the following method, and the evaluation of the surface smoothness and wear resistance of the rubber products in the examples was performed by the following methods. In the examples, all percentages are by weight.

(Method of Measuring Complex Viscosity)
Using a stress rheometer type CS (manufactured by Bolin Corporation), 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 of Folding Whitening Property) FPDM solid rubber (50 mm × 50 mm, thickness 2 mm) was bent by hand so that the coated surface was on the outside, and visually observed whether or not the bent portion was whitened. did. (Evaluation of surface smoothness) Solid rubber made of FPDM (10mm ×
Two pieces, each having a thickness of 50 mm and a thickness of 2 mm, were attached to a copper plate (50 mm × 50 mm) as shown in FIG. 1 and applied with a load of 1 kg using a dynamic friction coefficient measuring apparatus shown in FIG.
The dynamic friction coefficient with the glass plate was measured under the condition of mm / min.

(Evaluation of abrasion resistance) FPDM sponge rubber [15 mm × 150 mm, thickness 2 mm, hardness (JIS A) 36, specific gravity 0.
63] with a paper file AA80 using the wear resistance tester shown in FIG.
Using a glass cell (line contact, line width 5 mm) whose surface was polished with a number, a thrust load of 350 g was applied, and the friction speed was 60 reciprocations / minute.
When reciprocating friction was performed under the condition of a friction stroke of 70 mm, the number of reciprocating friction until the rubber surface was scraped was measured.

Synthesis Example 1 of Component (A) 350 g of octamethylcyclotetrasiloxane and 70 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 transition occurs from the mold to the O / W mold,
Thickening was observed, but stirring was continued for another 10 minutes. Then, while stirring at 2,000 rpm, add 280 g of water and pressurize.
When passed twice through a high-pressure homogenizer at 300 kg / cm ² , a stable white emulsion was obtained. Next, this emulsion was transferred to a 1-liter glass flask equipped with a stirrer, a thermometer and a reflux condenser, reacted at 70 ° C. for 6 hours, cooled to 15 ° C., aged for 12 hours, and then 10% An aqueous sodium carbonate solution (emulsion A-1) was obtained by adding 13 g of an aqueous solution of sodium carbonate and neutralizing the mixture to pH = 6.6 to obtain a uniform aqueous turbid emulsion. After drying this aqueous emulsion at 105 ° C for 3 hours, the nonvolatile content is
The content was 45.7%, the content of the component (A) was 45.0%, and the content of sodium dodecylbenzenesulfonate was 10%. After isopropyl alcohol was added to the aqueous emulsion to break the emulsion, the siloxane was extracted, dried at 105 ° C. for 3 hours, and measured for complex viscosity to show 2.3 × 10 ⁶ centipoise. This organopolysiloxane is GPC
The following formula was shown as a result of the analysis.

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Synthesis Example 2 of Component (A) Neutralization to pH = 6.4 in exactly the same manner as in Synthesis Example 1 except that the mixture was cooled to 25 ° C. and aged for 12 hours instead of “cooled to 15 ° C. and aged for 12 hours”. Thus, a uniform cloudy aqueous emulsion (emulsion A-2) was obtained. After drying this aqueous emulsion at 105 ° C. for 3 hours, the nonvolatile content was 45.7%, containing 44.7% of component (A) and 1.0% of sodium dodecylbenzenesulfonate. Isopropyl alcohol was added to this aqueous emulsion to break the emulsion, and siloxane was extracted.
After drying at ℃ for 3 hours and measuring the complex viscosity, 8.5 ×
Was 10 ⁵ centipoise. As a result of GPC analysis, the organopolysiloxane had the following formula.

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Synthesis Example 3 of Component (A) In Synthesis Example 1, the reaction was carried out at 70 ° C. for 6 hours and then at 15 ° C.
And aged for 12 hours ", except that the reaction was carried out at 85 ° C. for 6 hours to obtain a uniform, cloudy aqueous emulsion having a pH of 6.4 (Emulsion A-3). Was. The nonvolatile content of this aqueous emulsion after drying at 105 ° C. for 3 hours was 45.9%, the component (A) 44.9%, and sodium dodecylbenzenesulfonate.
1.0%. After isopropyl alcohol was added to this aqueous emulsion to break the emulsion, siloxane was extracted, dried at 105 ° C. for 3 hours, and the complex viscosity was measured. The result was 7.4 × 10 ³ centipoise. As a result of GPC analysis, this organopolysiloxane showed the following formula.

Embedded image

Synthesis Example of Component (C) 108 g of maleic anhydride and 350 g of ethanol were charged into a 1-liter glass flask equipped with a stirrer, a thermometer and a reflux condenser, and were uniformly dissolved. 242 g of triethoxysilane was added dropwise at room temperature for 1 hour. After completion of the dropwise addition, stirring was continued for another hour to carry out a reaction, and a pale yellow transparent solution (solution C) was obtained. This solution 1
The nonvolatile matter after heating at 05 ° C. for 3 hours was 49.5%, and the reaction product in the solution was subjected to instrumental analysis such as GPC, IR, and NMR, and was found to be a compound represented by the following formula. HOOCCH = CHCONHC ₃ H ₆ Si (OC ₂ H ₅ ) ₃

Synthesis Example 1 of F Component

Embedded image In the formula, 350 g of methylvinylsiloxane with a complex viscosity of 10 cp

Embedded image 100 g of methylhydrogenpolysiloxane with a complex viscosity of 200 cp

Embedded image Was charged into a 1-liter glass flask equipped with a stirrer and stirred at room temperature for 8 hours to uniformly dissolve the dimethylpolysiloxane having a complex viscosity of 5.8 × 10 ⁶ cp. Next, 350 g of this melt was transferred to a 1 liter glass beaker, and polyoxyethylene (addition moles =
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. As a result, the phase was changed from the W / O type to the O / W type, and the viscosity was increased.
Stirring was continued for 15 hours. Then, while stirring at 2,000 rpm, 307 g of water was added, whereby 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 under stirring with a toluene solution of chloroplatinic acid-olefin complex (platinum content).
A mixture of 1.1 g of 0.5%) and 4.2 g of polyoxyethylene (number of moles added: 9 mol) lauryl ether was added and stirred for 12 hours to obtain an aqueous emulsion F-1. The average particle size of the aqueous emulsion was measured using Multisizer II (a product name of Coulter, Inc.).
Was 4 μm, and several g of this aqueous emulsion was dried to obtain an elastic white rubber powder. This aqueous emulsion had a nonvolatile content of 50.9% after drying at 105 ° C. for 3 hours, contained 49.9% of the component (F), and contained 1.0% of polyoxyethylene (additional mole number = 9 mol) lauryl ether. Was something.

Synthesis Example 2 of Component F 50 g of dimethylpolysiloxane having a complex viscosity of 5.8 × 10 ⁶ cp was obtained by the formula

Embedded image The aqueous emulsion F-2 was obtained in the same manner as in Synthesis Example 1 of the F component except that 50 g of dimethylpolysiloxane having a complex viscosity of 3.0 × 10 ⁴ cp was used. The average particle size of this aqueous emulsion was 2 μm when measured using Multisizer II (trade name, manufactured by Coulter, Inc.).
When g was dried, an elastic white rubber powder was obtained. This aqueous emulsion has a nonvolatile content of 50.6% after drying at 105 ° C. for 3 hours, and contains 49.6% of the component (F) and 1.0% of polyoxyethylene (additional mole number = 9 mol) lauryl ether. Was something.

Synthesis Example 3 of Component F Methylvinylsiloxane 35 having a complex viscosity of 10 cp
0 g, 100 g of methylhydrogenpolysiloxane having a complex viscosity of 200 cp and 50 g of dimethylpolysiloxane having a complex viscosity of 5.8 × 10 ⁶ cp 390 g of methylvinylsiloxane having a complex viscosity of 10 cp and 200 cp of the above complex viscosity
An aqueous emulsion F-3 was obtained in the same manner as in Synthesis Example 1 for the F component except that the amount of methyl hydrogen polysiloxane was 110 g. The average particle size of this aqueous emulsion was measured using a Multisizer II (trade name, manufactured by Coulter, Inc.) and found to be 2 μm. When several g of this aqueous emulsion was dried, an elastic white rubber powder was obtained. was gotten. This aqueous emulsion contains 1
The nonvolatile content after drying at 05 ° C for 3 hours is 50.1%, (F)
49.1% of component and polyoxyethylene (addition mole number =
9 mol) lauryl ether was contained at 1.0%.

Examples 1 to 8 (about claim 1) and Examples 9 to 15 (about claim 2) The components (A), (C), (F) and The following components (B), (D) and (E) are shown in Tables 1 and 3.
To prepare an aqueous silicone composition for a surface treatment agent composition,
M is applied to the surface of solid rubber made of M (thickness 2mm) and sponge rubber made of FPDM [thickness 2mm, hardness (JIS A) 36, specific gravity 0.63] with a brush and placed in a hot-air circulating thermostat adjusted to 150 ° C. The surface treatment was carried out by leaving it to stand for a minute, and the surface smoothness was evaluated according to the method described above. The results are shown in Tables 1 and 3. [Component B] Silane B-1: phenyltriethoxysilane Silane B-2: methyltriethoxysilane Silane B-3: n-decyltrimethoxysilane Silane B-4: vinyltriethoxysilane [Component D] Silane D: γ -Glycidoxypropyltrimethoxysilane [E component] Emulsion E: 30% emulsion of dibutyltin dilaurate

[0035]

[Table 1]

[Table 3]

[Comparative Examples 1 to 4 (about claim 1) and Comparative Examples 5 to 9 (about claim 2)] The components (A), (C), (F) and The components (B), (D) and (E) are shown in Tables 2 and 4.
An aqueous silicone composition as a surface treating agent composition was prepared by mixing with the compounding composition shown in the above, and the FPDM rubber was subjected to a surface treatment using the same in the same manner as in the examples, and the surface smoothness was increased according to the method described above. evaluated. The results are shown in Tables 2 and 4. When the complex viscosity of the organopolysiloxane of the component (A) is less than the limit value defined in claim 1 as in Comparative Examples 1 and 5, the surface smoothness and abrasion resistance are poor.
When the organotrialkoxysilane of the component (B) is not blended as in Comparative Examples 2 and 6, the cured film is insufficiently cured, and as in Comparative Examples 3 and 7, If the organoalkoxysilane containing an amide group and a carboxyl group and the organoalkoxysilane containing an epoxy group as the component (D) are less than 1 part by weight or are not blended, the surface slip and abrasion resistance will be poor. . When the components (C) and (D) each exceeded 10 parts by weight as in Comparative Examples 4 and 8, the abrasion resistance was poor. When the amount of the component (F) exceeds the limit value in the second aspect as in Comparative Example 9, whitening occurs due to bending, and poor abrasion resistance is obtained.

[0037]

[Table 2]

[Table 4]

[0038]

The coating film of the aqueous composition of the present invention has excellent adhesion to the substrate surface, and the coated rubber or fiber material has excellent surface smoothness and abrasion resistance.

[Brief description of the drawings]

FIG. 1 is a perspective view of a combination sample of a solid rubber and a copper plate for measuring a dynamic friction coefficient.

FIG. 2 is a schematic longitudinal sectional view of a dynamic friction coefficient measuring device.

FIG. 3 is a schematic diagram of a wear resistance measuring device.

[Explanation of symbols]

 1 Solid rubber, 2 Sponge rubber, 3 Ground glass, 4 Copper plate, 5 Glass plate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83:08)

Claims (2)

[Claims] (A) The following general formula (Chemical Formula 1) (Where R ¹ is one or more substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, p Is a number of 800 to 20,000), and 100 parts by weight of a linear organopolysiloxane having a complex viscosity of 1 × 10 ⁴ to 1 × 10 ⁸ centipoise at 25 ° C., (B) the following general formula ( Chemical formula 2) Wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. 0.01 to 10 parts by weight of the partially hydrolyzed condensate, (C) 1 to 10 parts by weight of an organoalkoxysilane containing an amide group and a carboxyl group and / or (D) organoalkoxysilane containing an epoxy group An aqueous silicone composition comprising 1 to 10 parts by weight of a partially hydrolyzed condensate thereof and (E) 0.01 to 10 parts by weight of a curing catalyst. 2. The composition according to claim 1, further comprising (A) to (E).
(F) An aqueous silicone rubber composition comprising, as a main component, 1 to 100 parts by weight of a cured spherical silicone rubber particle having an average particle size of 0.1 to 100 μm.