JPH069937A - Polyorganosiloxane composition for binder - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which enables the production of a silicone- mica laminate and a silicone-glass laminate both excellent in mechanical and electrical properties and in resistances to heat, water, and humidity. CONSTITUTION:100 pts.wt. thermosetting polyorganosiloxane resin is compounded with 1-100 pts.wt. thermoplastic silicone resin comprising 50-99mol% R<1>SiO1.5 units and 1-50mol% R<2>SiO0.5 units (in those formulas, R<1> and R<2> are each an optionally substd. monovalent hydrocarbon group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyorganosiloxane composition for a binder suitable for producing an improved mica laminated product and a glass laminated product, and a silicone mica laminated product and a silicone glass laminated product using the same. It is a thing. More specifically, the present invention relates to a mica laminated product, a glass laminated product having excellent mechanical strength, electrical properties, water resistance, moisture resistance, and heat resistance, and a polyorganosiloxane composition for a binder used therefor.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Since mica and glass have excellent electric properties and heat resistance, they are generally widely used in various fields such as electric and electronic parts.
However, since mica and glass have low mechanical strength and moisture resistance, mica laminated products and glass that have been supplemented with mechanical strength and moisture resistance by molding or laminating with a binder are used for applications requiring these performances. A laminated product is used, and conventionally, a primary phosphate-based inorganic polymer or organic resin is used as the binder. However, the one using the inorganic polymer obtained by condensing the primary metal salt of phosphoric acid requires a high temperature of 400 ° C or more when forming a laminated product, and thus requires special equipment, and the manufacturing cost is high. Has the drawback of being expensive. Further, the mica laminated product and the glass laminated product thus obtained have excellent heat resistance, but on the other hand, they have poor water resistance and have the drawback of impairing mechanical strength and electrical properties due to the presence of moisture. On the other hand, when an organic resin such as an alkyd resin, polyester resin, epoxy resin, or acrylic resin is used as a binder, it has the advantage that it can be laminated and molded at a relatively low temperature of 100 to 200 ° C. Although the laminated product has excellent mechanical properties, it has a drawback that it is inferior in heat resistance and inferior in water resistance like the one using an inorganic polymer. Therefore, a polyorganosiloxane resin has been used as a binder for mica and glass products as a resin having higher heat resistance than the organic resin. However, the mica product and the glass laminated product using the polyorganosiloxane resin have excellent heat resistance as compared with those using the above organic resin, but are inferior in mechanical properties and are not always satisfactory in water resistance. There wasn't. Therefore, it has been proposed to use a polyorganosiloxane resin in combination with a carbon-functional silane for the purpose of improving its water resistance.
For example, a method is known in which a vinyl group-containing polyorganosiloxane is added with an amino group-containing silane, a ketoxime group-containing silane, an acetoxy group-containing silane, a silazane compound, and the like, and the mixture is cured with a peroxide (JP-A-48-2429).
No. 5 bulletin). This method is easy to laminate and mold, and the resulting molded article has very good water resistance. However, since expensive silicon-bonded vinyl groups are usually used in a large amount of 10 to 20 mol%, it is industrially difficult. However, because of the presence of vinyl groups in the polyorganosiloxane resin, it has more heat resistance problems than mica products and glass laminated products using ordinary polyorganosiloxane resin, and it is a heater plate used at high temperatures. When used as, there is a problem of seeing a lot of smoke. Another method is to add a mixture of phosphoric acid and an epoxy group-containing organosilicon compound to a polyorganosiloxane resin and cure the mixture (Japanese Patent Laid-Open No. 98-55050).
However, this mixture has poor compatibility with the polyorganosiloxane resin, and often contains water, so a large amount of alcohol must be added and dispersed, and when this system is processed into a laminated mica foil, It has the drawback of damaging the mica foil due to water and alcohol. In addition, the phosphoric acid in this mixture violently accelerates the condensation of the polyorganosiloxane resin, which impairs the storage stability. Also, using alkyl silicate as a binder,
A method of curing with an organic acid or an inorganic acid is known (JP-A-51-127106). However, although the mica product and the glass laminated product obtained by this method are excellent in heat resistance, they have a drawback that their mechanical properties are remarkably inferior. Further, a method for curing a polyorganosiloxane resin by using an acidic phosphoric acid ester is known (JP-A-53-149250), but the mica product obtained by this method has a mechanical strength and an electrical property. Although it has excellent heat resistance, it has a drawback that it is slightly inferior in water resistance and moisture resistance.

[0003]

It is an object of the present invention to solve the above drawbacks of conventional methods and to provide silicone mica laminated products and silicone glass laminated products which are excellent in mechanical strength, electrical properties, heat resistance, water resistance and moisture resistance. An object is to provide a polyorganosiloxane composition for a binder that can be produced.

[0004]

DETAILED DESCRIPTION OF THE INVENTION The inventors of the present invention have made extensive studies in order to achieve such an object. As a result, it is effective to use a thermosetting polyorganosiloxane resin in combination with a thermoplastic silicone resin containing a specific constituent unit. It was found that the present invention has been completed. That is, the present invention provides (A) 100 parts by weight of a thermosetting polyorganosiloxane resin and (B) R ¹ SiO _1.5 unit 50 to 99 mol% R ² ₃ SiO _0.5 unit 1 to 50 mol% (wherein R ¹ , R ² represents a substituted or unsubstituted monovalent hydrocarbon group), and a polyorganosiloxane composition for a binder comprising 1 to 100 parts by weight of a thermoplastic silicone resin. Further, the present invention, the polyorganosiloxane composition is adhered to mica pieces or glass fibers, the mica pieces or glass fibers are bonded and subjected to heat treatment, and the polyorganosiloxane composition is cured to give mica pieces or The present invention relates to a silicone mica laminated product and a silicone glass laminated product produced by integrating glass fibers.

The thermosetting polyorganosiloxane resin of the component (A) used in the present invention contains a hydroxyl group and / or an alkoxy group bonded to a silicon atom, and is a siloxane when cured by dehydration condensation and / or dealcohol condensation. There is no particular limitation as long as it forms a three-dimensional network structure with a bond skeleton, and generally it exhibits curability when heated at high temperature for a long time. As is well known, such a polyorganosiloxane resin can be obtained by hydrolysis or alcoholysis of one kind or a mixture of two or more kinds of organohalogenosilane, and generally, it is possible to obtain a silanol group or an alkoxy group. Contains hydrolyzable groups, and these groups are converted to silanol groups at 1-10% by weight
contains. These reactions are generally carried out in the presence of a solvent capable of dissolving the organohalogenosilane and the product. It can also be obtained by a method of synthesizing a block copolymer by cohydrolyzing a linear polyorganosiloxane having a hydroxyl group, an alkoxy group or a halogen atom at the terminal of the molecular chain with organotrichlorosilane. The silicone resin thus obtained generally contains residual HCl, but in the composition of the present invention, it has a storage stability of 10 ppm or less, preferably 1 ppm or less.
It is better to use the one below ppm. Such polyorganosiloxane resin generally average formula _{^{R 3 b Si (OR 4)}} c O
_{(4-bc) / 2} (wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is a group selected from hydrogen and R ³ , and b is 1.0 to 1.
The number 5 and c represent the numbers 0.05 to 0.2. ) Is used. Here, R ³ represents a substituted or unsubstituted monovalent hydrocarbon group. R ³ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; a cyclohexyl group or a cyclooctyl group Alkyl groups or groups in which hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, amino groups, etc., such as chloromethyl groups, 3,3,3-trifluoropropyl groups, cyanomethyl groups, γ- Examples thereof include an aminopropyl group and an N- (β-aminoethyl) -γ-aminopropyl group. Among them, as R ^3, it is advantageous to use a monovalent group selected from a methyl group and a phenyl group in terms of heat resistance and availability of raw materials. Further, R ⁴ is a group selected from hydrogen and R ³ , and among them, a methyl group, an ethyl group or hydrogen is preferable from the viewpoint of stability and curability of the composition. Also, as the value of b,
For non-flexible mica plate, b is 1.0 to 1.4,
For the purpose of a flexible mica plate, b is preferably in the range of 1.2 to 1.6 in order to obtain an appropriate hardness. The polyorganosiloxane resin used in the present invention is usually toluene,
It is used by dissolving it in a hydrocarbon solvent such as xylene or a petroleum solvent, or a mixture of these and a polar solvent. Further, compounds having different compositions may be blended and used within a range where they are mutually soluble. Further, it can be used by mixing or copolymerizing with an organic resin such as an alkyd resin, a polyester resin, an acrylic resin and an epoxy resin.

The component (B) used in the present invention is a component which characterizes the present invention. R ¹ SiO _1.5 unit 50 to 99 mol% R ² ₃ SiO _0.5 unit 1 to 50 mol% (in the formula, ¹ , R ² represents a substituted or unsubstituted monovalent hydrocarbon group.). Here, R ¹ and R ² respectively represent the same or different substituted or unsubstituted monovalent hydrocarbon groups. As R ¹ and R ² ,
Alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; cycloalkyl groups such as cyclohexyl group and cyclooctyl group or these A group in which a hydrogen atom bonded to a carbon atom of the group is substituted with a halogen atom, a cyano group, an amino group or the like, for example, a chloromethyl group, 3,3,3-trifluoropropyl group, cyanomethyl group, γ-aminopropyl group, N Examples include-(β-aminoethyl) -γ-aminopropyl group. A methyl group, an ethyl group and a phenyl group are preferable from the viewpoint of easiness of synthesis and availability of raw materials. R ² ₃ SiO _0.5 unit is R ¹ SiO
It is necessary to be 1 to 50 mol% with respect to _1.5 units of 50 to 99 mol%. If it is less than 1 mol%, the effect of the present invention cannot be sufficiently obtained, and if it is more than 50 mol%, the resin of the present invention Becomes difficult to synthesize. Preferably R ² ₃ SiO _0.5 units for R ¹ SiO _1.5 units 80-95 mol% is from 5 to 20 mol%. The thermoplastic silicone resin (B) used in the present invention is (a) a silanol group-containing organopolysilsesquioxane consisting of R ¹ SiO _1.5 units (wherein R ¹ is a substituted or unsubstituted 1
Represents a valent hydrocarbon group. (B) (R ² ₃ Si) _a Z (in the formula, R ² represents a substituted or unsubstituted monovalent hydrocarbon group,
a represents 1 or 2, Z is a hydrogen atom when a is 1,
Represents a hydroxyl group or hydrolyzable group, and when a is 2, -O-, -N
Represents (X)-, -S-. Where X is a hydrogen atom and has 1 to 4 carbon atoms
Of a monovalent hydrocarbon group or R ² ₃ Si-). This resin is characterized by low residual silanol content, 0.5
The amount of silanol is not more than 0.3% by weight, and the silanol content of the composition of the present invention is preferably not more than 0.3% by weight. Here, as the hydrolyzable group of Z in the component (b), an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group; an alkenyloxy group such as a propenoxy group; an acetoxy group, a benzoxy group. Acyloxy groups such as; Acetone oxime groups, butanone oxime groups, and other organooxime groups; Dimethylaminoxy groups, diethylaminoxy groups, and other organoaminoxy groups; Dimethylamino groups, diethylamino groups, cyclohexylamino groups, and other organoamino groups; N Examples thereof include an organoamide group such as a methylacetamide group.
An alkoxy group is preferable, and a methoxy group and an ethoxy group are particularly preferable because it is easy to obtain raw materials and control the reaction. The component (a), polysilsesquioxane, can be synthesized by a known method, and can be obtained, for example, by subjecting organotrichlorosilane or organotrialkoxysilane to hydrolysis / condensation reaction with excess water. The polysilsesquioxane thus obtained usually has 1 to 60 silanol groups.
Contains 10% by weight. The silicone compound represented by (R ² ₃ Si) _a Z of the component (b) is a compound that silates the silanol group of the component (a). Trimethylsilane as component (b),
Hydrogen silane such as triethylsilane; trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, chlorosilane such as CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ Cl; silanol such as trimethylsilanol; trimethylmethoxysilane, trimethylethoxysilane, alkoxysilanes such _{as; (CH 3) 3 SiNHCH 3} , (CH 3) 3 SiNHC 2
_{H 5, (CH 3) 3} SiN (CH 3) 2, (CH 3) 3 SiN (C 2 H 5) 2, an aminosilane such as; (CH _{3) 3} acyloxy such SiOCOCH _3; hexamethyldisilazane , 1,3-divinyltetramethyldisilazane, and silazanes such as [(CH ₃ ) ₃ Si] ₃ N. Among these, silazanes and chlorosilanes are preferable because they can easily control the reaction and remove unreacted substances. The reaction between the component (a) and the component (b) can be carried out by a known method of silylating silanol. For example, when the component (b) is silazane or chlorosilane, the reaction easily proceeds by mixing with the component (a) and heating. component
The amount of (b) used is 5 to 100 parts by weight per 100 parts by weight of component (a). If the amount is less than 5 parts by weight, sufficient silylation cannot be achieved,
Gelation occurs during the reaction and the thermal stability of the obtained silicone resin is impaired. On the other hand, if the amount is more than 100 parts by weight, the unreacted component (b) remains in excess, which is not economically disadvantageous, and it takes a long time to remove the unreacted component (b), which is not preferable. The silylation reaction is preferably carried out in an organic solvent in order to control the reaction temperature and to suppress the dehydration condensation reaction which is a side reaction. As such an organic solvent,
Examples thereof include hydrocarbon solvents such as toluene, xylene, hexane, industrial gasoline, mineral spirits and kerosene, ether solvents such as tetrahydrofuran and dioxane, chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane. The reaction temperature is not particularly limited,
Preferably, it may be arbitrarily set within the range of room temperature to 200 ° C. Hydrochloric acid, ammonia produced by the above reaction,
Ammonium chloride, alcohol, etc. can be removed by washing with water, or can be distilled off at the same time as the solvent. The silicone resin obtained by such a method is generally 5 to
It is a thermoplastic resin with a softening point of 300 ° C, is stable to high temperature and long-time heating, and exhibits almost no curability. The composition of the present invention particularly has a softening point of 60 to 200 ° C.
It is preferable to use those of

In order to produce the silicone mica laminated product and the silicone glass laminated product of the present invention using the polyorganosiloxane composition of the present invention, the polyorganosiloxane composition of the present invention is prepared by using a suitable good solvent such as toluene or xylene. And dilute with petroleum solvent etc.,
After peeling mica or laminated mica, it is applied by a method such as impregnation, spraying, brushing, etc., the solvent is volatilized at a relatively low temperature, and the resulting polyorganosiloxane resin-attached mica pieces are overlaid, and the temperature is adjusted to 150-250 ° C. Temperature, 10 to if necessary
It can be obtained by heating for 15 minutes to 2 hours while applying a pressure of 150 kgf / cm ² . When manufacturing glass laminated products, glass cloth is impregnated, sprayed, coated by a method such as brushing, pre-dried at 70 to 110 ° C, and the obtained polyorganosiloxane resin-adhered glass cloth is laminated, It can be obtained by heating at a temperature of 140 to 180 ° C. under a pressure of 40 to 100 kgf / cm ² for 1 to 1.5 hours, and performing heat treatment after pressure molding. The mica pieces used in the present invention may be hard or soft laminated mica, peeled mica, or the like. Any known glass cloth can be used. Further, when producing the above-mentioned silicone mica laminated product and silicone glass laminated product, a suitable catalyst may be added to the polyorganosiloxane composition for the purpose of accelerating the curing of the polyorganosiloxane composition. The catalyst in this case is (CH ₃ O)
₂ P (O) (OH), (i-C ₃ H ₇ O) P (O) (OH) ₂ and other acidic phosphoric acid esters, sodium acetate, alkali metal salts of carboxylic acids such as potassium formate, dimethylamine acetate , Ethanolamine acetate, amine carboxylates such as dimethylaniline formate, quaternary ammonium carboxylates such as tetramethylammonium acetate, metal salts of carboxylic acids such as tin octenoate, amines such as triethanolamine and pyridine, hydroxylation Alkaline hydroxides such as sodium and ammonium hydroxide, γ
Examples thereof include amine silane coupling agents such as -aminopropyltriethoxysilane and γ-ethylenediaminepropyltrimethoxysilane, and aluminum chelate compounds. These catalysts consist of component (A)
It is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the thermosetting polyorganosiloxane resin.

[0008]

By using the binder composition of the present invention, a mica laminated product and a glass laminated product having excellent mechanical strength, electrical properties, water resistance, moisture resistance and heat resistance can be easily produced with good workability. can do. Since the obtained mica laminated product and glass laminated product have the above-mentioned excellent properties, they are used for various purposes, and particularly effective for electrical parts.

[0009]

EXAMPLES The present invention will be described below with reference to examples. In the following examples, all parts are parts by weight, and% is% by weight. JIS K 6911 and JIS are used to measure the properties of mica plates and laminated glass plates.
According to C 2241. In the table, A indicates a normal state, and D indicates a measured value after submersion in water at 23 ° C. for 1 day.

Preparation Example 1 36 parts of methyltrichlorosilane, dimethyldichlorosilane
A mixture of 16 parts, 33 parts of phenyltrichlorosilane and 15 parts of diphenyldichlorosilane was cohydrolyzed in the presence of isopropyl alcohol and toluene to obtain a toluene solution of a polyorganosiloxane resin. This solution was diluted with toluene to prepare a diluted solution by adjusting the resin content to 10%. This was designated as polyorganosiloxane resin S-1. After distilling off toluene under reduced pressure, the silanol content of S-1 was measured and found to be 4.5%. Moreover, S-1 showed the thermosetting property. The silanol group content is determined by measuring the amount of water generated when the silicone resin is heated at 300 ° C. for 2 hours using a computer titration type water content measuring device CA-06 type (manufactured by Mitsubishi Kasei Co., Ltd.). It was calculated by

[0011]

[Equation 1]

Preparation Example 2 600 parts of isopropyl alcohol was charged and 500 parts of methyltrichlorosilane was added dropwise over 40 minutes while stirring. The reaction temperature rose from 20 ° C to 60 ° C and then dropped to 35 ° C with the release of hydrogen chloride gas. Then, the mixture was gradually heated to 100 ° C. and heated for 30 minutes while stirring to remove hydrogen chloride. The concentration of hydrochloric acid in the organoalkoxysilane produced by the reaction was 2.5%. After cooling to room temperature, 600 parts of xylene was added to obtain a xylene solution of organoalkoxysilane. While stirring this, 100 parts of water was added dropwise over 10 minutes. This operation increased the temperature to 45 ° C. After the dropping was completed, the temperature was raised to 78 ° C. and the mixture was refluxed for 10 minutes while stirring. Then heat
The stirring was stopped and the mixture was allowed to stand for 15 minutes to remove the acidic aqueous layer. Next, add 500 parts of water, heat and reflux at a temperature of 78 ° C for 30 minutes,
The mixture was allowed to stand for 15 minutes to remove the lower aqueous layer. Water again 50
0 part was added, the mixture was heated and refluxed at a temperature of 78 ° C. for 30 minutes, and allowed to stand for 15 minutes to remove the lower aqueous layer, which was repeated. The polymethylsiloxane resin thus produced had a hydrochloric acid content of 0.1 ppm or less. This solution was diluted with toluene to prepare a diluted solution by adjusting the resin content to 10%. This was designated as polyorganosiloxane resin S-2. After the toluene was distilled off under reduced pressure, the amount of silanol in S-2 was measured and found to be 5.5%. Moreover, S-2 showed the thermosetting property.

Preparation Example 3 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene were charged into a flask, and a 1% hydrochloric acid aqueous solution 108 was added.
Parts were added dropwise over 20 minutes to hydrolyze the silane. After 40 minutes from the dropping, stirring was stopped, and after liquid separation, the organic layer was washed with water to remove hydrochloric acid, and toluene was distilled off under reduced pressure to obtain a molecular weight of 12
A methylpolysilsesquioxane P-1 having a softening point of 115 DEG C. and a silanol group content of 1.2% was prepared at 000. Next, 100 parts of the methyl polysilsesquioxane P-1 and 20 parts of toluene
0 part, 10 parts of trimethylchlorosilane and 50 parts of hexamethyldisilazane were charged into a flask and heated and stirred.
After heating and stirring for 2 hours at the reflux temperature of toluene, ammonia, hydrochloric acid or salts thereof generated by the reaction are removed by washing with water, and toluene is removed under reduced pressure to remove trimethylsilylated thermoplastic silicone resin having a softening point of 80 ° C. Obtained. This resin was stable after heating at 150 ° C. for 1 hour. Using a jet mill crusher, the average particle size is 5 μm
Powder A-1. The silanol group content of A-1 was 0.3%. Here, the softening point was measured according to the ring and ball softening point measuring method of JIS C 2104. The molecular weight is GPC
(HLC-802U, manufactured by Tosoh Corporation) was used to measure the molecular weight (in terms of polystyrene). The average particle diameter was measured using a particle size distribution measuring device (CAPA-500, manufactured by Horiba, Ltd.).

Preparation Example 4 In the same manner as in Preparation Example 3 except that a 0.5% hydrochloric acid aqueous solution was used,
Methyl polysilsesquioxane P-2 having a molecular weight of 2000 and a softening point of 45 ° C. and a silanol group content of 4.5%, and a softening point of 10
A trimethylsilylated silicone resin at ℃ was obtained.
The silanol group content of this silicone resin was 0.4%. This silicone resin and the silicone resin having a softening point of 80 ° C. of Preparation Example 3 were heat-melted at a weight ratio of 1: 1 and uniformly mixed to obtain a silicone resin having a softening temperature of 60 ° C. This was crushed with a Rotoplex crusher to obtain powder A-2. The particle size distribution of this powder was measured using an air jet sieve particle size distribution measuring device (manufactured by ALPINE (Germany)). As a result, 24% of particles having a particle size of less than 150 μm,
The particle size distribution was such that particles having a particle size of less than 250 μm were 14%, particles having a particle size of 250 to less than 500 μm were 32%, particles having a particle size of 500 to less than 1000 μm were 25%, and particles having a particle size of 1000 μm or more were 5%.

Preparation Example 5 110 parts (0.5 mol) of silane and 105.8 parts (0.5 mol) of phenyltrichlorosilane were used in place of 220 parts (1.0 mol) of methyltriisopropoxysilane, and water was used instead of a 1% aqueous hydrochloric acid solution. Except that the same procedure as in Preparation Example 3 was used, the molecular weight was 13,000 and the silanol group content was 2.5 at a softening point of 130 ° C.
% Organopolysilsesquioxane P-3 and a trimethylsilylated silicone resin with a softening point of 95 ° C. were obtained. This was made into a powder A-3 having an average particle diameter of 5 μm with a jet mill pulverizer. Here, the average particle diameter was measured in the same manner as in Preparation Example 3. The silanol group content of A-3 was 0.4%.

Preparation Example 6 The silicone resin having a softening point of 10 ° C. obtained in Preparation Example 4 and the silicone resin having a softening point of 95 ° C. obtained in Preparation Example 5 were mixed in a ratio of 1: 1.
And was mixed uniformly to obtain a silicone resin having a softening point of 60 ° C. This was crushed with a Rotoplex crusher to obtain powder A-4. The particle size distribution of this powder was measured in the same manner as in Preparation Example 4. As a result, 30% of the particles having a particle size of less than 150 μm, 10% of the particles of 150 to less than 250 μm, and 250 to
The particle size distribution was such that particles having a particle size of less than 500 μm were 30%, particles having a particle size of 500 to less than 1000 μm were 21%, and particles having a particle size of 1000 μm or more were 9%.

Examples 1-12 and Comparative Examples 1-6 S-1 to S as thermosetting polyorganosiloxane resins
-2, A-1 to A-4 as the thermoplastic silicone powder,
As a curing catalyst, an equimolar mixture of (CH ₃ O) ₂ P (O) (OH) and (CH ₃ O) P (O) (OH) ₂ (referred to as C-1), tetramethylammonium acetate (C-2 Or γ-aminopropyltriethoxysilane (denoted as C-3).
The treatment liquid was prepared at the ratio shown in. These treatment liquids were applied to a hard laminated mica paper with a thickness of 0.09 mm and the resin content was
It was applied so as to adhere 10%. After evaporating the solvent, 11
After heat treatment at 0 ° C. for 10 minutes, six sheets of mica paper were stacked and heated and pressed at a pressure of 100 kg / cm ² and a temperature of 180 ° C. for 1 hour to prepare a mica plate. Further, this plate was put in a hot air dryer and after-cured at 220 ° C. for 3 hours to obtain a mica plate having a thickness of 0.5 mm. The bending strength, volume resistivity and water absorption of the obtained mica plate were measured. The results are shown in Table 2. In the example in which the thermoplastic silicone was used in combination, a very strong mica plate was obtained, and even after immersion in water, excellent flexural strength, volume resistivity, water absorption and other moisture resistance were retained.

Examples 13-24 and Comparative Examples 7-12 S-1 to S as thermosetting polyorganosiloxane resins
-2, A-1 to A-4 as the thermoplastic silicone powder,
As a curing catalyst, an equimolar mixture of (CH ₃ O) ₂ P (O) (OH) and (CH ₃ O) P (O) (OH) ₂ (referred to as C-1), tetramethylammonium acetate (C-2 Or γ-aminopropyltriethoxysilane (denoted as C-3) was used to prepare treatment solutions in the proportions shown in Table 1 in the same manner as in Examples 1-12 and Comparative Examples 1-6. Apply these treatment liquids to a non-alkali glass cloth with a thickness of 0.40 mm
It was applied so that 40% was adhered. After evaporating the solvent, 11
After preheating at 0 ° C. for 10 minutes, six glass cloths were stacked and heated and pressed at a pressure of 100 kg / cm ² and a temperature of 180 ° C. for 1 hour to prepare a glass cloth plate. Then, place this plate in a hot air dryer, gradually raise the temperature from 90 ° C, and perform after-curing at 220 ° C for 3 hours.
A glass laminated plate having a thickness of 2.0 mm was obtained. The bending strength, volume resistivity and water absorption of the obtained glass laminated plate were measured. The results are shown in Table 3.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

Claims (6)

[Claims] 1. A thermosetting polyorganosiloxane resin (A)
100 parts by weight and (B) R ¹ SiO _1.5 unit 50 to 99 mol% R ² ₃ SiO _0.5 unit 1 to 50 mol% (in the formula, R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group) Polyorganosiloxane composition for binder comprising 1 to 100 parts by weight of a thermoplastic silicone resin. 2. A thermoplastic silicone resin of component (B) is (a) a silanol group-containing organopolysilsesquioxane consisting of R ¹ SiO _1.5 units (wherein R ¹ is a substituted or unsubstituted 1
Represents a valent hydrocarbon group. (B) (R ² ₃ Si) _a Z (in the formula, R ² represents a substituted or unsubstituted monovalent hydrocarbon group,
a represents 1 or 2, Z is a hydrogen atom when a is 1,
Represents a hydroxyl group or hydrolyzable group, and when a is 2, -O-, -N
Represents (X)-, -S-. Where X is a hydrogen atom and has 1 to 4 carbon atoms
The polyorganosiloxane composition for a binder according to claim 1, which is obtained by reacting a silicone compound represented by the formula (1) which represents a monovalent hydrocarbon group or R ² ₃ Si-). 3. The component (A) has an average formula R ³ _b Si (OR ⁴ ) _c O _{(4-bc) / 2.}
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is a group selected from hydrogen and R ³ , b is a number of 1.0 to 1.5, and c is
Represents a number from 0.05 to 0.2. The polyorganosiloxane composition for a binder according to claim 1, which is a thermosetting polyorganosiloxane resin represented by the formula (1). 4. The polyorganosiloxane composition for a binder according to claim 3, wherein R ³ is a monovalent hydrocarbon group selected from a methyl group and a phenyl group. 5. A silicone mica laminated product obtained by laminating and bonding mica pieces using the polyorganosiloxane composition according to claim 1 as a binder. 6. A silicone glass laminated product obtained by laminating and bonding glass cloth using the polyorganosiloxane composition according to claim 1 as a binder.