JP3042358B2 - Integrated composite of silicone rubber and epoxy resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful in the fields of electric / electronics, OA equipment, automobiles, precision equipment, and the like, and is characterized in that an organic peroxide-curable or addition-curable silicone rubber and an epoxy resin cured product are firmly bonded. The present invention relates to an integrated composite and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, silicone rubber has been recognized for its high reliability in heat resistance, weather resistance, electric characteristics, etc., and its use is expanding in the fields of electric / electronics, OA equipment, automobiles, and the like. Epoxy resins, which are thermosetting resins, have excellent properties such as electrical properties, mechanical properties, adhesiveness, and the like, and their application fields are wide. Therefore, there has been a demand for a composite of such a silicone rubber and an epoxy resin. In this case, it is desired to supply an integrally molded product in which these are firmly bonded.

[0003] By the way, conventionally, many methods for bonding silicone rubber and organic resin have been proposed. For example, (1) a method in which a primer is applied to the surface of a molding resin and an uncured silicone rubber is applied and cured on the surface to bond the resin, and (2) a method in which a self-adhesive silicone rubber material is cured from the top of the molding resin (note that For the self-adhesive silicone rubber composition, many patents have been proposed, in particular, using the adhesive component as the essence). (3) An organic resin containing at least 30 mol% of hydrogen atoms directly bonded to silicon atoms on the organic resin side. US Patent No. 4,582,762, US Pat.
P4,686,124, USP4,814,231, U
SP4, 834, 721, JP-B-2-34311), (4) A method of physically fitting silicone rubber to an organic resin (JP-B-63-45292), (5)
A method in which silicone rubber is bonded and integrated to an olefin resin grafted with a compound having an aliphatic unsaturated group and a silicon-bonded hydrolyzable group (EP 276790A;
-183843) and the like.

[0004]

However, (1)
The method of bonding using a primer has the problem that it is necessary to remove the resin molded product once from the mold and apply the primer, which is troublesome,
The method of (2) applying the silicone self-adhesive to the molding resin and curing the resin has a great difficulty in that when the resin and silicone rubber are molded using a mold or the like, the silicone rubber itself adheres to the mold. . In the method (3) of adding a hydrogen siloxane to a resin, the properties of the resin itself may be changed due to the addition of the siloxane, and it may be difficult to obtain the original properties of the resin. The physical fitting method of 4) has a possibility that the fitting may be disengaged by a physical force, and the method of (5) has a drawback that a primer is necessary for integrating the addition-curable silicone rubber.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite in which a cured epoxy resin and a silicone rubber are firmly integrated, and a simple and reliable method for producing such a composite. I do.

[0006]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that an organic peroxide-curable or addition-curable silicone rubber composition, an epoxy resin composition, After one of them is cured at room temperature or by heating, the other composition is directly adhered to the cured or semi-cured material and cured at room temperature or by heating, so that the silicone rubber and the cured epoxy resin are tightly bonded. It was found that an integrated composite was obtained.

That is, the inventor of the present invention has developed an integrated composite (molded product) of a silicone rubber and an organic resin, which has been conventionally difficult to bond and, if possible, through a primer layer, has been complicated. An organic peroxide-curable or addition-reaction-curable silicone rubber is selected, and a specific epoxy resin cured product obtained from an epoxy resin composition containing the following components (A) to (D) as main components is selected as the organic resin. The present inventors have found that by selecting such a compound, it is possible to obtain an integral composite having an adhesive strength enough to withstand practical use in a simple and short time without using a primer, and have accomplished the present invention.

Hereinafter, the present invention will be described in more detail. The integrated composite of silicone rubber and epoxy resin of the present invention is:
An organic peroxide-curable or addition-reaction-curable silicone rubber and an epoxy resin cured product are integrated.

Here, the organic peroxide-curable silicone rubber includes (a) the following general formula (1): R ¹ _a SiO _{(4-a) / 2} (1) wherein R ¹ is carbon number of 1 to 10, but preferably 1 to 8 substituted or unsubstituted monovalent hydrocarbon group, the R ¹ 0.0
05 to 20 mol%, preferably 0.01 to 10 mol%, is an alkenyl group. a is a positive number of 1.9 to 2.4, preferably 1.95 to 2.2. A) an organopolysiloxane containing at least two or more alkenyl groups on average in one molecule, and (b) a silicone rubber composition comprising a catalytic amount of an organic peroxide as a main component, which is obtained. It is preferred that it is.

Here, in the alkenyl group-containing organopolysiloxane represented by the formula (1) of the component (a), R ¹ is specifically methyl, ethyl, propyl,
Alkyl groups such as isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, octyl, decyl, alkenyl groups such as vinyl, allyl, propenyl and butenyl, and aryl groups such as phenyl and xylyl;
Aralkyl groups such as benzyl and phenylethyl; halogen-substituted groups such as chloromethyl, bromoethyl, cyanoethyl, and 3,3,3-trifluoropropyl; and cyano-substituted hydrocarbon groups. May be 0.005 to 20 mol% in R ¹ ,
More preferably, 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, is an alkenyl group, and it is necessary that the molecule has at least two alkenyl groups on average. is there. R ¹ may be any of the above, but it is preferable to introduce a vinyl group as an alkenyl group and a methyl group or a phenyl group as another substituent.
The alkenyl group in the molecule may be bonded to either or both the silicon atom at the terminal of the molecular chain or the silicon atom in the middle of the molecular chain, but is preferably an alkenyl group bonded to at least the silicon atoms at both terminals of the molecular chain. Is desirable from the viewpoint of physical properties of the cured product. A is 1.9 to 2.4, preferably 1.95 to
2.2 is a positive number in the range of, the alkenyl group-containing organopolysiloxane main chain is basically R ¹ ₂ SiO
_Consisting of repeating _2/2 diorganosiloxane units,
Also be one in which both terminals of the molecular chain of the R ¹ ₃ are blocked with triorganosiloxy units represented by SiO _1/2 linear, R ¹
It may be a branched one containing SiO _3/2 units or SiO _4/2 units.

The alkenyl group-containing organopolysiloxane has a viscosity of 100 to 1,000,000 at 25.degree.
00 cp, particularly preferably 500 to 500,000 cp.

The organopolysiloxane can be produced by a known method. Specifically, an organocyclopolysiloxane and a hexaorganodisiloxane are subjected to an equilibration reaction in the presence of an alkali or acid catalyst. Can be obtained by

The organic peroxide as the component (b) is used as a catalyst for accelerating the crosslinking reaction of the alkenyl group-containing organopolysiloxane as the component (a). Can be mentioned.

[0014]

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The amount of the organic peroxide (b) to be added is a catalytic amount and can be appropriately selected according to the curing speed. Usually, the amount of the organopolysiloxane (a) is 100%.
The range is from 0.1 to 10 parts, preferably from 0.2 to 2 parts, per part.

The silicone rubber composition may contain, in addition to these main components, a filler or the like for adjusting the fluidity or improving the mechanical strength of the molded article. Such fillers, for example precipitated silica, fumed silica, calcined silica, usually as fumed titanium oxide, the specific surface area by BET method of 50 m ² / g or more, particularly 50 to 400 m ² / g approximately reinforcing Non-reinforcing fillers such as fillers, crushed quartz, diatomaceous earth, asbestos, aminosilicic acid, iron oxide, zinc oxide, calcium carbonate and the like are exemplified, and these fillers can be used as they are, or hexamethylsilazane, trimethylchlorosilane, Surface treatment with an organosilicon compound such as polymethylsiloxane may be used. In addition, pigments, heat-resistant agents, flame-retardant materials, plasticizers, and the like that are blended with ordinary silicone rubber may be blended.

The silicone rubber composition is preferably liquid or paste at room temperature.

Examples of the addition-curable silicone rubber include (a) the following general formula (1): R ¹ _a SiO _{(4-a) / 2} (1) (wherein R ¹ has 1 to ¹ carbon atoms) 10, is preferably a 1-8 substituted or unsubstituted monovalent hydrocarbon group, the R ¹ 0.0
1 to 20 mol% is an alkenyl group. a is 1.9 ~
It is a positive number of 2.4. ), 100 parts by weight of an organopolysiloxane containing at least two or more alkenyl groups on average per molecule, (c) the following general formula (2): R ² _b H _c SiO _{(4-bc) / 2} ... (2) (wherein, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms.
2.1, c is 0.005 to 1, and b + c is 0.9 to 3. (D) 0.1 to 30 parts by weight of a liquid organohydrogenpolysiloxane at room temperature, (d) obtained by curing a silicone rubber composition containing a catalytic amount of an addition reaction catalyst as a main component. Is preferred.

Here, the alkenyl group-containing organopolysiloxane of the component (a) is the same as the component (a).

In the organohydrogenpolysiloxane of the component (c) represented by the formula (2), R ² is the same as R ¹ but preferably does not have an aliphatic unsaturated bond. b is 0.8 to 2.1;
005 to 1, and b + c are preferably 0.9 to 3. More preferably, 1 ≦ b ≦ 2, 0.01 ≦ c ≦ 1,
1.5 ≦ b + c ≦ 2.6, especially 1.8 ≦ b + c ≦ 2.2
It is preferred that The molecular structure of the organohydrogenpolysiloxane of the component (c) is not particularly limited as long as it has a linear, branched, cyclic, three-dimensional network structure or the like. 2 to 500,
Preferably, the number is about 4 to 200, and at least two, usually about 2 to 500, preferably about 3 to 200 hydrogen atoms (SiH groups) bonded to silicon atoms are present in the molecule. Anything should do.

Examples of such organohydrogenpolysiloxanes include methylhydrogenpolysiloxane having trimethylsiloxy groups at both ends, dimethylsiloxane / methylhydrogenpolysiloxane copolymer having trimethylsiloxy groups at both ends, and dimethylhydrogensiloxy acid at both ends. Group-blocked dimethylsiloxane, dimethylhydrogenpolysiloxy at both ends, group-blocked dimethylsiloxane / methylhydrogenpolysiloxane copolymer,
Methyl hydrogen polysiloxane / diphenyl siloxane / dimethyl siloxane copolymer capped with trimethylsiloxy groups at both ends, (CH ₃ ) ₂ HSiO _1/2 unit and SiO
Copolymers composed of _4/2 units, and copolymers composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and (C ₆ H ₅ ) SiO _3/2 units can be exemplified. .

The amount of the organohydrogenpolysiloxane (c) is usually 0.1 to 30 parts, preferably 0 to 100 parts (parts by weight, hereinafter the same) of the organopolysiloxane (a). In the range of 3 to 10 parts. The compounding amount of the organohydrogenpolysiloxane of the component (c) is based on the alkenyl group bonded to the silicon atom in the component (a) and the hydrogen atom bonded to the silicon atom in the component (c) (that is, SiH group). May be blended in a molar ratio of 0.5 to 5 mol / mol, preferably 0.8 to 3 mol / mol.

Examples of the addition reaction catalyst for the component (d) include platinum group metal compounds such as platinum black, chloroplatinic chloride, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, Examples thereof include platinum bisacetoacetate, a palladium-based catalyst, and a rhodium-based catalyst. The addition amount of the addition reaction catalyst is a catalytic amount, and is usually 0.1 to 500 ppm, particularly 1 to 100 ppm as platinum or rhodium metal relative to the component (a).

In addition to the above components, the silicone rubber composition may contain the above-mentioned filler and other components similarly to the above-mentioned organic peroxide-curable silicone rubber composition.

It is preferable that the silicone rubber composition is liquid or paste at room temperature.

On the other hand, as the cured epoxy resin, (A)
100 parts of epoxy resin, (B) aluminum compound 0.
001 to 10 parts, (C) the following general formula (3) R^Three _m(H O)_nSiO_{(4-mn) / 2} ... (3) (where R^ThreeHas 1 to 20, preferably 1 to 10 carbon atoms
It is a substituted or unsubstituted monovalent hydrocarbon group. m is 0 <m ≦
3, n is 0 <n ≦ 3, and m + n is 1.5 to 4. )
Represented by a hydroxyl group bonded to a silicon atom (that is, a silano
Having one or more thiol groups in the molecule
0.1 to 25 parts of a run or organopolysiloxane,
(D) The following general formula (4) R^Four _pH_qSiO_{(4-pq) / 2} ... (4) (where R^FourIs a substituent having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms.
It is a substituted or unsubstituted monovalent hydrocarbon group. p is 0 <p <
3, q is 0 <q <3, and p + q is 1.5 to 2.6.
You. ), The hydrogen atom bonded to the silicon atom
Organohydrogen having one or more than one
Epoxy based on 0.2 to 25 parts of polysiloxane
It is obtained by curing the resin composition
Is preferred.

In this case, as the epoxy resin of the component (A), any epoxy resin which is usually used as an epoxy resin composition may be used. For example, bisphenol A
Epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, alicyclic epoxy resin, epoxy resin containing heterocycle such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A epoxy resin, propylene glycol diglycidyl Aliphatic epoxy resin such as ether or pentaerythritol polyglycidyl ether, epoxy resin obtained by reacting aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin, spiro ring-containing epoxy resin, o-allyl A glycidyl ether type epoxy resin which is a reaction product of a phenol novolak compound and epichlorohydrin, a diallyl bisphenol compound having an allyl group at an ortho position of each hydroxyl group of bisphenol A and an epichlorohydrin Glycidyl ether type epoxy resin is the reaction product of Rohidorin thereof.

The organoaluminum compound of the component (B) includes alkyl, phenyl, substituted phenyl, haloalkyl, alkoxy, phenoxy, substituted phenoxy, acyloxy, β-diketona, o-carbonylpheno. A compound in which an organic group selected from a group such as a rat group is bonded to aluminum.

Here, the alkyl group in the organic group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl and the like. And a substituted phenyl group having 1 to 10 carbon atoms such as a p-methoxyphenyl group, an o-methoxyphenyl group, and a p-ethoxyphenyl group.
10 to 10 alkoxy-substituted ones, haloalkyl groups include chloromethyl group, chloroethyl group, chloropropyl group and the like having 1 to 10 carbon atoms, and alkoxy groups include
Those having 1 to 10 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group and pentoxy group, and substituted phenoxy groups include o-methylphenoxy group, o-methoxyphenoxy group, o-nitrophenoxy group, , 6-
Lower alkyl such as dimethylphenoxy group, those substituted with lower alkoxy group or nitro group, and acyloxy groups include
Acetato group, propionato group, isopropionate group, butyrate group, stearato group, ethyl acetoacetato group, propyl acetonato group, butyl acetonato group, diethyl malato group, dipivaloyl methanato group having 2 to 10 carbon atoms The β-diketanato group is exemplified by an acetylacetonato group, a trifluoroacetonato group, a hexafluoroacetylacetonato group and the like, and the o-carbonylphenolato group is exemplified by a salicylaldehyde group.

Specific examples of such an organoaluminum compound include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, triphenoxyaluminum, tri (p-methylphenoxy) aluminum, isopropoxydiethoxyaluminum,
Aluminum tributoxy, triacetoxy aluminum, tristearato aluminum, tributyrat aluminum, tripropionate aluminum, triisopropionate aluminum, tris (acetylacetonate)
Aluminum, tris (trifluoroacetylacetonato) aluminum, tris (salicylaldehyde) aluminum, tris (pentafluoroacetylacetonato) aluminum, tris (ethylacetato) aluminum, ethylacetatodiisopropoxyaluminum,
Tris (diethylmalorato) aluminum, tris (propylacetato) aluminum, tris (butylacetoacetato) aluminum, tris (isopropylacetoacetato) aluminum, tris (dipivaloylmethanato) aluminum, diacetylacetonatodipivaloylmethanato Examples thereof include aluminum and ethyl acetoacetatodiisopropoxy aluminum, and the following compounds can also be exemplified.

[0031]

Embedded image

As the organoaluminum compound of the component (B), one of the above-mentioned organoaluminum compounds can be used alone or in combination of two or more.
0.001 to 100 parts of the epoxy resin (A)
The range is from 10 to 10 parts, preferably from 1 to 5 parts. If the amount is less than 0.001 part, sufficient curing properties cannot be obtained, while if it exceeds 10 parts, cost, physical properties, and adhesiveness are adversely affected.

(C) Component organosilane or organo
Polysiloxane is an organoaluminum compound of component (B).
Reacts with the substance and accelerates the curing of the epoxy resin.
Sila having at least one silanol group in one molecule
Compounds or organopolysiloxanes, specifically
Is bonded to a silicon atom represented by the following general formula (3)
One or more hydroxyl groups (ie, silanol groups) in the molecule
Organosilane or organopolysiloxane
You. The organopolysiloxane is a straight-chain, branched
It may be either a shape or a ring. Also the molecule
The number of silicon atoms therein is 2 to 500, preferably 2 to 1.
00 is sufficient. R^Three _m(H O)_nSiO_{(4-mn) / 2} … (3)

This R^ThreeHas 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms.
Is a substituted or unsubstituted monovalent hydrocarbon group, specifically
Are methyl, ethyl, propyl, butyl,
Silyl, octyl, decyl, undecyl, dodecyl
Alkyl group such as octadecyl group, cyclohexyl
Group, cycloalkyl group such as cyclooctyl group, phenyl
Group, naphthyl group, anthranyl group, methylphenyl group,
Aryl group such as xylyl group, benzyl group, phenylethyl
Aralkyl groups such as benzyl group, cumyl group, vinyl group, allyl
Group, alkenyl group such as cyclohexenyl group, or
Part or all of the hydrogen atoms in these groups may be halogen atoms or silicon atoms.
Groups substituted with an ano group or the like, for example, chloromethyl group, bromo
Ethyl group, p-chlorophenyl group, o-chlorophenyl
Group, p-trifluoropropyl group, o-trifluoromethyl
Tylphenyl group, 3,3,3-trifluoropropyl
Group, cyanoethyl group, trimethylsilyl group, tri
Β-trimethylsilyl substituted with an alkoxysilyl group or the like
Ethyl group, γ-trimethylsilylpropyl group, β-tri
Methoxysilylethyl group, β-triethoxysilylethyl
Group, γ-trimethoxysilylpropyl group, γ-trie
Toxisilylpropyl group, and further γ-glycidoxypropyl
Group, β- (3,4-epoxycyclohexyl) ethyl group
Examples of substituted hydrocarbon groups substituted with epoxy groups such as
can do. R^Three Is aliphatically unsaturated among these
An alkyl group containing no bond, such as a methyl group,
It is preferably an aryl group such as a nyl group.

Further, m is 0 ≦ m ≦ 3, and n is 0 <n ≦ 3.
And m + n is 1.5 to 4, preferably 2 to 4. In particular, when component (c) is an organosilane compound, m is 1, 2, or 3, and n is 1, 2, or 3, and m + n = 4. When component (c) is an organosiloxane compound, 1 ≦ 1. m <3, 0 <n ≦ 2, and 1.5 ≦ m + n ≦ 3, preferably 2 ≦ m + n ≦ 3.

The following compounds can be exemplified as typical examples of the component (C).

[0037]

Embedded image (In each of the above formulas, x is 1 to 500, preferably 1 to 1
Integer of 00, y and z are respectively y ≧ 0, z ≧ 1, 1 ≦ y
It is an integer satisfying + z ≦ 500. )

As the organosilane or organopolysiloxane of the component (C), one of the above-mentioned organosilanes or organopolysiloxanes can be used alone or in combination of two or more. 0.1 to 25 parts, and preferably 0.1 to 25 parts, per 100 parts of the epoxy resin component.
The range is 5 to 20 parts. If the compounding amount is less than 0.1 part, the effect of the compounding is not exhibited, while if it exceeds 25 parts, the inherent properties of the epoxy resin are impaired.

Further, the component (D) of the above epoxy resin composition is an organohydrogenpolysiloxane having at least one hydrogen atom bonded to one silicon atom in one molecule. 4) An organopolysiloxane having one or two or more hydrogen atoms bonded to silicon atoms (ie, SiH groups) in one molecule. The organopolysiloxane may be linear, branched or cyclic. Further, the number of silicon atoms in the molecule may be 2 to 50, preferably about 2 to 30, and at least one hydrogen atom (SiH group) bonded to the silicon atom in the molecule is preferable. Should just have about 2-30 pieces. R ⁴ _p H _q SiO _{(4-pq) / 2} ... (4)

Where R^FourIs R^Three Substituted or unsubstituted as in
A monovalent hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms
0 <p <3, 0 <q <3, and p + q is 1.
5 to 2.6.

This component (D) has at least one alkoxy-functional group as R ⁴ in the molecule, for example, γ-trimethoxysilylpropyl, γ-triethoxysilylpropyl, β-trimethoxysilylethyl, β- A trialkoxysilyl-substituted hydrocarbon group such as a triethoxysilylethyl group or an epoxy-functional hydrocarbon group such as an epoxy-functional hydrocarbon group such as a γ-glycidoxypropyl group or a β- (3,4-epoxycyclohexyl) ethyl group. It is preferred that it contains a group.

The following are examples of the organohydrogenpolysiloxane.

[0043]

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[0044]

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The compounding amount of the component (D) is in the range of 0.2 to 25 parts, preferably 0.5 to 20 parts with respect to 100 parts of the epoxy resin of the component (A). Is less than 0.2 part, the effect of the combination is not exhibited, while 25
Exceeding the part will impair the inherent properties of the epoxy resin.

In the epoxy resin composition, besides the above essential components, a filler can be blended in a range that does not impair the adhesion to the silicone rubber. Examples of such fillers include various kinds of fillers such as fused silica, crystalline silica, glass powder, glass fiber, clay, talc, mica, asbestos, zinc oxide, magnesia, aluminum silicate, zirconium silicate, alumina, and fumed silica. Fine powders, fibrous materials and the like can be mentioned.

The method for producing a composite of a silicone rubber and an epoxy resin according to the present invention is characterized in that one of the above-mentioned organic peroxide or addition-curable silicone rubber composition and the epoxy resin composition is heated at room temperature or by heating. Let it cure and mold. The molding method can be freely selected depending on its viscosity, and may be any of injection molding, compression molding, injection molding, extrusion molding, and transfer molding. After the primary molded product is cured, the other composition is brought into close contact with the primary molded product and cured at room temperature or by heating to obtain an integrated molded product. The molding method of the secondary molded product can be freely selected depending on its viscosity, and may be any of injection molding, compression molding, injection molding, extrusion molding, and transfer molding. The timing at which the secondary molded product is cured does not necessarily have to be completely cured, and there is no problem as long as the primary molded product is cured to such an extent that the two are not mixed and an interface can be formed.

The shape of the primary molded product and the secondary molded product is arbitrary, and can be any desired shape required for the composite, such as a sheet, a plate, a column, and a block.

[0049]

As described above, the one-piece composite of the present invention is a cured product of an epoxy resin composition and an organic peroxide, which have conventionally been difficult to bond, and even if they could be bonded, the steps such as the interposition of a primer layer were complicated. Since a composite in which a curable or addition-curable silicone rubber is firmly integrated can be obtained easily and in a short time without a primer, even those having complicated shapes can be efficiently produced. It can be applied to a wide range of applications, such as the equipment field, the automobile field, and the precision equipment field.

[0050]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples, all parts show a weight part and the viscosity shows the value in 25 degreeC.

Example 1 As an epoxy resin, Epicoat 828 (trade name, manufactured by Shell Chemical Company, Bisphenol A)
Mold, epoxy equivalent 190-210, molecular weight 380) 10
To 0 parts, 0.6 parts of aluminum benzoate, 6.0 parts of diphenylsilanediol, and 5 parts of an organopolysiloxane represented by the following formula were added to obtain an epoxy resin composition (A).

[0052]

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On the other hand, 100 parts of dimethylpolysiloxane having a viscosity of 100 poise and both ends of the molecular chain blocked with a dimethylvinylsilyl group, 30 parts of fumed silica having a specific surface area of 200 m ² / g, 6 parts of hexamethylsilazane, water 2 parts were added and mixed by heating at 150 ° C. for 3 hours, and 50 parts of dimethylpolysiloxane having a viscosity of 100 poise and 25 parts
0.4 parts of a methyl hydrogen siloxane copolymer capped at both ends with a trimethylsilyl group having a viscosity of 10 centipoise at 50 ° C. (dimethylsiloxane unit 50 mol%, methyl hydrogen siloxane unit 50 mol%), isopropanol solution of chloroplatinic acid (containing platinum) (Amount of 0.50% by weight) was added to obtain a silicone rubber composition (A).

Next, an integrated composite of epoxy resin and silicone rubber was molded using the mold shown in FIG. First, about half the amount of the epoxy resin composition (A) is injected into the cavity 2 of the lower mold 1 and heated and cured at 150 ° C. for 3 minutes, and then the upper mold 3 is placed on the lower mold 1 to lower the mold. 1, the silicone rubber composition (A) is injected at an injection pressure of about 60 kg / cm ² onto the cured epoxy resin composition (A) from the injection port 4 provided on the upper mold 3, C. for 5 minutes to obtain a composite in which the epoxy resin and the silicone rubber were firmly integrated. As a result of a tensile shear test of this composite, a rubber fracture with a cohesive failure rate of 100% was found.

Example 2 A specific surface area of 200 m ² / g was added to 100 parts of dimethylpolysiloxane having a viscosity of 1000 poise and both ends of a molecular chain blocked with a trivinylsiloxy group.
30 parts of fumed silica, 6 parts of hexadimethyldisilazane and 2 parts of water were added and mixed by heating at 150 ° C. for 3 hours, and 50 parts of dimethylpolysiloxane having a viscosity of 1000 poise and 1,6-bis (t- 1.0 part of butylperoxy) hexane was added to obtain a silicone rubber composition (B).

Next, using the same mold as in Example 1, the epoxy resin composition (A) obtained in Example 1 was similarly injected into the lower mold 1 and cured at 170 ° C. for 2 minutes. The silicone rubber composition (B) is injected onto the cured epoxy resin composition (A), and the mixture is cured by heating at 170 ° C. for 5 minutes to obtain a composite in which the epoxy resin and the silicone rubber are firmly integrated. Was. As a result of a tensile shear test of this composite, a rubber fracture with a cohesive failure rate of 100% was found.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a molding die used in an example.

[Explanation of symbols]

 1 Lower mold 2 Cavity 3 Upper mold 4 Injection

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-37265 (JP, A) JP-A-60-238378 (JP, A) JP-A-60-177030 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 5/12

Claims (4)

(57) [Claims] 1. An organic peroxide-curable or addition-reaction-curable silicone rubber, (A) 100 parts by weight of an epoxy resin, (B) 0.001 to 10 parts by weight of an organoaluminum compound, (C) the following general formula: (3) R ³ _m (HO) _n SiO _{(4-mn) / 2} (3) wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 0 <m ≦ 3, n is 0 <n ≦ 3
And m + n is 1.5 to 4. (D) 0.1 to 25 parts by weight of an organosilane or organopolysiloxane having one or more silanol groups in the molecule, (D) the following general formula (4): R ⁴ _p H _q SiO _{(4- pq) / 2} (4) (wherein, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. p is 0 <p <3, and q is 0 <q <3.
And p + q is 1.5 to 2.6. A) an organohydrogenpolysiloxane having one or more hydrogen atoms bonded to silicon atoms in the molecule,
An integrated composite of a silicone rubber and an epoxy resin, wherein an epoxy resin cured product obtained by curing an epoxy resin composition containing 主 成分 25 parts by weight as a main component is integrated. Wherein the organic peroxide curing type silicone rubber, (a) the following general formula _{^{(1) R 1 a SiO (}} 4-a) / 2 ... (1) ( In the formula, R ¹ 1 carbon atoms 10 to 10 substituted or unsubstituted monovalent hydrocarbon groups, wherein 0.005 to 20 mol% of R ¹ is an alkenyl group; a is a positive number of 1.9 to 2.4) An organopolysiloxane containing at least two or more alkenyl groups on average in one molecule, and (b) obtained by curing a silicone rubber composition containing a catalytic amount of an organic peroxide as a main component. The composite according to claim 1, which is: 3. An addition reaction-curable silicone rubber comprising: (a) the following general formula (1): R ¹ _a SiO _{(4-a) / 2} (1) (wherein, R ¹ has 1 to 10 carbon atoms) Is a substituted or unsubstituted monovalent hydrocarbon group, wherein 0.01 to 20 mol% of R ¹ is an alkenyl group, and a is a positive number of 1.9 to 2.4.) An organopolysiloxane 100 containing at least two or more alkenyl groups on average in one molecule
Parts by weight, (c) the following general formula (2): R ² _b H _c SiO _{(4-bc) / 2} (2) (wherein, R ² is a substituted or unsubstituted monovalent carbon having 1 to 10 carbon atoms) B is 0.8 to 2.1, and c is 0.00.
5-1 and b + c are 0.9-3. The organohydrogenpolysiloxane 0.1
The composite according to claim 1, which is obtained by curing a silicone rubber composition containing (d) a catalytic amount of an addition reaction catalyst as a main component. 4. An organic peroxide-curable silicone rubber composition according to claim 2 or an addition reaction-curable silicone rubber composition according to claim 3, and either the epoxy resin composition according to claim 1. A method for producing an integrated composite of silicone rubber and an epoxy resin, wherein the composition is cured and then the other composition is brought into close contact with the composition and cured.