JPH08224833A - Composite of silicone rubber and silicone epoxy resin, and manufacture thereof - Google Patents

Abstract

PURPOSE: To provide an integrally molded composite having stable quality wherein an epoxy thermosetting resin and a silicone rubber adhere to each other firmly, and a method for easily manufacturing the composite. CONSTITUTION: A cured body of an organic peroxide curing or addition curing silicone rubber composition and a cured body of a curing silicone-epoxy resin composition are directly integrated at the time of curing so as to form a composite. Either the organic peroxide curing or addition curing silicone rubber composition or the curing silicone-epoxy resin composition is cured at room temperature or with heat, and the other composition is adhered to it and cured at room temperature or with heat so as to form the composite.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an integrally molded body of silicone-epoxy resin and silicone rubber and a method for producing the same. In particular, the present invention relates to an integrally molded composite useful in the fields of electric, electronic, office automation equipment, automobiles, precision equipment, etc., and a method for producing this composite.

[0002]

2. Description of the Related Art Conventionally, many methods for adhering silicone rubber and organic resin have been proposed. For example, a method has been proposed in which a primer is applied to the surface of a molding resin and then an uncured silicone rubber is applied and cured to adhere the primer, and a method of curing a self-adhesive silicone rubber material from above the molding resin. This self-adhesive silicone rubber material (composition)
With respect to the above, many inventions in which the adhesive component is the essence have been filed. In addition, hydrogen atoms directly bonded to silicon atoms on the organic resin side are 30 mol% with respect to silicon atoms in one molecule.
A method of adding the above-mentioned organopolysiloxane and adhering it to an addition-curable silicone rubber (see Japanese Patent Publication No. 2-34311), and integrating the silicone rubber with an organic resin by a physical fitting method (Japanese Patent Publication No. 63-45292). (See Japanese Patent Laid-Open No. 63-183843), a method of adhering and integrating silicone rubber to an olefin resin grafted with a compound having an aliphatic unsaturated group and a silicon atom-bonded hydrolyzable group (see Japanese Patent Laid-Open No. 63-183843) has been proposed. ing.

[0003]

However, the method of adhering using a primer requires the labor of taking out the resin molded product once molded from a mold or the like and applying the primer. The method of applying a self-adhesive silicone to a resin molded product and curing the resin has a big drawback that the silicone rubber itself adheres to the mold when the resin and the silicone rubber are molded using a mold or the like. In addition, the method of adding an organopolysiloxane containing a hydrogen atom directly bonded to a silicon atom to the resin may change the physical properties of the resin itself due to the addition of siloxane, and it may be difficult to obtain the original characteristics. there were. Further, in the method of integrating by physical fitting, there is a concern that the fitting may come off due to physical force. On the other hand, in recent years, silicone rubber has been recognized for its high reliability in heat resistance, weather resistance, electrical characteristics, etc., and its application is spreading in the fields of electricity, electronics, OA equipment, automobiles, etc., and thermosetting resin and silicone rubber It has been desired to supply an integrally molded product having a stable adhesion and a stable quality. The present invention solves such a problem, and provides a integrally molded composite body in which a thermosetting resin and a silicone rubber are firmly adhered to each other and the quality is stable, and a method capable of easily manufacturing the composite body. It was made as.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an organic peroxide-curable or addition-curable organopolysiloxane composition is used as a silicone rubber, and a silicone resin is used as a resin. The present inventors have found that by selecting a polymer blend system with an epoxy resin, an integrally molded composite body can be easily obtained with an adhesive force that can sufficiently withstand practical use in a short time, and the present invention has been completed.
The composite and the method for producing the same of the present invention have solved the above-mentioned problems. The composite is a cured product of an organic peroxide-curable or addition-curable silicone rubber composition and a curable silicone-
A cured product of an epoxy resin composition is directly bonded and integrated during curing, and a method for producing a composite is an organic peroxide-curable or addition-curable silicone rubber composition, or a curable silicone-epoxy resin. One of the compositions is cured at room temperature or under heating, and then the other composition is adhered and cured at room temperature or under heating.

The present invention will be described in more detail below. Examples of the organic peroxide-curable silicone rubber composition that can be used in the present invention include A) an organopolysiloxane containing preferably at least two lower alkenyl groups on average in one molecule, and B) a catalytic amount of an organic peroxide. There is a liquid or paste-like composition containing, as a main component at room temperature, and when left at room temperature or heated, it cures into a rubber-like elastic body.

The organopolysiloxane of component A) has a viscosity of 100 cP to 10,000,000 cP, preferably 1,000 cP to 1,000,000 cP at room temperature (eg, 25 ° C.),
The one represented by the general composition formula R _a SiO _{(4-a) / 2} is used.
R is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, alkyl group such as decyl group, vinyl group, allyl group, propenyl group, Arpropyl group such as isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, phenyl group, tolyl group, aryl group such as xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc. A group, a chloromethyl group, a chloropropyl group, a bromoethyl group, a halogen-substituted hydrocarbon group such as 3,3,3-trifluoropropyl group, a cyano group-substituted hydrocarbon group such as a cyanoethyl group, and the like, having 1 to 12 carbon atoms, It is preferably selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and each group is the same as each other. May be made, preferably contains an average of at least two alkenyl groups in a molecule to improve crosslinking, more preferably contains the group at a molecular chain terminal. In order to obtain a rubber elastic body, a is in the range of 1.9 to 2.2, preferably 1.95 to 2.1. Even if this organopolysiloxane is linear,
It may have a branched structure containing RSiO _3/2 units or SiO _4/2 units, but usually, the main chain part is basically composed of repeating R ₂ SiO _2/2 units, and the molecular chain end is R _It is generally a linear structure that is blocked with ₃ SiO _1/2 units. The group bonded to the silicon atom may be basically any of the above groups, but the alkenyl group is preferably a vinyl group, and the other groups are preferably a methyl group and a phenyl group. This organopolysiloxane can be obtained by a known method, that is, by carrying out an equilibration reaction of an organocyclopolysiloxane and a hexaorganodisiloxane in the presence of an alkali or acid catalyst.

The organic peroxide of the component B) is used as a catalyst for promoting the crosslinking reaction of the component A), and for example, benzoyl peroxide, o-monochlorobenzoyl peroxide, bis-2,4. -Dichlorobenzoyl peroxide, dicumyl peroxide,
t-butyl peroxybenzoate, di-t-butyl peroxide, p-monochlorobenzoyl peroxide, t-butylcumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane , 2,5-dimethyl-2,5-bis (t-
Butylperoxy) hexane, 1,6-bis (t-butylperoxycarboxy) hexane and the like,
It is not limited to these. The addition amount of the component B) may be appropriately selected according to the desired curing speed, but is usually 0.1 to 100 parts by weight of the component A) (parts by weight, the same applies hereinafter).
The amount may be 10 parts, preferably 0.2 to 2 parts.

A filler may be added to these components A) and B) in order to adjust the fluidity and improve the mechanical strength of the molded product. Such fillers include precipitated silica, fumed silica, pyrogenic silica, reinforcing fillers such as fumed titanium oxide, ground quartz, diatomaceous earth, asbestos, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. Such non-reinforcing fillers are exemplified, and they may be used as they are or surface-treated with an organic silicon compound such as hexamethyldisilazane, trimethylchlorosilane, and polymethylsiloxane. In addition, a pigment, a heat resistance improver, a flame retardant, a plasticizer, etc. may be added if necessary.

The addition-curable silicone rubber composition includes C) an organopolysiloxane containing at least two lower alkenyl groups on average in one molecule, D) an organohydrogenpolysiloxane which is liquid at room temperature, and E) an addition reaction. There is a liquid or paste composition containing a catalyst as a main component at room temperature, and when left at room temperature or heated, it cures to a rubber-like elastic body.

The alkenyl group-containing organopolysiloxane as the component C) is from 100 cP at room temperature (for example, 25 ° C.).
Those having a viscosity of about 1,000,000 cP, preferably 1,000 to 300,000 cP and represented by the general composition formula R ¹ _b SiO _{(4-b) / 2} are used. R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, similar to those exemplified for R in the above-mentioned component A), for example, methyl group, ethyl group. Group, alkyl group such as propyl group, alkenyl group such as vinyl group, allyl group, propenyl group, butenyl group, aryl group such as phenyl group, tolyl group, xylyl group, aralkyl group such as benzyl group, 3, 3, 3 -A halogen-substituted hydrocarbon group such as a trifluoropropyl group and a cyano group-substituted hydrocarbon group such as a cyanoethyl group. Each group in one molecule may be the same or different, but in order to have crosslinkability, it is assumed that at least two alkenyl groups are included in one molecule on average, and preferably at the terminal of the molecular chain. It B indicates rubber elasticity
The range is 1.8 to 2.4, preferably 1.9 to 2.2, and the organopolysiloxane may be linear or branched containing R ¹ SiO _3/2 units or SiO _4/2 units. , Usually a linear diorganopolysiloxane whose main chain part is basically composed of repeating R ¹ ₂ SiO _2/2 units and whose molecular chain ends are blocked with R ¹ ₃ SiO _1/2 units. Is common. The group bonded to the silicon atom may be basically any of the above groups, but the alkenyl group is preferably a vinyl group, and the other groups are preferably a methyl group and a phenyl group. This organopolysiloxane can be produced by a known method.

The organohydrogenpolysiloxane of the component (D) has an average of at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms (that is, S
iH group) is used, and this SiH group acts as a cross-linking agent by the addition reaction of the SiH group with the alkenyl group of the component C) in the presence of the component E) described later. There is no limitation, and various kinds of conventionally produced linear, branched, cyclic and three-dimensional network structures can be used. Specifically, those represented by the following general formula can be preferably used. R ² _c H _d SiO _{(4-cd) / 2} where R ² has the same carbon number of 1 to 12 as those exemplified for R in the above-mentioned component A), and preferably has no aliphatic unsaturated bond. 1-8 unsubstituted or substituted monovalent hydrocarbon groups, alkyl groups such as methyl group, ethyl group, propyl group, aryl groups such as phenyl group, tolyl group, cycloalkyl groups such as cyclohexyl group, benzyl group And the like, and substituted alkyl groups such as 3,3,3-trifluoropropyl group. Also, the properties of this thing,
C, d, and c + d are 0.8 ≦ c ≦ 2.1, preferably 1.2 <c ≦ 2.0, 0.002 in view of reactivity and properties of the cured product.
≦ d ≦ 1, preferably 0.01 ≦ d ≦ 1, 1 ≦ c + d ≦ 3,
The number is preferably 1.5 ≦ c + d ≦ 2.7, and the viscosity of this organohydrogenpolysiloxane at 25 ° C. is preferably 1 to 1,000 cP, and particularly preferably 5 to 200 cP.

Examples of the organohydrogenpolysiloxane include methylhydrogenpolysiloxane having trimethylsiloxy groups blocked at both ends, dimethylsiloxane / methylhydrogensiloxane unit copolymer having trimethylsiloxy groups blocked at both ends, and dimethylhydrogensiloxy at both terminals. Group-blocked dimethylpolysiloxane, both-terminal dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane unit copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane unit copolymer, both-terminal trimethyl Siloxy group-blocked methyl hydrogen siloxane / diphenyl siloxane / dimethyl siloxane unit copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit copolymer, (CH ₃ ) ₂ H SiO _1/2 units, SiO _4/2 units, and (C ₆ H ₅ ) SiO _3/2 units. The amount of the organohydrogenpolysiloxane blended is preferably 0.1 to 30 parts, more preferably 0.3 to 10 parts based on 100 parts of the component C) organopolysiloxane in view of the characteristics of the cured product. Further, this blending amount is 0.2 to 10 mol / mol in terms of the molar ratio of the hydrogen atom (SiH group) bonded to the silicon atom in the component D) to the alkenyl group in the component C),
The amount may preferably be 0.5 to 5 mol / mol.

As the addition reaction catalyst of the component E), platinum black, chloroplatinic acid, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, platinum bisacetate Examples thereof include platinum group metal compounds such as acetate, palladium-based catalysts and rhodium-based catalysts.
The addition amount of this addition reaction catalyst may be a catalytic amount, but usually, C or C component by weight of platinum or platinum group metal,
0.1 to 1,000 ppm, preferably 1 with respect to the total of D)
~ 500ppm

Fillers may be added to these components C), D) and E) in order to adjust the fluidity and to improve the mechanical strength of the molded product. Such fillers include precipitated silica, fumed silica, pyrogenic silica, reinforcing fillers such as fumed titanium oxide, ground quartz, diatomaceous earth,
Non-reinforcing fillers such as asbestos, aluminosilicate, iron oxide, zinc oxide, calcium carbonate are exemplified, and as they are, surface-treated with an organic silicon compound such as hexamethyldisilazane, trimethylchlorosilane, polymethylsiloxane. But it's okay. In addition, a pigment, a heat resistance improver, a flame retardant, a plasticizer, etc. may be added if necessary.

On the other hand, the curable silicone-epoxy resin composition used in the present invention is not particularly limited as long as it has curability and becomes a uniform cured product, but the following are preferable. That is, 1) 100 parts of a curable epoxy resin, 2) 5 to 500 parts of organopolysiloxane containing at least two lower alkenyl groups on average in one molecule, 3) at least one silicon atom bonded to one molecule. It has a hydrogen atom and has a general formula R ⁴ _f H _g SiO _{(4-fg) / 2} (in the formula, R ⁴ may be the same or different from each other, and may have 1 to 12 carbon atoms. Organohydrogenpolysiloxane second component represented by an unsubstituted or substituted monovalent hydrocarbon group containing no valence bond, f is 1 ≦ f ≦ 2.4, and g is 0 <g ≦ 1. 1 to 50 parts per part, 4) 0.1 to 10 parts of organosilicon compound having at least one silanol group in one molecule, 5) 0.001 to 10 parts of organoaluminum compound, and 6) Platinum group compound As platinum group metal Composition of 0.1 to 500 parts for 1 million parts of the second component The thing is suitable.

The curable epoxy resin as the first component may be any one as long as it is one that is usually used in curable epoxy resin compositions, and specific examples thereof include bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, epoxy resin containing heterocyclic ring such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resin Resin, aliphatic epoxy resin such as propylene glycol diglycidyl ether or pentaerythritol polyglycidyl ether, epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin, spiro ring-containing Epoxy resin, o-
A glycidyl ether type epoxy resin which is a reaction product of an allylphenol novolak compound and epichlorohydrin, and a reaction product of a diallylbisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin. Examples thereof include certain glycidyl ether type epoxy resins.

The organopolysiloxane having an average of at least two lower alkenyl groups in one molecule of the second component is 100 cP to 1,000,000 cP at room temperature (eg 25 ° C.).
Preferably, those having a viscosity of about 1,000 cP to 300,000 cP and having essentially no silanol group in the molecule, which are represented by the general composition formula R ³ _e SiO _{(4-e) / 2} , are used. R ³
Is R in the component A) of the silicone rubber composition described above.
A monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which is unsubstituted or substituted, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. An alkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, a propenyl group and a butenyl group, an aryl group such as a phenyl group, a tolyl group and a xylyl group, an aralkyl group such as a benzyl group, 3,3,3- Examples thereof include halogen-substituted hydrocarbon groups such as trifluoropropyl group and cyano group-substituted hydrocarbon groups such as cyanoethyl group. Each group in one molecule may be the same or different, but in order to have crosslinkability, it is said that at least two alkenyl groups are contained on average in one molecule, and preferably at both ends of the molecular chain. . From the physical properties of the cured product, e is 1.8 to 2.
The number is in the range of 4, and even if this organopolysiloxane is linear, it is a branched or three-dimensional reticulated resinous substance containing R ³ SiO _3/2 units or SiO _4/2 units. It may be present, but usually, the main chain is basically composed of repeating R ³ ₂ SiO _2/2 units, and the end of the molecular chain is a linear di-chain which is blocked with R ³ ₃ SiO _1/2 units. It is generally an organopolysiloxane. The group bonded to the silicon atom may be basically any of the above, but the alkenyl group is preferably a vinyl group, the other groups are methyl groups, and it is said that the compatibility with the epoxy resin is improved. From the viewpoint, a phenyl group is desirable. The second component, organopolysiloxane, essentially does not contain a silanol group in the molecule. This organopolysiloxane can be produced by a known method. When the blending amount of this second component is less than 5 parts with respect to 100 parts of the curable epoxy resin as the first component, when the obtained silicone-epoxy resin composition is cured, the heat resistance characteristic of the silicone resin is Property, release property, etc. are not sufficiently obtained, and on the other hand, when the blending amount is more than 500 parts, sufficient strength cannot be obtained in the cured product, so it is set to 5 to 500 parts, preferably 20 to 200 parts. It

The third component organohydrogenpolysiloxane has at least one hydrogen atom bonded to a silicon atom (that is, SiH group) in one molecule, and at least one, preferably one, contained in one molecule is preferable. Two or more SiH groups undergo an addition reaction with the alkenyl group in the second component in the presence of a catalyst to extend or crosslink the chain, and have a general composition formula R ⁴ _f H _g SiO _{(4-fg) / 2} (In the formula, R ⁴ may be the same or different from each other, and is an unsubstituted or substituted monovalent hydrocarbon having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which does not contain an aliphatic unsaturated bond. Represents a group,
f is 1 ≦ f ≦ 2.4, preferably 1.6 ≦ f ≦ 2, and g is 0 <
g ≦ 1, preferably 0.002 ≦ g ≦ 1, and f + g is preferably a number satisfying 1.6 <f + g ≦ 3). From the properties, reactivity, properties of the cured product, etc., f and g are in the above ranges, but the reason why R ⁴ does not contain an aliphatic unsaturated bond is that the aliphatic unsaturated bond and S
This is because the addition reaction with the iH group is not preferable. This organohydrogenpolysiloxane is linear, branched,
It does not matter whether it is a resinous material having a cyclic structure or a three-dimensional network structure, and the viscosity of this organohydrogenpolysiloxane at 25 ° C. is preferably 1 to 1,000 cP, particularly preferably 5 to 200 cP, and The number of hydrogen atoms bonded to silicon atoms per molecule of the organohydrogenpolysiloxane is 1 from the viewpoint of the strength of the cured product.
The number of molecules is preferably 1 to 200, particularly 2 to 20 in the molecule. The third component essentially does not contain a silanol group in the molecule. This component can be produced by a known method.

Examples of R ⁴ in the above formula are the same as those described above as R in the component A) of the silicone rubber composition except the alkenyl group. Examples include methyl group, ethyl group and propyl group. Group, butyl group, hexyl group, octyl group, decyl group, undecyl group, alkyl group such as dodecyl group, cyclohexyl group,
Cycloalkyl group such as cyclooctyl group, phenyl group,
Naphtyl group, methylphenyl group, aryl group such as xylyl group, benzyl group, phenylethyl group, aralkyl group such as cumyl group, or part or all of hydrogen atoms bonded to carbon atoms of these groups are replaced by halogen atoms or the like. A substituted group,
For example, chloromethyl group, p-chlorophenyl group, m-
Γ substituted with a chlorophenyl group, o-chlorophenyl group, p-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, trimethylsilyl group or trialkoxysilyl group -Trimethylsilylpropyl group, γ-trimethoxysilylpropyl group, γ-triethoxysilylpropyl group, γ-glycidoxypropyl group substituted with an epoxy group, β- (3,4-epoxycyclohexyl) ethyl group, etc. It The mixing amount of the third component is 1 to 50 parts, preferably 5 parts to 100 parts of the second component.
However, if the compounding amount is less than 1 part, the crosslinking property, which is the function of this component, is insufficient.
If it exceeds the amount, the amount of the crosslinking agent component is too large, and in any case, the strength of the cured product may not be obtained. Also,
This amount is 0.2 to 10 mol / mol, preferably 0.5 to 5 mol / mol, in terms of the molar ratio of the hydrogen atom (SiH group) directly bonded to the silicon atom in the third component to the alkenyl group in the second component. May be

As the organosilicon compound having at least one silanol group in one molecule of the fourth component, organohydroxysilane or organohydroxy (poly) siloxane is used. The organohydroxysilane is represented by the general formula R ⁵ _h Si (OH) _4-h (h is 1, 2 or 3), R ^{5 s} may be the same or different from each other, and have 1 to 12 carbon atoms, Preferably, it represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not contain an aliphatic unsaturated bond, and examples thereof are the same as those exemplified as R in the component A) of the silicone rubber. For example, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, undecyl group, dodecyl group, cycloalkyl group such as cyclohexyl group, cyclooctyl group, vinyl group, etc. , Alkenyl groups such as allyl group and propenyl group, aryl groups such as phenyl group, naphthyl group, methylphenyl group, xylyl group, aralkyl groups such as benzyl group, phenylethyl group and cumyl group, Or a group in which a part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom or the like, for example, a chloromethyl group, p-chlorophenyl group, m-chlorophenyl group, o-chlorophenyl group, p-tri Fluoromethylphenyl group, o-trifluoromethylphenyl group, 3,
Examples include 3,3-trifluoropropyl group and cyanoethyl group.

The organohydroxy (poly) siloxane has the general composition formula: R ⁶ _i (HO) _j SiO _{(4-ij) / 2} (wherein R ⁶ may be the same or different from each other, and the number of carbon atoms may be different). 1-12, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1-8 carbon atoms which does not contain an aliphatic unsaturated bond, i is 1≤i≤2.5, preferably 1.5≤i≤2.2 , J
Is 0 <j ≦ 2, preferably 0.05 ≦ j ≦ 2, especially 0.1 ≦ j
≦ 1.5, 1 <i + j ≦ 3, preferably 1.6 ≦ i +
It represents a number satisfying j ≦ 2.5).
From the properties, reactivity, properties of the cured product, etc., i, j
Is within the above range, but the organopolysiloxane may be any of linear, branched, cyclic or resinous substances having a three-dimensional network structure. Examples of R ⁶ are the same as those exemplified as R in the component A) of the silicone rubber, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a decyl group. Undecyl group, dodecyl group, etc. alkyl group, cyclohexyl group, cyclooctyl group, etc. cycloalkyl group, vinyl group, allyl group, propenyl group, etc. alkenyl group, phenyl group, naphthyl group, methylphenyl group, xylyl group, etc. aryl Group, benzyl group, phenylethyl group, aralkyl group such as cumyl group, or a group in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, for example, chloromethyl group, p- Chlorophenyl group, m-chlorophenyl group, o
-Chlorophenyl group, p-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 3,3,3-
Γ-trimethylsilylpropyl group substituted with trifluoropropyl group, cyanoethyl group, trimethylsilyl group or trialkoxysilyl group, γ-trimethoxysilylpropyl group, γ-triethoxysilylpropyl group, γ-glycid substituted with epoxy group Examples thereof include a xypropyl group and a β- (3,4-epoxycyclohexyl) ethyl group.

In this organohydroxysilane or organohydroxy (poly) siloxane compound,
If the content of the silanol group is too small, sufficient cross-linking with the epoxy resin cannot be achieved, the required strength cannot be obtained, and the curing reaction itself becomes extremely slow. Conversely, if the silanol group content is too high, the silicone compound becomes unstable. Such organohydroxysilane or organohydroxy (poly) siloxane can be produced by a known method. Regarding the latter, for example, vinylmethyldichlorosilane and phenyltrichlorosilane may be optionally selected from tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, diphenyldichlorosilane, and one or more selected from methylphenyldichlorosilane. Co-hydrolysis of the added mixture, one or two selected from tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane as needed for vinyldimethylchlorosilane and phenyltrichlorosilane. Co-hydrolysis of a mixture containing the above,
Methoxysilane corresponding to each chlorosilane exemplified above, can be obtained by cohydrolysis of a mixture of alkoxysilanes such as ethoxysilane in the presence of an alkali or acid catalyst, among these, trifunctional silane and An organopolysiloxane resin or an organopolysiloxane resin intermediate obtained by cohydrolyzing a silane mixture containing a tetrafunctional silane is preferred.

The content of the silanol group can be adjusted by the concentration of the catalyst, the reaction temperature and the like. Further, the produced silanol group is treated with a silylating agent such as trimethylchlorosilane, hexamethyldisilazane and divinyltetramethyldisilazane in the next step. It is also possible to modify. With respect to 100 parts of the curable epoxy resin as the first component, if the amount of the fourth component is too small, the curing of the epoxy resin will be insufficient, and conversely, if it is too large, it will be uneconomical. However, since it may reduce the physical properties of the cured product,
The amount is 0.1 to 10 parts, preferably 1 to 5 parts.

The organoaluminum compound as the fifth component is an alkyl group, an unsubstituted or substituted phenyl group, a haloalkyl group, an alkoxy group, an unsubstituted or substituted phenoxy group, an acyloxy group, a β-diketonato group, an o-carbonylphenolato group, etc. A compound in which an organic group selected from the group is bonded or coordinated to an aluminum atom. Among the above organic groups, as the alkyl group, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
-Butyl group, n-pentyl group and the like are exemplified, and the unsubstituted or substituted phenyl group is exemplified by phenyl group, p-methoxyphenyl group, o-methoxyphenyl group and p-ethoxyphenyl group, and the haloalkyl group is chloromethyl. Group, chloroethyl group, chloropropyl group are exemplified,
Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, and a pentoxy group. Examples of the unsubstituted or substituted phenoxy group include a phenoxy group and o
-Methylphenoxy group, o-methoxyphenoxy group, o
-Nitrophenoxy group and 2,6-dimethylphenoxy group are exemplified, and as the acyloxy group, an acetato group, a propionato group, an isopropionato group, a butyrato group, a stearato group, an ethylacetoacetato group, a propylacetoacetato group, and a butylaceto group. Acetato group, diethyl malato group,
Examples of dipivaloylmethanato group, as the β-diketonato group, an acetylacetonato group, a trifluoroacetylacetonato group, a hexafluoroacetylacetonato group,

Embedded image (The above formula is a compound before coordination), and the o-carbonylphenolato group is exemplified by a salicylaldehyde group.

Specific examples of the aluminum compound include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, triphenoxyaluminum, tri (p-methylphenoxy) aluminum, isopropoxydiethoxyaluminum, tributoxyaluminum, triacetoxyaluminum, Aluminum tristearate, aluminum tributyrate, aluminum tripropionate, aluminum triisopropionate, aluminum tris (acetylacetonate),
Tris (trifluoroacetylacetonato) aluminum, tris (salicylaldehyde) aluminum, tris (pentafluoroacetylacetonato) aluminum, tris (ethylacetato) aluminum, ethylacetatodiisopropoxyaluminum, tris (diethylmalolato) aluminum, Tris (propylacetoacetato) aluminum, Tris (butylacetoacetato) aluminum, Tris (isopropylacetoacetato) aluminum, Tris (dipivaloylmethanato) aluminum, Diacetylacetonatodipivaloylmethanatoaluminum, Ethylacetoa Cetatodiisopropoxyaluminum,

[0026]

Embedded image And the like.

These aluminum compounds may be used alone or in combination of two or more, and the addition amount thereof is 0.001 to 10 parts, preferably 100 parts by weight of the epoxy resin.
It is in the range of 0.01 to 5 parts. If the compounding amount is less than 0.001 part, sufficient curing characteristics cannot be obtained, and if it exceeds 10 parts, the cost becomes high and the physical properties and adhesiveness are adversely affected.

The platinum group compound of the sixth component serves as a catalyst for the addition reaction of the alkenyl group-containing organopolysiloxane of the second component and the organohydrogenpolysiloxane of the third component. For example, platinum black, chloroplatinum chloride. , Chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, platinum bisacetoacetate, a palladium catalyst, a rhodium catalyst, and the like. These are 0.1 to 500 parts, preferably 0.5 to 0.5 parts of the second component as platinum, palladium or rhodium metal.
Add up to 200 parts. If the amount is less than 0.1 part, sufficient curing cannot be obtained, and conversely, if the amount is more than 500 parts, no further effect is obtained, which is economically disadvantageous.

The first to sixth components described above do not necessarily have to be independent components, and for example, each molecule has at least two lower alkenyl groups and has at least one silanol. The organopolysiloxane having a group can serve both as the second component and the fourth component. In this case, the following are preferable as the curable silicone-epoxy resin composition. That is, 1) 100 parts of curable epoxy resin, 3) having at least one hydrogen atom bonded to a silicon atom in one molecule, and having a general formula R ⁴ _f H _g SiO _{(4-fg) / 2} (formula R ^{4 s} may be the same or different from each other and represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and f is 1 ≦ f ≦ 2.4, g represents 0 <g ≦ 1) 1 to 50 parts per 100 parts of the following 4'component of 4 '), 4') at least 2 lower alkenyls in one molecule on average Group and at least one silanol group, and has a general composition formula R ⁷ _i (HO) _j SiO _{(4-ij) / 2} (wherein R ⁷ may be the same or different from each other and has 1 carbon atom). To 12 unsubstituted or substituted monovalent hydrocarbon groups, 2 to 80 mol% of which are lower alkenyl groups, and i is 1≤i≤2.5, j 0 <j≤2, i + j represents 1 <i + j≤3) 5 to 500 parts of organopolysiloxane, 5) 0.001 to 10 parts of organoaluminum compound and 6) platinum group compound 4'as a platinum group metal Compositions consisting of 0.1 to 500 parts per million parts of component are preferred.

Each component except the 4'th component has already been described. In the above general formula, R ⁷ is a monovalent hydrocarbon radical unsubstituted or substituted with 1 to 12 carbon atoms, those this as R ⁷ is the same as those exemplified as R ⁵ or R ⁶ and the Examples of the 4'component include, in the general composition formula, at least 2 as R ⁷ in one molecule on average, and 2 to 80 mol% of all R ⁷ groups, preferably 2 to 20 mol. Those containing a lower alkenyl group such as% vinyl group are used.
The component is blended in an amount of 5 to 500 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the first component curable epoxy resin. This makes it possible to achieve the purpose. In addition to these first to sixth components, as a filler, fused silica, crystalline silica, glass powder, glass fiber, clay,
Talc, mica, asbestos, zinc oxide, magnesia,
Addition of various fine powdery substances such as aluminum silicate, zirconium silicate, alumina, fumed silica, precipitated silica and the like, fibrous substances and the like can be carried out as long as the adhesiveness to the silicone rubber is not impaired.

In the method for producing a composite of a silicone rubber and a silicone-epoxy resin of the present invention, first, one of the above-mentioned organic peroxide-curable or addition-curable silicone rubber composition and silicone-epoxy resin composition is used. One composition is cured or molded at room temperature or by heating. The molding method can be freely selected according to the viscosity of the composition, and may be injection molding, compression molding, injection molding, extrusion molding, transfer molding or the like. After one composition is cured and molded (primary molding), the other composition is brought into close contact with the primary molded product and cured or molded at room temperature or by heating (secondary molding) to obtain an integrally molded product with good adhesiveness. Easily obtained. The molding method of this secondary molded article can also be freely selected according to the viscosity of the composition, injection molding, compression molding, injection molding,
Either extrusion molding or transfer molding may be used. The timing of curing the secondary molded product does not necessarily have to be after the primary molded product is completely cured, and there is no problem as long as the primary molded product is cured to such an extent that the two can be mixed and an interface can be formed.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described with reference to examples. In the following examples, "part" means "part by weight" and "%" means "% by weight". The viscosity shows a value at 25 ° C.

[0033]

【Example】

(Example 1) Epicoat 828 of epoxy resin (trade name, manufactured by Shell Chemical Co., bisphenol A type, epoxy equivalent 190 to 210, molecular weight 380) is added to 100 parts, and 10 parts of an epoxy compound represented by the following formula (I), 10 parts of organopolysiloxane having a viscosity of 4,000 centipoise represented by the formula (II), 2 parts of organohydrogenpolysiloxane having a viscosity of 25 centipoise represented by the following formula (III), 1.5 parts of diphenylsilanediol, and aluminum benzoate.
0.6 part and 0.1 part of an isopropanol solution of chloroplatinic acid (platinum content 0.5%) were added to obtain a silicone-epoxy resin composition (A).

Embedded image

On the other hand, fumed silica having a specific surface area (by the BET method; the same applies hereinafter) of 200 m ² / g was added to 100 parts of dimethylpolysiloxane having a viscosity of 10,000 centipoises, the both ends of which were blocked with dimethylvinylsiloxy groups. 30 copies,
Hexamethyldisilazane (6 parts) and water (2 parts) were added, and the mixture was heated and mixed at 150 ° C. for 3 hours. 0.4 parts of methyl hydrogen siloxane copolymer (50 mol% of dimethyl siloxane unit, 50 mol% of methyl hydrogen siloxane unit) and 0.1 part of chloroplatinic acid in isopropanol (platinum content 0.5%) were added, and a silicone rubber composition ( B) was obtained.

Next, about half the amount of the silicone-epoxy resin composition (A) was injected into the cavity 2 of the lower mold 1 of the mold whose longitudinal section is schematically shown in FIG. 1, and heated at 150 ° C. for 3 minutes to cure. After that, the upper mold 3 is placed on the lower mold 1, the lower mold 1 is closed, and the silicone-epoxy resin composition (A) is placed on the silicone-epoxy resin composition (A) through the injection port 4 provided in the upper part of the upper mold 3. The rubber composition (B) was injected at an injection pressure of 60 kg / cm ² and heat-cured at 150 ° C. for 5 minutes to obtain an integrated product in which the silicone-epoxy resin and the silicone rubber were firmly bonded. After this integrated product was post-cured at 150 ° C for 3 hours, the hardness of each was measured.
A was 95 or more (that is, the measurement limit was exceeded), and the silicone rubber portion was 35 in JIS A. The JIS A hardness was measured according to JIS K6301. (Same below)

(Example 2) Epicoat 8 of epoxy resin
After co-hydrolyzing 100 parts of 28 (supra) with a mixture of 10 parts of the epoxy compound of the formula (I) used in Example 1, vinylmethyldichlorosilane, dimethyldichlorosilane and phenyltrichlorosilane at 90 ° C. , Separated, washed with water until neutral, and then left with hexamethyldisilazane
After converting the OH group to trimethylsilyl, further washing with water and neutralization,
The following average compositional formula (IV) (CH ₃ ) _1.02 (C ₆ H ₅ ) _0.40 (CH ₂ = CH) _0.08 SiO _1.25 (50) obtained by isolation was used. 2 parts of the organohydrogenpolysiloxane represented by the formula (III) used in Example 1, 3 parts of a methylhydrogenpolysiloxane represented by the following formula (V) and having a viscosity of 2 centipoise,
1.5 parts of diphenylsilanediol, 0.6 part of aluminum benzoate, and 0.3 part of an isopropanol solution of chloroplatinic acid (platinum content 0.5%) were added to obtain a silicone-epoxy resin composition (C).

[Chemical 4]

Next, a molded product integrated in the same manner as in Example 1 except that the silicone-epoxy resin composition (C) was used in place of the silicone-epoxy resin composition (A) of Example 1. Got When the obtained integrated product was treated in the same manner as in Example 1 and the hardness was measured, the silicone-epoxy resin part had a JIS A of 95 or more, and the silicone rubber part had a JIS A of 35.

Example 3 100 parts of dimethylpolysiloxane having a viscosity of 100,000 centipoise with both ends of the molecular chain blocked with trivinylsiloxy groups, 30 parts of fumed silica having a specific surface area of 200 m ² / g, and hexamethyldisiloxane 6 parts of silazane,
Add 2 parts of water and mix by heating at 150 ° C for 3 hours. Add 50 parts of the above-mentioned dimethylpolysiloxane blocked with trivinylsiloxy group.
Parts, 1,6-bis (t-butylperoxy) hexane
1.0 part was added to obtain a silicone rubber composition (D). Silicone-epoxy resin composition (C) used in Example 2
Was injected in the same manner as in Example 1 and cured at 170 ° C. for 2 minutes, and then the silicone rubber composition (D) was similarly injected onto the silicone-epoxy resin composition (C). It was heated and cured at 170 ° C. for 5 minutes to obtain an integrated product in which the silicone-epoxy resin and the silicone rubber were firmly bonded. After this integrated product was post-cured at 170 ° C for 3 hours, the hardness of each was measured, and the silicone-epoxy resin part was 95 or more in JIS A, and the silicone rubber part was J
It was 40 by ISA.

Example 4 Epoxy Coat of Epoxy Resin 8
After co-hydrolyzing 100 parts of 28 (supra) with a mixture of 10 parts of the epoxy compound of the formula (I) used in Example 1, vinylmethyldichlorosilane, dimethyldichlorosilane and phenyltrichlorosilane at 90 ° C. The following average compositional formula (VI) (CH ₂ = CH) _0.1 (CH ₃ ) _0.6 (C ₆ H ₅ ) _0.55 (HO) _0.25 SiO _1.25 .. (VI) 50 parts of the organopolysiloxane, 8 parts of the organohydrogenpolysiloxane of formula (III) used in Example 1, 0.6 parts of aluminum benzoate, and an isopropanol solution of chloroplatinic acid (platinum) 0.5%)
Silicone-epoxy resin composition (E) by adding 0.1 part
I got Next, an integrated molding was obtained in the same manner as in Example 1 except that the silicone-epoxy resin composition (E) was used in place of the silicone-epoxy resin composition (A) of Example 1. . When the obtained integrated product was treated in the same manner as in Example 1 and the hardness was measured, the silicone-epoxy resin part had a JIS A of 95 or more, and the silicone rubber part had a JIS A of 35.

Example 5 To 70 parts of dimethylpolysiloxane having a viscosity of 5,000 centipoise whose both ends were blocked with dimethylvinylsiloxy groups, 30 parts of fumed silica having a specific surface area of 300 m ² / g, and hexamethyldisiloxane 6 parts of silazane,
3 parts of water was added and heated and mixed at 150 ° C. for 3 hours, and 50 parts of the above-mentioned dimethylpolysiloxane capped with dimethylvinylsiloxy group, a dimethylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsilyl groups at both ends and having a viscosity of 10 centipoise. (Dimethylsiloxane unit 50 mol%,
Methyl hydrogen siloxane unit 50 mol%) 0.45
Parts, chloroplatinic acid in isopropanol (Platinum content
0.5%) 0.1 part was added to obtain a silicone rubber composition (G). Next, the cavity 2 of the lower mold 1 of the mold shown in FIG.
Inject the above silicone rubber composition (G) into
After heating and curing for 90 seconds at 90 ° C., the upper mold 3 is placed on the lower mold 1 and the lower mold 1 is closed. From the injection port 4 provided in the upper part of the upper mold 3, described in Example 4. The silicone-epoxy resin composition (E) was injected at an injection pressure of 60 kg / cm ² and heat-cured at 150 ° C. for 7 minutes to obtain an integrated product in which the silicone-epoxy resin and silicone rubber were firmly bonded. After this integrated product was post-cured at 150 ° C for 3 hours, the hardness of each was measured and the silicone rubber part was 40 according to JIS A.
According to JIS A, the silicone-epoxy resin part was 95 or more (above the measurement limit).

Comparative Example 1 Epicoat 8 of epoxy resin
28 (supra) 100 parts by weight, 10 parts by weight of the epoxy compound represented by the formula (I) used in Example 1 and diphenylsilanediol
1.5 parts and 0.5 part of aluminum benzoate were added to obtain an epoxy resin composition (F). Next, about half the amount of the epoxy resin composition (F) was injected into the cavity 2 of the lower mold 1 shown in FIG. 1 and heated and cured at 150 ° C. for 3 minutes, and then the upper mold 3 was changed to the lower mold 1. Then, the lower mold 1 is closed, and the silicone rubber composition (B) used in Example 1 is injected onto the epoxy resin composition (F) through the injection port 4 provided on the upper mold 3. It was injected at 60 kg / cm ² and heat-cured at 150 ° C for 5 minutes, but it was not possible to obtain a product in which both were integrated. Furthermore, the epoxy resin adhered to the mold and was removed from the mold. I couldn't.

[0042]

EFFECT OF THE INVENTION The silicone-epoxy resin and silicone rubber composite of the present invention is an integrated product in which both are firmly adhered, and each of them is sufficiently cured to exhibit its original characteristics. It is advantageous for use in various fields such as electronics, OA equipment, automobiles and precision equipment. Further, this composite can be easily manufactured by the manufacturing method of the present invention.

[Brief description of drawings]

FIG. 1 is a view schematically showing a vertical cross section of a mold used in Examples and Comparative Examples of the present invention, for explaining a molding operation.

[Explanation of symbols]

 1 Lower mold 2 Cavity 3 Upper mold 4 Injection port

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 83/04 LRM C08L 83/04 LRM (72) Inventor Yoshiteru Kobayashi Matsudaira-cho, Usui-gun, Gunma Mi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (4)

[Claims] 1. A silicone rubber and a silicone-epoxy in which a cured product of an organic peroxide-curable or addition-curable silicone rubber composition and a cured product of a curable silicone-epoxy resin composition are directly bonded and integrated during curing. Resin composite. 2. The curable silicone-epoxy resin composition comprises 1) 100 parts by weight of a curable epoxy resin, 2) 5 to 500 parts by weight of organopolysiloxane containing at least two lower alkenyl groups on average in one molecule. 3) Each molecule has at least one hydrogen atom bonded to a silicon atom, and has the general formula R ⁴ _f H _g SiO _{(4-fg) / 2} (wherein R ⁴ is the same or different). It may be an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturation bond, f is 1 ≦ f ≦ 2.4, and g is 0 <g ≦ 1. 1 to 50 parts by weight per 100 parts by weight of the second component of the organohydrogenpolysiloxane represented by: 4) 0.1 to 10 parts by weight of an organosilicon compound having at least one silanol group in one molecule, 5 ) 0.001 to 10 parts by weight of organoaluminum compound and 6) Platinum Is made of 0.1 to 500 parts by weight with respect to the second component million parts as a compound of platinum group metal according to claim 1, wherein the silicone rubber and silicone - a complex of epoxy resin. 3. The curable silicone-epoxy resin composition comprises 1) 100 parts by weight of a curable epoxy resin, and 3) at least one hydrogen atom bonded to a silicon atom in one molecule, and has a general compositional formula. R ⁴ _f H _g SiO _{(4-fg) / 2} (In the formula, R ^{4 s} may be the same as or different from each other and may be an unsubstituted or substituted C 1-12 aliphatic unsaturated bond. Organohydrogenpolysiloxane represented by a monovalent hydrocarbon group, f is 1 ≦ f ≦ 2.4, and g is 0 <g ≦ 1. 1 to 50 parts by weight relative to 100 parts by weight of the following 4'component Parts by weight, 4 ') having at least two lower alkenyl groups and at least one silanol group in one molecule on average, and having a general composition formula, R ⁷ _i (HO) _j SiO _{(4-ij) / 2} (formula among, R ⁷ may be the same or different from each other, represent a monovalent hydrocarbon radical unsubstituted or substituted with 1 to 12 carbon atoms, the 2 to 80 mol% is a lower alkenyl group, i is 1 ≦ i ≦ 2.5, j is 0 <j ≦ 2, and i + j is 1 <i + j ≦ 3). 2. The silicone according to claim 1, which comprises 5 parts by weight, 5) an organoaluminum compound, 0.001 to 10 parts by weight, and 6) a platinum group compound, which is 0.1 to 500 parts by weight with respect to 1 million parts by weight of the 4'th component as a platinum group metal. Composite of rubber and silicone-epoxy resin. 4. One of an organic peroxide-curable or addition-curable silicone rubber composition or a curable silicone-epoxy resin composition is cured at room temperature or under heating and then the other composition is adhered. A method for producing a composite of silicone rubber and silicone-epoxy resin, which is cured at room temperature or under heating.