JP2003041231A - Oil-bleed silicone rubber adhesive composition and integrally molded article of oil-bleed silicone rubber and thermoplastic resin - Google Patents

Abstract

(A) 100 parts by weight of a heat-curable organopolysiloxane composition (B) Reinforcing silica fine powder
1 to 100 parts by weight (C) The epoxy equivalent is 100 to 5000 g / mol,
Organic compound or organosilicon compound having at least one aromatic ring in the molecule 0.1 to 50 parts by weight (D) Nonfunctional phenyl group-containing silicone oil
An oil-bleed silicone rubber adhesive composition comprising 0.1 to 50 parts by weight. According to the present invention, in an integrally molded article of a silicone rubber and a thermoplastic resin, it can be molded easily and in a short time by injection molding or the like, and has an adhesive property with a thermoplastic resin suitable for primerless molding. Provides a good silicone rubber adhesive composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an integrally molded body of silicone rubber and a thermoplastic resin, which can be molded easily and in a short time by injection molding, extrusion, or machine application by a robot, and is suitable for primerless molding. ,
Further, in the process of manufacturing a molded body, for example, when a mold surface-treated with chrome plating or the like or a non-surface-treated mold is used, it does not adhere to the mold, and has a specific adhesive property only to the resin. The present invention relates to an oil bleeding silicone rubber adhesive composition capable of exhibiting properties, and an integrally molded product of a cured product (oil bleeding silicone rubber) and a thermoplastic resin, which can be used for electric, electronic, automobile, precision machinery. It is useful for construction, etc.

[0002]

2. Description of the Related Art In recent years,
Utilizing the characteristics of silicone rubber, its applications are expanding in the fields of electricity, electronics, automobiles, construction, etc. Especially when manufacturing silicone rubber with oil bleeding properties such as oil seals, connectors, O-rings, etc. Properties, hermeticity, and insulation are required. Further, adhesion with a resin is required depending on the intended use, and adhesion is often performed via a primer, but a primer application step is required in terms of work, which is troublesome. Therefore, when a self-adhesive type silicone rubber material in which an adhesive is added to a silicone rubber composition is used, the application step is unnecessary, so that the working time can be shortened, the cost can be reduced, and the workability can be improved. It is an effective means for producing an integrally molded product with a resin.

In the primerless molding of an addition type heat-curable silicone rubber material, there have been reported many methods of adhering it to an organic resin. For example, there is a method of curing a self-adhesive silicone rubber material on a resin, and for this self-adhesive silicone rubber composition, many techniques for specifying an adhesive component have been proposed. Further, a method of adding an organopolysiloxane containing 30 mol% or more of hydrogen atoms directly bonded to silicon atoms to an organic resin and adhering it to an addition-curable silicone rubber (Japanese Patent Publication No. 2-34311), silicone to organic resin A method in which rubber is integrated by a physical fitting method (Japanese Patent Publication No. 63-45292), and silicone rubber is adhered integrally to an olefin resin grafted with a compound having an aliphatic unsaturated group and a silicon atom-bonded hydrolyzable group. Method (Japanese Patent Application Laid-Open No. 63-18384)
No. 3), a method of adhering and integrating a thermoplastic resin to which a compound containing an unsaturated group and a hydrogen atom directly bonded to a silicon atom, which is reported by the present applicant, and a silicone rubber are adhered and integrated, and an aliphatic compound is not added to the thermoplastic resin. An integrally formed product of a resin containing a saturated group-containing thermoplastic oligomer and an oil bleeding silicone rubber (Japanese Patent Laid-Open No. 9-165516,
JP-A-9-165517) and the like have been proposed.

However, in the case of the addition type thermosetting silicone rubber, general-purpose thermoplastic resins, fibers, films such as ABS, PPO, PPS, PC, PE, PP, PB are used.
T, acrylic, phenol resin, polyimide resin, P
In order to obtain sufficient adhesiveness to each resin, fiber, film such as A, aromatic PA and other copolymers, in a short time, and to have sufficient adhesiveness, the above proposal As described above, the resin needs to be modified. When the resin is modified, extra steps are required, the cost is increased, and the characteristics of the resin are likely to change due to the modification. Further, in the case of adhering without resin modification, there is a difficulty in adhering to the mold when molding using a mold, and in particular, none of the polyamide resins and fibers can sufficiently satisfy the requirements. Under these circumstances, when a mold is used to form an integrally molded body of a thermoplastic resin and an oil bleeding silicone rubber, molding is possible without adhering to the mold, and each thermoplastic resin and silicone rubber There has been a strong demand for the supply of an integrally formed body in which and are firmly bonded.

The present invention has been made in response to the above-mentioned needs, and is an oil bleeding silicone rubber adhesive composition which can be firmly integrated with a thermoplastic resin and a cured product thereof (oil bleeding silicone rubber) and a thermoplastic resin. An object is to provide an integrally molded body with a resin.

[0006]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that the epoxy equivalent of the thermosetting organopolysiloxane composition is 100 to 5000 g / An oil bleeding silicone rubber adhesive composition containing an organic compound or organosilicon compound having at least one aromatic ring in the molecule and a non-functional phenyl group-containing silicone oil in a molar ratio of When integrally molded with a resin, an integrally molded product of a cured product of an oil bleeding silicone rubber adhesive composition and a thermoplastic resin, which is an oil bleeding silicone rubber, firmly adhered to each other, is obtained. Even if the molding method is used, it has sufficient adhesive strength to the above thermoplastic resin under a curing condition for a short time, and can be used practically from a molding die. It is possible to obtain an integrally molded body of the above oil bleeding silicone rubber and a thermoplastic resin that sufficiently peels off, and it is particularly effective for polyamide resin such as nylon 66 and aromatic polyamide having high crystallinity and polyamide fiber. That is, the present invention has been completed.

Therefore, the present invention provides (A) a heat-curable organopolysiloxane composition 100 parts by weight (B) a reinforcing silica fine powder 1 to 100 parts by weight (C) an epoxy equivalent of 100 to 5000 g / mol, Organic compound or organic silicon compound having at least one aromatic ring in the molecule 0.1 to 50 parts by weight (D) Nonfunctional phenyl group-containing silicone oil 0.1 to 50 parts by weight, preferably, Provided is an oil bleeding silicone rubber adhesive composition, which is characterized by having a larger adhesive force to an organic resin than a metal. Further, the present invention is
Provided is an integrally molded product of a cured product (oil bleeding silicone rubber) of this adhesive composition and a thermoplastic resin.

The present invention will be described in more detail below.
The oil-bleedable silicone rubber adhesive composition of the present invention comprises (A) a heat-curable organopolysiloxane composition, (B) a reinforcing silica fine powder, and (C) an epoxy equivalent of 100 to 5000 g / mol, and a molecular weight. An organic compound or organic silicon compound having at least one aromatic ring therein,
(D) A non-functional phenyl group-containing silicone oil is an essential component.

The thermosetting organopolysiloxane composition according to the component (A) is preferably an addition reaction-curable organopolysiloxane composition or an organic peroxide-curable organopolysiloxane composition, and particularly addition Reaction-curable organopolysiloxane compositions are preferred. In this case, the addition reaction-curable organopolysiloxane composition is (1) 100 parts by weight of organopolysiloxane having an average of 2 or more alkenyl groups in 1 molecule (2) 2 or more silicon atoms in an average of 1 molecule. Organohydrogenpolysiloxane having hydrogen atoms bonded to 0.1 to 50 parts by weight (3) Addition reaction catalyst It is preferable that the organohydrogenpolysiloxane has a catalytic amount, and the organic peroxide-curable organopolysiloxane composition is i) Organopolysiloxane having an average of 2 or more alkenyl groups in one molecule 100 parts by weight (ii) organic peroxide It is preferable that the catalyst comprises a catalytic amount.

Here, the organopolysiloxane having an average of two or more alkenyl groups in one molecule of the component (1) of the addition reaction curable organopolysiloxane composition is represented by the following average composition formula (1). Any thing can be used.

R ¹ _a SiO _{(4-a) / 2} (1) (In the formula, R ¹ is the same or different from each other and has 1 to 12 carbon atoms;
It is preferably 1 to 8 unsubstituted or substituted monovalent hydrocarbon group, and a is 1.5 to 2.8, preferably 1.8 to 2.
5, and more preferably a positive number in the range of 1.95 to 2.05. )

The unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group. , Pentyl group,
Alkyl groups such as neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. Alkenyl groups such as aralkyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group,
Some or all of the hydrogen atoms of these groups are fluorine, bromine,
Those substituted with a halogen atom such as chlorine and a cyano group, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like can be mentioned.

In this case, it is necessary that at least two of R ¹ are alkenyl groups (in particular, those having 2 to 8 carbon atoms are preferable, and 2 to 6 are more preferable). The content of the alkenyl group is 0.001 to 20 in all the organic groups bonded to silicon atoms (that is, in the unsubstituted or substituted monovalent hydrocarbon group as R ¹ in the average composition formula (1)). It is preferable to set it as mol%, especially 0.01 to 10 mol%. This alkenyl group, whether bonded to a silicon atom at the end of the molecular chain or bonded to a silicon atom in the middle of the molecular chain,
Although it may be bonded to both, the organopolysiloxane used in the present invention contains at least an alkenyl group bonded to the silicon atom at the terminal of the molecular chain from the viewpoints of the curing rate of the composition, the physical properties of the cured product, and the like. Is preferred. As R ¹ other than the alkenyl group, an alkyl group such as a methyl group, an aryl group such as a phenyl group, and a fluoroalkyl group such as a trifluoropropyl group are preferable, and an alkyl group is particularly preferable.

The structure of the above organopolysiloxane is
Usually the main chain is R¹ ₂SiO_2/2The diorganoshiro
It consists of repeating xanthane units, and both ends of the molecular chain are R¹ ₃S
iO _1/2Blocked with a triorganosiloxy group represented by
Diorganopolysiloxane having an essentially linear structure
Sun, but partly R¹SiO_3/2Unit or SiO
_4/2Even if it has a branched structure containing units, a cyclic structure, etc.
Good. Of the alkenyl group-containing organopolysiloxane
There is no particular limitation on the degree of polymerization (or viscosity), and the room temperature (25
(° C) from a low degree of polymerization of liquid to a raw rubber (gum-like)
Although it is possible to use even those with a high degree of polymerization,
Degree (weight average degree of polymerization) of 10 to 10,000, especially 50
To 10,000, preferably 100 to 10,000
0, more preferably about 100 to 2,000 is used.
Used. If the average degree of polymerization is less than 10, it will be a cured product.
The physical properties of rubber may be insufficient. The stickiness
100 to 1,000,000 cps at 25 ° C
(Centipoise), especially 500-500,000 cps
Is preferred.

The organohydrogenpolysiloxane as the component (2) is represented by the following average composition formula (2) R ² _b H _c SiO ² _{(4-bc) / 2} (2) and has at least 2 in one molecule. Individual (usually 2-300
), Preferably 3 or more, more preferably 3 to 150
It is necessary to have about several silicon-bonded hydrogen atoms (that is, Si-H groups).

In the above formula (2), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and this R ² is the same as R ¹ in the above formula (1). Although a group can be mentioned, a group having no aliphatic unsaturated group is preferable,
An alkyl group such as a methyl group is particularly preferable. Further, b is a positive number satisfying 0.7 to 2.1, c is 0.001 to 1, and b + c is 0.8 to 3, and preferably b is 1 to 1.
2, c is 0.01 to 1, and b + c is 1.5 to 2.8.

At least 2, preferably 3 in one molecule
The Si-H groups contained in the number of not less than one may be located at the terminal of the molecular chain, in the middle of the molecular chain, or at both of them. The molecular structure of this organohydrogenpolysiloxane may be linear, cyclic, branched, or three-dimensional network structure, but the number of silicon atoms in one molecule (or the degree of polymerization) is usually , Average 2-3
00, preferably 3 to 150 room temperature (25 ° C)
The liquid form is desirable, and its viscosity is 0.1 to 10,000 cps at 25 ° C., especially 0.5 to 5,000.
cps is desirable.

Specific examples of the organohydrogenpolysiloxane of the formula (2) include 1,1,3,3-
Tetramethyldisiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane
Dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, dimethylsiloxy group-blocked dimethylsiloxane-methylhydrogensiloxane copolymer at both ends, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends, both ends Dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer at both ends, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane at both ends Copolymer, dimethylhydrogensiloxy group-capped methylhydrogensiloxane / dimethylsiloxane / diphenylsilane at both ends Hexane copolymer, (CH _{3) 2} HSi
Copolymer consisting of O _1/2 unit, (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit, (CH ₃ ) ₂ HSiO _1/2 unit and S
A copolymer consisting of iO _4/2 units, (CH ₃ ) ₂ HSiO
Such as _1/2 units and SiO _4/2 units, and the (C ₆ H _{5) 3} consisting of SiO _1/2 units copolymers.

The amount of this organohydrogenpolysiloxane blended is 1) of the organopolysiloxane of component (1).
0.1 to 300 for 00 parts (weight part, the same applies below)
Parts, preferably 0.3 to 200 parts, particularly preferably 0.
It is 5 to 100 parts. In addition, the organohydrogenpolysiloxane of the component (2) has a hydrogen atom (Si—H) bonded to the silicon atom in the component (2) with respect to 1 mol of the alkenyl group bonded to the silicon atom in the component (1). The amount of the group) may be 0.3 to 20 mol, preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, and particularly 0.8 to 2.5 mol. .

As the addition reaction catalyst of the component (3), platinum black, secondary platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and platinum bis Examples include platinum group catalysts such as acetoacetate, palladium group catalysts, and platinum group metal catalysts such as rhodium catalysts. The addition reaction catalyst may be used in a catalytic amount.
000 ppm, preferably 0.5-1,000 ppm,
Particularly, it may be about 1 to 500 ppm.

The addition reaction-curable organopolysiloxane composition comprises the above-mentioned components (1), (2) and (3).

On the other hand, the organopolysiloxane having an average of two or more alkenyl groups in one molecule of the component (i) of the organic peroxide-curable organopolysiloxane composition is the same as the component (1). Can be used.

As the organic peroxide of the component (ii), conventionally known ones can be used, for example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide,
o-Methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-bis (2,5-
t-butylperoxy) hexane, di-t-butylperoxide, t-butylperbenzoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,6-bis (t -Butylperoxycarboxy) hexane and the like.

The amount of the organic peroxide compounded is a catalytic amount, and is usually 0.01 to 10 parts, preferably 0.1 to 10 parts with respect to 100 parts of the component (i) organopolysiloxane. it can.

The organic peroxide-curable organopolysiloxane composition is composed of the above-mentioned components (i) and (ii).

The reinforcing silica fine powder as the component (B) is not particularly limited in the kind of silica, and any commonly used silica may be used, and it is used as a rubber reinforcing material.

As the reinforcing silica fine powder, those used in conventional silicone rubber compositions can be used, but the reinforcing silica fine powder having a specific surface area of 50 m ² / g or more is preferably used. Especially 50 to 400 m ² / g
Precipitated silica, fumed silica, calcined silica and the like are preferably used. Fumed silica is suitable for improving rubber strength. Further, the reinforcing silica fine powder may be a silica fine powder whose surface is hydrophobized with an organic silicon compound or the like.

In this case, as the fine silica powder, those which have been directly treated in a powder state in advance can be used. As the treatment method, it can be treated by a generally known technique. For example, the untreated silica fine powder and the treatment agent are put into a mechanical kneading apparatus or a fluidized tank which is closed under normal pressure, and an inert gas is present as necessary. The mixture may be mixed at room temperature or heat treatment below, and the treatment may be promoted by using a catalyst in some cases, but it can be prepared by kneading and then drying. The compounding amount of the treating agent may be the amount calculated from the coating area of the treating agent or more.

The treating agent is an organosilazane such as hexamethyldisilazane or divinyltetramethyldisilazane,
Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) ) Silane coupling agents such as organoalkoxysilanes such as silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane, and chloropropyltrimethoxysilane; organosilicon compounds such as organopolysiloxanes such as polydimethylsiloxane and organohydrogenpolysiloxane. And is surface-treated with these treatment agents and used as a hydrophobic silica fine powder. The treating agent is preferably a silane coupling agent or silazanes.

The blending amount of the component (B) is 100 parts of the component (A).
The amount is preferably 1 to 100 parts with respect to the parts, and if it is less than 1 part, the mechanical strength becomes weak, and if it exceeds 100 parts, it becomes difficult to fill the component (B) and workability and workability deteriorate. It is preferably 2 to 80 parts.

It is more preferable that the hydrophobized silica fine powder is further hydrophobized at the time of compounding. In that case, as the surface treatment agent which imparts hydrophobicity used at the time of compounding, a silane coupling agent or a partial hydrolyzate thereof,
Examples thereof include organosilazanes, titanate coupling agents, organopolysiloxane oils and organohydrogenpolysiloxane oils.

In the surface treatment agent used, the silane coupling agent is methyltrimethoxysilane,
Ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane , Trimethylaminosilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane, (epoxycyclohexyl) ethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, dimethyldimethoxysilane, divinyldimethoxy Examples include silane and organoalkoxysilanes such as chloropropyltrimethoxysilane. Is the but, if silane can be used without particular limitation, and partial hydrolyzate of the silane may be used.

The organosilazanes used include:
Hexamethyldisilazane, divinyltetramethyldisilazane, diphenyltetramethyldisilazane and the like are exemplified.

Examples of titanate coupling agents used include tetra i-propyl titanate, tetra n-butyl titanate, butyl titanate dimer, tetrastearyl titanate, triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium. Lactate and octylene glycol titanate, isopropyl tristearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, etc. are exemplified. It

The organopolysiloxane oil used may be cyclic, chain, branched or network structure, but linear or cyclic with a viscosity of 0.65 to 100,000 centistokes (25 ° C.). Dimethylpolysiloxane is preferably used. The organohydrogenpolysiloxane oil used has a cyclic molecular structure,
It may have a chain structure, a branched structure, or a network structure, but a linear methyl hydrogen polysiloxane represented by the following average composition formula (3) is preferably used.

[0036]

[Chemical 1]

In the formula, r is an integer of 0 to 50 and s is 1 to
It is in the range of 50 integers. When r is more than 50, the viscosity is high and it becomes difficult to process. Even if s is more than 50, the viscosity is similarly high and the surface is difficult to wet, which is not preferable.

The blending amount of the treating agent is not less than the amount calculated from the coating area of the treating agent, but if there is no particular problem, the blending amount may be smaller than that. Particularly, if it is less than 0.1 part with respect to 100 parts of the above silica fine powder, there is no effect as a treating agent, and if it is more than 20 parts, it is wasted in the process and disadvantageous in terms of cost. 1 to
The amount is 20 parts, preferably 0.5-10.
It is the quantity that becomes a part.

The treatment method may be either fine silica powder alone or kneading with other components, but the treatment can be carried out by a generally known technique.
The other compound and the treating agent are put into the mechanical kneading device under normal pressure, and if necessary, the mixture is treated at room temperature or heat treatment in the presence of an inert gas, and optionally a catalyst may be used to accelerate the treatment. Can be prepared by kneading.

The component (C) used in the present invention is essential for imparting adhesiveness, and has an epoxy equivalent of 100 to 5000 g / mol and an organic compound having at least one aromatic ring in the molecule. It is a compound or an organosilicon compound.

The component (C) of the present invention contains at least one aromatic ring (benzene ring, naphthalene ring, anthracene ring, etc.) in the molecule, preferably 1 to 20 aromatic rings. By having an aromatic ring in the molecule, the compatibility with the component (A) is lowered, and thereby the adhesiveness at the rubber-resin interface is improved. When the component (A) and the component (C) are compatible with each other, the adhesiveness-imparting component is likely to exist in the rubber component and the adhesiveness with the resin is deteriorated. Therefore, the component (C) becomes the component (A). It may be semi-compatible or incompatible.

The component (C) has at least one epoxy group such as glycidoxy group in the molecule. The epoxy group such as the glycidoxy group is necessary for exhibiting adhesiveness, and the epoxy equivalent is 1
00-5000 g / mol, preferably 120-400
It is in the range of 0 g / mol. Epoxy equivalent is 100 g /
If it is less than mol, the synthesis is difficult, the compatibility with the silicone rubber composition becomes too poor, and the rubber physical properties are also affected. If it exceeds 5000 g / mol, the desired adhesiveness will be insufficient.

The component (C) of the present invention is preferably one containing at least one Si-H group (that is, a hydrogen atom bonded to a silicon atom) in the molecule, and preferably at least 1 in one molecule. 1 to 100, preferably 1 to
It has about 50, especially about 2 to 20, Si-H groups,
Organosilicon compounds having 1 to 500, preferably 1 to 200, silicon atoms such as organosilane and organosiloxane can be preferably used.

As described above, the present invention has, as the component (C), an epoxy group having an epoxy equivalent of 100 to 5000 g / mol, and a benzene skeleton represented by a phenyl skeleton or a phenyl group as an aromatic ring in the molecule. A ring, an organic compound having at least one naphthalene ring, an anthracene ring or the like or an organosilicon compound such as an organosilane or an organosiloxane, more preferably an epoxy equivalent of 100 to 5
An organosilicon compound having an epoxy group of 000 g / mol, having at least one benzene ring such as a phenyl skeleton or a phenyl group in the molecule, and containing at least one Si—H group is used. The adhesiveness imparting component used in the adhesive silicone rubber composition (Japanese Unexamined Patent Publication No. 6-172738) and the silicone adhesive composition (Japanese Unexamined Patent Publication No. 8-53661) which the applicant of the present invention previously applied is phenyl in the molecule. It has a skeleton or a benzene ring such as a phenyl group, but does not have an epoxy group, and these adhesive silicone rubber compositions are thermoplastic such as polymethylmethacrylate, polyphenylene sulfide, polyamide, polyphthalamide, etc. The adhesiveness to the resin was insufficient. On the other hand, an example of a composition containing a Si-H group and an epoxy group as an adhesion-imparting component has been previously proposed, but this adhesion-imparting component has a phenyl skeleton or a benzene ring such as a phenyl group in the molecule. It did not contain a structure, and it also did not have sufficient adhesiveness to the thermoplastic resin.

Specific examples of the component (C) used in the present invention are shown below.

[Chemical 2] R _w and R _x are substituted or unsubstituted monovalent hydrocarbon groups. q = 1 to 50, h = 0 to 50, preferably q = 1 to 20 and h = 1 to 100. ), R '' is

[Chemical 3] (R _w and R _x are the same as above, y = 0 to 100), and Y ′ is a group selected from

[Chemical 4] (R _w , R _x , q, and h are the same as above). z
= 1 to 10. ]

Further, the above compound is allowed to contain an alkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, acryl group, methacryl group, ester group, anhydrous carboxy group, amino group, amide group and the like. Other organic compounds and organic silicon compounds can also be used.

The substituted or unsubstituted monovalent hydrocarbon group for R _w and R _x is preferably one having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, such as an alkyl group, an aryl group, an aralkyl group or an alkenyl group. , R ¹ and the like, and examples of the substituted monovalent hydrocarbon group substituted with an alkoxy group, an acryl group, a methacryl group, an acryloyl group, a methacryloyl group, an amino group, an alkylamino group, and the like. To be

The above adhesiveness-imparting components may be used alone or in combination. Alternatively, it may be a reaction product of the above components.

The compounding amount of the adhesiveness-imparting component is 0.1 with respect to 100 parts of the organopolysiloxane composition as the component (A).
If the amount is less than 0.1 part, sufficient adhesiveness cannot be obtained, and if it exceeds 50 parts, physical properties may be deteriorated. It is preferably 0.2 to 30 parts, more preferably 0.5 to 20 parts.

For the purpose of effectively assisting the adhesiveness imparting component of the component (C), an organic compound or organic silicon compound having one alkenyl group and at least one ester group in the molecule, such as acrylic acid. An organic compound or an organosilicon compound containing an unsaturated carboxylic acid such as methacrylic acid or vinylacetic acid, an allyl ester such as allyl benzoate, diallyl phthalate, tetraallyl pyromellitic acid or allyl alkylate. You may mix. Further, an organic group chelate, an amine-based, an amide-based, an imidazole-based, an acid anhydride-based epoxy group ring-opening catalyst may be added. These can be added within a range that does not impair the effects of the present invention.

The non-functional phenyl group-containing silicone oil of the component (D) used in the present invention is an essential component for imparting the slipperiness of the rubber part of the integrally molded product. It is necessary to reduce the insertion force and to provide a sealing property for a connector that overlaps each other. Such a bleeding oil component does not participate in the curing reaction in the composition and has a phenyl group content (that is, a monovalent organic group (unsubstituted or substituted 1) bonded to a silicon atom in the organopolysiloxane). (Valent hydrocarbon group)
Non-functional silicone oil having a phenyl group content of 1 mol% or more and 90 mol% or less, and more preferably 3 mol% or more and 85 mol% or less. Silicone oil. The non-functional phenyl group-containing silicone oil may be used alone or in combination of two or more.

By using such a non-functional phenyl group-containing silicone oil, the adhesiveness with the resin is good, the amount of bleeding on the rubber surface after molding is sufficient, and the bleeding speed is good. Become. The non-functional silicone oil is a reactive functional group (eg, an alkenyl group bonded to a silicon atom) capable of undergoing a crosslinking reaction with the organopolysiloxane component constituting the heat-curable organopolysiloxane composition of the component (A). Hydrogen atom (Si-H
Group)) or other reactive functional groups in the molecule.

The non-functional phenyl group-containing silicone oil of the present invention has a viscosity at 25 ° C. of 1 cps or more and 50 or more.
It is preferably 50,000 cps or less, particularly 5 c
It is preferably not less than ps and not more than 100,000 cps.

Examples of such a non-functional silicone oil containing a phenyl group include diphenylpolysiloxane blocked with trimethylsiloxy groups at both molecular chain terminals, phenylmethylpolysiloxane blocked with trimethylsiloxy groups at both molecular chain terminals, and trimethylsiloxy group at both molecular chain ends. Examples include linear phenylmethylpolysiloxane (phenylmethylsilicone oil) such as group-blocked diphenylsiloxane / dimethylsiloxane copolymers and trimethylsiloxy group-blocked phenylmethylsiloxane / dimethylsiloxane copolymers at both molecular chain ends. It may have any of a ring structure, a chain structure, a branched structure and a network structure, and a straight chain structure is particularly preferable.

The amount of the nonfunctional phenyl group-containing silicone oil as the component (D) is 0.1 to 50 parts, preferably 0.5 to 40 parts, relative to 100 parts of the organopolysiloxane composition as the component (A). It is mixed in the range of parts. If it is less than 0.1 part, sufficient oil bleeding property cannot be obtained, and if it exceeds 50 parts, the adhesiveness is adversely affected.

In addition to the above-mentioned phenyl group-containing non-functional silicone oil, a non-functional fluorosilicone oil containing a trifluoropropyl group and a perfluoroalkyl ether group, and a silicone-modified perfluoroalkyl ether, within the range not impairing the above conditions. You may use together a compound etc.

Further, polyether-modified silicone oil, amino-modified silicone oil, amide-modified silicone oil, imide-modified silicone oil, urethane-modified silicone oil, etc. may be added within a range that does not impair the adhesiveness.

In addition to the above-mentioned components, the oil bleeding silicone rubber adhesive composition of the present invention contains various additives such as titanium oxide, iron oxide, cerium oxide, vanadium oxide, cobalt oxide and oxides. Metal oxides such as chromium and manganese oxide and their composites, quartz powder, diatomaceous earth, calcium carbonate, magnesium carbonate, alumina,
Inorganic fillers such as carbon can be added, and pigments, heat-resistant agents, flame retardants, plasticizers, reaction control agents and the like may be added as long as the intended characteristics are not impaired. In addition, the addition amount of these optional components can be a normal amount within a range that does not impair the effects of the present invention.

When the addition-curable organopolysiloxane composition is used, vinyl group-containing organopolysiloxanes such as vinylcyclotetrasiloxane, triallyl isocyanate, alkyl maleates, acetylene alcohols such as ethynylcyclohexanol, silanes and siloxanes. Addition reaction control agents such as modified compounds, hydroperoxides, compounds selected from the group consisting of tetramethylethylenediamine, benzotriazole and mixtures thereof can be added within a range that does not impair the effects of the present invention.

The oil bleeding silicone rubber adhesive composition of the present invention can be obtained by simply uniformly mixing the above-mentioned components (A) to (D) and optional components at room temperature, but it is preferable. The component (B) is a component (A) other than the components (2) and (3), or the component (ii) and 100 to 200 by a planetary mixer, a kneader or the like.
You may heat-process in the range of (degreeC) for 1-4 hours, and may add the said processing agent at that time. After that, at room temperature, the components (2) and (3),
Alternatively, the composition can be obtained by mixing the component (ii), the component (C) and the component (D). The molding method can be freely selected according to the viscosity of the mixture, coating,
Screen coating molding, injection molding, compression molding, injection molding,
Any method such as extrusion molding or transfer molding may be adopted. The curing condition is usually 60 to 200 ° C. and 10
Heat molding can be performed within a range of seconds to 24 hours.

The oil-bleedable silicone rubber adhesive composition of the present invention is preferably used when an integrally molded product with an organic resin is obtained. In this case, the organic resin used in the present invention may be a usual thermoplastic resin such as olefin polymerization system or polycondensation system, and specifically, acrylonitrile-
Butadiene-styrene (ABS) resin, styrene resin,
Polyethylene resin, polypropylene resin, polyacetal resin, acrylic resin, polycarbonate (PC) resin, polyethylene terephthalate resin, polybutylene terephthalate (PBT) resin, polyphenylene oxide resin, phenol resin, epoxy resin, polyphenylene sulfide resin, polysulfone resin, nylon resin , Aromatic polyamide resin, polyimide resin, liquid crystal resin, etc., or a mixture thereof. Note that these may be fibrous or film-shaped.

As a method for integrally molding the uncured oil bleeding silicone rubber adhesive composition according to the present invention on the above-mentioned thermoplastic resin, an uncured silicone rubber adhesive is formed on a preformed thermoplastic resin. A method of placing the composition in a desired shape and heating it at a temperature not higher than the melting temperature of the thermoplastic resin, placing an uncured silicone rubber adhesive composition on a preformed thermoplastic resin, and applying the thermoplastic resin And a method of compressing the thermoplastic resin in a mold with an injection molding machine, and then heat-injecting the silicone rubber adhesive composition into the mold. As an example of a method for producing a molded body of the thermoplastic resin, for example, the thermoplastic resin is pelletized, poured into a molding die heated to a softening point of the thermoplastic resin or higher, and then the die is molded with the thermoplastic resin. A known method of cooling below the softening point is convenient. In this case, equipment generally called an injection molding machine or a transfer molding machine can be used. The mold is usually made of metal such as steel or stainless steel, which is not surface treated,
It is possible to use those metals which have been subjected to surface treatment such as chrome plating and nickel plating.

On the other hand, the oil bleeding silicone rubber adhesive composition may be in a liquid state, a putty state, or a paste state in an uncured state, but a liquid or paste state is preferable from the viewpoint of easy molding. The silicone rubber adhesive composition according to the present invention needs to be cured at a temperature and a curing time at which the resin is not deformed, melted, or deteriorated in order to exhibit strong adhesiveness with the thermoplastic resin. is there. Depending on the type of resin, 0.2 to 50 at 150 to 150 ° C
An integrally molded body can be obtained under a curing condition of about 5 hours, especially about 0.4 to 30 minutes.

[0064]

According to the present invention, an integrally molded body of silicone rubber and a thermoplastic resin can be molded easily by injection molding or the like in a short time, and is suitable for primerless molding. A silicone rubber adhesive composition having good adhesiveness can be provided, and an integrally molded body that can be bonded without modifying a thermoplastic resin can be obtained.
Two-color molding and a design suitable for a complex structure are possible, and since no solvent is used, the working environment is safe, and it is useful for electricity, electronics, automobiles, precision machinery, construction, etc.

[0065]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

Oil bleeding silicone rubber adhesive set
Product Preparation Example As shown in Table 1, as the component (1) in the component (A), dimethylpolysiloxane having a viscosity of 10,000 cps at 25 ° C. and having both ends blocked with dimethylvinylsiloxy groups, (B). Specific surface area of 20 as silica fine powder
After using 0 m ² / g of fumed silica, 8 parts of hexamethyldisilazane was added to 100 parts of the component (1), mixed in a kneader mixer and uniformly mixed, and then 15
The mixture was heated and mixed at 0 ° C. for 1 hour to obtain a silicone rubber base. Methylhydrogenpolysiloxane represented by the following average composition formula (4) as the component (2) in the remaining component (A), and a 1% 2-ethylhexanol solution of chloroplatinic acid as the component (3) in the silicone rubber base. Further, a 50% ethanol solution of ethynylcyclohexanol was added as a reaction control agent, and the following I to I were added as the component (C)
As the component for imparting V adhesion and the component (D),
The non-functional oil bleed component of was uniformly mixed to obtain an oil bleed silicone rubber adhesive composition.

[0067]

[Chemical 5]

[0068]

[Chemical 6]

Component (D) has a phenyl group content of 1 at 25 ° C. and a viscosity of 200 cps.
Methylphenylpolysiloxane blocked with 0 mol% of trimethylsiloxy groups at both ends. Phenyl group content having a viscosity of 200 cps at 25 ° C. 2
Methylphenyl polysiloxane blocked with trimethylsiloxy groups at both ends of 3 mol% Phenyl group content having a viscosity of 380 cps at 25 ° C. 2
Methylphenylpolysiloxane capped with 8 mol% of trimethylsiloxy groups at both ends. Phenyl group content having a viscosity of 170 cps at 25 ° C. 6
Methylphenyl polysiloxane blocked with 0 mol% of diphenylmethylsiloxy groups at both ends

[Example 1] A polycarbonate resin having a number average molecular weight of about 10,000 (P
C), polybutylene terephthalate resin (PBT) having a number average molecular weight of about 20,000, polymethylmethacrylate resin (PMMA), polyphenylene sulfide resin (PP
S), nylon 6-6 (PA66) and polyphthalamide (PPA), respectively, and after plasticizing at 290 ° C., they are injected into a multi-cavity sheet mold cavity (injection condition: injection time 6 seconds , Cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
Several resin sheets each having a size of mm were obtained. Next, the prepared resin sheets and chrome-plated metal plates of the same size were fixed to a tensile shear adhesion test piece preparation jig, and the component of formula (I) was used as the component (C) in the above preparation example. The non-functional oil bleeding component of No. 1 was used, and the silicone rubber adhesive composition obtained by the addition was poured into the jig in an appropriate amount, and
It was heated for 10 minutes in a constant temperature bath at ℃ to cure. Using the test piece of FIG. 1 thus obtained, JIS K6850
Adhesiveness was investigated according to the method of. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

In FIG. 1, a and b are resin sheets, c and d are support holding parts, and e is a cured product of a silicone rubber adhesive composition.

[Example 2] The same resin as in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, the component of formula (I) was used as the component (C) and the component (D) was not added. Using the functional oil bleed component, the silicone rubber adhesive composition obtained by addition was poured into the jig in an appropriate amount and heated in a thermostatic bath at 120 ° C. for 10 minutes to cure. The test piece of FIG. 1 thus obtained was used to examine the adhesiveness according to the method of JIS K6850. Further, the bleeding property is
The sliding property of the rubber surface was examined.

[Example 3] A resin similar to that used in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, the component of formula (I) was used as the component (C) and the component (D) was not added. Using the functional oil bleed component, the silicone rubber adhesive composition obtained by addition was poured into the jig in an appropriate amount and heated in a thermostatic bath at 120 ° C. for 10 minutes to cure. The test piece of FIG. 1 thus obtained was used to examine the adhesiveness according to the method of JIS K6850. Further, the bleeding property is
The sliding property of the rubber surface was examined.

[Example 4] The same resin as in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, as the component (C), the formula (II) was used.
The non-functional oil bleed component of the component (D) is used, and the silicone rubber adhesive composition obtained by adding is poured into the jig in an appropriate amount and heated in a constant temperature bath at 120 ° C. for 10 minutes. And cured. The test piece of FIG. 1 thus obtained was used to examine the adhesiveness according to the method of JIS K6850. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

[Embodiment 5] The same resin as in Embodiment 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C., and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, as the component (C), the formula (II) was used.
As the non-functional oil bleed component of the component (D), used in combination, and the silicone rubber adhesive composition obtained by the addition is poured into the jig in an appropriate amount.
It was heated and cured in a constant temperature bath at 0 ° C. for 10 minutes. Using the test piece of FIG. 1 thus obtained, JIS K685
The adhesiveness was examined according to the method of No. 0. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

Comparative Example 1 The same resin as in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C., and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, the component of formula (I) was used as the component (C), and the nonfunctionality of the component (D) was used. An appropriate amount of the silicone rubber adhesive composition obtained without using the oil bleed component was poured into the same jig and heated in a constant temperature bath at 120 ° C. for 10 minutes to be cured. Using the test piece of FIG. 1 thus obtained, J
Adhesion was examined according to the method of IS K6850. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

[Comparative Example 2] The same resin as in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, as the component (C), the formula (II) was used.
Using I) as the non-functional oil bleed component of component (D), an appropriate amount of the silicone rubber adhesive composition obtained by pouring is poured into the same jig, and the mixture is placed in a thermostat at 120 ° C. for 10 minutes. Heated for a minute to cure. The test piece of FIG. 1 thus obtained was used to examine the adhesiveness according to the method of JIS K6850. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

[Comparative Example 3] A resin similar to that used in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and a chrome-plated metal plate of the same size were fixed to a tensile shear adhesion test piece preparation jig, and in the above preparation example, as the component (C), the formula (IV) was used.
The non-functional oil bleed component of the component (D) is used, and the silicone rubber adhesive composition obtained by adding is poured into the jig in an appropriate amount and heated in a constant temperature bath at 120 ° C. for 10 minutes. And cured. The test piece of FIG. 1 thus obtained was used to examine the adhesiveness according to the method of JIS K6850. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

[Comparative Example 4] The same resin as in Example 1 was charged into a thermoplastic resin injection molding machine, plasticized at 290 ° C, and then injected into a multi-cavity sheet mold cavity (injection conditions: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hard clamping pressure 35 ton, cavity temperature 100 ° C.), thickness 2 mm × width 25 mm × length 100
A few mm sheets were obtained. Next, the prepared sheet and the chrome-plated metal plate having the same dimensions were fixed to a tensile shear adhesion test piece preparation jig, and the component (C) obtained in the above preparation example was not used,
Using a non-functional oil bleed component as component (D), an appropriate amount of the silicone rubber adhesive composition obtained by pouring is poured into the same jig and heated in a constant temperature bath at 120 ° C. for 10 minutes to cure. It was Using the test piece of FIG. 1 thus obtained, the adhesiveness was examined according to the method of JISK6850. Further, the bleeding property and the sliding property of the rubber surface were examined by the methods described below.

Example 6 The same resin and silicone rubber adhesive composition as in Example 3 were molded using a two-color injection molding machine equipped with two injection devices. In this molding machine, nozzle parts (1) and (2) of an injection device are connected to a mold as shown in FIG. The nozzle part (1) is injected from the mold parting line, and the nozzle part (2) is injected from the center part of the right side surface of the mold. The mold used is composed of a left mold piece (3) and a right mold piece (4), and molding recesses are formed at two locations on the surfaces facing each other. Thus, the cavity portions (5) and (6) are formed as shown in FIG. 2 (see FIG. 2).

Each resin was melted at 290 ° C. by this injection molding machine and injected from the nozzle portion (1) into the cavity portion (5) to form a resin sheet molding (7). The conditions were such that the injection time was 6 seconds, the cooling time was 35 seconds, and the temperatures of the cavity part (5) and the left mold piece (3) were 100 ° C. (see FIG. 3).

Next, the right-side mold piece (4) is removed to open the left-side mold piece (3) while the resin sheet molding (7) is held in the recess of the left-side mold piece (3). By 180 °, and the mold pieces on the right side (4) are aligned and clamped again to form a cavity portion for forming a silicone rubber sheet molded body on the surface formed on the sheet molded body (7) and on the left side mold piece (4). ) And a concave portion (see FIG. 4).

In this state, the same silicone rubber adhesive composition as in Example 3 was applied to the surface of the resin sheet molded body (7) formed from the nozzle portion (2) of the injection device (the composition is shown in Table 1).
Was injected to form a rubber sheet molded body (8). The conditions are as follows: injection time is 6 seconds, cooling time is 90 seconds, the temperature of the left mold piece (3) is 100 ° C., and the temperature of the right mold piece (4) is 1.
It was 20 ° C. (see FIG. 5).

Through the above manufacturing process, a composite body (width: 25 mm, consisting of a resin sheet and a rubber sheet as shown in FIG.
A length of 15 cm and a thickness of 2 mm (resin and rubber have the same dimensions) were obtained. The mold releasability, dimensional accuracy, and productivity were good. Moreover, the adhesiveness was examined.

Table 1 shows the evaluation results of the above examples. The evaluation method is as follows. Adhesiveness: In JIS K6850 tensile shear adhesion test, 25 kgf / cm ² or more was taken as adhesion. Oil bleeding property: The state of oil droplets on the rubber surface was visually confirmed, and the state in which the oil droplets bleed on the rubber surface and the oil adhered when touched was considered good. Sliding property: The state in which the sliding did not stop when a metal rod was put on the rubber surface and slid was considered good.

[0086]

[Table 1]

The silicone rubber adhesive composition of the present invention shown in Table 1 was capable of being cured for a short period of time, and was capable of obtaining an integrally molded product firmly bonded to each resin.
The mold releasability, dimensional accuracy, and productivity were also good.

[Brief description of drawings]

1A and 1B show a test piece whose adhesiveness is examined, (A) is a cross-sectional view, and (B) is a plan view.

FIG. 2 is a schematic view of a two-color injection molding device.

FIG. 3 is a schematic view showing a state where resin is injected into the first cavity portion using the same apparatus.

FIG. 4 is a schematic view showing a state in which a resin molded body is inserted into a second cavity portion.

FIG. 5 is a schematic view showing a state where a silicone rubber adhesive composition is injected into the second cavity portion.

FIG. 6 is a perspective view of a composite body obtained by using a two-color injection molding device.

[Explanation of symbols]

1 nozzle 2 nozzle 3 Left mold piece 4 Right mold piece 5 Cavity part 6 cavity 7 Resin sheet molding 8 Rubber sheet molding

Continued front page    (72) Inventor Naoki Yamakawa             Gunma Prefecture Usui District, Matsuida Town             Shin-Etsu Chemical Co., Ltd. Silicone electronic materials             Inside the technical laboratory F term (reference) 4J040 EC182 EK032 EK042 GA11                       GA30 HA306 JB02 KA03                       KA16 KA42 LA05 LA06 MA10                       NA12 NA16 NA19

Claims (7)

[Claims] 1. A heat-curable organopolysiloxane composition (A) 100 parts by weight (B) Reinforcing silica fine powder 1-100 parts by weight (C) Epoxy equivalent is 100-5000 g / mol and aromatic in the molecule. Organic compound or organosilicon compound having at least one group ring 0.1-50 parts by weight (D) Nonfunctional phenyl group-containing silicone oil 0.1-50 parts by weight Oil-bleeding silicone Rubber adhesive composition. 2. The component (C) is an organosilicon compound containing at least one Si—H group in the molecule.
The oil bleeding silicone rubber adhesive composition described. 3. A non-functional silicone oil having a phenyl group content of 1 mol% or more and 90 mol% or less as the component (D).
The oil bleeding silicone rubber adhesive composition according to claim 1 or 2, which is one kind or two or more kinds. 4. The oil-bleedable silicone rubber adhesive composition according to claim 1, wherein the adhesive force to an organic resin is greater than that of a metal. 5. A heat-curable organopolysiloxane composition (A) 100 parts by weight (B) Reinforcing silica fine powder 1 to 100 parts by weight (C) Epoxy equivalent is 100 to 5000 g / mol and aromatic in the molecule. Organic compound or organosilicon compound having at least one group ring 0.1 to 50 parts by weight (D) Nonfunctional phenyl group-containing silicone oil 0.1 to 50 parts by weight of oil bleeding silicone rubber adhesive composition An integrally molded product of the cured product of and the thermoplastic resin. 6. The component (C) is an organosilicon compound containing at least one Si—H group in the molecule.
An integrally molded product of a cured product of the described oil bleeding silicone rubber adhesive composition and a thermoplastic resin. 7. The component (D) is a nonfunctional silicone oil having a phenyl group content of 1 mol% or more and 90 mol% or less.
7. An integrally molded product of a cured product of the oil bleeding silicone rubber adhesive composition according to claim 5 or 6, which is one kind or two or more kinds, and a thermoplastic resin.