JP2002020720A - Oil-bleeding silicone rubber adhesive composition and integrated molded article of the adhesive composition with thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-bleeding rubber adhesive composition which can simply integrally be molded with a thermoplastic resin in a short time by an injection molding method, is suitable for primer-less molding processes, has good adhesivity to the thermoplastic resin, can be adhered to the thermoplastic resin to give the integrally molded article without modifying the thermoplastic resin, and is useful for electric machines, electronic machines, automobiles, precision machines, construction-related articles, and so on. SOLUTION: This oil-bleeding silicone rubber adhesive composition characterized by containing at least two kinds of bleeding oil components comprising a non-functional silicone oil having a phenyl group content of >=28 mol.% and a non-functional silicone oil having a phenyl group content of >=1 mol.% and <28 mol.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of a silicone rubber composition and a thermoplastic resin, which can be molded easily and in a short time by injection molding and has good adhesiveness suitable for primerless molding. The present invention relates to a novel oil-bleed silicone rubber adhesive composition and an integrally molded article thereof with a thermoplastic resin, and is useful for electrical, electronic, automotive, precision machine, architectural, and the like.

[0002]

2. Description of the Related Art In recent years,
Taking advantage of the properties of silicone rubber, its applications are expanding in the fields of electricity, electronics, automobiles, and construction.Especially when manufacturing silicone rubber with oil bleeding properties such as oil seals, connectors, O-rings, etc. ,
Hermeticity and insulation are required. In addition, adhesion to a resin is required depending on the intended use, and in many cases, adhesion is performed via a primer. However, a primer coating step is required for work, which is troublesome. Therefore, when a self-adhesive silicone rubber obtained by adding an adhesive to a silicone rubber composition is used, the application step is not required, so that the working time can be reduced, the cost can be reduced, and the workability is improved, and the resin is used. This is an effective means for producing an integrally molded article with the above.

[0003] In the primerless molding of an addition-type heat-curable silicone rubber, there have been reported many methods of bonding to an organic resin. For example, there is a method of curing a self-adhesive silicone rubber material on a resin. For this self-adhesive silicone rubber composition, many techniques in which an adhesive component is specified have been proposed. A method of adding an organopolysiloxane containing 30 mol% or more of a hydrogen atom directly bonded to a silicon atom to an organic resin and adhering it to an addition-curable silicone rubber (Japanese Patent Publication No. 2-34311);
A method in which silicone rubber is integrated into an organic resin by a physical fitting method (Japanese Patent Publication No. 4529/1988), and an olefin resin obtained by grafting a compound having an aliphatic unsaturated group and a silicon-bonded hydrolyzable group to an olefin resin. A method of bonding and integrating silicone rubber (Japanese Patent Application Laid-Open No. 63-183843), a thermoplastic resin to which a compound containing an unsaturated group and a hydrogen atom directly bonded to a silicon atom added by the present applicant and a silicone rubber are used. And an oil-bleed silicone rubber molded integrally with a resin in which a thermoplastic oligomer containing an aliphatic unsaturated group is blended into a thermoplastic resin (JP-A-9-165516, JP-A-9-165516) No. 9-165517) has been proposed.

However, in the case of an oil bleed addition type heat-cured silicone rubber obtained by blending a bleed component with silicone rubber, a general-purpose thermoplastic resin such as AB
In order not to obtain sufficient adhesiveness to resins such as S, PPO, PPS, PC, PE, PP, PBT, acrylic, PA, aromatic PA, etc. Modification of the resin was necessary as proposed. In the case where the resin is modified, an extra step is required, the cost is increased, and the property of the resin is likely to change due to the modification. In addition, in the case of bonding without modifying the resin, there is a problem in that the resin is bonded to the mold when molding is performed using the mold. Under these circumstances, when a mold is used to form an integral molded body of the thermoplastic resin and the oil-bleed silicone rubber, it can be molded without bonding to the mold and the thermoplastic resin and the silicone rubber are strongly bonded. There has been a strong demand for the supply of an integrally molded article adhered to a resin.

SUMMARY OF THE INVENTION The present invention meets the above-mentioned demand and provides an oil-bleed silicone rubber adhesive composition which can be firmly integrated with a thermoplastic resin and which provides oil bleeding performance. An object of the present invention is to provide an integrally molded article with the same.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the silicone rubber has a phenyl group content of 28 mol%.
An oil bleed silicone rubber adhesive composition comprising at least two types of bleed oil components comprising the above non-functional silicone oil and a non-functional silicone oil having a phenyl group content of 1 mol% or more and less than 28 mol%. By using this, when integrally molded with the resin, while the silicone rubber has oil bleeding properties, an integrally molded body of the oil bleed silicone rubber and the thermoplastic resin, both of which are firmly adhered, is obtained, Using the injection molding method, the silicone rubber and thermoplastic resin have sufficient adhesion to the thermoplastic resin under short-time curing conditions, and peel sufficiently from the molding die for practical use. The inventors have found that a molded article can be obtained, and have accomplished the present invention.

[0007] Accordingly, the present invention provides a phenyl group having a content of 2
An oil characterized in that at least two types of bleeding oil components of 8 mol% or more of a non-functional silicone oil and a non-functional silicone oil having a phenyl group content of 1 mol% or more and less than 28 mol% are blended. A bleed silicone rubber adhesive composition is provided.

In this case, the adhesive composition comprises: (A) 100 parts by weight of a heat-curable organopolysiloxane composition; (B) 1 to 100 parts by weight of a reinforcing silica fine powder; 1 to 50 parts by weight (D) Nonfunctional silicone oil having a phenyl group content of 28 mol% or more and a phenyl group content of 1 mol% or more 28
Bleeding oil component containing at least two kinds of non-functional silicone oils in an amount of 0.5 to 20 parts by weight based on a total of 100 parts by weight of components (A) to (C). It is preferred that The present invention also provides an integrally molded article of a cured product of the adhesive composition (silicone rubber) and a thermoplastic resin.

Hereinafter, the present invention will be described in more detail.
The oil-bleed silicone rubber adhesive composition of the present invention is characterized by containing a specific bleed oil, and particularly (A) a heat-curable organopolysiloxane composition and (B) a reinforcing silica fine particle. Powder (C) Adhesiveness-imparting component (D) Bleeding oil component is preferable.

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

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). Can be used. R ¹ _a SiO _{(4-a) / 2} (1) (wherein, R ¹ is the same or different and has 1 to 12 carbon atoms;
It is preferably 1 to 8 unsubstituted or substituted monovalent hydrocarbon groups, and a is 1.5 to 2.8, preferably 1.8 to 2.5,
More preferably, it is a positive number in the range of 1.95 to 2.05. )

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

In this case, at least two of R ¹ must be an alkenyl group (especially those having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms). The content of the alkenyl group is 0.001 to 20 in all the organic groups bonded to the silicon atom (that is, in the unsubstituted or substituted monovalent hydrocarbon group as R ¹ in the above average composition formula (1)). It is preferable that the content be set to 0.1 mol%, particularly 0.01 to 10 mol%. This alkenyl group may be bonded to a silicon atom at the terminal of the molecular chain or to a silicon atom in the middle of the molecular chain,
The organopolysiloxane used in the present invention contains at least an alkenyl group bonded to a silicon atom at the molecular chain end, although it may be bonded to both, in view of the curing speed of the composition, the physical properties of the cured product, and the like. It is preferred that Preferably, R ¹ other than the alkenyl group is an alkyl group such as a methyl group.

The structure of the above organopolysiloxane is
Usually, the main chain is R¹ _TwoSiO_2/2Diorganoshiro represented by
Consisting of repeating xan units, wherein both ends of the molecular chain are R¹ _ThreeS
iO _1/2Blocked by a triorganosiloxy group represented by
Diorganopolysiloxy having an essentially linear structure
Sun, but partially R¹SiO_3/2Units and SiO
_4/2Even if it has a branched structure or a cyclic structure containing units
Good. This alkenyl group-containing organopolysiloxane
There is no particular limitation on the degree of polymerization (or viscosity),
° C), from liquid and low polymerization degree to raw rubber-like (gum-like)
Can be used up to a high degree of polymerization.
Coupling (weight average degree of polymerization) 10 to 10,000, especially 50
-10,000, preferably 100-10,000
0, more preferably 100 to 2,000
Used. If the average degree of polymerization is less than 10, the cured product is
Rubber properties may be insufficient. In addition, the viscosity
The degree is 100-1,000,000 cp at 25 ° C.
s, particularly preferably 500 to 500,000 cps.
Good.

The organohydrogenpolysiloxane of the component (2) is represented by the following average composition formula (2): R ² _b H _c SiO _{(4-bc) / 2} (2) Pieces (usually 2-300
), Preferably 3 or more, more preferably 3 to 150
It is necessary to have about silicon-bonded hydrogen atoms (that is, Si-H groups).

[0016] In the above formula (2), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the R ^2, the same as R ¹ in formula (1) Examples of the group include those having no aliphatic unsaturated group,
Particularly, an alkyl group such as a methyl group is preferable. B is 0.7 to 2.1, c is 0.001 to 1.0, and b +
c is a positive number satisfying 0.8 to 3.0, preferably b is 1.0 to 2.0, c is 0.01 to 1.0, and b + c is 1.5 to 2.5. .

At least two, preferably three, in one molecule
The Si-H groups contained in the molecule may be located at the terminal of the molecular chain, at the middle of the molecular chain, or at both of them. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms (or degree of polymerization) in one molecule is usually 2 to 300
And preferably 3 to 150 liquid at room temperature (25 ° C.), and has a viscosity of 0.1 at 25 ° C.
-10,000 cps, especially 0.5-5,000 cps
It is desirable that

Specific examples of the organohydrogenpolysiloxane of the formula (2) include, for example, 1,1,3,3-
Tetramethyldisiloxane, methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane
Dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends Dimethyl hydrogen siloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer, both ends trimethyl siloxy group-blocked methyl hydrogen siloxane / diphenyl siloxane copolymer, both ends trimethyl siloxy group-blocked methyl hydrogen siloxane / diphenyl siloxane / dimethyl siloxane Copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane, dimethylsiloxane, diphenylsilane Hexane copolymer, (CH _{3) 2} HSi
Copolymer consisting of O _1/2 units, (CH ₃ ) ₃ SiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and S
a copolymer composed 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 the organohydrogenpolysiloxane is as follows:
0.1 to 300 with respect to 00 parts (parts by weight, hereinafter the same)
Part, preferably 0.3 to 200 parts, particularly preferably 0.1 part.
5 to 100 parts. Further, the organohydrogenpolysiloxane of the component (2) has a hydrogen atom (Si-H) bonded to a silicon atom in the component (2) per mole of an alkenyl group bonded to a silicon atom in the component (1). Group) can be compounded in an amount of 0.3 to 20 mol, preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, particularly about 0.8 to 2.5 mol. .

Examples of the addition reaction catalyst of the component (3) include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, platinum bis Platinum catalysts such as acetoacetate, palladium catalysts, and rhodium catalysts include platinum group metal catalysts. The amount of the addition reaction catalyst can be a catalytic amount, and is usually 0.1 to 1, as a platinum group metal.
000 ppm, preferably 0.5 to 1,000 ppm,
In particular, it may be about 1 to 500 ppm.

The addition reaction-curable organopolysiloxane composition comprises the above 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 above-mentioned component (1). Can be used.

As the organic peroxide of the component (ii), conventionally known organic peroxides 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 compounding amount of the organic peroxide is a catalytic amount, and can be usually 0.01 to 10 parts based on 100 parts of the organopolysiloxane of the component (i).

The organic peroxide-curable organopolysiloxane composition comprises the above components (i) and (ii).

The type of the reinforcing silica fine powder of the component (B) is not particularly limited as long as it is a commonly used type of silica, and is used as a rubber reinforcing material.

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

In this case, these silica fine powders which have been directly treated in a powder state in advance can be used. As a treatment method, the treatment can be carried out by a generally known technique. For example, the above-mentioned untreated silica fine powder and a treating agent are placed in a mechanical kneading device or a fluidized vessel sealed at normal pressure, and if necessary, an inert gas is present. Mixing treatment may be performed at room temperature or under heat treatment, and the treatment may be accelerated by using a catalyst in some cases. However, it can be prepared by kneading and drying. The compounding amount of the treatment agent may be any amount as long as it is equal to or more than the amount calculated from the coverage area of the treatment agent.

The treating agents include organosilazanes such as hexamethyldisilazane and divinyltetramethyldisilazane;
Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) ) Silane coupling agents such as silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and organoalkoxysilane such as chloropropyltrimethoxysilane, and organic silicon compounds such as organopolysiloxane such as polydimethylsiloxane and organohydrogenpolysiloxane. Surface-treated with these treating agents and used as hydrophobic silica fine powder. As the treatment agent, a silane coupling agent or silazane is preferable.

The amount of the component (B) is 100 parts (A)
The amount is preferably 1 to 100 parts per part, and if it is less than 1 part, the mechanical strength becomes weak, and if it exceeds 100 parts, the filling of the component (B) becomes difficult, and workability and workability deteriorate. Preferably 2 to 80 parts is good.

It is more preferable that the silica fine powder subjected to the hydrophobic treatment is further subjected to a hydrophobic treatment at the time of compounding. In such a case, the surface treatment agent for imparting hydrophobicity used at the time of compounding includes a silane coupling agent or a partial hydrolyzate thereof, an organosilazane, a titanate coupling agent, an organopolysiloxane oil or an organohydrogenpolysiloxane oil. And the like.

In the surface treatment agent used, silane coupling agents include 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 silanes 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.

The 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, and titanium. Lactate and octylene glycol titanate, isopropyl tristearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate and the like are exemplified. You.

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

[0036]

Embedded image

In the formula, r is in the range of 0 to 50, and s is in the range of 1 to 50. When r is more than 50, the viscosity becomes high and the treatment becomes difficult. If s is more than 50, the viscosity is similarly high and the surface is hardly wetted, which is not preferable.

The compounding amount of the treating agent may be at least the amount calculated from the coating area of the treating agent, but if there is no particular problem, the compounding amount may be smaller. In particular, if the amount 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 the amount is more than 20 parts, it becomes wasteful in the process and disadvantageous in cost. 1 to
20 parts, preferably 0.5 to 10 parts.
It is the quantity which becomes part.

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

As the adhesiveness-imparting component (C) used in the present invention, an adhesive component conventionally used for an addition-curable silicone adhesive or the like is effectively used.

In this case, the component (C) as the adhesion-imparting component has at least one Si—H group in the molecule,
An organosilicon compound containing one or more of an alkenyl group, an acryl group, a methacryl group, an epoxy group, an alkoxysilyl group, an ester group, an anhydrous carboxy group, an amino group and an amide group, or a mixture thereof; An organic silicon compound having at least one Si-H group therein and having at least one phenyl skeleton or phenylene skeleton having 1 to 30 silicon atoms, and having at least one Si-H group in a molecule And having at least one phenyl skeleton or phenylene skeleton having 1 to 1 silicon atoms
30 containing an organosilicon compound having a functional group capable of undergoing an addition reaction with an addition-curable organopolysiloxane composition and being incompatible with the composition; And an organosilicon compound having 1 to 30 silicon atoms and having at least one phenyl skeleton or phenylene skeleton, and an alkenyl group or S bonded to at least one silicon atom in the molecule.
an organic silicon compound having an iH group and having at least one phenyl group bonded to a silicon atom,
An organosilicon compound having at least one Si-H group in the molecule and having at least one phenyl skeleton or phenylene skeleton and having 1 to 30 silicon atoms, and at least one alkenyl group and at least one ester group in the molecule; A compound containing an organic compound or an organosilicon compound is preferably used.

As the adhesion-imparting component, for example, a compound represented by the formula: Si--H group, alkenyl group, acryl group, methacryl group, epoxy group, alkoxysilyl group, ester group, carboxy anhydride group, amino group and amide group can be used. An organic compound or an organosilicon compound containing one or more kinds,
Or a mixture thereof, but preferably at least one, usually 1 to 10, particularly 2
An epoxy group such as a glycidoxy group, which has about 6 Si-H groups (that is, hydrogen atoms bonded to silicon atoms) and / or alkenyl groups, a trimethoxysilyl group, a triethoxysilyl group, and a methyldimethoxysilyl group Having 1 to 30, preferably 2 silicon atoms containing one or more of an alkoxysilyl group, an acryl group, a methacryl group, an ester group, an anhydrous carboxy group, an amino group and an amide group.
An organic silicon compound such as a linear or cyclic organosiloxane oligomer or organoalkoxysilane having about 20 to 20, especially about 4 to 10 can be used.

More specifically, as those containing an epoxy group, an alkoxysilyl group, an ester group, an alkenyl group, an amino group, an anhydrous carboxy group, an acrylic group and a methacryl group, for example, an alkenyl group such as allyl glycidyl ether and an epoxy group Non-silicon based organic compound having γ-glycidoxypropyltrimethoxysilane, β- (3,4
Epoxy-functional group-containing alkoxysilanes such as -epoxycyclohexyl) ethyltrimethoxysilane, alkenyl-containing alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri (methoxyethoxy) silane; γ-aminopropyltrimethoxysilane; γ-aminopropyltriethoxysilane, N-β
Amino group-containing alkoxysilanes such as (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- In addition to organoalkoxysilanes such as acryl- or methacryl-group-containing alkoxysilanes such as methacryloxypropyltrimethoxysilane and γ-acryloxypropyltrimethoxysilane, the following compounds are exemplified as organosiloxane oligomers.

[0044]

Embedded image

[0045]

Embedded image

The non-silicon compound having a phenylene skeleton in the molecule shown below and having at least two functional groups selected from an epoxy group, an alkenyl group, and a hydroxyl group as an adhesion-imparting component of the component (C). Organic compounds of the system can also be exemplified.

Embedded image (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n is 0
Or an integer of 1 to 16. )

As the component (C) used in the present invention, the above compounds are effective. When such a compound is used as the component (C), a sufficient adhesive strength can be obtained, but a mold or the like is used. When the metal forming jig is used, there is a possibility that the metal jig adheres to the forming jig. Using a material with poor adhesiveness, such as applying a Teflon (registered trademark) resin coat to the molding jig, is one way to solve the problem, but if the reliability is poor in terms of service life, There is. In such a case, a silicon compound containing no epoxy group, alkoxy group, or carboxy anhydride group is useful. Specifically, at least one compound per molecule, usually 1 to 20, as a compound that is difficult to adhere to a metal while satisfactorily adhering to a thermoplastic resin or a composition containing the resin,
In particular, the number of silicon atoms is 1 to 30, preferably 2 to 3 having about 3 to 10 Si-H groups and having a 1 to 3 valent phenyl skeleton or a phenylene skeleton which is not directly bonded to a silicon atom. 20, especially about 4 to 12 linear, branched or cyclic organosiloxane compounds such as organosiloxane oligomers can be used. Examples of such compounds include the following compounds. Among them, compounds containing two or more phenyl skeletons or phenylene skeletons are particularly preferable.

[0048]

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[0049]

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Adhesiveness having amino group and amide group
As the imparting component, those usually used may be used,
Other examples include the following. X-C_ThreeH₆-NH-Ph-NH-C_ThreeH₆-XX-C_ThreeH₆-NH-Ph-Ph-NH-C_ThreeH₆-XX-C_ThreeH₆-NH-Ph-CH_Two-Ph-NH-C_ThreeH₆
-XX-C_TwoH_Four-CO-NH-Ph-NH-CO-C_TwoH_Four−
X X-C_TwoH_Four-CO-NH-Ph-CH_Two-Ph-NH-
CO-C_TwoH_Four-XX-C_ThreeH₆-CO-NH-Ph-CH_Two-Ph-NH-
CO-C_ThreeH₆-XX-C_TwoH_Four-CO-NH-Ph-O-Ph-NH-CO
-C_TwoH_Four-XX-C_ThreeH₆-NH-CO-Ph-CO-NH-C_ThreeH₆−
X X-C_ThreeH₆-NH-CO-Ph-CO-Ph-CO-N
HC_ThreeH₆-XX-C_ThreeH₆-O-CO-NH-Ph-NH-CO-O-
C_ThreeH₆-XX-C_ThreeH₆-O-CO-NH-CH_Two-Ph-CH_Two-N
H-CO-OC_ThreeH₆-XX-C_ThreeH₆-O-CO-NH-Ph-CH_Two-Ph-N
H-CO-OC_ThreeH₆-XX-C_ThreeH₆-NH-CO-NH-Ph-NH-CO-N
HC_ThreeH₆-XX-C_ThreeH₆-NH-CO-NH-Ph-CH_Two-Ph-
NH-CO-NH-C_ThreeH ₆-X where X is 1,3,5,7-tetramethyl-3,5,
Indicates a 7-trihydrocyclotetrasiloxane group. Ma
Ph represents a phenyl group or a phenylene group.

The above components for imparting adhesion may be used alone or in combination. It is even more preferable that a component containing a functional group which undergoes an addition reaction with the addition reaction-curable organopolysiloxane composition of the component (A) and which is incompatible with the above-mentioned component (A) is added and combined. As such a component, for example, a phenyl group and / or a trifluoropropyl group containing an alkenyl group or a Si—H group bonded to a silicon atom in a molecule, and bonded to a silicon atom,
An organic silicon compound such as an organopolysiloxane containing either a C ₄ F ₉ CH ₂ CH ₂ — group or a C ₈ F ₁₇ CH ₂ CH ₂ — group is exemplified.

In particular, the adhesion-imparting component in the oil-bleed silicone rubber adhesive composition has at least one Si-H group in the above molecule and at least one phenyl skeleton or phenylene skeleton. 1 silicon atom
30 organic silicon compounds and an organic silicon compound having at least one alkenyl group or Si—H group bonded to at least one silicon atom in the molecule and at least one phenyl group bonded to the silicon atom, for example, a silicon atom It is preferable that at least one of each contains a bonded phenyl group and an organopolysiloxane oil containing an alkenyl group or a Si—H group.

The adhesiveness-imparting component in the oil-bleed silicone rubber adhesive composition may be a silicone rubber having at least one Si—H group in the molecule and at least one phenyl skeleton or phenylene skeleton. 1 to 3 atoms
Organic compounds having at least one alkenyl group and at least one ester group in the molecule, such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid and vinyl acetic acid, allyl benzoate, and phthalic acid. An organic compound containing an allyl ester such as diallyl ester, pyromellitic acid tetraallyl ester or alkyl acid allyl ester, or an organosilicon compound such as an organopolysiloxane;
Seeds may be contained. Alternatively, a reaction product of the above components may be used.

The amount of the adhesiveness-imparting component is 0.1 parts per 100 parts of the organopolysiloxane composition of 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. Preferably it is 0.2 to 30 parts.

The bleeding oil component (D) used in the present invention is an essential component for imparting lubricity to the rubber portion. Depending on the application, for example, in a connector for superimposing resin molded products, It is necessary to reduce insertion force and to provide sealing properties. The bleeding oil component does not participate in the addition reaction, and has a phenyl group content (that is, a total of monovalent organic groups (unsubstituted or substituted monovalent hydrocarbon groups) bonded to silicon atoms in the organopolysiloxane). Mol% to the same, the same shall apply hereinafter) of 28 mol% or more, preferably 30 to 90 mol%, more preferably 35 to 80 mol%.
Mole% of non-functional silicone oil and phenyl group content of 1 mole% or more and less than 28 mole%, usually 1-27 mole%,
It is characterized in that it preferably contains 3 to 26 mol%, more preferably 5 to 25 mol% of both non-functional silicone oils, and is blended with a bleeding oil component containing at least one of both. Thereby, the adhesiveness to the resin is good, the amount of bleeding on the rubber surface after molding is sufficient, and the bleeding speed is good. In addition,
The non-functional silicone oil is a reactive functional group capable of undergoing a cross-linking reaction with the organopolysiloxane component of the heat-curable organopolysiloxane composition (A) (for example, an alkenyl group or a hydrogen atom bonded to a silicon atom). (Si
—H group) and other reactive functional groups in the molecule.

In particular, each of the two non-functional silicone oils has a viscosity at 25 ° C. of 10 cps to 40 cps.
It is preferably 0 cps or less. Examples of such a phenyl group-containing silicone oil include a dimethylsiloxane / diphenylsiloxane copolymer and a dimethylsiloxane / methylphenylsiloxane copolymer. In particular, a linear chain is preferable, and both ends of the molecular chain are preferably blocked with a triorganosiloxy group such as a trimethylsiloxy group, a phenyldimethylsiloxy group, and a diphenylmethylsiloxy group.

Further, a nonfunctional silicone oil having a phenyl group content of at least 28 mol% and a nonfunctional silicone oil having a phenyl group content of at least 1 mol% and less than 28 mol% are 10/90 by weight. The total amount of the two non-functional silicone oils is 80% by weight or more in the bleeding oil component, and the silicone rubber adhesive composition 100 excluding the bleeding oil component is mixed.
The total bleeding oil component is 0.5 to 20 parts by weight (that is, 100 parts by weight of the total of the components (A) to (C)).
What is necessary is just to mix | blend in the range of a weight part. If the amount is less than 0.5 part by weight, sufficient oil bleeding property cannot be obtained, and if it exceeds 50 parts by weight, the adhesiveness may be adversely affected.

In addition to the above-mentioned phenyl group-containing silicone oil, a non-functional silicone oil containing a trifluoropropyl group or a perfluoroalkyl ether group, a silicone-modified perfluoroalkyl ether compound, or the like is used unless the above conditions are impaired. You may use it.

The oil-bleed silicone rubber adhesive composition of the present invention may contain various additives other than the above-mentioned components depending on the purpose, for example, titanium oxide, iron oxide, cerium oxide, vanadium oxide, cobalt oxide, and oxide. Chromium, metal oxides such as manganese oxide and their composites, quartz powder, diatomaceous earth, calcium carbonate, magnesium carbonate, alumina,
An inorganic filler such as carbon can be added, and a pigment, a heat-resistant agent, a flame retardant, a plasticizer, a reaction control agent and the like may be added as long as the desired properties are not impaired. In addition, the addition amount of these optional components can be a usual amount as long as the effect of the present invention is not hindered.

When an addition reaction-curable organopolysiloxane composition is used, a vinyl group-containing organopolysiloxane such as vinylcyclotetrasiloxane, acetylene alcohols such as triallyl isocyanate, alkyl maleate and ethynylcyclohexanol, silane,
An addition reaction control agent such as a compound selected from the group consisting of a siloxane modified product, hydroperoxide, tetramethylethylenediamine, benzotriazole, and a mixture thereof, and the like can be added as long as the effects of the present invention are not impaired.

The oil-bleed silicone rubber adhesive composition of the present invention can be obtained by simply mixing the above-mentioned components (A) to (D) and optional components uniformly at room temperature. The component (B) is a component (A), the component (2), the component (3) or the component excluding the component (ii), and 100 to 200 using a planetary mixer or a kneader.
Heat treatment may be performed at a temperature in the range of 1 to 4 hours, and the treatment agent may be added at that time. Then, at room temperature, components (2) and (3)
Alternatively, the composition can be obtained by mixing the components (ii), (C) and (D). The molding method can be freely selected depending on the viscosity of the mixture, such as injection molding, compression molding,
Any method such as injection molding, extrusion molding, and transfer molding may be employed. The curing condition is usually 60 to 20
Heat molding can be performed at 0 ° C. within a range of 10 seconds to 24 hours.

The oil-bleed silicone rubber adhesive composition of the present invention is suitably used when obtaining an integrally molded article with an organic resin. In this case, examples of the thermoplastic resin used in the present invention include ordinary thermoplastic resins such as an olefin polymerization type or a polycondensation type. Specific examples thereof include acrylonitrile-butadiene-styrene (ABS) resin, styrene resin, and polyethylene. Resin, polypropylene resin, acrylic resin, polycarbonate (PC) resin, polyethylene terephthalate resin, polybutylene terephthalate (PB
T) Resins, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfone resins, nylon resins, aromatic polyamide resins, polyimide resins, liquid crystal resins, and the like, or a mixture thereof.

As a method for integrally molding the above-mentioned uncured silicone rubber adhesive composition having the above composition on the above-mentioned thermoplastic resin, an uncured silicone rubber adhesive is formed on a previously molded thermoplastic resin. A method in which the composition is placed in a desired shape and heated at a temperature not higher than the temperature at which the thermoplastic resin melts, and an uncured silicone rubber adhesive composition is placed on a preformed thermoplastic resin, and the thermoplastic resin Or a method in which a thermoplastic resin is first injection-molded into a mold by an injection molding machine, and then the silicone rubber adhesive composition is heated and injected into the mold. As an example of a method for producing a molded article of the thermoplastic resin, for example, the thermoplastic resin is pelletized and injected into a molding die heated to a temperature equal to or higher than the softening point of the thermoplastic resin. A known method for cooling to below the softening point is convenient. In this case, a device generally called an injection molding machine or a transfer molding machine can be used.

On the other hand, the silicone rubber adhesive composition may be liquid, putty, or paste in an uncured state, but is preferably liquid or paste because of ease of molding. The curing conditions of the silicone rubber adhesive composition according to the present invention are such that the resin is deformed, melted, and degraded in order to exhibit strong adhesiveness with a thermoplastic resin,
It is necessary to perform in the curing time. Although it depends on the type of the resin, an integrally molded article can be obtained under the curing conditions at 100 to 150 ° C. for about 0.2 to 30 minutes, especially about 0.4 to 10 minutes.

[0065]

According to the present invention, an oil-bleed silicone rubber adhesive composition and a thermoplastic resin can be molded easily and in a short time by injection molding in an integrally molded article, which is suitable for primerless molding. To provide an oil-bleed silicone rubber adhesive composition having good adhesiveness to a thermoplastic resin, and to obtain an integrally molded article that can be bonded without modifying the thermoplastic resin, for electric, electronic and automotive applications. It is useful for precision machinery, construction, etc.

[0066]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight. Preparation Examples of Oil-Bleed Silicone Rubber Composition As shown in Tables 1 and 2, as the component (1) in the component (A), both ends were blocked with a dimethylvinylsiloxy group and the viscosity at 25 ° C was 10,000 cps. Dimethylpolysiloxane, fumed silica having a specific surface area of 200 m ² / g as a silica fine powder of the component (B), 8 parts of hexamethyldisilazane was added to 100 parts of the component (1), and the mixture was blended in a kneader mixer. After mixing uniformly, the mixture was further heated and mixed at 150 ° C. for 1 hour to obtain a silicone rubber base. A 1% 2-ethylhexanol solution of methyl hydrogen polysiloxane represented by the following average composition formula (4) as the component (2) and a component (3) of chloroplatinic acid as the component (3) in the remaining component (A) in the silicone rubber base. And 50% of ethynylcyclohexanol as a reaction control agent
An ethanol solution was added, and the following (I)
III as an adhesiveness-imparting component and (D) a component described below.
The linear non-functional oil bleed components <1> to <6> were uniformly mixed to obtain an oil bleed silicone rubber composition.

[0067]

Embedded image

Bleed component <1> Methylphenylpolysiloxane capped with trimethylsiloxy groups at both terminals having a phenyl group content of 10 mol% having a viscosity of 200 cps at 25 ° C. <2> Phenyl group content having a viscosity of 200 cps at 25 ° C. 20 mol% methylphenylpolysiloxane capped with trimethylsiloxy groups at both ends <3> Methylphenylpolysiloxane capped at 25 ° C. with a viscosity of 380 cps and phenyl group content of 25 mol% capped with trimethylsiloxy groups at both terminals <4 > Methylphenylpolysiloxane capped with diphenylmethylsiloxy groups at both ends having a phenyl group content of 60 mol% with a viscosity of 170 cps at 25 ° C. <5> 0.5 mol% of a phenyl group content with a viscosity of 500 cps at 25 ° C. Methylphenyl policy blocked with trimethylsiloxy groups at both ends Roxane <6> Methylphenylpolysiloxane blocked at both ends by trimethylsiloxy groups having a phenyl group content of 28 mol% and a viscosity at 25 ° C. of 800 cps

[0069]

Embedded image

Example 1 A thermoplastic resin injection molding machine was used to prepare a polycarbonate resin having a number average molecular weight of about 10,000, a polybutylene terephthalate resin having a number average molecular weight of about 20,000, nylon 6-6, and aromatic polyamide H-. PA (manufactured by Teijin Amoco Engineering Plastics Co., Ltd.) was charged, and after plasticizing at 290 ° C., the mixture was injected into a multi-cavity sheet-type mold cavity (injection conditions were: injection time 6 seconds, cooling time 30 seconds, injection pressure 1,000kg / cm ² , hard tightening pressure 35ton, cavity temperature 100 ° C), thickness 2m
Several resin sheets of mx 25 mm width x 100 mm length were obtained. Next, each of the prepared resin sheets and the chrome-plated metal plate of the same dimensions were fixed to a tensile shear adhesion test piece preparation jig,
An oil bleed silicone rubber composition obtained by combining the nonfunctional oil bleed component of <1> and <4> with the non-functional oil bleed component of the formula (I) was used in the above jig, and the jig was used. The mixture was poured and heated in a thermostat at 120 ° C. for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Here, in FIG. 1, a and b denote resin sheets, c and d denote support holding parts, respectively, and e denotes a cured product of the silicone rubber 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
I) and the non-functional oil bleed component is <1
An appropriate amount of the oil-bleed silicone rubber composition obtained by using the combination of <> and <4> was poured into the same jig, and was heated in a thermostat at 120 ° C for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Example 3 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
An appropriate amount of the oil-bleed silicone rubber composition obtained by using both 1> and <4> was poured into the same jig, and heated in a thermostat at 120 ° C. for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
An appropriate amount of the oil-bleed silicone rubber composition obtained by using both 2> and <4> was poured into the same jig, and heated in a thermostat at 120 ° C. for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Example 5 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II) and a methylphenylpolysiloxane oil having a viscosity of 3,000 cps at 25 ° C. and a phenyl group content of 5 mol% and capped with dimethylvinylsiloxy groups at both terminals are used, and <2>, <2 An appropriate amount of the oil-bleed silicone rubber composition obtained by using <4> in combination was poured into the same jig, and heated in a thermostat at 120 ° C for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Example 6 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II) and lauric acid allyl ester, an appropriate amount of an oil-bleed silicone rubber composition obtained by using <2> and <4> in combination with a non-functional oil bleed component into the same jig, and put into a thermostat at 120 ° C. For 10 minutes to cure. Using the test piece thus obtained in FIG.
The adhesion was examined according to the method of K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

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 type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
5> Pour an appropriate amount of the oil-bleed silicone rubber composition obtained in <1> into the same jig, and place it in a thermostat at 120 ° C.
Heated for 0 minutes to cure. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

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 type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
3> Pour an appropriate amount of the oil-bleed silicone rubber composition obtained using the above method into the same jig, and place in a thermostat at 120 ° C. 1
Heated for 0 minutes to cure. Using the test piece of FIG. 1 thus obtained, the adhesion was examined according to the method of J1SK6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Comparative Example 3 The same resin as in Example 1 was put into a thermoplastic resin injection molding machine, plasticized at 290 ° C., and then injected into a multi-cavity sheet-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
4> Pour an appropriate amount of the oil-bleed silicone rubber composition obtained using <1> into the same jig, and place it in a thermostat at 120 ° C.
Heated for 0 minutes to cure. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
An appropriate amount of the oil bleed silicone rubber composition obtained by using both 4> and <5> was poured into the same jig, and was heated in a thermostat at 120 ° C. for 10 minutes to be cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Comparative Example 5 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet, a chrome-plated metal plate of the same dimensions were fixed to a tensile shear adhesion test piece preparation jig, without using the adhesion imparting component in the above preparation example,
An appropriate amount of the oil bleed silicone rubber composition obtained by using <2> and <4> together with the non-functional oil bleed component is poured into the same jig and heated in a 120 ° C. constant temperature bath for 10 minutes.
Cured. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Comparative Example 6 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-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
An appropriate amount of the oil-bleed silicone rubber composition obtained by using the above 3> was poured into the same jig, and the mixture was placed in a thermostat at 120 ° C. for 1 hour.
Heated for 0 minutes to cure. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Comparative Example 7 The same resin as in Example 1 was put into a thermoplastic resin injection molding machine, plasticized at 290 ° C., and then injected into a multi-cavity sheet-type mold cavity (injection conditions were: , Injection time 6 seconds, cooling time 30 seconds, injection pressure 1,
000 kg / cm ² , hardening pressure 35 ton, cavity temperature 100 ° C), thickness 2 mm x width 25 mm x length 100
Several mm sheets were obtained. Next, the prepared sheet and the chromium-plated metal plate of the same dimensions were fixed on a jig for preparing a tensile shear adhesive test piece, and the formula (I) was used as an adhesion imparting component in the above preparation example.
II), and the non-functional oil bleed component is <
An appropriate amount of the oil-bleed silicone rubber composition obtained by using both 4> and <6> was poured into the same jig, and was heated and cured in a thermostat at 120 ° C. for 10 minutes. Using the test piece thus obtained in FIG. 1, the adhesiveness was examined according to the method of JIS K6850. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the following methods.

Example 7 The same resin and silicone rubber composition as in Example 1 was molded using a two-color injection molding machine equipped with two injection devices. In this molding machine, the nozzles (1) and (2) of the injection device are connected to a mold as shown in FIG. The nozzle part (1) is from the mold parting line
The nozzle (2) is injected from the center of the right side of the mold. The used mold is composed of a left mold piece (3) and a right mold piece (4), and molding recesses are formed at two locations on each of opposing surfaces. Figure 2
As shown in (1), the cavity portions (5) and (6) are formed.

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 molded body (7). The injection time was 6 seconds, the cooling time was 35 seconds, and the temperature of the cavity (5) and the left mold piece (3) was 100 ° C. (see FIG. 3).

Next, the right mold piece (4) is removed, the one-sided opening is performed, and the left mold piece (3) is held while the resin sheet molded body (7) is held in the concave portion of the left mold piece (3). Is rotated by 180 °, the right mold piece (4) is aligned, and the mold is clamped again. The cavity for forming the silicone rubber sheet molded body is aligned with the surface formed on the sheet molded body (7) and the left mold piece (4). ) (See FIG. 4).

In this state, the same oil-bleed silicone rubber composition as in Example 1 (compositions are shown in Tables 1 and 2) on the surface formed on the resin sheet molded body (7) from the nozzle portion (2) of the injection device. ) Was injected to form a molded rubber sheet (8). The conditions are: injection time 6 seconds, curing time 90 seconds,
The temperature of the left mold piece (3) is 100 ° C, and the right mold piece (4)
Was 120 ° C. (see FIG. 5).

By the above-described manufacturing process, a composite (2.5 m wide) composed of a resin sheet and a rubber sheet as shown in FIG.
m, length 15cm, thickness 2mm (resin and rubber have the same dimensions)
I got The mold releasability, dimensional accuracy, and productivity were good. The adhesiveness was also examined. Further, the bleeding property, the slip property of the rubber surface, and the like were examined by the methods described below.

Tables 1 and 2 show the evaluation results of the above examples.
The evaluation items and evaluation methods are as follows. Evaluation items, evaluation method Adhesion test conditions: In JIS K6850 tensile shear adhesion test, 25 kgf / cm ² or more was regarded as adhesion. Initial oil bleeding property: The state of oil droplets on the rubber surface was visually checked. Slip property: A state in which the sliding did not stop when the metal rod was slid on the rubber surface. Time-dependent change 1: After 100 hours, the oil on the rubber surface was wiped off, and after 24 hours, bleeding property and slipperiness were confirmed. Time-dependent change 2: After 100 hours, the oil on the rubber surface was wiped off, and after 200 hours, the oil on the rubber surface was removed again Wipe off, then check bleed and slip after 24 hours

[0090]

[Table 1]

[0091]

[Table 2]

The silicone rubber adhesive compositions of the present invention shown in Tables 1 and 2 can be cured in a short time, have good oil bleeding property over time, have good slipperiness, and are formed into an integrally molded article firmly adhered to each resin. Could be obtained. In addition, mold releasability, dimensional accuracy, and productivity were good.

[Brief description of the drawings]

FIG. 1 shows a test piece for which adhesion was examined, (A) is a sectional view, and (B) is a plan view.

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

FIG. 3 is a schematic diagram showing a state in which a resin is injected into a first cavity using the same device.

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

FIG. 5 is a schematic view showing a state where a silicone rubber composition has been injected into a second cavity.

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Nozzle part 2 Nozzle part 3 Left mold piece 4 Right mold piece 5 Cavity part 6 Cavity part 7 Resin sheet molding 8 Rubber sheet molding

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA67 AB26 AC16 AF58 AH12 BB01 BC07 4J040 EK032 EK042 EK081 GA01 GA03 GA07 GA11 GA12 GA13 GA22 GA30 GA31 HA066 HA096 HA306 HB41 HD41 HD43 JB02 KA14 KA16 KA10 LA10 NA16 NA19 NA20 PA30

Claims (13)

[Claims] 1. A non-functional silicone oil having a phenyl group content of at least 28 mol% and a phenyl group content of 1 mol%.
An oil bleed silicone rubber adhesive composition comprising at least two types of bleed oil components with at least 28 mol% of a non-functional silicone oil. 2. (A) 100 parts by weight of a heat-curable organopolysiloxane composition (B) 1 to 100 parts by weight of a reinforcing silica fine powder (C) 0.1 to 50 parts by weight of an adhesion-imparting component (D) A non-functional silicone oil having a phenyl group content of 28 mol% or more and a phenyl group content of 1 mol% or more 28
The bleeding oil component containing at least two kinds of non-functional silicone oils in an amount of less than 0.5 mol%, and 0.5 to 20 parts by weight based on 100 parts by weight in total of the components (A) to (C). The oil-bleeding silicone rubber adhesive composition according to claim 1, characterized in that: 3. The oil-bleed silicone rubber adhesive composition according to claim 2, wherein the heat-curable organopolysiloxane composition (A) is an addition-curable organopolysiloxane composition. 4. The oil-bleed silicone rubber adhesive composition according to claim 2, wherein the heat-curable organopolysiloxane composition (A) is an organic peroxide-curable organopolysiloxane composition. 5. The adhesion-imparting component (C) has at least one Si—H group in the molecule, and has an alkenyl group, an acryl group, a methacryl group, an epoxy group, an alkoxysilyl group, and an ester group. 5. An organosilicon compound containing at least one of a carboxylic acid group, an anhydrous carboxy group, an amino group and an amide group, or a mixture thereof.
Item 8. The oil-bleeding silicone rubber adhesive composition according to Item 1. 6. An organic compound having at least one Si—H group in the molecule and having at least one phenyl skeleton or phenylene skeleton and having 1 to 30 silicon atoms, wherein the component (C) for imparting adhesion is a component. The oil-bleed silicone rubber adhesive composition according to any one of claims 2 to 4, which is a silicon compound. 7. An organic compound having at least one Si—H group in the molecule and having at least one phenyl skeleton or phenylene skeleton and having 1 to 30 silicon atoms, wherein the component (C) for imparting adhesion is a component. It contains a silicon compound and a functional group that undergoes an addition reaction to an addition-curable organopolysiloxane composition,
4. The oil-bleed silicone rubber adhesive composition according to claim 3, wherein said composition contains an organic silicon compound which is incompatible with said composition. 8. An organic compound having 1 to 30 silicon atoms, wherein the adhesion-imparting component (C) has at least one Si—H group in the molecule and at least one phenyl skeleton or phenylene skeleton. A silicon compound and at least one
At least one phenyl group having an alkenyl group or a SiH group bonded to a silicon atom and bonded to the silicon atom.
The oil-bleed silicone rubber adhesive composition according to any one of claims 2 to 4, wherein the composition comprises an organosilicon compound. 9. An organic compound having at least one Si—H group in the molecule and having at least one phenyl skeleton or phenylene skeleton and having 1 to 30 silicon atoms, wherein the component (C) for imparting adhesion is a component. The oil-bleed silicone rubber adhesive composition according to any one of claims 2 to 4, comprising a silicon compound and an organic compound or an organic silicon compound having at least one alkenyl group and ester group in the molecule. object. 10. A non-functional silicone oil having a phenyl group content of 28 mol% or more in a bleeding oil component, having a viscosity at 25 ° C. of 10 cps to 400 cps.
The oil-bleed silicone rubber adhesive composition according to any one of claims 1 to 9, which is: 11. The non-functional silicone oil having a phenyl group content of 1 mol% or more and less than 28 mol% in the bleeding oil component has a viscosity at 25 ° C. of 10 cps to 400 cps. Any one
Item 8. The oil-bleeding silicone rubber adhesive composition according to Item 1. 12. The bleeding oil component comprises a nonfunctional silicone oil having a phenyl group content of 28 mol% or more and a nonfunctional silicone oil having a phenyl group content of 1 mol% or more and less than 28 mol% by weight. 10/90 ~
90/10, and the total of the two non-functional silicone oils is 80% by weight or more in the bleeding oil component, and based on 100 parts by weight of the silicone rubber adhesive composition excluding the bleeding oil component. The oil-bleed silicone rubber adhesive composition according to any one of claims 1 to 11, wherein all the bleed oil components are blended in a range of 0.5 to 20 parts by weight. 13. An integrally molded article of a cured product of the oil-bleeding silicone rubber adhesive composition according to claim 1 and a thermoplastic resin.