JPH10316844A - One-piece molding of thermoplastic resin and silicone rubber - Google Patents

Abstract

(57) [Summary] (Modified) [PROBLEMS] Even if a commonly used release agent is added to polybutylene terephthalate resin, a poly-silicon rubber is integrated with silicone rubber with adhesive strength enough to withstand practical use. Provided is an integrally molded article of butylene terephthalate resin and silicone rubber. (A) Polybutylene terephthalate includes:
(B) a silicon-containing compound having at least one hydrogen atom directly bonded to a silicon atom in one molecule and / or a polymer thereof, (C) a phenolic antioxidant, (D) a thioether antioxidant, E) Polyester-based elastomer (F) A coating liquid composed of an organopolysiloxane composition is applied to the surface of a molded product obtained by molding a polybutylene terephthalate resin composition containing a specific release agent, and cured. An integrated molded product of thermoplastic polyester and silicone rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an integrally molded article in which a molded article of a polybutylene terephthalate resin composition having excellent durability, especially hydrolysis resistance and heat aging resistance, and silicone rubber are firmly combined and integrated. .

[0002]

2. Description of the Related Art Thermoplastic polyester resins, especially polybutylene terephthalate resins, are excellent in chemical resistance, heat resistance and mechanical properties and are widely used as industrial resins. In recent years, as the durability, the demand for hydrolysis resistance and heat aging resistance has increased, and the silicone rubber which satisfies the above required properties in the electric / electronic field and the automobile field, and has excellent heat resistance, electric properties, and weather resistance. There is a demand for the supply of a strongly bonded integrally formed body.

Conventionally, as a method of adhering an addition-curable silicone rubber to a resin molded product, for example, a primer is applied to the surface of the resin molded product, and an uncured silicone rubber material is applied thereon, and then cured and adhered. And a method in which a self-adhesive silicone rubber material is cured from the top of a molded product during resin molding and integrated.

However, the method of bonding using a primer requires a complicated process of taking out the resin once molded from a mold and applying the primer.

A method of curing a self-adhesive silicone rubber material on a resin molded product is as follows. When an integrated molded body of resin and silicone rubber is formed using a mold or the like, the silicone rubber itself adheres to the mold. There is a major drawback to doing so. Further, it is known to add a silicon-containing compound in which a hydrogen atom or a vinyl group is directly bonded to a silicon atom to a polybutylene terephthalate resin for the purpose of improving the adhesiveness with a self-adhesive silicone rubber material. The adhesion between the silicone rubber and the molded product of polybutylene terephthalate resin may be unstable due to the effect of a release agent generally added to ensure the releasability of the resin.

[0006]

SUMMARY OF THE INVENTION The present invention significantly improves the hydrolysis resistance and heat aging resistance of a polybutylene terephthalate resin, and ensures that the polybutylene terephthalate resin has a releasability from a mold of a molded product. For this reason, even if a commonly used release agent is added, the silicone rubber has sufficient adhesive strength to withstand practical use, and furthermore, a molded body of polybutylene terephthalate resin and silicone rubber can be easily and reliably formed. It is an object of the present invention to provide an integrally molded article of polybutylene terephthalate resin and silicone rubber obtained by molding in a short time, for example, injection molding.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a phenolic antioxidant was added to a polybutylene terephthalate resin having a titanium compound as a polymerization catalyst and having a low terminal carboxyl group concentration. And a thioether-based antioxidant and a polyester-based elastomer, and further blended with a specific silicon-containing compound and / or a polymer thereof. As an integrated silicone rubber, an organopolysiloxane terminated with a trivinylsilyl group is used. By using an addition-curable silicone rubber containing as an adhesion-imparting component, the resin can be integrally molded with the silicone rubber with a stable adhesive force even when a release agent is added to the resin. Adhesion to the polybutylene terephthalate resin composition using a short curing condition, Duck silicone rubber itself found that obtained with readily peeled can polybutylene terephthalate resin composition and molded body of the silicone rubber from the mold and have reached the present invention.

More specifically, the present invention relates to (A) (A) per 100 parts by weight of a polybutylene terephthalate resin using a titanium compound as a polymerization catalyst with a terminal carboxyl group concentration of 15 equivalents / ton or less; 0.05 to 3 parts by weight of a silicon-containing compound having a hydrogen atom directly bonded to at least one silicon atom and / or a polymer thereof,
(C) 0.01 to 0.5 part by weight of a phenolic antioxidant, (D) 0.01 to 0.5 part by weight of a thioether antioxidant, (E) 0.5 to 10 parts of a polyester elastomer
Part by weight and (F) a polybutylene terephthalate resin composition in which 0 to 1.0 part by weight of one or more release agents selected from coal-based synthetic wax, polyethylene wax, and oil-based synthetic wax are blended. (B) (G) an organopolysiloxane having at least two vinyl groups bonded to silicon atoms in one molecule, and (H) hydrogen bonded to silicon atoms in one molecule. An organohydrogenpolysiloxane having at least two atoms, (I) a platinum compound, and (J) a compound represented by the following general formula (1)

[0009]

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[0010] (wherein, R ¹ is free of aliphatic unsaturation, a monovalent hydrocarbon group substituted or unsubstituted, R ¹
When there are a plurality of, they may be different. k is an integer of 0 or an integer of 1 or more.) A polybutylene terephthalate resin in which a silicone rubber obtained by curing an organopolysiloxane composition containing an organopolysiloxane terminated with trivinylsilyl is cured and integrated. And silicone rubber.

The polybutylene terephthalate resin as the component (A) of the present invention is a polyester containing terephthalic acid as a main acid component and 1,4-butanediol as a main glycol component. Here, “main” means 80 mol% or more, preferably 90 mol% or more, based on all acid components or all glycol components.

The acid components which can be copolymerized include aromatic dicarboxylic acids other than terephthalic acid, such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylketonedicarboxylic acid, diphenylsulfone. Examples include aliphatic dicarboxylic acids such as dicarboxylic acids, such as succinic acid, adipic acid, and sebacic acid, and alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid, tetralindicarboxylic acid, and decalindicarboxylic acid.

The copolymerizable glycol components other than 1,4-butanediol include ethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, tricyclodecanedimethylol, xylylene glycol, bisphenol A and bisphenol B. , Bishydroxyethoxybisphenol A
Etc. are exemplified.

Further, a polyfunctional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, trimesic acid, pyromellitic acid and the like may be copolymerized as long as the polyester does not substantially lose the molding performance.

Further, the polybutylene terephthalate resin in the present invention is produced using a titanium compound as a polymerization catalyst, and the terminal carboxyl group concentration needs to be 15 equivalents / ton or less. Terminal carboxyl group concentration of 15
When the equivalent amount / ton is exceeded, a significant improvement in hydrolysis resistance, which is one of the main effects of the present invention, is not observed. Further, when a tin compound is used as a polymerization catalyst, the curing of the silicone rubber is inhibited, which is not preferable.

The polybutylene terephthalate resin of the present invention has an intrinsic viscosity (a value calculated based on a value measured in orthochlorophenol at 35 ° C.) of 0.3 or more.
Preferably it is 0.5 or more. If the intrinsic viscosity is lower than this, the strength is low, the melt viscosity is low, and it is difficult to use, and the application to the present invention is of little significance.

The component (B) in the present invention is a silicon-containing compound having at least one hydrogen atom directly bonded to at least one silicon atom in one molecule and / or a polymer thereof, and a SiH group represented by the following formula (2): Contains compound.

[0018]

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(Where m is 0 or an integer of 1 to 100, and n is an integer of 1 to 100)

The phenolic antioxidant as the component (C) of the present invention is a hindered phenol compound.

As the phenolic antioxidant, 2,6-di-tert-butyl-p-cresol, 2,2′-methylene-bis (4-methyl-6-di-tert-butylphenol), 4,4′-thiobis (3-methyl-tert-butylphenol) 1,1,3 tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-diethyl) T-butyl-4-hydroxyphenyl) propionate is preferred, and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is particularly preferred.

One or more phenolic antioxidants can be used simultaneously. The compounding amount of the phenolic antioxidant is 100 parts of polybutylene terephthalate resin.
It is necessary to be 0.01 to 0.5 part by weight, preferably 0.1 to 0.3 part by weight based on part by weight. If the amount is less than 0.01 part by weight, the effect of improving the heat resistance is small, while if the amount is more than 0.5 part by weight, the effect of improving the heat aging resistance cannot be expected.

The thioether antioxidant which is the component (D) of the present invention is preferably ditridecyl-thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate], bis [2-methyl-4- メ チ ル 3]. -N-alkyl (C12 or C14) thiopropionyloxy {-5-t-butylphenyl] sulfide.

The compounding amount of the thioether-based antioxidant is based on 100 parts by weight of the polybutylene terephthalate resin.
It is necessary to be 0.01 to 0.5 parts by weight.
1 to 0.3 parts by weight is preferred. If the amount is less than 0.01 part by weight, the effect of improving heat resistance cannot be expected.

It should be noted that a general-purpose phosphorus antioxidant as an antioxidant should not be used because it inhibits the curing of silicone rubber.

The polyester elastomer as the component (E) of the present invention is a polyether polyester block copolymer containing terephthalic acid, tetramethylene glycol, and polytetramethylene glycol as main components, and terephthalic acid or an ester-forming derivative thereof. And tetramethylene glycol or its ester-forming derivative and polytetramethylene glycol or its ester-forming derivative. If desired, a third component (short-chain component) other than the terephthalic acid component and the tetramethylene glycol component may be copolymerized in the copolymer. For example, one or more kinds of aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and alicyclic dicarboxylic acids such as dichlorohexanedicarboxylic acid can be used. In addition, one or more of aliphatic diols such as ethylene glycol and hexamethylene glycol, aliphatic diols such as cyclohexanedimethanol, and aromatic diols such as 2,2-bis (4-hydroxyphenyl) propane and hydroquinone can be used. These copolymerization ratios are 30 mol% or less, preferably 20 mol% or less, based on the dicarboxylic acid component. If the copolymerization ratio is higher than this, the melting point is low, and the adhesiveness during molding is undesirably high. As the long-chain component polytetramethylene glycol, those having an average molecular weight of 500 to 3,000 are preferably used. Such a block copolymer is produced by a method similar to a usual polyester polymerization method.

The component (F) in the present invention is at least one synthetic wax selected from coal-based synthetic wax, polyethylene wax, and oil-based synthetic wax. They are,
Generally used as a release agent for polybutylene terephthalate resin. Examples of the coal-based synthetic wax include acid wax, ester wax, emulsifier-containing ester wax, partially saponified ester wax, and metal salt.
Types of polyethylene wax include high-density type (density 0.96 or more) and medium-density type (density 0.94 to
0.95) and low density type (density 0.93 or less). Examples of the oil-based synthetic wax include hardened castor oil-based, amide-based, ketone-based, amine-based, imide-based, and ester-based waxes. Of these, ester waxes of coal-based synthetic waxes are particularly preferred, and include, for example, montanic acid ester waxes. The compounding amount of the release agent may be omitted as long as there is no problem during molding, but is preferably 0.05 to 100 parts by weight of the polybutylene terephthalate resin.
1.0 part by weight. Particularly preferably, it is 0.1 to 0.5 part by weight. Even if more than 1.0 part by weight is blended, better releasability cannot be expected but rather impairs the measurement stability during molding.

The polybutylene terephthalate resin composition of the present invention may further contain a reinforcing material such as glass fiber, an inorganic filler, a pigment, a flame retardant, a flame retardant auxiliary, a crystal nucleating agent, and a light stabilizer. I can do it.

The vinyl group-containing organopolysiloxane (G) used in the organopolysiloxane composition (composition for forming silicone rubber) of the present invention has at least two vinyl groups bonded to silicon atoms in one molecule. doing. Further, the molecular structure of the vinyl group-containing organopolysiloxane may be linear or branched, and even if the vinyl group is present only at the terminal of the molecule, It may be present only in the middle, or may be present at the end of the molecule and in the middle of the molecular chain. In particular, the following general formula (3)

[0030]

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(Wherein, a plurality of R ^{2 to} R ⁸ may be the same or different and each is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond; Or 1 to 1
00 is an integer, and j is 0 or an integer of 1 to 100. The diorganopolysiloxane having a vinyl group represented by the formula (1) is preferably used.

R ^{2 to} R ⁸ in the general formula (3) are a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and usually have 1 to 10 carbon atoms. And preferably a group having 1 to 6 carbon atoms. As R ^{2 to} R ⁸ , specifically, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group;
Aryl groups such as a tolyl group, xylyl group and benzyl group; for example, a cycloalkyl group such as a cyclohexyl group, and a chloromethyl group in which some or all of the hydrogen atoms of these groups have been substituted with a substituent such as a halogen atom or a cyano group , Cyanoethyl group, 3,3,3-trifluoropropyl group and the like.

In the general formula (3), i is 0 or 1.
J is 0 or an integer of 1 to 100, and i and j are 0 <m + j <j / (i + j) ≦ 0.
It is an integer satisfying 2.

The vinyl group-containing organopolysiloxane (G) has a viscosity at 25 ° C. of 10 to 1,000,
000 centistokes (cSt), and more preferably 100 to 10,000 cSt. The vinyl group-containing organopolysiloxane (G) can be produced by a method known per se.

The organohydrogenpolysiloxane of the component (H) has at least two hydrogen atoms bonded to silicon atoms in one molecule. The component (H) acts as a cross-linking agent. The silicone rubber-forming composition of the present invention is characterized in that the hydrogen atom bonded to the silicon atom and the vinyl group of the component (G) undergo an addition reaction. It is cured by

The molecular structure of the organohydrogenpolysiloxane of the component (H) is not particularly limited, and may be any of linear, branched and cyclic structures. In addition, 25 of this organohydrogenpolysiloxane
The viscosity at ℃ is usually 0.5 to 1000 cSt, preferably 1 to 200 cSt.

As the organohydrogenpolysiloxane of the component (H), for example, the following average composition formula (4):

[0038]

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(Wherein R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, a and b are 0 <a <2, 1 ≦ b ≦ 2 and , 2 ≦ a + b ≦ 3
Is a number that satisfies ) Are suitably used.

R ⁹ in the above average composition formula (4) is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and is usually a group having 1 to 10 carbon atoms. And preferably groups 1 to 7. As R ⁹ , the groups exemplified as R ^{2 to} R ⁸ above are specifically exemplified.

A and b are respectively 0 <a <
It is a number that satisfies 2,1 ≦ b ≦ 2, 2 ≦ a + b ≦ 3, preferably a number that satisfies 0.3 ≦ a ≦ 1 and 2 ≦ a + b ≦ 2.7.

The organohydrogenpolysiloxane of component (H) can be prepared in a manner known per se, _{^{typically, R 3 SiHCl 2, R 8}} 3 SiCl, R 8 2 SiC
_{^{l 2, R 8 2 SiHCl,}} ( In the formulas, R ^3, R ⁸ are the same as those described for the formula (3).) chlorosilane or hydrolysis, such as, or, thus hydrolyzed Can be produced by equilibrating the obtained siloxane.

As the organohydrogenpolysiloxane of the component (H), specifically, the following formulas (5-1 to 5)
Compounds represented by -5) can be exemplified.

[0044]

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The blending amount of the organohydrogenpolysiloxane of the component (H) is not particularly limited, but is based on one vinyl group bonded to a silicon atom contained in the component (G) and the component (J) described later. The amount is preferably such that 1 to 5 hydrogen atoms are bonded to silicon atoms of the organohydrogenpolysiloxane of the component (H).

The platinum compound of the component (I) is an addition reaction catalyst, and promotes the addition reaction between the vinyl group of the component (G) and the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane of the component (H). It is used to make

As the platinum compound of the component (I), those which are usually used as an addition reaction catalyst for an organopolysiloxane composition can be used. Specifically, a single platinum and, for example, H ₂ PtCl ₆ .XH
_{2 O, NaHPtCl 6 · XH 2} O, KHPtCl 6 · XH 2 O,
Na ₂ PtCl ₆ .XH ₂ O, K ₂ PtCl ₆ .XH ₂ O, PtCl
_4. XH ₂ O, PtCl ₂ , Na ₂ PtCl ₄ • XH ₂ O, H ₂ PtC
and platinum compounds such as l ₄ .XH ₂ O (where X is a positive integer). Further, a complex of the platinum compound with, for example, a hydrocarbon, an alcohol, a vinyl group-containing cyclic siloxane, or the like can also be used.

The compounding amount of the platinum compound of the component (I) may be an amount sufficient to promote the addition reaction between the component (G) and the component (H). It is preferable that the total amount of the component (H) and the component (H) is 0.1 to 100 ppm in terms of platinum metal.

The component (J) is an organopolysiloxane terminated by trivinylsilyl represented by the general formula (1). The silicone rubber-forming composition of the present invention has an appropriate pot life at room temperature by blending the component (J), and has good curability such that the composition is quickly cured by heating. . The component (J) can be produced by a conventionally known method.

In the general formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, preferably a group having 1 to 10 carbon atoms. And more preferably 1 to 7 groups. As R ¹ ,
Specifically, for example, a lower alkyl group such as a methyl group, an ethyl group, and a propyl group; for example, a phenyl group, a tolyl group,
Aryl groups such as xylyl group and benzyl group; for example, cycloalkyl groups such as cyclohexyl group; chloromethyl group and cyanoethyl group in which part or all of the hydrogen atoms of these groups have been substituted with substituent groups such as halogen atoms and cyano groups 3,
A 3,3-trifluoropropyl group is exemplified.

In the general formula (1), k is 0 or 1.
It is the above integer, preferably 0 or an integer of 1 to 100, more preferably 0 or an integer of 1 to 20.
K is preferably 0 or an integer of 1 to 20 in consideration of the compatibility of the component (J) with the component (G).

The amount of the component (J) is from 1 to 200 mol per mol of the platinum metal contained in the platinum compound of the component (I).
A range of 00 mol is preferable, and a range of 10 to 500 mol is more preferable.

In practical use, the silicone rubber molding composition of the present invention may contain various additives other than the above-mentioned components (G) to (J), as long as the object of the present invention is not impaired. Can be blended. For example, in order to reinforce the strength of a cured product, the composition for forming a silicone rubber has an SiO ₂ unit, (CH ₂ = CH) R ′ ₂ SiO _2.
0.5 units, and R _'2 SiO _0.5 units (wherein, R' is a monovalent hydrocarbon group containing no aliphatic unsaturated bond.) Organopolysiloxane resin structure consisting of (Kokoku 3
8-26771, JP-B-45-9476)
Even when these are blended, it is necessary that 1 to 5 hydrogen atoms bonded to silicon atoms be present for every vinyl group bonded to all silicon atoms contained in the composition. There is.

Further, the composition for forming a silicone rubber of the present invention has a reduced thermal contraction during curing, a reduced thermal expansion coefficient of an elastic body obtained by curing, a thermal stability, weather resistance, chemical resistance, A filler may be blended for the purpose of improving flame retardancy, mechanical strength, etc., and reducing gas permeability. Examples of such a filler include fumed silica; quartz powder; glass fiber; carbon black; metal compounds such as alumina, iron oxide, and titanium oxide; and metal carbonates such as calcium carbonate and magnesium carbonate. And
If necessary, suitable pigments, dyes, antioxidants and the like can be added. The filler is generally added in an amount of 5 to 200 parts by weight per 100 parts by weight of the organopolysiloxane (G).

The silicone rubber-forming composition of the present invention usually comprises a mixture of the component (G) and the component (I) and a mixture of the component (H) and the component (J) in separate packages. It is prepared as a two-pack type in which these are mixed. The component (J) may not be mixed with the component (H) but may be mixed with the components (G) and (I).

When the above composition is used, the intended use
Depending on the purpose, it may be used after being dispersed or dissolved in an appropriate organic solvent, for example, toluene, xylene or the like.

In the present invention, the means for integral molding is 2
A two-color molding method using a color molding machine, a method in which a resin molded body is set in a silicone rubber molding die, and a silicone rubber-forming composition is molded and integrated, and a silicone rubber is formed on the surface of the resin molded body. A conventionally known method such as a method of applying the composition, curing and integrating the composition can be used. Further, the shape of the composite body is not particularly limited, and examples thereof include a switch, a connector, and various cases used in the electric / electronic fields and the automobile field.

[0058]

EXAMPLES The present invention will be specifically described below with reference to examples. In Examples, “parts” means “parts by weight”. The intrinsic viscosity [η] of the polymer is 25 in orthochlorophenol.
It is a value calculated from the solution viscosity measured at ° C. The terminal carboxyl group concentration (COOH) was determined by the method of A. Conix (Makromol. Ch.).
em, a number of equivalents of polymer per 10 ⁶ g as measured by the 226 (1958)}.

Examples 1 to 3 and Comparative Examples 1 to 6 Polybutylene terephthalate (intrinsic viscosity: 0.90) using tetrabutoxide titanate as a polymerization catalyst was heated to 130 ° C. ×
After drying for 5 hours, methyl hydrogen silicone oil as a silicon-containing compound and pentaerythrityl-tetrakis [3- (3,5-g
-Butyl-4-hydroxyphenyl) propionate] and tetrakis [methylene-3- (dodecylthio) propionate] as a thioether antioxidant are shown in Table 1.
Were uniformly mixed in a V-type blender at various ratios as shown in Table 1.
The obtained mixture was melt-kneaded at a barrel temperature of 250 ° C. using a 44 mm-diameter twin-screw extruder, and the thread discharged from the die was cooled and cut to obtain molding pellets.

Next, the pellets were dried at 130 ° C. for 5 hours, and then heated at a mold temperature of 4 using an 5-ounce injection molding machine.
Tensile test pieces (ASTM No. 4), impact test pieces, and adhesion test pieces (see FIG. 1) were formed at 0 ° C.

The hydrolysis resistance test was conducted at 122 ° C. and a humidity of 1
The test was performed by measuring the tensile strength and the elongation at break of a test piece subjected to a wet heat treatment for 60 hours under the condition of 00% RH. The heat resistance test was performed at a temperature of 170 ° C. for 5 minutes.
The test was carried out by measuring the tensile strength and the elongation at break of the test piece that had been heat-treated for 00 hours.

In Table 1, PCT means pressure cooker test. In Table 1, the polyester elastomer is B4032AN manufactured by Teijin Limited (hard segment 40 made of polytetramethylene terephthalate).
Polyetherester comprising 60% by weight of a soft segment composed of polytetramethylene glycol having a molecular weight of 1,000 to 3,000 by weight.

Preparation of Composition for Forming Silicone Rubber:
As the component (G), 100 parts of dimethylpolysiloxane (viscosity at 25 ° C .: 1000 cSt) having two methylvinylsiloxane units in one molecule and terminated with a dimethylvinylsiloxy group, and silicon as the component (H) The hydrogen atom bonded to the atom is 0.739 per 100 g.
Molecules of methylhydrogenpolysiloxane 4.6
Part, 0.12 part of octyl alcohol-modified chloroplatinic acid solution (platinum content: 0.5%) as component (I), (J)
The following formula (1) is used as a component with a reaction inhibitor.

[0064]

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(K = 8, manufactured by a conventionally known method, appearance: colorless and transparent, at 25 ° C .: 1)
3cSt) 0.5 part was mixed to prepare a liquid composition.

As shown in FIGS. 1 and 2, the above-mentioned composition for forming a silicone rubber was applied to the above-mentioned adhesive test piece of polybutylene terephthalate resin, with a width of 25 mm, a length of 15 mm and a thickness of 0.1 mm.
A metal jig having the same size as that of the adhesion test piece which was applied under a condition of 2 mm and further plated with chromium was overlaid and heated and cured at 130 ° C. for 1 minute to obtain an integrally formed body.

The adhesion test was carried out by using the above-mentioned integrally molded article shown in FIGS. 1 and 2 to measure the adhesion strength between the polybutylene terephthalate resin composition and the silicone rubber, and the metal having the same size as the adhesion test piece of the silicone rubber and the chromium plating. The removability from the jig was evaluated. Table 1 shows the obtained results.

[0068]

[Table 1]

As shown in Table 1, a polybutylene terephthalate resin having a terminal carboxyl group concentration of 35 eq / ton is inferior in hydrolysis resistance as shown by the results of hydrolysis resistance (PCT), while having a terminal carboxyl group concentration of 35 eq / ton. 10 eq
It can be seen that the polybutylene terephthalate resin of / ton exhibits good results. Further, the heat aging property is greatly improved by combining a phenolic antioxidant and a thioether antioxidant. Furthermore, when a methyl hydrogen silicone oil and a polyester elastomer are blended into the polybutylene terephthalate resin composition, and the adhesion-imparting component (J) is added to the addition-curable silicone rubber, the presence or absence of the mold release agent is increased. In addition, it has good releasability from metals and can firmly adhere silicone rubber to polybutylene terephthalate resin.

[0070]

According to the present invention, it is possible to provide an integrally molded article of a polybutylene terephthalate resin and a silicone rubber having excellent resistance to hydrolysis and heat aging and excellent adhesion to the silicone rubber. .

[Brief description of the drawings]

FIG. 1 is an explanatory view of an adhesion test piece.

FIG. 2 is an explanatory view of an adhesion test piece.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/36 C08K 5/36 5/54 5/54 C08L 83/05 C08L 83/05 83/07 83/07 // (C08L 67/02 83:04 91:06) B29K 67:00 83:00 B29L 9:00

Claims (1)

[Claims] (A) per 100 parts by weight of a polybutylene terephthalate resin using a titanium compound as a polymerization catalyst with a terminal carboxyl group concentration of 15 equivalents / ton or less,
(B) 0.05 to 3 parts by weight of a silicon-containing compound and / or a polymer thereof having a hydrogen atom directly bonded to at least one silicon atom in one molecule, and (C) a phenolic antioxidant 0.01 to 0.5 parts by weight, (D) 0.01 to 0.5 parts by weight of a thioether-based antioxidant, (E) 0.5 to 10 parts by weight of a polyester-based elastomer, and (F) synthetic coal-based wax, polyethylene wax, oil and fat (G) At least a part of the surface of a molded body made of a polybutylene terephthalate resin composition in which 0 to 1.0 part by weight of at least one selected from synthetic waxes is blended. (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom per molecule, (H) an organohydrogenpolysiloxane having at least two vinyl groups bonded to (I) a platinum compound and (J) the following general formula (1) (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and when there are a plurality of R ^{1 s} , they may be different. A polybutyrene terephthalate resin and a silicone rubber in which a silicone rubber obtained by curing an organopolysiloxane containing a trivinylsilyl-terminated organopolysiloxane represented by the formula: One-piece molding.