JPH09241493A - Integrally molded product of thermoplastic resin with silicone rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject molded product largely improved in hydrolysis resistance and thermal ageing resistance and useful in electric and electronic fields by coating a specific polybutylene terephthalate resin composition with a specified coating liquid and subsequently curing the applied coating material. SOLUTION: (A) A molded product produced from a composition comprising (i) 100 pts.wt. of polybutylene terephthalate having a terminal carboxyl group concentration of <=15 equivalent/10<6> g, (ii) 0.05-5 pts.wt. of a polyethylene copolymer of formula I produced by addition-reacting a silanol terminal group- containing organopolysilane to low density polyethylene graft-copolymerized with a silicon compound having methoxy groups directly bound to the silicon atom, (iii) 0.01-0.5 pt.wt. of a phenolic antioxidizing agent, and (iv) 0.01-0.5 pt.wt. of a thioether antioxidizing agent is coated with (B) a composition comprising (v) an organopolysiloxane having at least two Si-bound vinyl groups in the molecule, (vi) an organo hydrogen polysiloxane having at least two H atoms bound to Si atoms in the molecule, (vii) a platinum compound and (viii) a trivinylsilyl group-terminated organopolysiloxane of formula II, and subsequently the applied coating materialy is cured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded product obtained by integrating a polybutylene terephthalate resin, which is excellent in durability, particularly hydrolysis resistance and heat aging resistance, with a silicone rubber.

[0002]

2. Description of the Related Art Thermoplastic polyester resins, especially polybutylene terephthalate, are widely used as industrial resins because of their excellent chemical resistance, heat resistance and mechanical properties. In recent years, the demands for hydrolysis resistance and heat aging resistance have increased as durability, and in addition to silicone rubber that satisfies the above required characteristics in the electrical and electronic fields and automobile fields, and has excellent heat resistance, electrical characteristics, and weather resistance. It is desired to supply an integrally molded body adhered to the. Conventionally, as a method of adhering a molded product of an addition-curable silicone rubber and an organic resin, for example, a method of applying a primer to the surface of the molded product and curing an uncured silicone material from the top of the molded resin is known. There is.

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

Further, in the method of applying a self-adhesive silicone rubber material to a molding resin to cure it, when a molded product and an integrally molded product with the silicone rubber are formed by using a mold or the like, the silicone rubber itself is a metal. There is a big problem that it adheres to the mold. Further, when applied and cured on a resin molded product, most of self-adhesive addition-curable silicone rubber materials do not have sufficient adhesive force for polybutylene terephthalate resin to be used as an integrally molded product.

[0005]

DISCLOSURE OF THE INVENTION The present invention significantly improves the hydrolysis resistance and heat aging resistance of polybutylene terephthalate resin, which are increasing in demand as industrial resin materials, and also improves the impact strength. In addition, the polybutylene terephthalate resin and the silicone rubber can be bonded easily and reliably in a short time, and an integrally molded product of the polybutylene terephthalate resin and the silicone rubber, which are adhered to each other with an adhesive strength that can withstand practical use. The purpose is to provide technology. In the past, the adhesive strength of addition-curable silicone rubber was low, and it was not possible to bond it under curing conditions for a short time.

[0006]

According to the present invention, a phenol-based antioxidant and a thioether-based antioxidant are added to a polybutylene terephthalate resin having a low terminal carboxyl group concentration, and a specific silicon-containing compound and / or its weight is added. By using an addition-curable silicone rubber containing an organopolysiloxane whose end is terminated by a trivinylsilyl group as an adhesiveness-imparting component, the silicone rubber-integrated molded product I will get it. In particular, the polybutylene terephthalate resin composition can be adhered to the above polybutylene terephthalate resin composition under a curing condition for a short time using an injection molding method, and the silicone rubber itself can be easily peeled from the molding die. It is the body.

The specific solution is (a) (A) the terminal carboxyl concentration is 15 equivalents / 10 ^6.
per 100 parts by weight of polybutylene terephthalate using a titanium compound as a polymerization catalyst in an amount of g or less, (B) a low density polyethylene obtained by graft polymerization of a silicon compound having a methoxy group directly bonded to a silicon atom, and an organopolysiloxane having a silanol end. Addition-reacted polyethylene graft copolymer 0.05 to 5 parts by weight, (C) phenolic antioxidant 0.01 to 0.5 parts by weight and (D) thioether antioxidant 0.01 to 0.5 parts by weight On the surface of a molded article obtained by molding a polybutylene terephthalate resin composition obtained by blending parts by weight, (E) at least a vinyl group bonded to a silicon atom in one molecule as an addition-curable silicone rubber. An organopolysiloxane having two (F) an organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. Ganohydrogenpolysiloxane, (G) platinum compound, and (H) the following general formula (2)

[0008]

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(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and when plural R ^1's are present, they may be different from each other.
Is an integer of 0 or 1 or more), and a coating solution comprising an organopolysiloxane composition containing a terminal trivinylsilyl-terminated organopolysiloxane represented by
When cured, (c) a polybutylene terephthalate resin molded product and a silicone rubber composition are in close contact with each other to form an integrally molded product.

Polybutylene terephthalate, which is the component (A) of the present invention, contains terephthalic acid as the main acid component,
A polyester containing 1,4-butanediol as a main glycol component. Here, "mainly" means 80 mol% or more with respect to all acid components or all glycol components,
It is preferably 90 mol% or more.

As the copolymerizable acid component, an aromatic dicarboxylic acid other than terephthalic acid, for example, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, difoxyethanedicarboxylic acid, diphenylketonedicarboxylic acid, diphenylsulfone. Examples thereof include dicarboxylic acids and the like, aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, tetralindicarboxylic acid and decalindicarboxylic acid.

Copolymerizable glycol components other than butanediol include ethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, tricyclodecane dimethylol, xylylene glycol, bisphenol A, bisphenol B and bishydroxyethoxy bisphenol. A etc. are illustrated.

Further, monofunctional compounds such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, trimesic acid and pyromellitic acid may be copolymerized within the range in which the polyester does not substantially lose the molding performance.

The polybutylene terephthalate used in the present invention must use a titanium compound as a polymerization catalyst and have a terminal carboxyl group concentration of 15 equivalents / 10 ⁶ or less. Terminal carboxyl group concentration is 15 equivalents /
When it exceeds 10 ⁶ g, the hydrolysis resistance, which is one of the main effects of the present invention, is not significantly improved. Further, when a tin compound is used as the polymerization catalyst, it is not preferable because it inhibits the curing of the silicone rubber.

The polybutylene terephthalate used in the present invention has an intrinsic viscosity (value calculated based on the measured value in orthochlorophenol at 35 ° C.) of 0.3 or more, preferably 0.5 or more. Is. This is because if the intrinsic viscosity is lower than this, the strength is low and the viscosity is low, and it is difficult to use, and it is meaningless to apply the present invention.

The component (B) used in the present invention is represented by the following formula in which low-density polyethylene graft-copolymerized with a silicon compound having a methoxy group directly bonded to a silicon atom is subjected to an addition reaction with an organopolysiloxane having a silanol end. It is a polyethylene graft copolymer compound.

[0017]

Embedded image

(Wherein l, m and n are 0 or 1 to 1 respectively)
00 is an integer)

The phenolic antioxidant which is the component (C) used in the present invention is a hindered phenol compound.

The phenolic antioxidant is preferably 2,
6-t-butyl-p-cresol, 2,2'-methylene-bis- (4-methyl-6-di-t-butylphenol 4,4'-thiobis (3-methyl-t-butylphenol), 1,1 , 3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4]
-Hydroxyphenylpropionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, particularly preferably pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate].

The phenolic antioxidant can be used alone or in combination of two or more. The compounding amount of the phenolic antioxidant is 100 parts of polybutylene terephthalate resin.
It is necessary that the amount is 0.01 to 0.5 part by weight, and preferably 0.1 to 1.3 part by weight. 0.01
If it is less than the weight part, the heat resistance improving effect is small,
Even if the amount is more than 0.5 parts by weight, the effect of improving the heat aging resistance cannot be expected.

The thioether type antioxidant as the component (D) used in the present invention is preferably di-tridecyl-thio-dipropionate, tetrakis [methylene-3- (dodecylthio) propionate], bis [2-methyl-].
4- is a {3-n-alkyl (C ₁₂ or C ₁₄₎ thio propionyloxy} -5-t-butylphenyl] sulfide.

The compounding amount of the thioether type antioxidant is 0.01 with respect to 100 parts by weight of the polybutylene terephthalate resin.
.About.0.5 part by weight, and 0.1 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.

Further, phosphorus antioxidants which are widely used as antioxidants should not be used because they inhibit the curing of silicone rubber.

The composition of the polybutylene terephthalate resin 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 aid, a crystal nucleating agent and a light stabilizer. it can.

In the composition of the addition-curable silicone rubber used in the present invention, the vinyl group-containing organosiloxane as the component (E) has at least two vinyl groups bonded to silicon atoms in one molecule. The molecular structure of the vinyl group-containing organopolysiloxane may be linear or branched, and the vinyl group may be present only at the terminal of the molecule or only in the middle of the molecular chain. Alternatively, it may be present at the end of the molecule or in the middle of the molecular chain. In particular, the following general formula (3):

[0027]

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(In the formula, 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, and i is 0 or 1-1
The vinyl group-containing diorganopolysiloxane represented by the formula (1) is an integer of 00, and j is 0 or an integer of 1 or more.

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

In the general formula (3), i is 0 or an integer of 1 to 100, j is 0 or an integer of 1 to 100, and i and j are preferably 0 <m + j <j / (I +
j) An integer that satisfies ≦ 0.2.

The vinyl group-containing organopolysiloxane of component (E) has a viscosity at 25 ° C. of 10 to 1,000 cS.
It is preferably t (centistokes). still,
The vinyl group-containing organopolysiloxane as the component (E) can be produced by a method known per se.

The organohydrogenpolysiloxane as the component (F) has at least two hydrogen atoms bonded to silicon atoms in one molecule. The component (B) acts as a crosslinking agent, and the composition of the present invention is cured by an addition reaction between the hydrogen atom bonded to the silicon atom and the vinyl group of the component (E). .

The molecular structure of the organohydrogenpolysiloxane of the component (F) is not particularly limited, and any of linear, branched and cyclic structures can be used. The viscosity of this organohydrogenpolysiloxane at 25 ° C. is usually 0.5 to 1000 cSt.
It is.

Examples of the organohydrogenpolysiloxane of the component (F) include the following average composition formula (4):

[0035]

Embedded image H _a (R ⁹ ) _b SiO _{(4-ab) / 2} (4) (In the formula, R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, A and b are numbers represented by 0 <a <2 and 1 ≦ b ≦ 2, 2 ≦ a + b ≦ 3) are preferably used.

R ^{9 in} the average composition formula (4) is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond.

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

The organohydrogenpolysiloxane as the component (F) can be produced by a method known per se and is usually R ⁸ SiHCl ₂ , R ⁸ ₃ SiCl, R ⁸ ₂ SiCl.
By hydrolyzing a chlorosilane such as ₂ , R ⁸ ₂ SiHCl, (wherein R ⁸ is as described above), or by equilibrating a siloxane obtained by such hydrolysis. Can be manufactured.

Specific examples of the organohydrogenpolysiloxane as the component (F) include compounds represented by the following formula.

[0040]

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The blending amount of the organohydrogenpolysiloxane as the component (F) is not particularly limited, but is based on one vinyl group bonded to a silicon atom contained in the component (E) and the component (H) described later. It is preferable to mix the organohydrogenpolysiloxane as the component (F) in an amount such that the number of hydrogen atoms bonded to silicon atoms is 1 to 5.

The platinum compound as the component (G) is an addition reaction catalyst, and promotes the addition reaction between the vinyl group of the component (E) and the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane of the component (F). Is used for.

As the platinum catalyst of the component (G), those which are usually used as the addition reaction catalyst of the organopolysiloxane composition can be used. Specifically, elemental platinum and, for example, H ₂ PtCl ₆ · XH ₂ O, Na
HPtCl ₆ · XH ₂ O, K ₂ PtCl ₆ · XH ₂ O, Pt
Cl ₄ · XH ₂ O, PtCl ₂ , Na ₂ PtCl ₄ · XH
₂ O, Na ₂ PtCl ₄ · XH ₂ O, H ₂ PtCl ₄ · XH ₂
Examples thereof include platinum compounds such as O and (where X is a positive integer). Further, with the platinum catalyst, for example, a hydrocarbon
A complex with an alcohol / vinyl group-containing cyclic siloxane or the like can also be used.

The amount of the platinum compound as the component (G) may be an amount sufficient to promote the addition reaction between the component (A) and the component (B), and is usually the component (A) and the above ( It is converted to platinum metal with respect to the total amount of the F) component and is 0.
It is desirable to be 1 to 100 ppm.

Component (H) is a terminal trivinylsilyl-terminated organopolysiloxane represented by the general formula (1). The composition of the present invention has a suitable pot life at room temperature by blending the component (H), and has good curability such that it is rapidly cured by heating. The component (H) can be manufactured by a known method.

In the above general formula (2), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, preferably a group having 1 to 10 carbon atoms, and further preferably Is a group of 1 to 7. As R ¹ , for example,
Lower alkyl group such as methyl group, ethyl group, propyl group, etc .; aryl group such as phenyl group, tolyl group, xylyl group, benzyl group; cycloalkyl group such as cyclohexyl group; one of the hydrogen atoms of these groups Examples thereof include a chloromethyl group, a cyanoethyl group, and a 3,3,3-trifluoroprobiyl group in which a part or all is substituted with a substituent such as a halogen atom and a cyano group.

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

The blending amount of the component (H) is 1 to 2000 with respect to 1 mol of platinum metal contained in the platinum compound of the component (G).
The range of 0 mol is preferable, and the range of 10 to 500 mol is more preferable.

In addition to the components (E) to (H) described above for practical use, various additives may be added to the composition of the present invention, if necessary, within a range that does not impair the curing of the present invention. . For example, in order to reinforce the strength of the cured product obtained by curing the composition of the present invention, the composition of the present invention contains SiO ₂ units, (CH ₂ ═CH) R ₂ SiO _0.5 units, and R ′. ₂ An organopolysiloxane having a resin structure composed of _0.5 units of SiO ₂ (wherein R ′ is a monovalent hydrocarbon group having no aliphatic unsaturated bond) (Japanese Patent Publication No. 38-3).
No. 6771, Japanese Patent Publication No. 45-9476), etc., and even when these are blended, vinyl groups 1 bonded to all silicon atoms contained in the composition are still present.
It is necessary to allow 1 to 5 hydrogen atoms bonded to silicon atoms to be present for each.

Further, the composition of the present invention reduces the heat shrinkage at the time of curing, the thermal expansion coefficient of the elastic body obtained by curing, thermal stability, weather resistance, chemical resistance, flame retardancy, and mechanical properties. A filler may be added for the purpose of improving the mechanical strength and lowering the gas permeability. Examples of such fillers include fumed silica, quartz powder, glass fibers, carbon black, and metal compounds such as alumina, iron oxide, and titanium oxide, for example, metal carbonates of calcium oxide and magnesium carbonate. It is also possible to add appropriate pigments, paints, antioxidants, etc., if necessary. The filler is usually added in an amount of 5 to 200 parts by weight per 100 parts by weight of the organopolysiloxane as the component (E).

In the curable silicone rubber composition of the present invention, the mixture of the above-mentioned components (E) and (G) and the mixture of the above-mentioned components (F) and (H) are usually packaged separately,
It is prepared as a two-pack type in which these are mixed at the time of use. The component (H) may be mixed with the component (E) and the component (G) instead of the component (F).

When the composition of the present invention is used, it may be dispersed or dissolved in an appropriate organic solvent, such as toluene or xylene, depending on the use and purpose.

As a method for evaluating the adhesiveness between the polybutylene terephthalate resin composition and the addition-curable silicone rubber, a molded product of the polybutylene terephthalate composition is molded in advance, and the liquid addition-curable mold described above is molded on the molded product. By coating the silicone rubber and curing at room temperature for 24 to 48 hours and at 80 to 200 ° C. for 60 to 4 hours, the silicone rubber is cured and the polybutylene terephthalate resin composition is molded. It is possible to obtain good adhesion with the product.

[0054]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" means "parts by weight". The intrinsic viscosity [η] of the polymer is a value calculated from the solution viscosity measured at 35 ° C. in orthochlorophenol. Further, the terminal carboxyl group concentration (COOH) is A. Conix (A.
Conix) method {(Makromol. Chim,
Vol. 26,226 (1958)}, and is the number of equivalents per 10 ^{6 of} polymer.

Examples 1 to 3 and Comparative Examples 1 to 6 Polybutylene terephthalate (intrinsic viscosity: 0.90) using tetrabutoxyside titanate was used as a polymerization catalyst.
After drying at 0 ° C. for 5 hours, a low-density polyethylene organopolysiloxane graft copolymer (Neste Co .: trade name PACRENE) as a graft copolymer, and pentaerythrityl-tetrakis as a phenolic antioxidant
[3- (3,5-di-t-butyl-4-hydroxyphenyl) poropinate], tetrakis [methylene-3- (dodecylthio) propionate] as a thioether antioxidant at various ratios shown in Table 1 Mix evenly with a mold blender. 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, after drying the pellets at 130 ° C. for 5 hours, a test piece mold for physical properties was attached to a 5 ounce injection molding machine, the cylinder temperature was 260 ° C., and the mold temperature was 4 °.
Tensile test piece (AS) under the molding conditions of 0 ° C, injection pressure 700 kg / cm 2, cooling time 20 seconds, and total cycle 35 seconds.
TM4) and an adhesion test piece were molded. The hydrolysis resistance test was carried out by measuring the tensile strength and room rupture elongation of a test piece that had been subjected to a wet heat treatment for 60 hours at 122 ° C. and a humidity of 100%.

Preparation of addition type silicone rubber: dimethylpolysiloxane having two methylvinylsiloxane units in one molecule as the component (A) and terminated with a dimethylvinylsiloxy group (viscosity 1000 c at 25 ° C.).
St) 100 parts by weight, 4.6 parts by weight of methylhydrogenpolysiloxane having 0.739 mol of hydrogen atoms bonded to silicon atoms as the component (B) per 100 g.
0.12 parts by weight of an octyl alcohol-denaturing solution of chloroplatinic acid as component (C) (platinum content: 0.5%), (D)
The following formula is a reaction inhibitor as a component,

[0058]

Embedded image

Polymer represented by (manufactured by a conventionally known method, appearance: colorless and transparent, viscosity at 25 ° C .: 13c
St) 0.5 part by weight was prepared.

The adhesion test between the polybutylene terephthalate resin composition and the addition-curable silicone rubber was carried out on the adhesion test pieces shown in FIGS. 2 and 3 with a width of 25 mm and a length of 15 m.
m, thickness 0.2 mm, applied and heated at 130 ° C. for 1 minute to cure, and the polybutylene terephthalate resin composition has the same adhesive strength with silicone rubber and the same dimensions as the adhesive test piece of silicone rubber and chrome plated. The peelability from the metal jig was evaluated.

The results obtained are shown in Table 1.

[0062]

[Table 1]

As shown by the PCT results in Table 1, the polybutylene terephthalate resin having a terminal carboxyl group concentration of 35 equivalents / 10 ⁶ g has poor hydrolysis resistance, while the terminal carboxyl group concentration is 10 equivalents / 10 ⁶ g. It can be seen that the polybutylene terephthalate resin shows good results.

The heat aging property is greatly improved by combining a phenol antioxidant and a thioether antioxidant.

On the other hand, when a low-density polyethylene organopolysiloxane graft copolymer is blended with the polybutylene terephthalate resin composition and the adhesion-providing component (H) is added to the addition-curable silicone rubber, the polybutylene terephthalate resin is added. It is possible to obtain a result in which the silicone rubber is firmly bonded to the silicone rubber and the peelability from the metal is good.

Further, when the polybutylene terephthalate resin composition is blended with a low density polyethylene organopolysiloxane graft copolymer, the impact strength is improved as shown in the results of Table 1.

[Example 4, Comparative Examples 7 to 8] In the same manner as in Example 1, the same evaluation was performed on the compositions having the blending ratios shown in Table 2.

As a result, it was found that when a polybutylene terephthalate resin and a phosphorus-based antioxidant were added using a tin compound as a catalyst, the silicone rubber did not cure and could not be used.

[0069]

[Table 2]

[Brief description of drawings]

FIG. 1 is a flow chart showing an example of integral molding of the present invention and a conventional method (comparative example).

FIG. 2 is a plan view of an adhesion test piece used in an example of the present invention.

FIG. 3 is a side view (elevation view) of an adhesion test piece used in an example of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/13 KJW C08K 5/13 KJW 5/37 KKA 5/37 KKA C08L 83/05 LRZ C08L 83 / 05 LRZ 83/07 LRY 83/07 LRY // (C08L 67/02 83:10)

Claims (1)

[Claims] (A) (A) The terminal carboxyl concentration is 1
For 100 parts by weight of polybutylene terephthalate having an amount of 5 equivalents / 10 ⁶ g or less, (B) the following general formula (1): In low density polyethylene graft-copolymerized with a silicon compound having a methoxy group directly bonded to a silicon atom,
0.05 to 5 parts by weight of a polyethylene copolymer compound obtained by addition reaction of an organopolysiloxane having a silanol end, 0.01 to 0.5 parts by weight of a (C) phenolic antioxidant, and (D) a thioether antioxidant 0.01-0.5
A molded product obtained by molding a polybutylene terephthalate resin composition obtained by blending parts by weight has (E) at least two vinyl groups bonded to silicon atoms in one molecule as (E) addition-curing silicone rubber Organopolysiloxane, (F) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, (G) platinum compound and (H)
The following general formula (2) (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and when plural R ^1's are present, they may be different. K is 0, or Which is an integer of 1 or more) and a coating liquid comprising an organopolysiloxane composition containing a terminal trivinylsilyl-terminated organopolysiloxane, which is applied and cured to form an integral body of a thermoplastic polyester and a silicone rubber. Molded body.