JPH1046025A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a PPE-based resin composition containing a filler having a shape anisotropy and a phosphoric acid ester-based fire retardant, and having improved fire retarding property, stiffness, strength, impact resistance, tenacity, heat resistance, etc. SOLUTION: This thermoplastic resin composition is obtained by melt kneading 100 pts.wt. polyphenylene ether-based resin or resin obtained by blending the same with a polystyrene resin, 5-60 pt.wt. filler having a shape anisotropy, 1-30 pt.wt. phosphoric acid ester-based fire retardant, and 0.01-20 pt.wt. silicone polymer powder consisting of (a) 100 pts.wt. polydiorganosiloxane and (b) 10-150 pt.wt. silica.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether (hereinafter sometimes referred to as PPE) resin composition.

[0002]

2. Description of the Related Art PPE resins are thermoplastic engineering plastic resins which have excellent hydrolysis stability, dimensional stability, toughness, heat resistance and dielectric properties and are widely used.

[0003] For the purpose of imparting rigidity, strength or dimensional stability to PPE resin, glass fiber, mica and other fillers have been blended. Also, PPE
In order to make the system resin flame-retardant, a phosphate ester such as TPP (triphenyl phosphate) or RDP (resorcinol diphosphate) is blended.

[0004] PP containing filler having anisotropic shape
The E-based resin has a problem that the burning time is not shortened as compared with the one containing no filler despite the addition of the flame retardant. This is probably because fillers with higher thermal conductivity than resin have anisotropy, forming a network structure of heat conduction paths, increasing the thermal conductivity of the composite as a whole and increasing the burning rate. Conceivable. Therefore, in order to provide sufficient flame retardancy, the amount of the flame retardant must be increased. However, PPE
When a flame retardant such as TPP is blended with the system resin, many adverse effects such as a decrease in rigidity, strength, impact, and heat resistance occur.

Also, US Pat. Nos. 4,273,691 and 4,387,176 show blending a high viscosity silicone fluid with a thermoplastic resin to produce a flame retardant thermoplastic material. However, since the silicone fluid has a high viscosity, there are problems such as difficulty in handling, difficulty in controlling the dispersion in the matrix resin, and difficulty in supplying the silicone fluid to a conventional blending device.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a P containing a filler having shape anisotropy and a phosphate ester-based flame retardant.
An object of the present invention is to provide a PPE-based resin composition having improved flame retardancy, rigidity, strength, impact, toughness, heat resistance, and the like.

[0007]

According to the present invention, there are provided (A) 100 parts by weight of a polyphenylene ether resin or a resin obtained by combining the same with a polystyrene resin, and (B) 5 to 100 parts by weight of a filler having shape anisotropy. , (C) 1 to 30 parts by weight of a phosphate ester-based flame retardant, and (D) the following (a):
The present invention relates to a thermoplastic resin composition obtained by melt-kneading 0.01 to 20 parts by weight of a silicon polymer powder composed of (b). (A) 100 parts by weight of polydiorganosiloxane (b) 10 to 150 parts by weight of silica

As the PPE resin in the component (A) of the present invention, known resins can be used. As the PPE-based resin, for example, general formula (1),

[0009] (Wherein, R _{1 to} R ₄ are each independently a hydrogen atom,
A halogen atom, an alkyl group, an alkoxy group, and a haloalkyl group or a haloalkoxy group having at least two carbon atoms between the halogen atom and the phenyl ring;
-Represents a monovalent substituent selected from those containing no carbon,
m is an integer representing the degree of polymerization) is a general term for the polymer represented by the general formula, even if it is a single kind of the polymer represented by the above general formula, or a copolymer of two or more kinds Good. In a preferred embodiment, R ₁ and R ₂ have 1 carbon atom.
And R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) Ether, poly (2-methyl-6-propyl-
1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether and the like. Examples of the PPE copolymer include a copolymer in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. In addition, these PP
A copolymer obtained by grafting a styrene-based compound onto E may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, or the like as the styrene-based compound on the PPE.

As the styrene resin in the component (A) of the present invention, known resins can be used. As the styrene-based resin, for example, general formula (2),

(Wherein, R ₅ is a hydrogen atom or 1 carbon atom)
And Z represents a halogen atom or a substituent that is an alkyl group having 1 to 4 carbon atoms.
The polymer must have at least 25% by weight or more of a repeating structural unit derived from an aromatic vinyl compound represented by the following formula: As such a styrene-based polymer, a homopolymer of styrene or a derivative thereof (for example, p-methylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene, bromostyrene, and the like) and, for example, polybutadiene, Styrene-butadiene block copolymer,
Partially hydrogenated product, styrene-isoprene block copolymer, partially hydrogenated product, polyisoprene, butyl rubber, E
PDM, ethylene-propylene copolymer, a styrene-based copolymer obtained by modifying an elastomer material such as natural rubber alone or a mixture thereof, and further a styrene-containing copolymer such as a styrene-butadiene block and a random copolymer, Partially hydrogenated product, styrene-isoprene block and random copolymer, partially hydrogenated product thereof, styrene-acrylonitrile copolymer (SAN), styrene-methyl methacrylate copolymer (MS resin), styrene-methyl methacrylate-butadiene Copolymer (MB
S), styrene-acrylonitrile-butadiene copolymer (ABS) and the like. Preferred styrenic resins for the present invention are homopolystyrene and rubber reinforced polystyrene (HIPS).

The ratio of the PPE resin and the styrene resin in the component (A) is preferably 90 to 0 parts by weight, more preferably 10 to 100 parts by weight of the PPE resin.
Styrene resin 9 to 10 to 90 parts by weight of PE resin
0 to 10 parts by weight, more preferably a PPE resin 20 to 8
The styrene resin is 80 to 20 parts by weight with respect to 0 parts by weight.

The filler having the shape anisotropy of the component (B) of the present invention is defined as having an aspect ratio (average major axis / average minor axis of filler) of 10 or more, preferably 20 when dispersed in a resin. Above, more preferably 30 or more fillers. As the filler having shape anisotropy of the component (B) of the present invention, known fillers can be used. For example, glass fiber, carbon fiber, boron fiber, stainless steel fiber, wollastonite, whisker, zonotolite, fibrous such as asbestos, acicular filler, and flakes such as mica, talc, glass flakes, aluminum flakes, sericite, A plate-like filler is mentioned. These can be used alone or in combination of two or more. Particularly preferred fillers are glass fibers, carbon fibers, mica, talc, glass flakes.

The upper limit of the component (B) is 100 parts by weight, preferably 80 parts by weight, and the lower limit is 5 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the component (A).
If the amount of the component (B) is less than the above range, the rigidity, strength, low warpage and the like are insufficient, and if it is more than the above range, manufacturing difficulties accompany.

As the component (C) of the present invention, the following formulas (Chemical Formula 3), wherein R _{6 to} R ₉ each independently represent a hydrogen atom or an organic group, wherein R ₆ = R ₇ = R ₈ = R ₉ = H
Except in the case of X represents a divalent or higher valent organic group, p is 0 or 1, and q is an integer of 1 or more, for example, an integer of 30 or less, and r represents an integer of 0 or more. No. However, it is not limited to these.

[0016] In the above formula, examples of the organic group include an alkyl group which may or may not be substituted, a cycloalkyl group, and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group,
Arylthio groups, halogenated aryl groups and the like,
Further, a group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents with an oxygen atom, a sulfur atom, a nitrogen atom, or the like (eg, an arylsulfonylaryl group) is substituted. It may be used as a group. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-described organic group. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p,
p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.

Specific examples of the phosphoric ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl. Phosphate,
Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate,
Bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl diphosphate, Bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate
, Hydroquinone tetracresyl diphosphate, hydroquinone tetraxylyl diphosphate, R ₆ -R
Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisdiphenyl phosphate, resorcin bisxylyl phosphate, hydroquinone, where ₉ is alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy Bisxylyl phosphate, trioxybenzene triphosphate and the like can be mentioned, and preferred are triphenyl phosphate, various bisdiphenyl phosphates, and various bisxylyl phosphates.

The upper limit of the component (C) is 30 parts by weight, preferably 20 parts by weight, and the lower limit is 1 part by weight, preferably 2 parts by weight, based on 100 parts by weight of the component (A). If the amount of the component (C) is less than the above range, the flame retardancy will not be sufficiently exhibited, and if it is more than the above range, the heat resistance will be impaired.

Component (D) of the present invention is a silicon polymer powder comprising (a) 100 parts by weight of a blend of one or more polydiorganosiloxanes and (b) 10 to 150 parts by weight of silica.

The component (a) is preferably a liquid or high-viscosity polydiorganosiloxane polymer or copolymer, and preferably contains at least one functional group selected from a hydroxyl group and a vinyl group in the molecule. The polymer has a molecular weight of 10,000 to 100,000,000 centipoise at 25 ° C., preferably 1,000,000 to 100,000 centipoise.
It has a molecular weight enough to show a viscosity of about 1,000,000 centipoise, and more preferably shows a gum-like viscosity.

(A) The organic group in the polydiorganosiloxane is independently selected from a hydrocarbon group and a halogenated hydrocarbon group. These organic groups are, for example, having 1 to 1 carbon atoms.
20 alkyl groups and substituted alkyl groups, alkenyl groups, cycloalkyl groups, aromatic hydrocarbon groups and the like. Preferred organic groups are lower alkyl groups having 1 to 4 carbon atoms, phenyl groups and halogen-substituted alkyl groups. Therefore, the polydiorganosiloxane can take the form of a homopolymer, a copolymer, a terpolymer or the like depending on the combination of such organic groups. Examples include gums containing dimethylsiloxy units and phenylmethylsiloxy units, gums containing dimethylsiloxy units and diphenylsiloxy units, gums containing dimethylsiloxy units, diphenylsiloxy units and phenylmethylsiloxy units, and others. There are also many things. Polydimethylsiloxanes containing vinyl groups at both ends and / or at least one vinyl group along the main chain are preferred.

The above polydiorganosiloxane can be produced by a well-known method, for example, polymerization of a cyclic organosiloxane using an acid or a base as a catalyst.

The component (b) is fumed silica or precipitated silica or finely divided silica obtained from a silica aerosol, and these three types can be used alone or in combination. Its surface area is 900
As large as m ² / g can be used,
Those having a form of ４００400 m ² / g are preferred.

For the purposes of the present invention, silica is preferably
It is treated by reaction with a liquid organosilicon compound containing a silanol group or a precursor of a hydrolyzable silanol group. The liquid organosilicon compound contains a low molecular weight liquid polydiorganosiloxane, hexaorganodisiloxane, hexaorganodisilazane, or the like having a hydroxyl group or an alkoxy group as a terminal group. The hydrocarbon group bonded to silicon in all or a part of the silica treating agent can have a substituent such as a carbon-carbon double bond. Preferred as the silica-treated compound are polydimethylsiloxane oligomers having an average hydroxy-terminal polymerization degree of 2 to 100, more preferably an average hydroxy-terminated polymerization degree of 2 to 10.

The silica is (a) 10 to 45% by weight, based on the weight of the silica, before blending with the polydiorganosiloxane.
Is preferably reacted with the above silica treating agent.

(C) The alkoxysilane adhesion promoter has in its molecule at least one alkoxy group having 1 to 4 carbon atoms and at least one group selected from epoxy, amine, acryloxy, methacryloxy, vinyl and phenyl. ing. It preferably has at least one alkoxy group having 1 to 4 carbon atoms and at least one group selected from epoxy, amine and methacryloxy in the molecule, and more preferably has the general formula QSi (OMe) ₃ , Me represents a methyl group below, Q is an epoxyalkyl group, a methacryloxyalkyl group, N-β
-(N-vinylbenzylamino) ethyl-γ-aminoalkyl monohydrogen chloride is an alkoxysilane selected from the group consisting of: For example, γ-
Acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β- (N-vinylbenzylamino) ethyl-γ-aminopropyltrimethoxysilane monohydrogen chloride, Examples include phenyltrimethoxysilane and vinyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylamino) ethyl-γ
-Aminopropyltrimethoxysilane monohydrogen chloride is preferred.

(C) The alkoxysilane is added, if necessary, in an amount of 0.5 to 15 parts by weight per 100 parts by weight of the silicon polymer powder. This addition is preferably carried out after mixing the polydiorganosiloxane with the treated silica. You.

The average particle size of the (D) silicon polymer powder comprising (a), (b) and, if necessary, component (c) is 0.1 to 10000 μm, preferably 1 to 10 μm.
00 μm.

The methods for producing (a) and (b) and the method for producing (D) a silicon polymer powder are described in, for example, JP-A-5-23.
No. 0362 and US Pat. No. 5,391,594, but are not particularly limited.

The upper limit of component (D) is 20 parts by weight, preferably 10 parts by weight, and the lower limit is 0.01 part by weight, preferably 0.3 part by weight, per 100 parts by weight of component (A). . When the amount of the component (D) is less than the above range, the flame retardancy is not sufficiently exhibited, and when it is more than the above range, the rigidity is reduced.

The component (E) of the present invention contains (d) carbon-
Specific examples of compounds having a carbon double bond or a carbon-carbon triple bond and (e) a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic ester group, an epoxy group, an amino group or a hydroxyl group simultaneously Examples include maleic anhydride, maleic acid, fumaric acid, and the like. Compounds containing two or more (d) functional groups and two or more (e) functional groups (same or different) are also included. Also, two or more compounds (E) may be used alone or as a mixture.

[0032] In addition to the above components, the resin composition of the present invention
A filler other than the component (B) can be included. The filler is not particularly limited, and may include all conventional fillers. Specific examples include carbon black, calcium carbonate, barium sulfate, glass beads, milled glass, clay and the like.

In addition to the above components, the resin composition of the present invention may contain other additives, such as pigments and dyes, at the time of kneading and molding the resin according to the purpose, as long as the physical properties are not impaired. , Reinforcing agents (such as carbon fiber), other fillers,
Heat-resistant agents, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, flow improvers, antistatic agents, elastomers, stabilizers and the like can be added.

The above elastomers are natural and synthetic rubbery substances which are elastic at room temperature. Specific examples thereof include natural rubber, butadiene polymer, and a styrene content of 2.
Styrene-isoprene copolymer of less than 5% by weight, butadiene-styrene copolymer of less than 25% by weight of styrene, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene Copolymer, isobutylene-isoprene copolymer, acrylate ester polymer, ethylene-propylene copolymer, ethylene-propylene-
Non-conjugated diene copolymer, thiocol rubber, polysulfide rubber,
Examples include polyurethane rubber, polyether rubber (eg, polypropylene oxide), epichlorohydrin rubber, and the like.

These rubbery substances may be prepared by any polymerization method (eg, emulsion polymerization, solution polymerization) and any catalyst (eg, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst).
Furthermore, those having various degrees of crosslinking and those having microstructures of various ratios (for example, cis structure, trans structure,
Vinyl groups) are also used. As the copolymer, any of various copolymers such as a random copolymer, a block copolymer, and a graft copolymer can be used.
Further, a partially modified rubbery substance can be used,
For example, hydroxy or carboxy-terminal modified polybutadiene, partially hydrogenated styrene-butadiene copolymer,
And partially hydrogenated styrene-isoprene copolymers.

The stabilizer is not particularly limited, and includes all conventional stabilizers. The stabilizer includes a heat stabilizer, an antioxidant, a light stabilizer, and a polymerization inhibitor.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt-kneading method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Equipment includes extruders, Banbury mixers, rollers, kneaders,
Various molding machines and the like can be mentioned as examples, and these are operated batchwise or continuously. The order of mixing the components is not particularly limited.

The reason why the PPE resin composition containing the polysiloxane and the phosphate ester of the present invention exhibited improved flame retardancy and improved mechanical properties such as toughness, strength and heat resistance is that Even if the amount of phosphate ester that reduces the properties is reduced, the increase in the burning rate due to the addition of filler having shape anisotropy was suppressed by favorably dispersing the polysiloxane of a specific structure in the matrix. it is conceivable that.

[0039]

The present invention will be described in more detail with reference to the following examples. The following compounds were used in the following Examples and Comparative Examples. (A) PPE resin PPE: intrinsic viscosity (measured in chloroform at 25 ° C.)
0.46 dl / g of poly (2,6-dimethyl-1,4-
(Phenylene) ether, trademark YPX100L, styrene resin manufactured by Mitsubishi Gas Chemical Company, Inc. PS-1: High Impact Polystyrene, trademark Sumibrite M588, Sumitomo Chemical Co., Ltd. PS-2: polystyrene (PS), trademark Sumibrite E183N, Sumitomo Chemical Co., Ltd. (B) Filler having shape anisotropy GF: Glass fiber, trademark TP66, treated with aminosilane-based surface treatment agent, diameter 10 μm, manufactured by Nippon Sheet Glass, Aspect ratio 30 Mica: Suzulite Mica 200KI, manufactured by Kuraray , Aspect ratio 50 (C) phosphate ester flame retardant RDP: resorcinol diphosphate, trademark CR7
33S, Daihachi Chemical Industry Co., Ltd. TPP: Triphenyl phosphate, Daihachi Chemical Industry Co., Ltd. (D) Silicon powder SIP-1: Epoxy group-containing alkoxysilane-containing silicon powder, Trademark DC4-7051, Dow Corning Asia, SIP -2: methacryloxy group-containing alkoxysilane-containing silicon powder, trade name DC4-7081,
Dow Corning Asia Co., Ltd. SIP-3: amine group-containing alkoxysilane-containing silicon powder, trademark DC1-9641, Dow Corning Asia Co., Ltd. SIP-4: alkoxysilane-free silicon powder without an adhesion promoter, trademark DC4-7105, Dow Corning Asia (A) Polydiorganosiloxane in SIP-1 to 4 is a gum at 25 ° C. SIP-5: Liquid polydiorganosiloxane having a viscosity of 50 centipoise at 25 ° C. and a surface area of 380 m ² / g
TSF: methylhydrogenpolysiloxane, trade name, mixed powder of fumed silica in a ratio of 25/75
TSF484, manufactured by Toshiba Silicone Co., Ltd., having a viscosity at 25 ° C. of 25 cSt SGM: polydiorganosiloxane, trade name BY16-140, manufactured by Toray Dow Corning Silicone Co., Ltd., 25
Gum at ℃

Examples 1 to 9 and Comparative Examples 1 to 9 At the ratio (weight ratio) shown in Table 1, the components excluding the component (B) were supplied from the first inlet of the twin-screw extruder to the component (B). Is fed from the second inlet and melt-kneaded at a set temperature of 280 ° C.
A pellet was made. Using the pellets, injection molding was performed under the conditions of a set temperature of 290 ° C. and a mold temperature of 80 ° C. The following tests were performed on the obtained molded articles. Table 1 shows the results
Are shown in FIGS. (1) Izod Impact Strength 1/8 inch notched Izod impact strength was measured according to ASTM D256. (2) Tensile strength and tensile elongation Measured according to ASTM D638. ASTM No. 1 dumbbells were used. (3) Flexural strength and flexural rigidity Measured according to ASTM D790. A test piece having a thickness of 1/8 inch was used. (4) Thermal deflection temperature Measured according to ASTM D646. A test piece having a thickness of 1/4 inch was used. (5) Flammability Measured according to the method shown in the UL94 vertical combustion test of Underwriters Laboratories Inc. Using five test pieces having a thickness of 1.6 mm, the operation of measuring the combustion time (time until digestion) after one second of flame contact for one test piece was repeated twice. The results are shown in Tables 1 to 5 (the average and maximum combustion time of each of the first and second combustion times in the five tests are shown on the left and right of /).

From the results, in the system containing the filler having shape anisotropy (Examples 1 to 9 and Comparative Examples 1 to 5, 9),
Although the effect of improving the flame retardancy by the combination of the phosphoric ester flame retardant and the silicon powder is remarkable, in the system containing no filler having shape anisotropy (Comparative Examples 6 to 8),
The effect of the combination use of phosphate ester flame retardant and silicon powder is not shown.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

As described above, according to the present invention, in a PPE resin composition containing a filler having shape anisotropy and a phosphate ester flame retardant, flame retardancy, rigidity, strength, impact, toughness, heat resistance It was possible to provide a PPE-based resin composition having improved properties and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08K 5/092 C08K 5/092 5/521 5/521 9/06 9/06 C08L 25/00 LED C08L 25 / 00 LED LEE LEE 83/04 LRY 83/04 LRY

Claims (6)

[Claims] 1. A resin (A) comprising a polyphenylene ether-based resin or a resin obtained by combining the same with a polystyrene-based resin.
0 parts by weight, (B) Filler 5-10 having shape anisotropy
By melt-kneading 0 parts by weight, (C) 1 to 30 parts by weight of a phosphate ester-based flame retardant, and (D) 0.01 to 20 parts by weight of a silicon polymer powder composed of the following (a) and (b). The resulting thermoplastic resin composition. (A) 100 parts by weight of polydiorganosiloxane (b) 10 to 150 parts by weight of silica 2. The thermoplastic resin composition according to claim 1, wherein the component (a) is a polydimethylsiloxane gum having at least one functional group selected from a hydroxyl group and a vinyl group. 3. The thermoplastic resin composition according to claim 1, wherein the component (D) contains 0.5 to 15 parts by weight of the alkoxysilane adhesion promoter (c) per 100 parts by weight of the component (D). 4. The thermoplastic resin composition according to claim 3, wherein said component (c) contains at least one alkoxy group having 1 to 4 carbon atoms and at least one group selected from epoxy, amine and methacryloxy in the molecule. Stuff. 5. In addition to (A), (B), (C) and (D), (d) a carbon-carbon double bond or a carbon-carbon triple bond and (e) ) Carboxylic acid groups,
A compound having an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an epoxy group, an amino group or a hydroxyl group at the same time is used in an amount of 0.01 to 5 per 100 parts by weight of the component (A).
The thermoplastic resin composition according to claim 4, wherein 0 part by weight is added. 6. The (b) silica in the component (D) is treated with a polydimethylsiloxane oligomer having an average hydroxy-terminated polymerization degree of 2 to 100, and has a surface area of 50 to 400 m ² / g.
The thermoplastic resin composition according to claim 1, wherein