JP2003105177A - Thermoplastic resin composition having good tracking resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in flowability and giving a molded article improved in tracking resistance, toughness and impact resistance. SOLUTION: The thermoplastic resin composition comprises 100 pts.-mass of a thermoplastic polyester resin (A) and, incorporated therewith, 0.1-30 pts. mass of a polyterafluoroethylene-containing graft copolymer (B) comprising a polytetrafluoroethylene (b1) having a particle size of 10 μm or less and a polyorganosiloxane-based graft copolymer (b2) obtained by graft polymerizing a vinyl monomer comprising at least one epoxy group-containing vinyl monomer onto a composite rubber comprising a polyorganosiloxane rubber and a polyalkyl(meth)acrylate rubber.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing a thermoplastic polyester resin and a polytetrafluoroethylene-containing graft copolymer.

[0002]

2. Description of the Related Art A resin composition containing a thermoplastic polyester resin, glass fibers, and a flame retardant is used as a material for producing various electronic parts which require flame retardancy. In electrical and electronic parts, it is desired to improve mechanical properties, fluidity and moldability as well as flame retardancy and electrical properties (tracking resistance). As a method for improving the tracking resistance and impact strength of a thermoplastic polyester resin, JP-A-7-145304 and JP-A-7-304304 have been proposed.
A composition containing a glycidyl group-containing polyolefin resin described in JP-A-196859 has been proposed.

[0003]

However, even in the polyester type thermoplastic resin composition containing the above-mentioned glycidyl group-containing polyolefin resin, it is possible to significantly improve the fluidity, tracking resistance and impact resistance. Have difficulty. An object of the present invention is to provide a thermoplastic resin composition which is excellent in fluidity and can be used to obtain a molded product having improved tracking resistance, toughness and impact resistance.

[0004]

[Means for Solving the Problems] In order to solve the above problems, as a result of extensive studies, a thermoplastic polyester resin,
Polytetrafluoroethylene having a particle diameter of 10 μm or less,
By adding a polytetrafluoroethylene-containing graft copolymer consisting of a polyorganosiloxane rubber having an epoxy group and a graft copolymer consisting of a polyalkyl (meth) acrylate rubber, tracking resistance and impact resistance, They have found that the fluidity is remarkably improved and have reached the present invention. That is, the thermoplastic resin composition of the present invention comprises polytetrafluoroethylene (b1) having a particle diameter of 10 μm or less, polyorganosiloxane rubber and polyalkyl (meth) with respect to 100 parts by mass of the thermoplastic polyester resin (A). Polytetrafluoro comprising a polyorganosiloxane-based graft copolymer (b2) obtained by graft-polymerizing a vinyl-based monomer containing at least one kind of epoxy-group-containing vinyl-based monomer into a composite rubber including an acrylate rubber Ethylene-containing graft copolymer (B)
In a thermoplastic resin composition blended with 0.1 to 30 parts by mass.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin (A) used in the present invention is a polycondensation reaction of a mixture containing a dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative) as main components. It is a polymer or copolymer obtained by. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, biphenyl. -4,4'-dicarboxylic acid, 5-
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecadioic acid, and alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Acids and their ester-forming derivatives and the like. The diol component is an aliphatic or alicyclic glycol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexane. Examples include diols, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, and the like, and ester-forming derivatives thereof.

[0006] Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxyl). Rate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polyethylene (terephthalate / 5-sodium isophthalate), polyethylene (terephthalate / biphenyl-) 4,4'-dicarboxylate), polyethylene naphthalate, polycyclohexane dimethylene terephthalate The rate may be used, and they may be used alone or in combination of two or more. Of these, polybutylene terephthalate and polybutylene (terephthalate / terephthalate /
Decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc. are particularly preferably used. Further, these thermoplastic polyester resins have relative viscosities of 1.2 to 2. When a 0.5% o-chlorophenol solution is measured at 25 ° C.
A value of 0, particularly in the range of 1.3 to 1.8 is suitable. When the relative viscosity is less than 1.2, the mechanical properties tend to deteriorate, and when the relative viscosity exceeds 2.0, the moldability tends to decrease.

The polytetrafluoroethylene-containing graft copolymer (B) used in the present invention is a composite of polytetrafluoroethylene (b1) having a particle diameter of 10 μm or less, polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber. A polyorganosiloxane-based graft copolymer (b2) obtained by graft-polymerizing one or more vinyl-based monomers containing at least one epoxy-group-containing vinyl-based monomer onto rubber. At this time, it is preferable that the polytetrafluoroethylene (b1) is not an aggregate of 10 μm or more in the powder of the polytetrafluoroethylene-containing graft copolymer. The particle size used to obtain the polytetrafluoroethylene-containing graft copolymer (B) used in the present invention is from 0.05 to 1.0 μm.
The polytetrafluoroethylene particle aqueous dispersion of m can be obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorine-containing surfactant.

[0008] During emulsion polymerization of polytetrafluoroethylene particles, hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether and the like are included as copolymerization components as long as the characteristics of polytetrafluoroethylene are not impaired. Fluorine olefins and fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylates can be used. The content of the copolymerization component is preferably 10% by mass or less based on tetrafluoroethylene. As a commercially available raw material for the polytetrafluoroethylene particle dispersion, Asahi Fluoropolymers Fluoron AD-
1, AD936, Polyflon D- manufactured by Daikin Industries, Ltd.
1, D-2, Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemicals, and the like can be mentioned as typical examples.

[0009] The polyorganosiloxane-based graft copolymer (b2) contained in the polytetrafluoroethylene-containing graft copolymer (B) used in the present invention comprises a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. A graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers containing at least one epoxy-group-containing vinyl-based monomer onto a composite rubber. The composition of the two rubbers constituting the composite rubber is such that the polyorganosiloxane rubber component is 1 to 99% by mass, and the polyalkyl (meth) is
The acrylate component is preferably in the range of 99 to 1% by mass (however, the total amount of both components is 100% by mass).

[0010] The method for producing the composite rubber is not particularly limited,
The most suitable method is the emulsion polymerization method. First, a latex of polyorganosiloxane is prepared, and then an alkyl (meth) acrylate monomer constituting a (meth) acrylate rubber is impregnated into particles of the polyorganosiloxane latex. It is preferable to polymerize this. The polyorganosiloxane rubber component constituting the composite rubber can be prepared by emulsion polymerization using the following organosiloxane and cross-linking agent (CI), and at the same time, a graft crossing agent (GI) may be used in combination. it can. Examples of the organosiloxane include various cyclic compounds having a 3-membered ring or more, and a 3- to 6-membered ring is preferably used. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These may be used alone or in combination of two or more. The amount of these used is preferably 50% by mass or more, and more preferably 70% by mass or more in the polyorganosiloxane component.

[0011] As the crosslinking agent (CI), a trifunctional or tetrafunctional silane-based crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetrabutoxysilane or the like is used. Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The amount of the crosslinking agent used is 0.1 to 30% by mass in the polyorganosiloxane component.

[0012] As the graft crossing agent (GI), a compound capable of forming a unit represented by the following formula and the like are used. _{CH 2 = C (R 2)} -COO- (CH 2) p -SiR 1n O (3-n) / 2 (GI-1) CH 2 = C (R 2) -C 6 H 4 -SiR 1n O ( _{3-n) / 2 (GI} -2) CH 2 = CH-SiR 1n O (3-n) / 2 (GI-3) HS- (CH 2) p -SiR 1n O (3-n) / 2 (GI-4) ( wherein, R ₁ is a methyl group, an ethyl group, a propyl group or a phenyl group,, R ₂ is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number of 1 to 6.)

[0013] Of the monomers constituting the above formula (GI-1),
Since (meth) acryloyloxysiloxane has high grafting efficiency, it can form an effective graft chain,
The thermoplastic resin composition finally obtained exhibits high impact resistance, and is preferably methacryloyloxysiloxane. Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl. Ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane,
γ-methacryloyloxybutyldiethoxymethylsilane and the like can be mentioned. Vinyl siloxane is mentioned as a monomer which comprises said formula (GI-2), and tetramethyl tetravinyl cyclotetrasiloxane is mentioned as a specific example. Examples of the monomer constituting the above formula (GI-3) include p-vinylphenyldimethoxymethylsilane. Examples of the monomer constituting the formula (GI-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane and γ-mercaptopropyldiethoxymethylsilane. The amount of the graft crossing agent used is 0 to 10% by mass, preferably 0.5 to 5% by mass in the polyorganosiloxane component.

For the production of the latex of this polyorganosiloxane component, for example, the method described in US Pat. Nos. 2,891,920 and 3,294,725 can be used. Specifically, for example, an organosiloxane, a cross-linking agent (CI), and optionally a mixed solution of a graft crossing agent (GI) are mixed in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid, for example, a homogenizer or the like. It is preferable to produce by a method of shear mixing with water using. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization.

Next, the polyalkyl (meth) acrylate component constituting the composite rubber can be synthesized by using the following alkyl (meth) acrylate, crosslinking agent (CII) and graft crossing agent (GII). . Examples of alkyl (meth) acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, n-.
Examples thereof include alkyl methacrylates such as lauryl methacrylate, and it is particularly preferable to use n-butyl acrylate.

[0016] Examples of the cross-linking agent (CII) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. Examples of the graft crossing agent (GII) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a cross-linking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the crosslinking agent and the graft crossing agent used is 0.1 to 20% by mass in the polyalkyl (meth) acrylate component.

The polymerization of the polyalkyl (meth) acrylate component is carried out by adding the above alkyl (meth) acrylate into the latex of the polyorganosiloxane component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. After adding a crosslinking agent and a graft crossing agent and impregnating the polyorganosiloxane particles,
It is carried out by using a normal radical polymerization initiator. A latex of a composite rubber of a polyorganosiloxane component and a polyalkyl (meth) acrylate component is obtained as the polymerization proceeds. In carrying out the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate component has a repeating unit of n-butyl acrylate. Composite rubber is preferably used. The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer. The composite rubber preferably has a gel content of 80% by mass or more measured by extraction with toluene at 90 ° C. for 4 hours.

The polyorganosiloxane-based graft copolymer (b2) in the present invention is a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate component from the viewpoint of improving dispersibility in the thermoplastic polyester resin (A). A vinyl-based monomer containing at least an epoxy group-containing vinyl monomer is graft-polymerized to a composite rubber composed of The epoxy group-containing vinyl monomer used in the synthesis of the polyorganosiloxane-based graft copolymer (b2) used in the present invention is glycidyl (meth)
Examples thereof include acrylate, vinyl glycidyl ether, allyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, and diglycidyl itaconate. Among these, glycidyl (meth) acrylate , One or more selected from the group consisting of diglycidyl itaconate.

[0019] In the graft copolymerization to the composite rubber, only the above-mentioned epoxy group-containing vinyl monomer may be grafted, or the epoxy group-containing vinyl monomer and another vinyl type copolymerizable therewith. A monomer mixture with a monomer may be subjected to graft copolymerization. Examples of the vinyl monomer copolymerizable with the epoxy group-containing vinyl monomer include styrene and α-
Aromatic alkenyl compounds such as methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; cyanation of acrylonitrile and methacrylonitrile. Various vinyl-based monomers such as vinyl compounds may be mentioned, and one or more of them may be used in combination with an epoxy group-containing vinyl monomer. Among these vinyl monomers, methyl methacrylate, butyl acrylate, and styrene are preferably used. In the present invention, the vinyl monomer unit containing at least an epoxy group-containing vinyl monomer in the polyorganosiloxane-based graft copolymer (b2) is a polyorganosiloxane-based graft copolymer (from the viewpoint of impact strength improving effect). b2) is preferably 2 to 50% by weight, and 5 to
It is more preferably 30% by weight.

In the present invention, the amount of the epoxy group-containing vinyl monomer unit in the polyorganosiloxane-based graft copolymer (b2) is 0.05 to 15 mass from the viewpoint of fluidity and impact strength improving effect. % Is preferable,
It is more preferably 0.1 to 10% by mass. In the graft copolymerization, since the free polymer obtained by polymerizing the component corresponding to the branch of the graft copolymer without grafting to the composite rubber is a by-product, a mixture of the graft copolymer and the free polymer is finally obtained. A polymer is obtained as the above, but in the present invention, these are referred to as a graft copolymer.

[0021] The polytetrafluoroethylene-containing graft copolymer (B) is composed of polytetrafluoroethylene particles (b).
A method in which the aqueous dispersion of 1) and the polyorganosiloxane-based graft polymer (b2) particle aqueous dispersion are mixed and powdered by coagulation or spray drying, and polytetrafluoroethylene particles (b1) aqueous dispersion are present. The polyorganosiloxane-based graft polymer (b2) can be obtained by a method in which the monomer constituting the particles is polymerized below and then powdered by coagulation or spray drying. Preferably, the monomer having an ethylenically unsaturated bond is emulsified in a dispersion liquid obtained by mixing the polytetrafluoroethylene particle (b1) aqueous dispersion liquid and the polyorganosiloxane-based graft polymer (b2) particle aqueous dispersion liquid. Those obtained by polymerizing and then pulverizing by coagulation or spray drying are preferable. The content ratio of the polytetrafluoroethylene-containing graft copolymer (B) used in the present invention is 0 based on 100 mass% of the thermoplastic polyester resin (A) from the viewpoints of impact strength development, tracking resistance, and fluidity. 1 ~
It is preferably 30% by mass. More preferably, 1
Is about 20% by mass.

As the fibrous filler (C) used in the present invention,
Examples thereof include glass fibers, wollastonite, carbon fibers, whiskers such as potassium titanate, and organic fibers. Among them, particularly preferable fibrous fillers include glass fibers. The diameter of the fibrous filler (C) used in the present invention is usually 5 to 15 μm, preferably 9 to 13 μm. The fibrous filler (c) can exhibit the performance even if it is blended as it is, but an appropriate surface treatment agent can be used in order to enhance the affinity and adhesiveness with the resin. Examples of the surface treatment agent include silane coupling agents, zircoaluminate coupling agents, titanate coupling agents, and the like, and silane coupling agents (for example, aminosilane and epoxysilane) can be preferably used. The mechanical properties are further improved by using those obtained by these surface treatments.

[0023] The flame retardant (D) used in the present invention is not particularly limited as long as it has an effect of improving combustibility within the range of the effect of the present invention, and a halogen-based flame retardant, red phosphorus, phosphorus. Acid ester flame retardants, organic sulfonates, and silicone flame retardants can be used. Preferably, it is selected from halogen-based flame retardants and / or phosphate ester-based flame retardants and / or organic sulfonates. Examples of the halogen-based flame retardant include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonate resins, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenyl ethers, halogenated polyphenyl thioethers, etc. Preferably, decabromodiphenyl oxide, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate resin,
Brominated polystyrene resin, brominated crosslinked polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate (tetrabromobisphenol A, oligomers thereof, etc.). As the phosphoric acid ester flame retardant, phosphoric acid ester or oligomeric phosphoric acid ester can be used. Examples of these phosphoric acid esters include phosphoric acid esters obtained by reacting an alcohol or a phenol compound with a phosphorus compound such as phosphorus oxychloride or phosphorus pentachloride. When a phenol compound having a high valency (for example, resorcin, hydroquinone, diphenol compound) is used, an oligomeric phosphate ester is obtained. Specific examples of the phosphate ester flame retardant, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxycotyl phosphate, triphenyl phosphate, tricresyl phosphate,
Non-halogen phosphates such as cresyl diphenyl phosphate, octyl diphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3 dibromopropyl)
2,3-dichloropropyl phosphate, tris (2,
Examples thereof include halogen-containing phosphate such as 3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate. Examples of the organic sulfonic acid metal salt include potassium perfluorobutane sulfonate, potassium trichlorobenzene sulfonate, potassium diphenylsulfone-3-sulfonate, and the like.

[0024] The composition of the present invention includes a nucleating agent for a thermoplastic polyester resin (eg, sodium stearate, barium stearate, sodium montanate, barium montanate, a partial sodium salt of a montanic acid ester, or a barium salt). Organic carboxylic acid metal salts, ionomers, etc., and crystallization accelerators (eg, polyethylene glycol, polyethylene glycol dibenzoate, neopentyl glycol dibenzoate, polyethylene glycol bis (2-ethylhexanote) and other polyalkylene glycol derivatives and benzoin. Acid ester, polylactones, N-substituted toluenesulfoamide, etc.) can be used in combination. In the present invention, other various additives (eg, montanic acid wax, polyethylene wax, mold release agents such as silicone oil, heat stabilizers, UV absorbers, pigments, dyes, etc.) can be added, if necessary. Still other fillers (eg talc, kaolin, mica,
Clay, silica, sericite, titanium oxide, glass beads, glass balloons, glass flakes, glass powder, etc.) can be added.

[0025] Furthermore, the thermoplastic resin composition of the present invention contains a vinyl copolymer such as polyphenylene ether resin, polyamide resin, polycarbonate resin, polymethylmethacrylate (PMMA), vinyl chloride resin, or the like, if necessary.
ABS resins, styrene resins, polyolefin resins such as polyethylene and polypropylene, and ethylene / propylene copolymers, ethylene / butene-1 copolymers, ethylene / propylene / dicyclopentadiene copolymers,
Olefin rubber such as ethylene / propylene / 5-ethylidene-2-rubornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / vinyl acetate copolymer, ethylene / butyl acrylate copolymer By blending them, more desirable physical properties and characteristics can be adjusted. A predetermined amount of these above-mentioned essential components and optional components are blended if desired, and the composition is prepared by kneading with a usual kneader such as a roll, a Banbury mixer, a single-screw extruder or a twin-screw extruder, but usually pellets It is preferable to make the shape. The thermoplastic resin composition of the present invention thus obtained can be formed into a desired molded article by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding. Further, the obtained molded product has high rigidity and impact strength, and also has a high degree of tracking resistance, so that it is useful as a withstand voltage component that requires high voltage resistance, particularly a socket for a lighting fixture and a switch component. is there.

[0026]

[Examples] "Parts" and "%" in each description mean "parts by mass" and "% by mass" respectively. Moreover, various physical properties were measured by the following methods. (1) Solid content concentration: determined by drying the particle dispersion at 170 ° C. for 30 minutes. (2) Particle size distribution, weight average particle size: The particle dispersion diluted with water was used as a sample solution by dynamic light scattering method (ELS800 manufactured by Otsuka Electronics Co., Ltd., temperature 25 ° C., scattering angle 90 °). It was measured. (3) Izod impact strength: Using a test piece obtained by injection molding, in accordance with ASTM D256, thickness 3.2 m
m, notched, and measured at 23 ° C. (4) Tracking resistance: A test piece obtained by injection molding was used and the applied voltage at which tracking occurred was measured according to IEC112 3rd edition. (5) Fluidity: Using a 75t injection molding machine, 2mm thick, 2
The spiral flow was measured under the condition of 50 ° C.

[0027] The thermoplastic resin (A-1), the rubbery polymer having an epoxy group (M-1), and the substances shown in Reference Examples used the following commercially available products. Polyester resin (A-1): Polybutylene terephthalate resin (Mitsubishi Rayon Tuffpet PBT, N130
0) Epoxy group-containing rubbery polymer (M-1): ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Bondfast E)

Reference Example 1 <Production of polytetrafluoroethylene-containing graft copolymer (B-1)> 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 99.5 parts of octamethylcyclotetrasiloxane were mixed, 100 parts of siloxane mixture are obtained. 300 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate was dissolved was added thereto, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then passed through a homogenizer twice at a pressure of 30 MPa to obtain a stable premixed organosiloxane latex. Obtained. On the other hand, a separable flask equipped with a condenser and a stirring blade was charged with 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water to prepare a 10 wt% dodecylbenzenesulfonic acid aqueous solution.
With this aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours, and after the completion of the addition, the temperature was maintained for 3 hours and then cooled. The reaction was then kept at room temperature for 12 hours and then neutralized with aqueous sodium hydroxide. The latex thus obtained (L
-1) was dried at 170 ° C. for 30 minutes to obtain a solid content, which was 18.1%. The number average particle size of the latex was 32 nm.

[0029] 55.2 parts of the silicone latex (L-1) was sampled, placed in a separable flask equipped with a stirring blade, 144.8 parts of distilled water was added, and the atmosphere was replaced with nitrogen.
The temperature was raised to 0 ° C., and a mixed solution of 74.8 parts of n-butyl acrylate, 0.05 part of allyl methacrylate and 0.2 part of cumene hydroperoxide was added. Then, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalite and distilled water was added to start radical polymerization, and then the internal temperature was kept at 50 ° C for 2 hours. Thus, a silicone / acrylic composite rubber latex (S-1) was obtained. The solid content concentration of (S-1) is 29.
At 8%, the particle size distribution showed a single peak and the weight average molecular weight was 100 nm. Fluon AD936 manufactured by Asahi Fluoropolymers was used as the polytetrafluoroethylene-based particle dispersion. The solid concentration of AD936 is 63.
It is 0% and contains 5 parts of polyoxyethylene alkylphenyl ether based on 100 parts of polytetrafluoroethylene. The particle size distribution of AD936 showed a single peak, the weight average particle size was 290 nm, and the surface potential was -20 mV. 1198 parts of distilled water was added to 802 parts of AD936 to obtain a 24.2% polytetrafluoroethylene particle dispersion (F-1). (F-1) is 2
It contains 3% of polytetrafluoroethylene particles and 1.2% of polyoxyethylene alkylphenyl ether.

[0030] 8 parts of glycidyl methacrylate and 0.02 of cumene hydroperoxide were added to the composite rubber latex (S-1).
After 5 parts of the mixed solution was added dropwise over 8 minutes and the internal temperature was kept at 60 ° C. for 1 hour, the polytetrafluoroethylene particle dispersion (F
After adding 16.7 parts of -1), methyl methacrylate 1
A mixed solution of 0 part and 0.05 part of cumene hydroperoxide was added dropwise over 15 minutes, and the internal temperature was kept at 60 ° C. for 2 hours to complete the grafting to the composite rubber, and the polytetrafluoroethylene-containing graft copolymer (B -1) latex was obtained.
The number average particle size of the latex (B-1) was 120 nm. (B-1) Latex was added to a calcium chloride aqueous solution having a concentration of 5% by weight at 40 ° C. so that the weight ratio of the latex and the aqueous solution was 1: 2, and then the temperature was raised to 90 ° C. to coagulate the mixture. After repeating washing with water, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a dry powder of (B-1). After B-1 was shaped into a strip at 250 ° C. by a press molding machine, an ultrathin section obtained with a microtome was observed with a transmission electron microscope without staining. Polytetrafluoroethylene was observed as a dark area, but no aggregate exceeding 10 μm was observed.

Reference Examples 2 and 3 <Production of polytetrafluoroethylene-containing graft copolymers (B-2) and (B-3)> Except that the amount of glycidyl methacrylate and methyl methacrylate added was changed to the amounts shown in Table 1. Then, dry powders of polytetrafluoroethylene-containing graft copolymers (B-2) and (B-3) were obtained in the same manner as in Reference Example 1. (B-2),
(B-3) was shaped into a strip at 250 ° C. by a press molding machine, and then an ultrathin section obtained with a microtome was observed with a transmission electron microscope without staining. Polytetrafluoroethylene was observed as a dark area, but no aggregate exceeding 10 μm was observed.

Reference Examples 4 and 5 <Production of Polytetrafluoroethylene-Containing Graft Copolymer (B-4) and (B-5)> The addition amount of (F-1) used in Reference Example 1 is shown in Table 2. Dry powders of polytetrafluoroethylene-containing mixed powders (B-4) and (B-5) were obtained in the same manner as in Reference Example 1 except that the amount was changed. (B-4) and (B-5) were shaped into strips by a press molding machine at 250 ° C., and then ultrathin sections were microtomed and observed with a transmission electron microscope without staining. Polytetrafluoroethylene was observed as a dark area, but no aggregate exceeding 10 μm was observed.

Reference Example 6 <Production of Graft Copolymer (M-1) Having Epoxy Group> The epoxy group has an epoxy group in the same manner as in Reference Example 1 except that (F-1) used in Reference Example 1 is not added. Rubbery polymer (M
-1) dry powder was obtained.

[0034] Examples 1 to 7, Comparative Examples 1 to 5, thermoplastic resin (A-1), polytetrafluoroethylene-containing graft copolymer (B) or epoxy group-containing graft copolymer (M-1), Glass fiber and, if necessary, polytetrafluoroethylene fine powder (Asahi IC
(Computer I, CD123) was blended in the ratio shown in Table 43, and a stabilizer was added.
The pellets were prepared by extrusion at 00 rpm. Next, after drying the pellets at 130 ° C. for 5 hours, the mold clamping pressure is 75
A test piece for measuring various physical properties was prepared with an injection molding machine, and impact strength, tracking resistance, and spiral flow were evaluated.
The results are shown in Table 4. The cylinder temperature of the extruder and the injection molding machine was 250 ° C, and the mold temperature was 80 ° C.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

According to the thermoplastic resin composition of the present invention,
Polytetrafluoroethylene-containing graft comprising thermoplastic polyester resin and polytetrafluoroethylene having a particle size of 10 μm or less, and a graft copolymer comprising polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber having an epoxy group. It consists of the addition of a copolymer and has excellent tracking resistance, impact resistance and fluidity without degrading the performance of the thermoplastic resin.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 51:00) (72) Inventor Shinobu Fujie 4-1-2 Ushikawa-dori Toyohashi-shi, Aichi Mitsubishi Rayon Co., Ltd. Company F-term in Toyohashi office (reference) 4J002 BB00Y BD15Y BG00Y BN15Y BN222 CF00W CF07W CG00Y CL00Y CN01Y DA016 DE186 DJ006 DL006 FA046 FA066 4J026 AA26 AA45 AA46 AA47 AB20 AB44 AC15 AC19 BA05 BA06 BA16 BA36 BA50

Claims (3)

[Claims] 1. A thermoplastic polyester resin (A) 100.
At least one kind of epoxy group-containing vinyl monomer in a composite rubber composed of polytetrafluoroethylene (b1) having a particle diameter of 10 μm or less, polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber, based on parts by mass. 0.1 to 30 parts by mass of a polytetrafluoroethylene-containing graft copolymer (B) composed of a polyorganosiloxane-based graft copolymer (b2) obtained by graft-polymerizing a vinyl-based monomer containing Thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, which contains a fibrous filler (C). 3. A thermoplastic resin comprising a thermoplastic polyester resin (A) containing at least one thermoplastic resin selected from a polycarbonate resin, a polyamide resin, a polyarylene sulfide resin, a polyolefin resin, an acrylic resin and an ABS resin. The thermoplastic resin composition according to claim 1 or 2, which is a polyester resin (A).