JP2009173860A - Thermoplastic polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyester resin composition excellent in flowability, mechanical characteristics and cold impact resistance, and to provide a molded article comprising the same. <P>SOLUTION: Provided is the thermoplastic polyester resin composition characterized by compounding (D) 0.01 to 5 pts.wt. of a multi-functional compound having three or more functional groups to 100 pts.wt. of a resin composition comprising (A) 48 to 88 wt% of polybutylene terephthalate resin, (B) 10 to 50 wt% of reinforcing fibers, and (C) 2.0 to 40 wt% of an olefinic elastomer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic polyester resin composition having excellent fluidity, mechanical properties, and cold and thermal shock resistance useful as electrical / electronic equipment parts, automobile parts, machine parts, and the like, and a molded article comprising the same.

  Thermoplastic polyester resins have excellent mechanical properties, heat resistance, and moldability, and thus are widely used in automobile parts, films, electrical / electronic parts, and the like. Among them, polybutylene terephthalate, a type of polyester resin, has a high reinforcing effect with inorganic fillers and excellent chemical resistance. Therefore, it is a material for industrial molded products such as connectors, relays and switches for automobiles and electrical / electronic equipment. As widely used.

However, in recent years, there has been an increasing demand for miniaturization and weight reduction of industrial molded products. In particular, polybutylene terephthalate for use in automobiles and electrical / electronic equipment can meet these requirements without degrading mechanical properties. It is desired to improve the fluidity at the time of melting.
Patent Document 1 describes a fluidity improving method in which a combination of a specific thermoplastic resin and a compound having a specific at least three functional groups is melt mixed, but the fluidity improving effect is insufficient, and The mechanical properties also tended to decrease. In addition, the thermal shock resistance is not studied.

  Patent Document 2 discloses that an insert-molded product made of a resin composition comprising a polybutylene terephthalate resin and a fibrous filler, and a graft copolymer of an alkyl ester copolymer and a vinyl copolymer has excellent high and low temperature impact characteristics. It is described. However, since this resin composition has insufficient fluidity, there has been a problem that it cannot cope with the recent reduction in size and weight of industrial molded products.

Furthermore, Patent Document 3 describes a resin composition comprising an aromatic polyester resin and an inorganic filler, an acid group-containing olefin copolymer and an epoxy group-containing ethylene copolymer, and is described as having excellent impact resistance characteristics. Yes. However, this resin composition also has insufficient fluidity, and has a problem that it cannot cope with the recent reduction in size and weight of industrial molded products.
Japanese Patent Laid-Open No. 7-304970 JP-A-6-304964 JP-A-4-275371

  An object of the present invention is to provide a polybutylene terephthalate resin composition excellent in fluidity, mechanical properties and thermal shock resistance, and a molded article comprising the same.

  The inventors of the present invention have reached the present invention as a result of intensive studies and examinations in order to solve such problems.

That is, the present invention
(1) (A) 48 to 88% by weight of polybutylene terephthalate resin, (B) 10 to 50% by weight of reinforcing fiber, (C) 100 parts by weight of resin composition consisting of 2.0 to 40% by weight of olefin elastomer (D) A thermoplastic polyester resin composition comprising 0.01 to 5 parts by weight of a polyfunctional compound having three or more functional groups.
(2) (C) Olefin-based elastomer is (C1) a copolymer of α-olefin and α, β-ethylenically unsaturated carboxylic acid or derivative thereof, 1.0 to 20% by weight, (C2) α-olefin and The thermoplastic polyester resin composition according to the above (1), which is a mixture of 1.0 to 20% by weight of a glycidyl group-containing copolymer comprising a glycidyl ester of an α, β-unsaturated acid.
(3) (D) The thermoplastic polyester resin composition as described in (1) or (2) above, wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units.
(4) (D) At least one group in which the functional group of the polyfunctional compound having three or more functional groups is selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group The thermoplastic polyester resin composition according to any one of (1) to (3) above, wherein
(5) (D) The flame-retardant thermoplastic according to any one of (1) to (4), wherein the polyfunctional compound having three or more functional groups has a trifunctional or tetrafunctional hydroxyl group. Polyester resin composition.
(6) Said (1)-(5) which mix | blends 0.05-2.0 weight part of (E) epoxy compounds with respect to the resin composition total 100 weight part of (A)-(C). The thermoplastic polyester resin composition according to any one of the above.
(7) A molded article comprising the thermoplastic polyester resin composition according to any one of (1) to (6) above is provided.

  The polyester resin composition of the present invention is excellent in fluidity and can have both mechanical properties and cold shock resistance.

  The polyester resin composition of the present invention is a resin composition comprising (A) 48 to 88% by weight of polybutylene terephthalate resin, (B) 10 to 50% by weight of reinforcing fibers, and (C) 2.0 to 40% by weight of olefin elastomer. (D) 0.01-5 weight part of polyfunctional compounds which have a 3 or more functional group are mix | blended with respect to a total of 100 weight part of a thing.

  The (A) polybutylene terephthalate resin constituting the present invention is a normal polymerization such as a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. It is a polymer obtained by the method, and may contain other copolymerization components in a range that does not impair the characteristics, for example, about 20 parts by weight or less. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene. (Terephthalate / Naphthalate), poly (butylene / ethylene) terephthalate and the like may be mentioned, and these may be used alone or in combination of two or more.

  The (A) polybutylene terephthalate resin used in the present invention has an intrinsic viscosity of 0.60 to 1.60, particularly 0.80 to 1.30 when an o-chlorophenol solution is measured at 25 ° C. Those are preferred. If the intrinsic viscosity is less than 0.60, the mechanical properties are poor. On the other hand, if the intrinsic viscosity exceeds 1.60, the moldability tends to be poor.

  The production method of the (A) polybutylene terephthalate resin used in the present invention can be produced by a known polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. Although any of the reactions by direct polymerization can be applied, continuous polymerization is preferable in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and direct polymerization is performed in terms of cost. Is preferred. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexyldistin oxide, Didodecyltin oxide, Triethyltin hydroxide, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Tin compounds such as alkylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, etc. Among these, organic titanium compounds and tin compounds are preferred, Furthermore, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferred, and titanic acid is preferred. Tetra -n- butyl ester is particularly preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin in terms of mechanical properties, moldability, and color tone, and is preferably 0.01 to 0.8. A range of 2 parts by weight is more preferred.

  The compounding quantity of (A) polybutylene terephthalate in this invention is 48 to 88 weight% of a resin composition. When the blending amount of polybutylene terephthalate is less than 48% by weight, the fluidity of the resin composition is inferior, and when it exceeds 88% by weight, the mechanical properties of the resin composition tend to deteriorate.

  As the reinforcing fiber (B) used in the present invention, glass fiber, carbon fiber, metal fiber and organic fiber (nylon, polyester, aramid, polyphenylene sulfide, liquid crystal polymer, acrylic, etc.) can be used, One or two or more types can be used in combination, but glass fiber is most desirable. The fiber diameter is preferably 4 to 25 μm, particularly 6 to 20 μm.

  Further, in the present invention, the reinforcing fiber is preferably opened in the composition, and such openability means a state in which the reinforcing fiber in the composition is substantially opened to a single fiber, Specifically, it means that the number of reinforcing fibers in a bundle of 10 or more of the observed reinforcing fibers is about 40% or less of the total number of reinforcing fibers.

  The compounding quantity of (B) reinforcement fiber in this invention is 10 to 50 weight% of a resin composition. When the compounding amount of the reinforcing fiber is less than 10% by weight, the mechanical properties of the resin composition are inferior, and when it exceeds 50% by weight, the fluidity of the resin composition is inferior.

  Examples of the (C) olefin elastomer used in the present invention include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer, an ethylene / propylene / conjugated diene copolymer, and an ethylene / propylene copolymer. Ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methacrylic acid copolymer, ethylene / glycidyl copolymer, ethylene / methacrylic acid / glycidyl copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer Polymer, ethylene / ethyl acrylate-g-methyl methacrylate / butyl acrylate copolymer, ethylene / ethyl acrylate-g-methyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer Copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer , Ethylene / ethyl acrylate-g-maleimide copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-maleic anhydride copolymer, and the like. Can be used alone or in the form of a mixture.

  (C) The compounding quantity of an olefin type elastomer is 2.0 to 40 weight% of a resin composition. When the blending amount is less than 2.0% by weight, the thermal shock resistance of the resin composition is inferior, and when it exceeds 40% by weight, the mechanical properties of the resin composition are inferior. From the viewpoint of mechanical properties and cold-heat shock resistance, (C) the olefin elastomer is preferably blended in the range of 3.0 to 15% by weight, more preferably in the range of 5.0 to 10% by weight. preferable.

  The olefin elastomer is particularly preferably (C1) a copolymer of an α-olefin and an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof in an amount of 1.0 to 20% by weight, (C2) an α-olefin and an α, It is a mixture of 1.0 to 20% by weight of a glycidyl group-containing copolymer comprising a glycidyl ester of β-unsaturated acid.

  (C1) As an α-olefin of a copolymer of an α-olefin and an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof, an α-olefin polymer such as ethylene, propylene, butene-1, and pentene-1 And olefin rubbers such as ethylene-propylene-copolymer rubber and ethylene-butene-1 copolymer rubber. These α-olefins may be used alone or in combination of two or more. Examples of the α, β-ethylenically unsaturated carboxylic acid include ethylene-α, β such as ethylene vinyl ester copolymer such as ethylene-vinyl acetate copolymer and ethylene- (meth) acrylic acid alkyl ester copolymer. -Ethylene (co) polymers such as a copolymer with a carboxylic acid or a derivative thereof. Among these, an ethylene- (meth) -acrylic acid alkyl ester copolymer is preferable. Specific examples include an ethylene / ethyl acrylate copolymer, an ethylene / butyl acrylate copolymer, an ethylene / methyl acrylate copolymer, and an ethylene / acrylic acid / ethyl acrylate copolymer. Among these, an ethylene / ethyl acrylate copolymer and an ethylene butyl acrylate copolymer are preferable because the glass transition temperature is low and the thermal shock resistance can be improved.

  The preferred blending amount of the copolymer of (C1) α-olefin and α, β-ethylenically unsaturated carboxylic acid or derivative thereof in the present invention is 1.0 to 20% by weight of the resin composition. When the blending amount is less than 1.0% by weight, the thermal shock resistance of the resin composition is inferior, and when it exceeds 20% by weight, the mechanical properties of the resin composition tend to be inferior. From the viewpoint of mechanical properties and resistance to thermal shock, it is preferably blended in the range of 3.0 to 15% by weight, and more preferably in the range of 5.0 to 10% by weight.

  Examples of the α-olefin in the glycidyl group-containing copolymer comprising (C2) α-olefin and glycidyl ester of α, β-unsaturated acid used in the present invention include α such as ethylene, propylene, butene-1, and pentene-1. Examples thereof include olefin rubbers such as olefin polymer, ethylene-propylene-copolymer rubber, and ethylene-butene-1 copolymer rubber. These α-olefins may be used alone or in combination of two or more. Specific examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl methacrylate is preferably used. Further, if it is 40% by weight or less, unsaturated acid monomers copolymerizable with the above copolymer, that is, vinyl esters such as vinyl ethers, vinyl acetate and vinyl propionate, acrylics such as methyl, ethyl, propyl and butyl. One or more of acid and methacrylic acid esters, acrylonitrile, styrene and the like may be copolymerized.

  Preferred examples of the glycidyl group-containing copolymer comprising (C2) α-olefin and α, β-unsaturated glycidyl ester in the present invention include ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / acetic acid. Examples include vinyl copolymers, ethylene / glycidyl methacrylate / acrylic acid ester copolymers, ethylene / glycidyl acrylate / vinyl acetate copolymers, etc., but particularly good dispersibility in resin compositions and excellent thermal shock resistance. Therefore, an ethylene / glycidyl methacrylate / acrylic acid ester copolymer is preferable.

  The blending amount of the glycidyl group-containing copolymer comprising (C2) α-olefin and glycidyl ester of α, β-unsaturated acid in the present invention is 1.0 to 20% by weight of the resin composition. When the blending amount is less than 1.0% by weight, the thermal shock resistance of the resin composition is inferior, and when it exceeds 20% by weight, the mechanical properties and fluidity of the resin composition tend to be inferior. From the viewpoint of mechanical properties, fluidity, and resistance to thermal shock, it is preferably blended in the range of 2 to 10% by weight, and more preferably in the range of 3 to 7% by weight.

  The polyfunctional compound having three or more functional groups (D) used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. The component (D) may be a low molecular compound or a high molecular weight polymer. Such a functional group of component (D) is preferably at least one selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. Preferably has three or more functional groups that are the same or different from these.

  (D) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is a hydroxyl group, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2, 6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane , Tritrimethylolpropane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, mannitol, sucrose, 1,3,5- Trihydroxybe Zen, polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24 such as 1,2,4-trihydroxy benzene. Of these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol having a branched structure are preferable from the viewpoint of fluidity and mechanical properties.

  Of these, those having a trivalent or tetravalent hydroxyl group are preferred. More preferably, it has a trivalent hydroxyl group. When a material having a trivalent or tetravalent hydroxyl group is used, the fluidity is particularly good, and bleeding out of the component (D) on the surface of the molded product during wet heat treatment can be eliminated. By eliminating the bleed-out, it is possible to avoid the risk that a bleed-out product is mixed when used for, for example, an automobile fuel system part.

  (D) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is a carboxyl group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3 -Triscarboxylic acid, butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, Cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2 , 5,7-tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, naphthalene-1 4,5,8- polycarboxylic acid or acrylic acid, such as tetracarboxylic acid, include polymers such as methacrylic acid, may be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferable from the viewpoint of fluidity.

  (D) When the functional group of the polyfunctional compound having three or more functional groups is an amino group, at least one of the three or more substituents is preferably a primary or secondary amine, Is more preferably a primary or secondary amine, and both are particularly preferably primary amines. (D) As a preferable example of a polyfunctional compound having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methyl Propane, 1,2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-tri Aminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4 5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4 5 8 tetra amino naphthalene. Of these, 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane and 1,3,5-triaminobenzene having a branched structure are preferable from the viewpoint of fluidity.

  (D) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione or triglycidyl isocyanurate And polymers such as poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, and glycidyl group-containing acrylic / styrene polymer.

  (D) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is an isocyanate group, nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)) , Decane triisocyanate, undecane triisocyanate, dodecane triisocyanate and the like.

  (D) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, Examples include ester derivatives of compounds having three or more carboxylic acid groups.

  (D) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups may be mentioned.

  From the viewpoint of fluidity and mechanical properties, it is preferable that (D) the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units. As preferred examples of the alkylene oxide unit, aliphatic alkylene oxide units having 1 to 4 carbon atoms are effective. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, a tetramethylene oxide unit, 1,2-butylene oxide units, 2,3-butylene oxide units or isobutylene oxide units. In the present invention, it is particularly preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as the alkylene oxide unit, and the fluidity and bleeding out in which the component (D) appears on the surface of the molded product during wet heat treatment. It is particularly preferred to use compounds containing propylene oxide units in that they are not. By eliminating the bleed-out, it is possible to avoid the risk that a bleed-out product is mixed when used for, for example, an automobile fuel system part.

  Regarding the number of alkylene oxide units contained in the polyfunctional compound having three or more functional groups used in the present invention (D), the number of alkylene oxide units per functional group is preferably 0.1 to 20, More preferably, it is 0.5-10, and it is further more preferable that it is 1-5.

  As a preferred example of the polyfunctional compound having three or more functional groups (D) containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxyethylene glycerin, (Poly) oxytrimethylene glycerol, (Poly) oxypropylene glycerol, (Poly) oxyethylene- (Poly) oxypropylene glycerol, (Poly) oxytetramethylene glycerol, (Poly) oxymethylene diglycerol, (Poly) oxyethylene di- Glycerin, (poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) Xylpropylene trimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, ( Poly) oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol , (Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, ( (I) Oxymethylene dipentaerythritol, (Poly) oxyethylene dipentaerythritol, (Poly) oxypropylene trimethylolpropane ether, (Poly) oxytrimethylene dipentaerythritol, (Poly) oxypropylene dipentaerythritol, (Poly) oxy Methylene glucose, (poly) oxyethylene glucose, (poly) oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, (poly) oxytetramethylene glucose, etc. it can.

  When the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing a (poly) methylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly) ethylene oxide unit, (poly) tricarboxylic acid Propane-1,2,3-tricarboxylic acid containing methylene oxide units, Propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, Propane-1,2, containing (poly) tetramethylene oxide units 3-tricarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) methylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) ethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) trimethylene oxide units, (poly) propyl 2-methylpropane-1,2,3-triscarboxylic acid containing pyrene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units -1,2,4-tricarboxylic acid containing, butane-1,2,4-tricarboxylic acid containing (poly) ethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units , Butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) tetramethylene oxide units, butane containing (poly) methylene oxide units 1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-teto containing (poly) ethylene oxide units Carboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, (poly ) Butane-1,2,3,4-tetracarboxylic acid containing tetramethylene oxide units, trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, (poly) trimethylene oxide Includes trimellitic acid containing units, trimellitic acid containing (poly) propylene oxide units, trimellitic acid containing (poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units, and (poly) ethylene oxide units Trimesic acid, trimesic acid containing (poly) trimethylene oxide units, (I) trimesic acid containing propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, hemimellitic acid containing (poly) methylene oxide units, hemimellitic acid containing (poly) ethylene oxide units, (poly) trimethylene Hemimellitic acid containing oxide units, Hemimellitic acid containing (poly) propylene oxide units, Hemimellitic acid containing (poly) tetramethylene oxide units, Pyromellitic acid containing (poly) methylene oxide units, (Poly) ethylene oxide units Containing pyromellitic acid, pyromellitic acid containing (poly) trimethylene oxide units, pyromellitic acid containing (poly) propylene oxide units, pyromellitic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units Containing cyclohe Sun-1,3,5-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) trimethylene oxide units, Examples include cyclohexane-1,3,5-tricarboxylic acid containing a poly) propylene oxide unit, cyclohexane-1,3,5-tricarboxylic acid containing a (poly) tetramethylene oxide unit, and the like.

  When the functional group is an amino group, 1,2,3-triaminopropane containing (poly) methylene oxide units, 1,2,3-triaminopropane containing (poly) ethylene oxide units, (poly) trimethylene oxide units 1,2,3-triaminopropane containing 1,2,3-triaminopropane containing (poly) propylene oxide units, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, ( 1,2,3-triamino-2-methylpropane containing poly) methylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) ethylene oxide units, 1 containing (poly) trimethylene oxide units 1,2,3-triamino-2-methylpropane, 1,2,3-triamino-2 containing (poly) propylene oxide units Contains methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) tetramethylene oxide units, 1,2,4-triaminobutane containing (poly) methylene oxide units, (poly) ethylene oxide units 1,2,4-triaminobutane, 1,2,4-triaminobutane containing (poly) trimethylene oxide units, 1,2,4-triaminobutane containing (poly) propylene oxide units, (poly) 1,2,4-triaminobutane containing tetramethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) methylene oxide units, 1,2,3,4-containing (poly) ethylene oxide units Tetraminobutane, 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, (poly) propyleneoxy 1,2,3,4-tetraminobutane containing units, 1,2,3,4-tetraminobutane containing (poly) tetramethylene oxide units, 1,3,5-triamino containing (poly) methylene oxide units Cyclohexane, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) trimethylene oxide units, 1,3 containing (poly) propylene oxide units 5-triaminocyclohexane, 1,3,5-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) methylene oxide units, (poly) ethylene oxide units included 1,2,4-triaminocyclohexane, (poly) trimethylene oxide unit 1,2,4-triaminocyclohexane containing, 1,2,4-triaminocyclohexane containing (poly) propylene oxide units, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, ( 1,2,4,5-tetraminocyclohexane containing poly) methylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) ethylene oxide units, 1,2,4 containing (poly) trimethylene oxide units , 5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) tetramethylene oxide units, (poly) methylene oxide 1,3,5-triaminobenzene containing units, (poly) ethylene 1,3,5-triaminobenzene containing oxide units, 1,3,5-triaminobenzene containing (poly) trimethylene oxide units, 1,3,5-triaminobenzene containing (poly) propylene oxide units 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, 1,2,4-triaminobenzene containing (poly) methylene oxide units, 1,2,4 containing (poly) ethylene oxide units -Triaminobenzene, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, 1,2,4-triaminobenzene containing (poly) propylene oxide units, (poly) tetramethylene oxide units Examples thereof include 1,2,4-triaminobenzene.

  When the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of a compound having three or more hydroxyl groups containing the alkylene oxide unit, or a compound having three or more carboxylic acid groups containing the alkylene oxide unit is used. Examples include ester derivatives.

  When the functional group is an amide group, an amide derivative of a compound having three or more carboxylic acid groups containing the above-described alkylene oxide unit can be used.

  As a particularly preferred example of the polyfunctional compound having three or more functional groups (D) containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, ( Poly) oxypropylene glycerin, (poly) oxyethylene diglycerin, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, Examples include (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, and (poly) oxypropylene dipentaerythritol. When the functional group is a carboxylic acid, ) Propane-1,2,3-tricarboxylic acid containing ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, trimellitic acid containing (poly) ethylene oxide units, (poly) propylene Trimellitic acid containing oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, (poly) Examples include cyclohexane-1,3,5-tricarboxylic acid containing a propylene oxide unit. When the functional group is an amino group, 1,2,3-triaminopropane containing a (poly) ethylene oxide unit, (poly) propylene oxide unit 1,2,3-triaminopropane containing 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triamino containing (poly) ethylene oxide units Examples include benzene and 1,3,5-triaminobenzene containing a (poly) propylene oxide unit.

  The (D) polyfunctional compound having three or more functional groups used in the present invention reacts with the (A) polybutylene terephthalate resin component and is introduced into the main chain and side chain of the (A) polybutylene terephthalate resin component. The structure at the time of blending may be maintained without reacting with the (A) polybutylene terephthalate resin component. (D) The reaction rate of the functional group of the polyfunctional compound having three or more functional groups is preferably 40% or more, more preferably 50% or more, and particularly preferably 60% or more.

  The viscosity of the polyfunctional compound having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and is 5000 m · Pa or less from the viewpoint of fluidity and mechanical properties. More preferably, it is particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property at the time of molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or weight average molecular weight (Mw) of the polyfunctional compound having three or more functional groups used in the present invention is preferably in the range of 50 to 10,000 in terms of fluidity, A range of 8000 is more preferable, and a range of 200 to 3000 is more preferable. In the present invention, (D) Mw of a polyfunctional compound having three or more functional groups is converted to polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. Value.

  The moisture content of the polyfunctional compound having three or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less.

  In the present invention, (D) the compounding amount of the polyfunctional compound having three or more functional groups is such that (D) component is 0.1 parts per 100 parts by weight of the total of the resin compositions of components (A) to (C). It is essential to be in the range of 01 to 5 parts by weight, and in terms of fluidity and mechanical properties, it is preferably blended in the range of 0.1 to 3 parts by weight, and in the range of 0.1 to 1 part by weight. It is more preferable to mix.

  In the polyfunctional compound having (D) three or more functional groups used in the present invention, the component (D) preferably has at least one hydroxyl group or carboxylic acid group from the viewpoint of fluidity. More preferably, the component (D) has 3 or more hydroxyl groups or carboxylic acid groups, and the component (D) more preferably has 3 or more hydroxyl groups.

  Moreover, in the resin composition of this invention, it is preferable to mix | blend (E) an epoxy compound. (E) As an epoxy compound, the compound which has an epoxy group whose epoxy equivalent which is the gram number of the compound containing 1 gram equivalent epoxy group is 1000 or less is mentioned preferably from the point of the hydrolytic improvement effect, and generally It may be used by being added to a thermoplastic resin.

  Further preferred are compounds having a glycidyl ester in the molecule, compounds having a glycidyl ether, and compounds having both a glycidyl ester and a glycidyl ether. These epoxy compounds are used alone or in combination of two or more, and in particular, a combination of a compound having a glycidyl ester and a compound having a glycidyl ether or a compound having both a glycidyl ester and a glycidyl ether is preferable. Specific epoxy compounds include resorching ricidyl ether, sorbitol polyglycidyl ether, diethylene glycol diglycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, polyglycerin polyglycidyl ether, acrylic glycidyl ether, sorbitan polyglycidyl ether, pt-butylphenyl glycidyl ether, phenyl glycidyl ether, bisphenol-A-diglycidyl ether, bisphenol-S-diglycidyl ether, diglycidyl dimer Ester, o-phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Glycol ester, neodecanoic acid glycidyl ester, terephthalic acid diglycidyl ester, soybean glycidyl esters, benzoic acid monoglycidyl ester, stearic acid monoglycidyl ester, lauric acid monoglycidyl ester, p- hydroxy benzoic acid glycidyl ester ether.

  (E) The compounding quantity of an epoxy compound is a range of 0.05-2.0 weight part of (E) component with respect to a total of 100 weight part of the resin composition of (A)-(C) component. From the viewpoint of decomposability and fluidity, it is preferably 0.1 to 1.0 part by weight.

  The polyester resin composition of the present invention usually contains resin components, flame retardants, mold release agents, phosphorus antioxidants, stabilizers, ultraviolet absorbers, colorants, lubricants and the like within a range not impairing the effects of the present invention. And small amounts of other polymers can be added.

  The resin component may be any resin that can be melt-molded. For example, polycarbonate resin, polyethylene terephthalate resin, polybutylene naphthalene dicarboxylate resin, polyethylene naphthalene dicarboxylate resin, polypropylene terephthalate resin, ABS resin (acrylonitrile / Butadiene / styrene copolymer), AS resin (acrylonitrile / styrene copolymer), hydrogenated or non-hydrogenated SBS resin (styrene / butadiene / styrene triblock copolymer) and hydrogenated or non-hydrogenated SIS resin (styrene) / Isoprene / styrene triblock copolymer), SEBS resin (hydrogenated styrene / butadiene / styrene triblock copolymer), polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic o Examples include fin resins, cellulose resins such as cellulose acetate, polyamide resins, polyacetal resins, polysulfone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, polyether imide resins, and the like. There is no need to be, and two or more kinds may be used in combination.

  Specific examples of flame retardants include brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and inorganic flame retardants, each of which can be used alone or in a mixture. Preferably, a mixture of a brominated flame retardant and an inorganic flame retardant can be used.

  Specific examples of brominated flame retardants used in the present invention include tetrabromobisphenol-A, tetrabromobisphenol-A derivatives, tetrabromobisphenol-A-epoxy oligomers or polymers, tetrabromobisphenol-A-carbonate oligomers or polymers, bromo Brominated epoxy resins such as fluorinated phenol novolac epoxy, poly (pentabromobenzyl polyacrylate), pentabromobenzyl polyacrylate, N, N′-ethylene-bis-tetrabromophthalimide and the like. Of these, tetrabromobisphenol-A-epoxy oligomers or polymers and tetrabromobisphenol-A-carbonate oligomers or polymers are preferred.

  As the inorganic flame retardant used in the present invention, magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, oxidation Tin, zinc borate and the like can be mentioned. Of these, antimony trioxide is preferable.

  Release agents include plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and polyethylene wax, castor oil and its Fatty waxes such as derivatives, fatty acids and derivatives thereof may be mentioned.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, and the like.

  Stabilizers include benzotriazole compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and benzophenone compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, trimethyl phosphate And phosphoric acid esters.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. In other words, the classification is for convenience and does not limit the action.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone-based ultraviolet absorbers typified by, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5 The benzotriazole type ultraviolet absorber represented by the condensate with-(2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. It can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  Examples of the colorant include organic dyes, organic pigments, and inorganic pigments. Other examples include fluorescent brighteners, phosphorescent pigments, fluorescent dyes, flow modifiers, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, and photochromic agents.

  In the thermoplastic resin composition of the present invention, these blending components are preferably dispersed uniformly, and any blending method can be used. A typical example is a method of melt-kneading at a temperature of 200 to 350 ° C. using a known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Each component may be mixed in advance and then melt kneaded. In addition, although it is better that the water | moisture content adhering to each component is less and it is desirable to dry beforehand, not all the components need to be dried.

  In the present invention, the screw structure used in the twin-screw extruder is a combination of full flight and kneading disk. In order to obtain the composition of the present invention, uniform kneading with a screw is required. . Therefore, the ratio of the total length (kneading zone) of the kneading disk to the total screw length is preferably in the range of 5 to 50%, and more preferably in the range of 10 to 40%.

  In the present invention, when melt-kneading, a preferred method of charging each component is as follows. (A) Polybutylene terephthalate resin (C) from a main charging port installed on the screw root side using an extruder having two charging ports. ) Olefin-based elastomer, (D) a polyfunctional compound having three or more functional groups, and other components as necessary, and supplied from a sub-inlet installed between the main inlet and the extruder tip (B) There is a method in which reinforcing fibers are supplied and melt mixed.

  The resin composition of the present invention can be molded by any method such as generally known injection molding, extrusion molding, blow molding, press molding, and spinning, and can be processed and used in various molded products. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. In particular, in the present invention, it is possible to process into an injection-molded product having a thin portion having a thickness of 0.01 to 1.0 mm by taking advantage of the excellent fluidity.

  In the present invention, the above-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods.

  Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blades, washer levers, window regulator handles, knobs for window regulator handles, passing light levers, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, food louvers, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, and other automotive connectors, electrical connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop housings and internal parts, CRT display housings , And internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, housings and internal parts of recording media (CD, DVD, PD, FDD, etc.) drives, copiers And electrical / electronic parts such as a facsimile housing and internal parts, a parabolic antenna, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases , Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brushes Electric and electronic parts such as holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels Thermal insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weed bags Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection Non-woven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow-release fertilizers, root-proof sheets, garden nets , Insect repellent nets, young tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage nets, incentive strings, windproof nets and other agricultural materials, paper diapers, sanitary products packaging materials, cotton swabs, towels, toilet seat wipes, etc. Medical products such as hygiene products, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical films, etc. Packaging films for supplies, calendars, stationery, clothing, food, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers, tableware, hot-fill containers, electronic Range cooking containers Cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lids Materials, envelopes with windows, fruit baskets, hand cut tapes, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fibers Various clothing such as composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tapes, prints, thermal Film for stencil printing, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, hot melt binder, magnetic material, zinc sulfide, electrode material powder, etc. Binder, optical element, conductive embossed tape IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair, table, It is useful as a cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on. Since the resin composition of the present invention has fluidity, mechanical properties, and thermal shock resistance, among them, an ignition hobbin, an ignition case, a clutch bobbin, a sensor housing, an idle speed control valve, a vacuum switching valve, an ECU housing, It is particularly useful for automotive parts applications such as vacuum pump cases and inhibitor switches.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  Abbreviations and contents of raw materials used in Examples and Comparative Examples are shown below.

(A) Polybutylene terephthalate resin A-1: “1100S” manufactured by Toray Industries, Inc.

(B) Reinforcing fiber B-1: Glass fiber “T120H” manufactured by Nippon Electric Glass Co., Ltd.

(C) Elastomer (C1) Copolymer of α-olefin and α, β-ethylenically unsaturated carboxylic acid or derivative thereof C-11: Ethylene / ethyl acrylate copolymer “A709” manufactured by Mitsui DuPont Co., Ltd.
(C2) Glycidyl group-containing copolymer comprising α-olefin and glycidyl ester of α, β-unsaturated acid C-21: Ethylene / methacrylate / glycidyl methacrylate copolymer “BF7M” manufactured by Sumitomo Chemical Co., Ltd.
C-3: Ethylene / 1-butene copolymer “Tuffmer A-4085” manufactured by Mitsui Chemicals, Inc.
C-4: Ethylene / glycidyl methacrylate copolymer “ETX-6” manufactured by Sumitomo Chemical Co., Ltd.

(D) Polyfunctional compound having three or more functional groups D-1: Glycerin (molecular weight 92, number of alkylene oxide units 0 per functional group, Tokyo Kasei)
D-2: Trimethylolpropane (molecular weight 134, 0 alkylene oxide units per functional group, ARDRICH)
D-3: Pentaerythritol (molecular weight 136, number of alkylene oxide units 0 per functional group, Tokyo Kasei)
D-4: Polyoxyethylene diglycerin (molecular weight 410, number of alkylene oxide units 1.5 per functional group, “SC-E450” manufactured by Sakamoto Yakuhin)
D-5: Oxyethylenetrimethylolpropane (molecular weight 266, number of alkylene oxide units 1 per functional group, “TMP-30U” manufactured by Nippon Emulsifier)
D-6: Polyoxyethylene pentaerythritol (molecular weight 400, number of alkylene oxide units per functional group 1.5, manufactured by Nippon Emulsifier “PNT-60U”)
D-7: Polyoxypropylene trimethylolpropane ether (“TMP-F32” manufactured by Nippon Emulsifier).

(E) Epoxy compound E-1: Bisphenol-A-diglycidyl ether “Epicoat 819” manufactured by Japan Epoxy Resin.

(F) Polyfunctional compound having less than three functional groups F-1: 1,6-hexanediol (ARDRICH)
F-2: 4,4′-dihydroxybiphenyl (Honshu Chemical).

  Moreover, the evaluation method of an Example and a comparative example is collectively shown below.

(1) Fluidity Using a strip-shaped molded product having a thickness of 1 mm and a width of 10 mm, the fluidity was judged. The injection conditions were a cylinder temperature of 250 ° C., a mold temperature of 40 ° C., and an injection pressure of 100 MPa.

(2) Cold and thermal shock resistance A molded product in which an iron core made of S35C with a length of 47 mm, a width of 47 mm, and a height of 27 mm is placed in a mold for insert molding and coated with a resin thickness of 1.5 mm by injection molding ( Using a THERMAL SHOCK CHAMBER TSA-100S cold heat tester manufactured by Tabai Espec Co., Ltd., the number of cycles at which cracks occur in the resin was measured under the condition of −40 ° C. × 1 hour to 130 ° C. × 1 hour.

(3) Impact characteristics Notched Charpy impact strength was measured according to ISO179.

(4) Bending characteristics According to ISO178, bending strength and bending elastic modulus were measured.

(5) Tensile properties Tensile strength and elongation at break were measured in accordance with ISO527-1,2.

(6) Hydrolysis resistance Tensile properties after 100 hours of hydrolysis at 121 ° C. and 100% RH were measured with HAST CHAMBER EHS-221M manufactured by TABAI ESPEC Co., Ltd. to evaluate the hydrolysis resistance.

[Examples 1 to 22]
The composition of the resin composition was changed as shown in Tables 1 and 2, and the components (A), (C), (D), (E), and other additives were all contained in the original loading part of the twin screw extruder. And the component (B) was melt-kneaded with a twin screw extruder having a screw diameter of 57 mmφ supplied from a sub-inlet installed between the main input and the tip of the extruder and set at a cylinder temperature of 250 ° C.

  The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter. Each pellet obtained was dried in a hot air dryer at 130 ° C. for 3 hours or more, and then a test piece was prepared to obtain fluidity, cold shock resistance, impact characteristics, bending characteristics, tensile characteristics, and hydrolysis resistance. Evaluation was performed. The results are shown in Tables 1 and 2. All of the obtained compositions were excellent in fluidity, cold shock resistance, impact properties, bending properties, tensile properties, and hydrolysis resistance.

  About Examples 1-3 and 12-22, the test piece according to ISO527-1 and 2 shape | molded with the cylinder temperature of 260 degreeC and the mold temperature of 80 degreeC was used, and TABAI ESPEC Co., Ltd. HAST CHAMBER EHS-221M No bleed-out was observed on the surface of the molded article even when the hydrolysis treatment at 121 ° C. and 100% RH was carried out for 50 hours. Furthermore, in Examples 12 and 20 to 22, in which D-7 having a trivalent hydroxyl group and containing a propylene oxide unit was added, no bleed out was observed on the surface of the molded product even when the above treatment was performed for 100 hours.

[Comparative Examples 1-8]
The composition of the resin composition was changed as shown in Table 3, and the components (A), (C), (D), (E), (F), and other additives were all incorporated into the twin-screw extruder. The component (B) was supplied from a secondary charging port installed between the main charging port and the tip of the extruder and melt kneaded in a twin screw extruder with a screw diameter of 57 mmφ set at a cylinder temperature of 250 ° C. .

  The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter. Each of the obtained pellets was dried for 3 hours or longer with a hot air dryer at 130 ° C., and then molded using the method described in the evaluation method and subjected to various evaluations. The results are shown in Table 3. The obtained composition was inferior in any of fluidity, thermal shock resistance, impact properties, bending properties, tensile properties, and hydrolysis resistance.

  For Comparative Examples 1-2 and 7, a test piece according to ISO527-1 and 2 molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. was used, and it was 121 by HAST CHAMBER EHS-221M manufactured by Tabai ESPEC Co., Ltd. When the hydrolysis treatment at 100 ° C. and 100% RH was carried out for 50 hours, remarkable bleedout was observed on the surface of the molded product.

Claims (7)

  (A) 48 to 88% by weight of polybutylene terephthalate resin, (B) 10 to 50% by weight of reinforcing fiber, (C) 100 parts by weight of the total resin composition consisting of 2.0 to 40% by weight of olefin elastomer (D) A thermoplastic polyester resin composition comprising 0.01 to 5 parts by weight of a polyfunctional compound having three or more functional groups.   (C) Olefin elastomer is (C1) a copolymer of α-olefin and α, β-ethylenically unsaturated carboxylic acid or derivative thereof, 1.0 to 20% by weight, (C2) α-olefin and α, β The thermoplastic polyester resin composition according to claim 1, which is a mixture of 1.0 to 20% by weight of a glycidyl group-containing copolymer comprising a glycidyl ester of an unsaturated acid.   (D) The thermoplastic polyester resin composition according to claim 1 or 2, wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units.   (D) The functional group of the polyfunctional compound having three or more functional groups is at least one group selected from a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. The thermoplastic polyester resin composition according to any one of claims 1 to 3.   (D) The thermoplastic polyester resin composition according to any one of claims 1 to 4, wherein the polyfunctional compound having three or more functional groups has a trifunctional or tetrafunctional hydroxyl group.   6. The composition according to any one of claims 1 to 5, wherein 0.05 to 2.0 parts by weight of (E) an epoxy compound is further added to 100 parts by weight of the total resin composition of components (A) to (C). A thermoplastic polyester resin composition.   A molded article comprising the thermoplastic polyester resin composition according to any one of claims 1 to 6.