JP5428327B2 - Thermoplastic polyester resin composition - Google Patents

Description

  The present invention relates to a thermoplastic polyester resin composition having excellent fluidity, mechanical properties, good appearance, and dimensional stability before and after heat treatment, and a molded article comprising the same, which are useful as electrical / electronic equipment parts, automobile parts, machine parts, and the like. .

  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 resin and polyethylene terephthalate resin, which are a kind of polyester resin, are highly reinforced with inorganic reinforcing materials and excellent in chemical resistance. Therefore, the industry such as connectors, relays and switches for automobiles and electrical / electronic devices. It is widely used as a material for molding products.

  However, in recent years, there has been an increasing demand for miniaturization and weight reduction of industrial molded products. For example, polybutylene terephthalate resin and polyethylene terephthalate resin used for automobiles and electrical / electronic equipment applications have improved mechanical properties. It is desired to improve the fluidity at the time of melting without lowering.

  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.

  Further, Patent Document 2 uses polybutylene terephthalate resin and polyester resin or amorphous resin having a slower crystallization rate than polybutylene terephthalate resin, so that it has excellent impact resistance and chemical resistance and has gloss. However, although a method for providing a molded article having a good surface appearance has been reported, there is a problem that fluidity is lowered.

Further, Patent Document 3 reports a resin composition comprising a thermoplastic polyester resin and a special layered silicate, a fibrous inorganic filler, and a plate-like inorganic substance, and has excellent mechanical properties and excellent dimensional accuracy. It was. However, the problem is that the surface appearance and the fluidity improving effect are insufficient.
Japanese Patent Laid-Open No. 7-304970 JP 2003-26908 A JP 2000-212421 A

  The object of the present invention is to maintain high mechanical properties and dimensional stability before and after heat treatment, and even if it is reinforced by adding an inorganic reinforcing material, it has sufficient surface appearance and fluidity, and can be used in automobiles, An object of the present invention is to provide a thermoplastic polyester resin composition that can be suitably used for electronic device applications and the like, 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 studies in order to solve such problems.

That is, the present invention
(1) (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, (C) a polyfunctional compound containing one or more alkylene oxide units and having three or more functional groups, and (D) an inorganic reinforcing material. A polyester-based resin composition containing 100% by weight of (A) + (B), 10% to 90% by weight of (A), 90% to 10% by weight of (B), and ( A) It is comprised from 0.01-5 weight part and (D) 1-150 weight part with respect to a total of 100 weight part of (B) , Furthermore, ethylene, propylene, butene-1, vinyl acetate , acrylic acid, methacrylic acid, acrylic acid esters, thermoplastic polyether containing a copolymer of at least one methacrylic acid ester is selected from the group consisting of an acid anhydride and glycidyl methacrylate Ether resin composition,
(2) (C) 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 as described in (1) above, wherein
(3) (D) The thermoplastic polyester resin composition according to (1) or (2), wherein the inorganic reinforcing material is a fibrous inorganic reinforcing material and / or a plate-like inorganic reinforcing material,
(4) The thermoplastic polyester resin composition according to any one of (1) to (3), wherein (D) the inorganic reinforcing material is glass fiber and / or glass flake,
(5) In any one of the above (1) to (4), the total of components (A) to (D) is 100 parts by weight, and (E) 0.05 to 2.0 parts by weight of the epoxy compound is blended. The thermoplastic polyester resin composition according to the description,
(6) A molded article comprising the thermoplastic polyester resin composition according to any one of (1) to (5) above.

  According to the present invention, a thermoplastic polyester that maintains high mechanical properties and dimensional stability before and after heat treatment, has good fluidity even when it is reinforced with an inorganic reinforcing material, and has an excellent surface appearance. A resin composition and a molded product comprising the same can be provided.

  The (A) polybutylene terephthalate resin used in the present invention is a normal polymerization method 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. In other words, the copolymer may contain other copolymer 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. Is 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 is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization can be used. Both can be applied both by transesterification and by direct polymerization, but continuous polymerization is preferred in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of cost, direct polymerization is preferable. In order to effectively advance the esterification reaction or transesterification reaction and the 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, Cyclohexahexylditin 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 (B) polyethylene terephthalate resin used in the present invention refers to a high molecular weight thermoplastic polyester resin having an ester bond in the main chain obtained by polycondensation using terephthalic acid as an acid component and ethylene glycol as a glycol component. In addition to this, as an acid component, isophthalic acid, adipic acid, oxalic acid, etc., as a glycol component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, Decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like is copolymerized to 20 mol% or less. And it can also be. In addition, the polyethylene terephthalate resin has a composition in which an intrinsic viscosity measured at 25 ° C. using an o-chlorophenol solvent is 0.36 to 1.60, particularly 0.45 to 1.15. It is suitable from the point of impact strength and moldability.

  Further, the blending amount of the thermoplastic polyester resin constituting the present invention is such that (A) is 10 to 90% by weight when the total of (A) polybutylene terephthalate and (B) polyethylene terephthalate resin is 100% by weight, (B) It needs to be 90 to 10% by weight. Here, when the blending amount of (A) is less than 10% by weight, the fluidity of the resin composition is inferior, and when it exceeds 90% by weight, the dimensional stability and the surface appearance are deteriorated. The blending amount of (A) is preferably 20 to 80% by weight. When the blending amount of (B) is less than 10% by weight, the dimensional stability and surface appearance of the resin composition are inferior, and when it exceeds 90% by weight, the fluidity is lowered. The blending amount of (B) is preferably 20 to 80% by weight.

  Further, polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic with respect to 100 parts by weight of a mixture of (A) polybutylene terephthalate resin 10 to 90% by weight and (B) polyethylene terephthalate resin 90 to 10% by weight. One or more kinds of polyester resins such as liquid crystal polyester and polycyclohexanedimethylene terephthalate resin may be blended, and the blending amount is an amount within a range in which the effect of the present invention is not greatly reduced.

  The compound (C) having three or more functional groups used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. The component (C) is not limited as long as it has three or more functional groups in the molecule, and may be a low molecular compound or a high molecular weight polymer. Such a functional group of component (C) 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, Among these, it is preferable to have three or more functional groups that are the same or different.

  (C) As a preferred example of a 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- Xanthriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylol Propane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methyl glucoside, sorbitol, mannitol, sucrose, 1,3,5-trihydroxybenzene , Include polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24 such as 2,4-trihydroxybenzene. Of these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol having a branched structure are preferable from the viewpoint of fluidity and mechanical properties.

Compounds having three or more functional groups, preferably those having three or four hydroxyl groups. More preferably those having three hydroxyl groups. With the one having three or four hydroxyl groups, in particular the fluidity is improved, also eliminating the molded article surface during heat-moisture treatment of bleeding coming out component (C). 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.

  (C) As a preferred example of a 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 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 Polycarboxylic acid or acrylic acid, such as 8-tetracarboxylic acid, include polymers such as methacrylic acid, it 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.

  (C) When the functional group of a 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, both of which are primary Or it is more preferable that it is a secondary amine, and it is especially preferable that all are primary amines. (C) As a preferred example of a compound having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, , 2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetramino Benzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4,5,8 -Te La Mino naphthalene, and the like. 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.

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

  (C) As a preferred example of a 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)), decantrie Examples thereof include isocyanate, undecane triisocyanate, and dodecane triisocyanate.

  (C) As a preferable example of a 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, or the three or more groups described above And ester derivatives of compounds having a carboxylic acid group.

  (C) As a preferable example of the 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 is exemplified.

  From the viewpoint of fluidity and mechanical properties, it is preferable that the compound (C) 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 an alkylene oxide unit. The fluidity and the bleeding out in which the component (C) 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.

  (C) The number of alkylene oxide units contained in the compound having three or more functional groups used in the present invention is preferably 0.1 to 20 alkylene oxide units per functional group, 0.5 to 10 is more preferable, and 1 to 5 is more preferable.

  As a preferred example of the compound having three or more functional groups (C) 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 diglycerol, ( Poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) oxyp Pyrenetrimethylolpropane, (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, (poly) io Simethylenedipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxypropylene trimethylolpropane ether, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose (Poly) oxyethylene glucose, (poly) oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, (poly) oxytetramethylene glucose, and the like.

  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 Cyclohe containing 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 a compound having three or more functional groups (C) containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxy Propylene glycerin, (poly) oxyethylene diglycerin, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) Examples include oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, and (poly) oxypropylene dipentaerythritol. When the functional group is a carboxylic acid, (poly) ethyl Propane-1,2,3-tricarboxylic acid containing propane oxide unit, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide unit, trimellitic acid containing (poly) ethylene oxide unit, (poly) propylene oxide Trimellitic acid containing 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) propylene And cyclohexane-1,3,5-tricarboxylic acid containing an 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 (poly 1,3,5-triaminocyclohexane containing ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, ( 1,3,5-triaminobenzene containing poly) propylene oxide units.

  The compound (A) having three or more functional groups used in the present invention reacts with the component (A) and the component (B) and is introduced into the main chain and side chain of the component (A) and the component (B). The structure at the time of blending may be maintained without reacting with the component (A) and the component (B). (C) The reaction rate of the functional group of the 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 compound (C) having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and more preferably 5000 m · Pa or less in terms of fluidity and mechanical properties. It is 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 during 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 compound (C) having three or more functional groups used in the present invention is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. It is more preferable that it is in the range of 200 to 3000. In the present invention, (C) Mw of a compound having three or more functional groups is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. .

  The moisture content of the compound (C) having 3 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. There is no particular lower limit for the moisture content of the component (C). A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, the compounding amount of the compound (C) having three or more functional groups is 0.01 to 5 weights of the (C) component with respect to 100 parts by weight of the total of the (A) (A) + (B) components. It is essential that the amount be in the range of 0.1 part 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. More preferred.

  In the compound (C) having three or more functional groups used in the present invention, the component (C) preferably has at least one hydroxyl group or carboxylic acid group from the viewpoint of fluidity. It is more preferable that the component has three or more hydroxyl groups or carboxylic acid groups, and it is more preferable that the component (C) has three or more hydroxyl groups.

  The (D) inorganic reinforcing material used in the present invention may have various shapes, such as glass fiber, carbon fiber, aramid fiber, metal fiber, asbestos, whisker and other fibrous fillers, glass beads, and glass flakes. And natural or synthetic fillers in the form of spherical plates or amorphous powders such as talc, mica, clay, wallast, and metal powder.

  The inorganic reinforcing material (D) used in the present invention is preferably a fibrous inorganic reinforcing material and / or a plate-like inorganic reinforcing material, and more preferably a glass fiber from the viewpoint of mechanical strength and dimensional stability. , Asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elestite, plaster One or more kinds selected from fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and the like can be mentioned, and glass fiber is more preferable. More preferably, the plate-like inorganic reinforcing material includes at least one selected from glass flakes, non-swellable mica, graphite, and metal foil, and glass flakes are more preferable.

  The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. As the fibrous inorganic reinforcing material, those having an average fiber diameter of 2 to 50 μm can be preferably used, and those that are usually surface-treated with aminosilane or epoxysilane are more effective.

  The glass flakes are not particularly limited as long as they are generally used for resin reinforcement, and are coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. In addition, those having an average particle size of 3 to 3000 μm can be preferably used, and those usually surface-treated with aminosilane or epoxysilane are more effective. The average particle diameter here means that measured by a laser scattering method.

  In addition, the blending amount of (D) is preferably 1 to 150 parts by weight, and 10 to 100 parts by weight with respect to a total of 100 parts by weight of (A) + (B) from the viewpoints of fluidity, surface appearance, and dimensional stability. Part is more preferred.

  Moreover, in the resin composition of this invention, you may mix | blend (E) 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 the range of 0.05-2.0 weight part of (E) component with respect to a total of 100 weight part of (A) + (B), hydrolyzability and fluidity | liquidity. From this point, it is preferably 0.1 to 1.0 part by weight.

The polyester resin composition of the present invention includes a resin component, an elastomer component, a flame retardant, a release agent, a phosphorus-based antioxidant, a stabilizer, an ultraviolet absorber, a colorant, and a lubricant as long as the effects of the present invention are not impaired. Conventional additives such as 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, polybutylene naphthalene dicarboxylate resin, polyethylene naphthalene dicarboxylate resin, polypropylene terephthalate resin, ABS resin (acrylonitrile / butadiene / styrene copolymer) Polymer), AS resin (acrylonitrile / styrene copolymer), hydrogenated or unhydrogenated SBS resin (styrene / butadiene / styrene triblock copolymer) and hydrogenated or unhydrogenated SIS resin (styrene / isoprene / styrene). Triblock copolymer), SEBS resin (hydrogenated styrene / butadiene / styrene triblock copolymer), polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin, cellulose acetate, etc. Cellulosic resin, polyamide resin, polyacetal resin, polysulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, polyetherimide resin, etc., and the resin to be mixed is not necessarily one type. You may use together and use a seed | species or more.

  As an elastomer component, an ethylene (co) polymer or a core-shell rubber can be blended for the purpose of improving toughness such as impact strength. Examples of the ethylene (co) polymer include high-density polyethylene, low-density polyethylene, Examples include ethylene polymers such as low density polyethylene and / or ethylene copolymers. The above ethylene copolymers are obtained by copolymerizing ethylene and monomers copolymerizable therewith, and can be copolymerized. Examples of such monomers include propylene, butene-1, vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, ester acids thereof, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. The ethylene copolymer can be usually produced by a known method. Specific examples of the ethylene copolymer include ethylene / propylene, ethylene / butene 1, ethylene / vinyl acetate, ethylene / ethyl acrylate, ethylene / methyl acrylate, and ethylene / ethyl methacrylate acrylate. A copolymer obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate with the above ethylene (co) polymer is also preferably used. These may be used alone or in combination of two or more, and may be used in combination with one or more of the above ethylene (co) polymers. Among ethylene (co) polymers, a copolymer obtained by grafting or polymerizing an acid anhydride or glycidyl methacrylate to polyethylene is preferably used because of its good compatibility with PBT.

  The core-shell rubber is a multi-layered polymer comprising a rubber component in the core layer and a thermoplastic resin component in the outermost shell layer. For example, the core layer is a dimethylsiloxane / butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer, the core layer is a butanediene / styrene polymer and the outermost layer is a methyl methacrylate polymer, and the core layer Is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer. Furthermore, a polymer in which either one or both of the rubber layer and the outermost layer contain a glycidyl methacrylate unit is exemplified.

  The flame retardant is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin. Specifically, brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants are used. , Silicone flame retardants, inorganic flame retardants, and the like. These can be used alone or in the form of a mixture, and preferably a mixture of a brominated flame retardant and an inorganic flame retardant.

  Specific examples of the brominated flame retardant 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.

  Mold 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 of the kneading disk (kneading zone) to the total length of the screw 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 preferable method for charging each component is as follows. (A) Polybutylene terephthalate resin (B) from a main charging port installed on the screw base side using an extruder having two charging ports. ) Polyethylene terephthalate resin, (C) a polyfunctional compound having three or more functional groups, and other components as needed, and supplied from a sub-inlet installed between the main inlet and the extruder tip (D) A method of supplying an inorganic reinforcing material and melt-mixing it can be mentioned.

  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 blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, 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, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection 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 Nonwoven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow release fertilizers, root prevention 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: Polybutylene terephthalate resin: Inherent viscosity 0.85 ("Torcon" 1100T manufactured by Toray Industries, Inc.).

(B) Polyethylene terephthalate resin B-1: Polyethylene terephthalate resin: Intrinsic viscosity 0.65 (Mitsui PET J005, Mitsui PET Resin Co., Ltd.).

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

(D) Inorganic reinforcement D-1: Glass fiber (Nittobo Co., Ltd. 3J941)
D-2: Carbon fiber (Torayca T900 manufactured by Toray Industries, Inc.)
D-3: Glass flake (average particle diameter 90 μm)
D-4: Mica (average particle size 80 μm).

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

(F) Copolymer of elastomer α-olefin and α, β-ethylenically unsaturated carboxylic acid or derivative thereof F-1: ethylene / ethyl acrylate copolymer (“A709” manufactured by Mitsui DuPont Co., Ltd.)
Glycidyl group-containing copolymer consisting of α-olefin and glycidyl ester of α, β-unsaturated acid F-2: ethylene / methacrylate / glycidyl methacrylate copolymer (“BF7M” manufactured by Sumitomo Chemical Co., Ltd.)
F-3: Ethylene / 1-butene copolymer (“Tuffmer A-4085” manufactured by Mitsui Chemicals, Inc.)
F-4: Ethylene / glycidyl methacrylate copolymer (“ETX-6” manufactured by Sumitomo Chemical Co., Ltd.).

(G) Flame retardant G-1: Tetrabromobisphenol-A-polycarbonate oligomer (“FG-7500” manufactured by Teijin Chemicals Ltd.)
G-2: Antimony trioxide (“PATOX-MK” manufactured by Nippon Seiko Co., Ltd.).

(H) Compound H-1 having less than three functional groups: 1,6-hexanediol (ARDRICH)
H-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) Surface appearance <Center line average roughness Ra>
The surface roughness of Mitutoyo Corp. is selected from any 10 locations of the mirror surface of the mirror surface square plate that has been injection-molded under conditions of a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., and a surface roughness of the mold mirror surface of 0.03 s. The center line average roughness Ra defined in JIS B0601 was measured with a thickness measuring device “SURFTEST-500” and averaged. The lower the number, the better the surface appearance.

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

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

(5) 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.

(6) Dimensional stability A box-shaped molded product having a width of 30 mm, a height of 30 mm, a depth of 30 mm, and a thickness of 1.5 mm is molded from a side pin gate and left for 24 hours in a 23%, 50% RH environment. The amount of inclining of the surface on the side opposite to the gate side was measured five times with a three-dimensional dimension measuring machine made by MITUTOYO, and the average was taken as the amount of inner warpage, and the dimensional stability was evaluated. See Figure 1 for box molded products.

(7) Dimensional stability after heat treatment A box-shaped molded product (Fig. 1) having a width of 30 mm, a height of 30 mm, a depth of 30 mm, and a thickness of 1.5 mm is molded from the side pin gate and is 24% in a 23% and 50% RH environment. After standing for an hour, annealed at 130 ° C. for 2 hours. After that, it was left in a 23%, 50% RH environment for 24 hours, and the amount of inclining of the side of the side facing away from the gate side was measured five times with a 3D dimensional measuring machine made by MITUTOYO, and the average was taken as the amount of inward warping. The dimensional stability was evaluated.

(8) Moisture and heat resistance test Using a test piece according to ISO527-1, molded at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, it was treated for 100 hours in an environment of 121 ° C, 100% RH, 2 atm. If the surface of the molded product is visually observed and liquid adheres to the surface of the molded product, Δ. If the liquid is slightly attached to the surface of the molded product, Δ to ○. If the liquid did not adhere to the surface of the molded product, it was marked as ◯.

[Examples 1-4, Comparative Examples 9-33 ]
The composition of the resin composition is changed as shown in Table 1, Table 2, and Table 4, and the components (A), (B), (C), (E), (F), (G), and other additions are added. All of the agent is supplied from the main loading part of the twin screw extruder, and the component (D) is supplied from the auxiliary charging port installed between the main charging port and the tip of the extruder, and the cylinder temperature is set to 260 ° C. Melt kneading was performed with a twin screw extruder.

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. After fluidity, surface appearance, impact properties, tensile properties, hydrolysis resistance, dimensional stability, heat treatment The dimensional stability was evaluated. The results are shown in Table 1, Table 2 and Table 4 . All of the obtained compositions were excellent in fluidity, surface appearance, impact properties, tensile properties, hydrolysis resistance, dimensional stability, and dimensional stability after heat treatment.

In Comparative Example 9 , Comparative Example 21 , and Comparative Examples 30 to 33 , the type and amount of the C component are different. It was found that the addition of C-7 further improved the adhesion of the liquid on the surface of the molded article after the heat and humidity resistance test.

[Comparative Examples 1-8]
As shown in Table 3, the composition of the resin composition was changed, and all the components (A), (B), (C), (H) and other additives were supplied from the original loading section of the twin screw extruder. The component (D) 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 having 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 obtained composition was inferior in any of fluidity, surface appearance, impact properties, tensile properties, hydrolysis resistance, dimensional stability, and dimensional stability after heat treatment.

The schematic plan view of the box formation type | mold product for curvature amount measurement is shown. A schematic side view of a box-shaped product for warpage measurement is shown. The enlarged schematic plan view of the box formation type | mold part of curvature amount measurement is shown.

Explanation of symbols

1: Gate 2: Warpage amount

Claims (6)

(A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C) a polyfunctional compound containing one or more alkylene oxide units and having three or more functional groups, (D) a polyester containing an inorganic reinforcing material A resin composition comprising (A) + (B) as 100% by weight, (A) 10 to 90% by weight, (B) 90 to 10% by weight, and (A) + It is composed of (C) 0.01 to 5 parts by weight and (D) 1 to 150 parts by weight with respect to a total of 100 parts by weight of (B) , and further ethylene, propylene, butene-1, vinyl acetate, acrylic acid , methacrylic acid, acrylic acid esters, thermoplastic polyester containing a copolymer of at least one methacrylic acid ester is selected from the group consisting of an acid anhydride and glycidyl methacrylate Fat composition.   (C) 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 claim 1.   (D) The thermoplastic polyester resin composition according to claim 1 or 2, wherein the inorganic reinforcing material is a fibrous inorganic reinforcing material and / or a plate-like inorganic reinforcing material.   (D) The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein the inorganic reinforcing material is glass fiber and / or glass flake.   The thermoplastic polyester resin according to any one of claims 1 to 4, comprising 100 parts by weight of the total of components (A) to (D) and 0.05 to 2.0 parts by weight of (E) an epoxy compound. Composition.   A molded article comprising the thermoplastic polyester resin composition according to any one of claims 1 to 5.

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