JP2010006852A - Thermoplastic polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polybuthylene naphthalate (PBN) composition excellent in high-impact characteristic at a low temperature, hydrolysis resistance, heat resistance and dimensional accuracy. <P>SOLUTION: The thermoplastic polyester resin composition is prepared by compounding a filler (E) of 0 to 50 pts.mass, a flame-retardant (F) of 0 to 50 pts.mass and an anti-dripping agent (G) of 0 to 3 pts.mass to a resin composition of 100 pts.mass comprising: a polybuthylene naphthalate resin (A) having intrinsic viscosity of 0.60 to 1.30 dL/g and terminal carboxy group concentration of 30.0 eq/10<SP>3</SP>kg or less, of 15 to 80 pts.mass; a butadiene-type rubber-containing graft copolymer (B) made by graft-polymerizing at least one kind of monomer selected from vinyl cyanide compound, aromatic alkenyl compound and vinyl type compounds other than the vinyl cyanide compound and aromatic alkenyl compound to a rubbery polymer composed of butadiene units, of 10 to 50 pts.mass; a rubbery elastomer (C) besides (B), of 1 to 10 pts.mass; a vinyl cyanide type polymer (D) besides (B), having at least one kind selected from vinyl cyanide compound, aromatic alkenyl compound and vinyl type compounds other than the vinyl cyanide compound and aromatic alkenyl compound as a constitutional unit, of 4 to 74 pts.mass. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic polyester resin composition. More specifically, the present invention relates to a thermoplastic polyester resin composition excellent in impact resistance, thermal stability, hydrolysis resistance, and dimensional accuracy, and injection molding the thermoplastic polyester resin composition. It relates to a molded product.

  Thermoplastic polyester resins represented by polybutylene terephthalate resin (hereinafter referred to as PBT) are generally excellent in mechanical and physical properties, and are widely used in automobile parts, electrical / electronic parts, mechanical parts, etc. Has been. However, PBT has low impact resistance, especially notched impact strength, and a large molding shrinkage. Therefore, for the purpose of improving the impact resistance and dimensional accuracy of PBT, a method of blending ABS resin with PBT as described in Japanese Patent Publication No. 51-25261 has been proposed. However, the resin composition comprising PBT and ABS resin is insufficient in the effect of improving the molding shrinkage ratio and the warpage of the molded product, and the mechanical strength is caused by hydrolysis of PBT under high temperature and high humidity conditions. Has the problem of lowering.

  On the other hand, polybutylene naphthalate resin (hereinafter referred to as PBN or polybutylene naphthalate) has excellent mechanical and physical properties like other thermoplastic polyester resins. Compared to PBT, it has the characteristics of being superior in heat and humidity resistance, chemical resistance, gas barrier properties, hydrolysis resistance and the like. However, PBN, like other thermoplastic polyester resins, is inferior in impact resistance. Therefore, with the spread of thinning due to downsizing and weight reduction of parts, PBN also has impact resistance as in PBT. A shortage has been pointed out and improvements are needed.

  As a technique for improving the impact resistance characteristics of PBN, a method of blending glycidyl methacrylate / anhydride / α-olefin with PBN described in JP-A-5-339478, described in JP-A-6-145484. A method of blending an N-butyl acrylate rubber-containing methyl methacrylate graft copolymer with PBN, a method of blending glycidyl methacrylate / alkyl acrylate / α-olefin with PBN described in JP-A-6-157882, A method of blending PBN elastomer with PBN described in JP-A-6-172626, a method of blending styrene / ethylene / butylene / styrene block copolymer with PBN described in JP-A-6-240119, It is described in Kaihei 7-82443 A method of blending ABS resin with such PBN, a method of blending glycidyl methacrylate / α-olefin / vinyl acetate copolymer with PBN described in JP-A-9-104807, JP-A-2006-152062 The method etc. which mix | blend an olefin type elastomer with described PBN are proposed.

Japanese Patent Publication No.51-025261 JP 05-339478 A Japanese Patent Laid-Open No. 06-145484 Japanese Patent Laid-Open No. 06-157882 Japanese Patent Laid-Open No. 06-172626 Japanese Patent Laid-Open No. 06-240119 JP 07-084443 A Japanese Patent Laid-Open No. 09-104807 JP 2006-152062 A

However, according to the various methods described above, although the impact resistance near room temperature is excellent, it is difficult to say that the impact resistance at a low temperature of 0 ° C. or lower is sufficiently improved.
An object of the present invention is to provide a PBN composition excellent in impact resistance, hydrolysis resistance, heat resistance, and dimensional accuracy.

  In view of the problems of the prior art, the present inventors diligently studied a resin composition excellent in impact resistance, hydrolysis resistance, heat resistance, and dimensional accuracy, and reached the present invention.

That is, the present invention relates to (A) 15-80 parts by mass of a polybutylene naphthalate resin having an intrinsic viscosity of 0.60 to 1.30 dL / g and a terminal carboxyl group concentration of 30.0 eq / 10 ³ kg or less.
(B) At least one monomer selected from a vinyl cyanide compound, an aromatic alkenyl compound, and a vinyl compound other than the vinyl cyanide compound and the aromatic alkenyl compound as a rubbery polymer composed of butadiene units. 10-50 parts by mass of a butadiene rubber-containing graft copolymer obtained by graft polymerization of
(C) 1 to 10 parts by mass of a rubber-like elastic body other than (B),
(D) Vinyl polymers 4 to 4 other than (B) having at least one selected from vinyl cyanide compounds, aromatic alkenyl compounds, and vinyl compounds other than vinyl cyanide compounds and aromatic alkenyl compounds as constituent units (E) 0 to 50 parts by mass of filler, with respect to 100 parts by mass of the resin composition comprising 74 parts by mass,
(F) It exists in the thermoplastic polyester resin composition formed by mix | blending 0-50 mass parts of flame retardants, and (G) 0-3 mass parts of anti-dripping agents.

  The thermoplastic polyester resin composition of the present invention has good impact resistance and thermal stability, and a molded product obtained from the resin composition can withstand high and low temperature environments and is suitable for automobile parts, mechanism parts, etc. It is.

  The dicarboxylic acid component constituting the (A) polybutylene naphthalate resin (hereinafter referred to as PBN or polybutylene naphthalate) used in the thermoplastic polyester resin composition of the present invention includes 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid as a main component, but other dicarboxylic acids can be used in combination as long as the properties of PBN are not impaired. For example, terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, etc. Examples include aromatic dicarboxylic acids, adipic acid, sebacic acid, succinic acid, oxalic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, and one or more of these may be used. Well, you can choose arbitrarily according to the purpose. The range that does not impair the properties of PBN is 30 mol% or less, preferably 20 mol% or less, based on the total dicarboxylic acid component.

  The ester-forming derivative of dicarboxylic acid constituting (A) PBN used in the thermoplastic polyester resin composition of the present invention is mainly composed of dimethyl 2,6-naphthalenedicarboxylate and dimethyl 2,7-naphthalenedicarboxylate. However, other dicarboxylic acid ester-forming derivatives can be used in combination as long as the properties of PBN are not impaired. For example, terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, etc. Lower dialkyl esters of aromatic dicarboxylic acids, lower dialkyl esters of cycloaliphatic dicarboxylic acids such as cyclohexane dicarboxylic acid, lower dialkyl esters of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, oxalic acid, etc. One or more of these may be used and can be arbitrarily selected according to the purpose. The range that does not impair the properties of PBN is 30 mol% or less, preferably 20 mol% or less, based on the ester-forming derivative component of all dicarboxylic acids.

  Preferred examples of the ester-forming derivative of dicarboxylic acid constituting (A) PBN used in the thermoplastic polyester resin composition of the present invention also include lower dialkyl esters of other dicarboxylic acids. As the lower dialkyl ester of the dicarboxylic acid, it is preferable that dimethyl ester is a main component. However, as long as the characteristics of PBN are not impaired, one or more of diethyl ester, dipropyl ester, dibutyl ester and the like are used. It may be used and can be arbitrarily selected according to the purpose. The range that does not impair the properties of PBN is 30 mol% or less, preferably 20 mol% or less, based on the lower dialkyl ester-forming derivative component of all dicarboxylic acids.

  Further, a tri- or higher functional carboxylic acid component such as a small amount of trimellitic acid may be used, and a small amount of an acid anhydride such as trimellitic anhydride may be used. Further, a small amount of hydroxycarboxylic acid such as lactic acid or glycolic acid or an alkyl ester thereof may be used and can be arbitrarily selected depending on the purpose.

  The glycol component used in (A) PBN constituting the thermoplastic polyester resin composition of the present invention is mainly composed of 1,4-butanediol, but is used in combination with other glycol components as long as the properties of PBN are not impaired. can do. For example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, poly (oxy) ethylene glycol, poly One kind or two or more kinds of alkylene glycols such as (oxy) tetramethylene glycol and poly (oxy) methylene glycol may be used and can be arbitrarily selected according to the purpose. Furthermore, a small amount of a polyhydric alcohol component such as glycerin may be used. A small amount of an epoxy compound may be used. The range that does not impair the properties of PBN is 30 mol% or less, preferably 20 mol% or less, based on the total glycol component.

  The amount of the glycol component used is preferably 1.1 mol times or more and 1.4 mol times or less with respect to the dicarboxylic acid or the ester-forming derivative of dicarboxylic acid. When the amount of the glycol component used is less than 1.1 mole times, the esterification or transesterification reaction does not proceed sufficiently, which is not preferable. In addition, when the amount exceeds 1.4 mol times or more, the reason is not clear, but the reaction rate is slow, and the amount of by-products such as tetrahydrofuran from the excessive glycol component is undesirably increased.

  The titanium compound used as a polymerization catalyst component in (A) PBN constituting the thermoplastic polyester resin composition of the present invention is preferably a tetraalkyl titanate, specifically tetra-n-propyl titanate, tetraisopropyl titanate, tetra -N-butyl titanate, tetra-sec-butyl titanate, tetra-t-butyl titanate, tetra-t-hexyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate and the like, and these mixed titanates are used. Also good. Among these titanium compounds, tetra-n-propyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate are particularly preferable, and tetra-n-butyl titanate is most preferable.

  The addition amount of the titanium compound is preferably 10 ppm or more and 60 ppm or less, more preferably 15 ppm or more and 30 ppm or less as the titanium atom content in the produced PBN. When the titanium atom content in the produced PBN exceeds 60 ppm, the color tone and thermal stability of the thermoplastic polyester resin composition of the present invention are not preferred. On the other hand, when the titanium atom content is 10 ppm or less, good polymerization activity cannot be obtained, and PBN having a sufficiently high intrinsic viscosity cannot be obtained.

  Moreover, in the range which does not impair the characteristic of (A) PBN which comprises the thermoplastic polyester resin composition of this invention, for example, alkyl titanates other than tetraalkyl titanates, such as octaalkyl trititanate or hexaalkyl dititanate, titanium acetate, Weak acid salts of titanium such as titanium oxalate, titanium oxide such as titanium oxide, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydro Oxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin di Roraido, tributyltin chloride, dibutyltin sulfide, may be used organic tin compounds such as butyl hydroxy tin oxide. Furthermore, potassium chloride, potassium alum, potassium formate, tripotassium citrate, dipotassium hydrogen citrate, potassium dihydrogen citrate, potassium gluconate, potassium succinate, potassium butyrate, dipotassium oxalate, potassium hydrogen oxalate, stearic acid Potassium, potassium phthalate, potassium hydrogen phthalate, potassium metaphosphate, potassium malate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium nitrite, potassium benzoate, potassium hydrogen tartrate, potassium bicarbonate , Potassium biphthalate, potassium bitartrate, potassium bisulfate, potassium nitrate, potassium acetate, potassium hydroxide, potassium carbonate, sodium potassium carbonate, potassium hydrogen carbonate, potassium lactate, potassium hydrogen sulfate potassium sulfate, sodium chloride, sodium formate Lithium, trisodium citrate, disodium hydrogen citrate, sodium dihydrogen citrate, sodium gluconate, sodium succinate, sodium butyrate, sodium trisulfate, sodium hydrogen oxalate, sodium stearate, sodium phthalate, phthalic acid Sodium hydrogen, sodium metaphosphate, sodium malate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium nitrite, sodium benzoate, sodium hydrogen tartrate, sodium bioxalate, sodium biphthalate, Sodium bitartrate, sodium bisulfate, sodium nitrate, sodium acetate, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium lactate, sodium sulfate, sodium hydrogen sulfate, lithium chloride, lithium formate , Trilithium citrate, dilithium hydrogen citrate, lithium dihydrogen citrate, lithium gluconate, lithium succinate, lithium butyrate, dilithium oxalate, lithium hydrogen oxalate, lithium stearate, lithium phthalate, phthalic acid Lithium hydrogen, lithium metaphosphate, lithium malate, trilithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, lithium nitrite, lithium benzoate, lithium hydrogen tartrate, lithium heavy oxalate, lithium biphthalate, Lithium metal tartrate, lithium bisulfate, lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, lithium lactate, lithium sulfate, lithium hydrogen sulfate and other alkali metal salts, calcium chloride, calcium formate, calcium succinate, Calcium butyrate , Calcium oxalate, calcium stearate, calcium phosphate, calcium nitrate, calcium acetate, calcium hydroxide, calcium carbonate, calcium lactate, calcium sulfate, magnesium chloride, magnesium formate, magnesium succinate, magnesium butyrate, magnesium oxalate, magnesium stearate, One or more of alkali metal salts or alkaline earth metal salts such as magnesium phosphate, magnesium nitrate, magnesium acetate, magnesium hydroxide, and magnesium carbonate may be combined with the titanium compound.

  (A) PBN constituting the thermoplastic polyester resin composition of the present invention comprises a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and / or an ester-forming derivative thereof, and a glycol component mainly composed of 1,4-butanediol. Is produced via an esterification or transesterification reaction step and a subsequent polycondensation reaction step in the presence of a titanium compound, but at the end of the esterification or transesterification reaction, It is preferable that it exists in the range, and it is more preferable that it is 180 degreeC or more and 210 degrees C or less. When the temperature at the end of the esterification reaction or transesterification reaction exceeds 220 ° C., the reaction rate increases, but it is not preferable because by-products such as tetrahydrofuran increase. On the other hand, if the temperature is less than 180 ° C, the reaction does not proceed.

  The reaction product (bisglycol ether and / or its low polymer) obtained by esterification or transesterification is reduced to 0.4 kPa (3 Torr) or less at a temperature not lower than the melting point of PBN and not higher than 270 ° C. Preference is given to polycondensation below. If the polycondensation reaction temperature exceeds 270 ° C., the reaction rate is rather lowered, and coloring is increased, which is not preferable.

  In the polycondensation reaction, a catalyst usually used as a polymerization catalyst can be used in combination with the titanium compound, but the titanium compound is preferably used as a common catalyst for esterification or transesterification and polycondensation reactions. . When other catalysts are used in combination, the coloration of PBN becomes large, and the color tone of the thermoplastic polyester resin composition is also lowered, which is not preferable. Also, the polycondensation reaction rate is not much different from the case where the titanium compound is used alone, and the combined use effect cannot be obtained.

The terminal carboxyl group concentration in (A) PBN constituting the thermoplastic polyester resin composition of the present invention is 30.0 eq / 10 ³ kg or less, preferably 0.1 eq / 10 ³ kg or more, 25.0 eq / 10. ³ kg. When the terminal carboxyl group concentration exceeds 30.0 eq / 10 ³ kg, the thermal stability and hydrolyzability are lowered, and the thermal stability and hydrolyzability of the thermoplastic polyester resin composition are also lowered.

  The intrinsic viscosity of (A) PBN constituting the thermoplastic polyester resin composition of the present invention is preferably 0.60 to 1.30 dL / g from the viewpoint of mechanical strength and moldability. When the intrinsic viscosity is less than 0.60 dL / g, the mechanical strength is inferior, and when it exceeds 1.30 dL / g, the fluidity is lowered and the molding processability is inferior.

  (A) PBN which comprises the thermoplastic polyester resin composition of this invention can also perform a solid-phase polymerization reaction through a polycondensation reaction. The solid phase polymerization reaction can be performed using a known method. The solid phase polymerization reaction temperature is preferably 180 ° C to 230 ° C, more preferably 190 ° C to 220 ° C. If the solid phase polymerization reaction temperature is less than 180 ° C., the solid phase polymerization reaction rate is slow and the solid phase polymerization reactivity is poor. Moreover, when it exceeds 230 degreeC, solid-phase polymerization reactivity will improve, but since there exists a possibility that the color tone of PBN after a solid-phase polymerization reaction may fall, it is unpreferable.

  The usage-amount of (A) PBN in this invention is 15-80 mass parts in 100 mass parts of total amounts of resin component (A), (B), (C), (D) component. If it is less than 15 parts by mass, the chemical resistance is inferior, and if it exceeds 80 parts by mass, the impact resistance is inferior.

  The (B) butadiene rubber-containing graft copolymer used in the thermoplastic polyester resin composition of the present invention comprises a rubbery polymer composed of butadiene units, a vinyl cyanide compound, an aromatic alkenyl compound, and cyanide. It is obtained by graft polymerization of at least one monomer selected from vinyl compounds other than vinyl chloride compounds and aromatic alkenyl compounds. The rubbery polymer composed of butadiene units contains 50% by mass or more of polybutadiene units in the butadiene-based rubber-containing graft copolymer, and other rubbery polymers of inferior amounts include styrene units, acrylonitrile units, and the like. Examples of the copolymer include styrene-butadiene copolymer and acrylonitrile-butadiene copolymer.

  The content of the rubber-like polymer composed of butadiene units in the graft copolymer is preferably 50 to 80% by mass. When the amount is less than 50% by mass, the content of the resin component that is not graft-polymerized tends to increase, and when it exceeds 80% by mass, it is difficult to recover the graft copolymer as a powder.

  Examples of the vinyl cyanide compound used for graft polymerization include acrylonitrile and methacrylonitrile. These compounds can be used alone or in combination. The proportion of the vinyl cyanide compound in the total amount of monomers used for graft polymerization is preferably 15 to 40% by mass. If the amount is less than 15% by mass, the impact resistance and chemical resistance tend to be inferior, and if it exceeds 40% by mass, the resulting resin composition is highly colored.

  Examples of the aromatic alkenyl compound used for graft polymerization include styrene, α-methylstyrene o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, t-butylstyrene, and the like. These can be used alone or in combination. The proportion of the aromatic alkenyl compound in the total amount of monomers used for graft polymerization is preferably 25 to 85% by mass. When outside these ranges, at least one of impact resistance and moldability is inferior.

  Further, at the time of graft polymerization, other inferior amounts of copolymerizable vinyl compounds other than vinyl compounds other than vinyl cyanide compounds and aromatic alkenyl compounds can be copolymerized. Other vinyl compounds capable of co-polymerization include maleimide compounds such as N-phenylmaleimide; methacrylic acid alkyl esters such as methyl methacrylate and 2-ethylhexyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate Esters: Epoxy group-containing vinyl compounds such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, acetic acid Examples thereof include vinyl esters such as vinyl; dicarboxylic anhydrides such as maleic anhydride; and polyfunctional compounds such as divinylbenzene. These may be used alone or in combination of two or more. Further, these other copolymerizable vinyl compounds are used as needed within a range of up to 35% by mass in the graft monomer. Specific examples of the butadiene-based rubber-containing graft copolymer that satisfies the above-described requirements include a polybutadiene rubber-containing acrylonitrile-styrene graft copolymer manufactured by UMG ABS, trade name: R-80, and the like. .

  The amount of the (B) butadiene-based rubber-containing graft copolymer used in the present invention is 10 in 100 parts by mass of the total amount of the resin components (A), (B), (C), and (D) including the components described later. -50 mass parts. When it is out of the range of 10 to 50 parts by mass, at least one of impact resistance and chemical resistance is inferior.

  Examples of the rubber-like elastic body other than (C) and (B) in the present invention include, for example, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer, methyl methacrylate-butadiene-styrene copolymer, and butadiene. Rubber-containing methyl methacrylate-styrene graft copolymer, acrylonitrile-butadiene-styrene copolymer rubber, styrene-butadiene-styrene copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene-butylene-styrene Copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), acrylic rubber-containing methyl methacrylate graft copolymer, acrylic rubber-containing methyl methacrylate-styrene graft copolymer , Including acrylic rubber Acrylonitrile-styrene copolymer, silicone-containing acrylic rubber-containing methyl methacrylate graft copolymer, silicone-containing acrylic rubber-containing methyl methacrylate-styrene graft copolymer, silicone-containing acrylic rubber-containing acrylonitrile-styrene graft Examples thereof include a copolymer, a silicone rubber-containing methyl methacrylate graft copolymer, and a silicone rubber-containing acrylonitrile-styrene graft copolymer. As the diene of the ethylene-propylene-diene copolymer rubber (EPDM), 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like are used. These rubber-containing graft copolymers and copolymer rubbers can be used alone or in combination of two or more.

  The amount of the rubber-like elastic body other than (C) and (B) in the present invention is 100 parts by mass of the total amount of the resin components (A), (B), (C), and (D) including the components described later. 1 to 10 parts by mass. When it is out of the range of 1 to 10 parts by mass, it is not preferable because at least one of impact resistance and rigidity at low temperatures is inferior. As rubber-like elastic bodies other than (B) that satisfy the above requirements, specifically, silicone-containing acrylic rubber-containing methyl methacrylate graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name: S- 2001, methyl methacrylate-styrene graft copolymer containing styrene-butadiene copolymer rubber, manufactured by Mitsubishi Rayon Co., Ltd., trade name: C-223A, and the like.

  The vinyl (co) polymer (D) in the present invention comprises at least one selected from vinyl cyanide compounds, aromatic alkenyl compounds and other vinyl compounds as a constituent unit. “(Co)” means that it may be a polymer composed of a single component or a copolymer composed of two or more components. Further, it does not contain a vinyl polymer having the same constitution as (B).

  Examples of the vinyl cyanide compound used in the vinyl (co) polymer include acrylonitrile and methacrylonitrile. These can be used alone or in combination. The proportion of the vinyl cyanide compound in the vinyl (co) polymer is preferably 15 to 40% by mass. If the amount is less than 15% by mass, the impact resistance and chemical resistance tend to be inferior, and if it exceeds 40% by mass, the resulting resin composition is highly colored.

  Examples of the aromatic alkenyl compound used for the vinyl (co) polymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, and t-butyl. Examples include styrene. These can be used alone or in combination. The ratio of the aromatic alkenyl compound in the graft monomer is preferably 25 to 85% by mass. When outside these ranges, at least one of impact resistance and moldability is inferior.

  In addition, the vinyl (co) polymer can be copolymerized with an inferior amount of copolymerizable vinyl compound other than vinyl cyanide compound and aromatic alkenyl compound. Other vinyl compounds capable of co-polymerization include maleimide compounds such as N-phenylmaleimide; methacrylic acid alkyl esters such as methyl methacrylate and 2-ethylhexyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate Esters: Epoxy group-containing vinyl compounds such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, acetic acid Examples thereof include vinyl esters such as vinyl; dicarboxylic anhydrides such as maleic anhydride; and polyfunctional compounds such as divinylbenzene. These may be used alone or in combination of two or more. Further, these other copolymerizable vinyl compounds are used as needed within a range of up to 35% by mass in the graft monomer. Specific examples of vinyl-based (co) polymers that satisfy the above requirements include acrylonitrile-styrene copolymer UMG ABS, trade name: AP-20.

  The amount of the vinyl (co) polymer (D) used in the present invention is 4 to 74 parts by mass in 100 parts by mass of the total amount of the resin components (A), (B), (C) and (D). is there. When the amount is less than 4 parts by mass or exceeds 74 parts by mass, at least one of impact resistance and chemical resistance is inferior, which is not preferable.

  The thermoplastic polyester resin composition of the present invention can improve heat resistance, synthesis, and dimensional stability by further adding (E) a filler as necessary. Examples of the filler (E) include metals, oxides, hydroxides, silicic acid or silicates, carbonates, silicon carbide, synthetic fibers, animal fibers, plant fibers, and the like. As aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, clay, zeolite, talc , Wollastonite, acetate powder, silk powder, aramid fiber, glass fiber, carbon fiber, metal fiber, carbon black, graphite, glass beads and the like. One type of these (C) fillers may be used as necessary, or two or more types may be used in combination. More specifically, CS03JAFT792 (trade name) manufactured by Asahi Fiber Glass Co., Ltd. can be exemplified as the glass fiber.

  Further, (E) a regenerated filler material can also be used as the filler. Recycled filler materials include rice husk, bran, rice bran, corn waste, coconut husk, defatted soybeans, walnut husk, coconut coconut husk, suso, bagasse and other agricultural wastes, distilled spirits such as shochu, beer malt mash , Wine grape bowls, sake bowls, soy sauce bowls, tea bowls, coffee bowls, coffee bowls, citrus squeezed rice cakes, food processing waste such as okara and chlorella, oyster shells and shells, shrimp and carp shells, etc. Aquatic waste, sawdust, waste wood, bark, felled bamboo, wood-based waste such as waste wood produced by cutting wood at pharmaceutical plants and demolition of wooden houses, waste generated from waste paper and paper industry Examples of such waste include pulp and paper pieces.

  In addition, in order to improve dispersibility in the thermoplastic polyester resin composition of the present invention, polybasic acid anhydrides such as maleic anhydride, organic peroxides such as dicumyl peroxide, acid-modified modified polyolefins, polyesters (E) filler surface-treated with fine particles such as waxes, fatty acid metal salts such as zinc stearate, metal oxides such as titanium oxide and calcium oxide, and the like can also be used.

  These (E) fillers can be used alone or in admixture of two or more. Usually, it mix | blends in 0-50 mass parts with respect to 100 mass parts of total amounts of (A), (B) (C), (D) component. (C) If the filler is less than 5 parts by mass, the mechanical strength is insufficient, and if it exceeds 50 parts by mass, the molding processability, the appearance of molding may be deteriorated, and the impact resistance may be lowered.

The thermoplastic polyester resin composition of the present invention preferably further comprises (F) a flame retardant.
Examples of the flame retardant (F) include aromatic halogen compounds such as hexabromobromobenzene and decabromodiphenyl oxide, halogenated epoxy compounds such as brominated bisphenol-based epoxy resins, halogenated polycarbonate resins, brominated polystyrene resins, Brominated bisphenol cyanurate resin, brominated polyphenylene oxide, decabromodiphenyl oxide bisphenol condensate, antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate, triazine compounds such as melamine, cyanuric acid, melamine cyanurate, tri Cresyl phosphate, triallyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri (chloroethyl) phosphate, tris Phosphorus esters such as dichloropropyl) phosphate and tris (2,3-dibromopropyl) phosphate, condensed phosphates such as phenylenebis (phenylglycidylphosphate), red phosphorus, and phosphorous compounds such as ammonium polyphosphate / pentaerythritol complex , Phosphate polyols, halogen-containing polyols, phosphorus-containing polyols and other polyols, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium aluminate, hydrotalcite and other metal hydroxides, other kaolin clay, dosonite, calcium carbonate Examples thereof include zinc borate, a molybdenum compound, ferrocene, a tin compound, and an inorganic complex salt. More specifically, as halogenated epoxy oligomer, Bromine Compounds Ltd. F2400 (trade name) made by Nippon Seiko Co., Ltd. can be cited as antimony trioxide.

  In addition, alkali metal salts and alkaline earth metal salts can also be used as the flame retardant (F) as long as the effects of the thermoplastic polyester resin composition of the present invention are not impaired. Examples thereof include alkali metal salts or alkaline earth metal salts of organic sulfonic acids, alkali metal salts or alkaline earth metal salts of sulfate esters, and alkali metal salts or alkaline earth metal salts of organic sulfonamides.

  Specifically, alkali metal salts or alkaline earths of alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutylsulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, etc. Metal salt or alkali metal salt or alkaline earth metal salt of fluorinated alkanesulfonic acid in which part of hydrogen of the alkyl group is substituted with fluorine atom, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropane Alkaline of perfluoroalkanesulfonic acid such as sulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid or perfluorooctanesulfonic acid Alkali metal salt or alkali of sulfonic acid of aromatic sulfide on monomeric or polymer such as metal salt or alkaline earth metal salt, diphenyl sulfide-4,4'-disulfonic acid, diphenyl sulfide-4,4'-disulfonic acid Earth metal salt, alkali metal salt of polyethylene terephthalate copolymerized with 5-sulfoisophthalic acid, or alkali metal salt or alkaline earth metal salt of sulfonic acid of aromatic carboxylic acid and ester such as alkaline earth metal salt and polysulfonic acid 1-methoxynaphthalene-4-sulfonic acid, 4-dodecylphenyl ether disulfonic acid, poly (2,6-dimethylphenylene oxide) polysulfonic acid, poly (1,3-dimethylphenylene oxide) polysulfonic acid, poly (1,4 -Dimethylf Nylene oxide) polysulfonic acid, poly (2-fluoro-6-butylphenylene oxide) polysulfonic acid and other monomeric or polymeric aromatic ether sulfonic acid alkali metal salt or alkaline earth metal salt, benzene sulfonate sulfonic acid Monomers such as alkali metal salts or alkaline earth metal salts of sulfonic acids of aromatic sulfonates such as benzenesulfonic acid, p-benzenedisulfonic acid, naphthalene-2,6-disulfonic acid, biphenyl-3,3'-disulfonic acid Or polymeric aromatic sulfonic acid alkali metal salt or alkaline earth metal salt, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'-disulfonic acid, diphenylsulfone-3,4'-disulfonic acid, etc. Monomeric or poly Sulfur of aromatic ketone such as alkali metal salt or alkaline earth metal salt of mer-like aromatic sulfone sulfonic acid, α, α, α-trifluoroacetophenone-4-sulfonic acid, benzophenone-3,3′-disulfonic acid, etc. Alkali metal salts or alkaline earth metal salts of acids, alkali metal salts or alkaline earth metal salts of heterocyclic sulfonic acids such as thiophenone-2,5-disulfonic acid and sodium benzothiophenesulfonic acid, diphenyl sulfoxide-4 -Alkali metal salts or alkaline earth metal salts of sulfonic acids of aromatic sulfoxides such as sulfonic acids, by methylene type bonds of alkali metal salts or alkaline earth metal salts of aromatic sulfonic acids such as naphthalene sulfonic acid and anthracene sulfonic acid Condensate, methyl sulfate ester, ethyl sulfate Steal, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, lauric acid monoglyceride sulfate, palmitic acid monoglyceride sulfate, stearic acid monoglyceride Alkali metal salts or alkaline earth metal salts of sulfates of monovalent and / or polyhydric alcohols such as sulfates of saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N ′ Examples include alkali metal salts or alkaline earth metal salts of aromatic sulfonamides such as -benzylaminocarbonyl) sulfanilimide and N- (phenylcarboxyl) sulfanilimide.

  These (F) flame retardants can be used alone or in admixture of two or more. Usually, it mix | blends in 0-50 mass parts with respect to 100 mass parts of total consideration of (A), (B), (C), (D) component. (F) When a flame retardant exceeds 50 mass parts, there exists a possibility that mechanical strength, thermal stability, and low temperature impact resistance may fall.

The thermoplastic polyester resin composition of the present invention preferably further contains (G) an anti-dripping agent.
By using this anti-dripping agent in combination with the above flame retardant, it is possible to have better flame retardancy. Examples of the anti-dripping agent include fluorine-containing polymers having fibril-forming ability. Examples of such polymers include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers). Etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like, preferably polytetrafluoroethylene (hereinafter referred to as PTFE). It is.

PTFE having a fibril forming ability (fibrillated PTFE) has a very high molecular weight and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. Such adjustment is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of PTFE at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in the form of an aqueous dispersion in addition to a solid form. Such fibrillated PTFE can also be used in the form of PTFE mixed with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight PTFE as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F201L manufactured by Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include Asahi Glass Co., Ltd. full-on AD-1, AD-936, AD-938, Daikin Co., Ltd. full-on D-1, D-2, Mitsui -Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd. and the like.

  As such fibrillated PTFE mixed with other resins, (1) an aqueous dispersion of fibrillated PTFE described in JP-A-60-258263, JP-A-63-154744, etc. And an aqueous dispersion or solution of a courageous polymer and coprecipitation to obtain a coaggregated mixture, (2) an aqueous dispersion of fibrillated PTFE and drying described in JP-A-4-272957 (3) An aqueous dispersion of fibrillated PTFE and an organic polymer particle solution described in JP-A-06-220210, JP-A-08-188653, etc. are uniformly mixed. (4) Aqueous content of fibrillated PTFE described in JP-A-9-95583 A method of polymerizing monomers forming an organic polymer in a liquid; (5) after uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion described in JP-A-11-29679; Those obtained by polymerizing vinyl monomers in the mixed dispersion and then obtaining a mixture can be used.

  Commercial products of fibrillated PTFE in a mixed form with these other resins include METABRENE A3800, A3700, A3000 manufactured by Mitsubishi Rayon Co., Ltd., or BLENDEX B449 manufactured by GE Specialty Chemicals, manufactured by Pacific Interchem Corporation POLY TS AD001 (trade name) and the like.

  (G) A dripping inhibitor is mix | blended in 0-3 mass parts with respect to 100 mass parts of total amounts of (A), (B), (C), (D) component. If it exceeds 3 parts by mass, the molded appearance may be deteriorated.

  If necessary, a plasticizer can be added to the thermoplastic polyester resin composition of the present invention. Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diiso Phthalate ester plasticizers such as decyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate; tricresyl phosphate , Tri-2-ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl Phosphate ester plasticizers such as rudiphenyl phosphate and cresyl phenyl phosphate; di-2-ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl-normal nonyl adipate, diisooctyl adipate, diiso Adipate plasticizers such as normal octyl adipate, dinormal octyl adipate, and didecyl adipate; Sebate plastics such as dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, and butylbenzyl sebacate Agents: Azelaic acid ester plasticizers such as di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate; triethyl citrate, triethyl citrate Citrate plasticizers such as tributyl citrate, tributyl acetyl citrate, tris (2-ethylhexyl) citrate; methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. Glycolic acid type plasticizers: Tributyl trimellitate, Tris (normal hexyl) trimellitate, Tris (2-ethylhexyl) trimellitate, Tris (normal octyl) trimellitate, Tris (isooctyl) trimellitate, Tris (isodecyl) trimellitate, etc. Ester plasticizers; phthalic acid isomer ester plasticizers such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate; methyl acetyl ricinolate, butyl acetyl chloride Lisinoleic acid ester plasticizers such as sinolate; Polyester plasticizers such as polypropylene adipate, polypropylene sebacate and their modified polyesters; epoxidized soybean oil, epoxybutyl stearate, epoxy (2-ethylhexyl) stearate, epoxidized sesame In addition, there may be mentioned an epoxy plasticizer such as oil and 2-ethylhexyl epoxy torate. These may be used alone or in combination of two or more as required.

  If necessary, a stabilizer can be added to the thermoplastic polyester resin composition of the present invention. Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate; potassium, magnesium, valency, zinc, cadmium lead, etc. Metal soap based stability derived from metals and fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid Agents: organotin stabilizers derived from alkyl groups, ester groups and fatty acid salts, maleates, and sulfides; Ba—Zn, Ca—Zn, Ba—Ca, Ca—Mg—Sn, Composite metal soap stabilizers such as Ca—Zn—Sn, Pb—Sn, and Pb—Ba—Ca; metals such as barium and zinc, 2-ethylhexanoic acid isodecanoic acid, trials There are usually two types, such as branched fatty acids such as lucacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and substituted derivatives thereof. Metal salt stabilizers derived from organic acids as described above; these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, and further phosphites, epoxy compounds, color-preventing agents, Metal stabilizers such as metal salt liquid stabilizers that contain stabilizers such as transparency improvers, light stabilizers, antioxidants, and lubricants; epoxy resins, epoxidized soybean oil, epoxidized vegetable oils, epoxies Epoxy compounds such as alkylated fatty acid alkyl esters, phosphorus substituted with alkyl groups, aryl groups, cycloalkyl groups, alkoxyl groups, etc., and propylene glycol, etc. Organic phosphites having aromatic compounds such as dihydric alcohol, hydroquinone and bisphenol A, hindered phenols such as bisphenol dimerized with BHT and sulfur and methylene groups, salicylic acid esters, benzophenone, benzotriazole, etc. UV absorbers, hindered amine or nickel complex salt light stabilizers, UV screening agents such as carbon black and rutile type titanium oxide, polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol and mannitol, β-aminocrotonate 2- Nitrogenous compounds such as phenylindole, diphenylthiourea, dicyandiamide, sulfur-containing compounds such as dialkylthiopropionic acid esters, keto compounds such as acetoacetic acid esters, dehydroacetic acid, β-diketones, Silicon compounds, non-metallic stabilizers such as boric acid esters. These can be used alone or in combination of two or more.

  A lubricant may be added to the thermoplastic polyester resin composition of the present invention as necessary. Examples of lubricants include pure hydrocarbons such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; fatty acid amides, bis fatty acid amides, etc. Fatty acid amides; fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters such as glycerides, fatty acid polyglycol esters, fatty acid fatty alcohol esters (ester waxes), etc .; metal soaps, fatty alcohols, polyhydric acids Examples thereof include alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, and partial esters of polyglycerol.

  If necessary, a processing aid can be added to the thermoplastic polyester resin composition of the present invention. Examples of processing aids include (meth) acrylic acid ester copolymers, (meth) acrylic acid ester-styrene copolymers, (meth) acrylic acid ester-styrene-α-methylstyrene copolymers, acrylonitrile- Examples include styrene copolymers, acrylonitrile-styrene- (meth) acrylic acid ester copolymers, acrylonitrile-styrene-α-methylstyrene copolymers, acrylonitrile-styrene-maleimide copolymers, and the like.

  In the thermoplastic polyester resin composition of the present invention, a pigment, an antifogging agent, an antibacterial agent, in addition to the above additives or together with the above additives, as long as the properties are not impaired. Various additives such as an antistatic agent, a conductivity imparting agent, a surfactant, a crystal nucleating agent, and a heat resistance improver can be added.

  Examples of useful molded articles obtained using the thermoplastic polyester resin composition of the present invention include hollow molded bodies by injection molding, injection molded bodies, and the like. Specific examples thereof include electric / electronic parts, home appliance lighting parts, automobile parts, mechanism parts, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In each description, “parts” indicates mass parts, and “%” indicates mass%. Various physical properties were measured by the following methods.

(1) Intrinsic Viscosity (IV) Measurement According to a conventional method, it was measured at 35 ° C. in orthochlorophenol as a solvent.
(2) Titanium atom content measurement The titanium atom content in the produced PBN was quantified using a fluorescent X-ray measuring machine ZSX100e type manufactured by Rigaku Corporation.
(3) Terminal carboxyl group concentration measurement It is the value which melt | dissolved PBN in benzyl alcohol and titrated with 0.1N-NaOH, and is the equivalent concentration of the carboxyl group per 1 * 10 < ⁶ > g.
(4) Izod impact strength measurement It measured based on ASTM D256 using the test piece with a notch.
(5) Measurement of ductile brittle transition temperature The pre-dried thermoplastic polyester resin composition was injection molded with an injection molding machine under the condition of a melting temperature of 280 ° C., and an Izod impact test piece (1/8 inch thick). Create The obtained test piece was provided with a 0.25R notch, and this was adjusted for 2 hours at intervals of 5 ° C. between 30 ° C. and −50 ° C. using a low-temperature thermostatic bath. After the adjustment, ASTM D256 Measure Izod impact strength according to the above. The measured data was plotted on a section paper to determine the temperature at which the strength transitions from a ductile state to brittleness.
(6) Measurement of tensile strength The tensile strength was measured in accordance with ASTM D638. Two types of test specimens were used immediately after molding (referred to as before dry heat treatment) and after a dry heat deterioration test at 150 ° C. for 300 hours (after dry heat treatment).
(7) Extrusion processability measurement When the thermoplastic polyester resin composition blend of the present invention is pelletized by extrusion molding, it can be easily pelletized with ○, somewhat difficult with Δ, and pelletized with What was impossible was set as x.
(8) Molding appearance measurement The appearance of the molded product of the thermoplastic polyester resin composition of the present invention is visually observed. The glass fiber that is the filler is not floated. It was determined.
(9) Combustion test measurement A vertical combustion test was performed in accordance with the UL94 standard. A test piece having a thickness of 1.6 mm was used. The height of the flame of the burner was adjusted to 19 mm, and the lower end of the center of the test piece held vertically was exposed to the flame for 10 seconds, then separated from the flame and the burning time was recorded. Immediately after extinguishing the flame, the burner flame was further applied for 10 seconds to separate it from the flame, and the combustion time was measured. If there is no flammable drop (drip) and the time until extinction is within 10 seconds in both the first and second times, and the total burning time after 10 flames contacted 5 times is within 50 seconds, V When the total combustion time after −0 and the burning time within 30 seconds and after 10 flames contacted 5 specimens was within 250 seconds, it was determined as V-1. Moreover, it was determined as V-2 when there was a flammable drop even in the same combustion time as V-1, and as V-out when the combustion time was longer than that or when the test piece was burned up to the test piece holder.

(A) Polybutylene naphthalate resin (PBN)
<Production Example 1: PBN-1>
Diester of 2,6-naphthalenedicarboxylic acid dimethyl ester (315.0 parts), 1,4-butanediol (200.0 parts) and tetra-n-butyl titanate (0.062 parts) were placed in a transesterification reaction tank. The ester exchange reaction was carried out for 150 minutes while raising the temperature. Subsequently, the obtained reaction product was transferred to a polycondensation reaction tank to start a polycondensation reaction.

  In the polycondensation reaction, the pressure in the polycondensation reaction tank is gradually reduced from normal pressure to 0.13 kPa (1 Torr) or less over 40 minutes, and the temperature is simultaneously raised to a predetermined reaction temperature of 260 ° C. Thereafter, the predetermined polycondensation reaction temperature is reached. The polycondensation reaction was carried out for 140 minutes while maintaining the pressure at 0.13 kPa (1 Torr). When 140 minutes had elapsed, the polycondensation reaction was completed, PBN was extracted in a strand shape, and cut into chips using a cutter while cooling with water. The intrinsic viscosity, color tone, and terminal carboxyl group concentration of the obtained PBN were measured, and the results are shown in Table 1. The obtained PBN was subjected to solid state polymerization for 8 hours under the conditions of a temperature of 213 ° C. and a pressure of 0.13 kPa (1 Torr) or less. About the obtained PBN, the intrinsic viscosity, the terminal carboxyl group concentration, and the titanium atom content in the PBN were measured. The results are shown in Table 1.

<Production Example 2: PBN-2>
Except that solid phase polymerization was not performed, a transesterification reaction and a polycondensation reaction were performed in the same manner as in Production Example 1 to obtain PBN (PBN-2). The obtained PBN was measured for intrinsic viscosity, terminal carboxyl group concentration, and titanium atom content in the PBN. The results are shown in Table 1.

<Production Example 3: PBN-3>
Except for changing the polycondensation reaction time from 140 minutes to 60 minutes, a transesterification reaction and a polycondensation reaction were carried out in the same manner as in Production Example 1 to obtain PBN (PBN-3). Table 1 shows the results of measurement of intrinsic viscosity, terminal carboxyl group concentration, and titanium atom content in PBN for the obtained PBN.

<Production Example 4: PBN-4>
A transesterification reaction and a polycondensation reaction were carried out in the same manner as in Production Example 1 except that the amount of tetra-n-butyl titanate added was 0.242 parts to obtain PBN (PBN-4). Table 1 shows the results of measuring the intrinsic viscosity, terminal carboxyl group concentration, and titanium atom content in the produced PBN for the obtained PBN.

(Examples 1-9 and Comparative Examples 1-9)
The components (A) to (E) having the composition ratios (mass basis) shown in Tables 2 to 3 were melt-kneaded and pelletized by an extruder set at a cylinder temperature of 280 ° C., and then various thermoplastic polyester resin compositions. I got a thing. Moreover, a 1/8 inch Izod test piece and a tensile test piece were obtained by an injection molding machine set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. The results of evaluation using these are shown in Tables 2 and 3.

The details of each component used are as follows.
(A) Polybutylene naphthalate resin <A-1> Polybutylene naphthalate resin (PBN-1: Production Example 1)
<A-2> Polybutylene naphthalate resin (PBN-2: Production Example 2)
<A-3> Polybutylene naphthalate resin (PBN-3: Production Example 3)
<A-4> Polybutylene naphthalate resin (PBN-4: Production Example 4)
(B) Graft copolymer containing butadiene rubber <B-1> Acrylonitrile-styrene graft copolymer containing polybutadiene rubber
Product name: R-80, manufactured by UMG ABS
(C) Rubber-like elastic body <C-1> Silicone-containing acrylic rubber-containing methyl methacrylate graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name: S-2001
<C-2> Styrene-butadiene copolymer rubber-containing methyl methacrylate-styrene graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name: C-223A
・ (D) Vinyl-based (co) polymer <D-1> Acrylonitrile-styrene copolymer
Product name: AP-20, manufactured by UMG ABS
-(E) Filler <E-1> Glass fiber, Asahi Fiber Glass Co., Ltd., trade name: CS03JAFT792
-(F) Flame retardant <F-1> Halogenated epoxy oligomer Bromine Compounds Ltd. Product name F2400
<F-2> Antimony trioxide Nippon Seiko Co., Ltd., trade name Patox M
-(G) Anti-dripping agent <G-1> Polytetrafluoroethylene Daikin Chemical Industries, Ltd., trade name F201L

  From the results shown in Tables 2 and 3, in the present invention, by adding the above-mentioned components (B) to (G) to the polybutylene naphthalate resin, improvement in impact resistance characteristics, particularly impact resistance characteristics at low temperatures, is recognized. . It can also be seen that good thermal stability can be obtained by using PBN in which the amount of titanium atoms and the concentration of terminal carboxyl groups in the produced PBN are in appropriate ranges.

  The thermoplastic polyester resin composition of the present invention has good impact resistance and thermal stability, and a molded product obtained from the resin composition can withstand high and low temperature environments and is suitable for automobile parts, mechanism parts, etc. It is.

Claims (6)

(A) 15 to 80 parts by mass of a polybutylene naphthalate resin having an intrinsic viscosity of 0.60 to 1.30 dL / g and a terminal carboxyl group concentration of 30.0 eq / 10 ³ kg or less,
(B) At least one monomer selected from a vinyl cyanide compound, an aromatic alkenyl compound, and a vinyl compound other than the vinyl cyanide compound and the aromatic alkenyl compound as a rubbery polymer composed of butadiene units. 10-50 parts by mass of a butadiene rubber-containing graft copolymer obtained by graft polymerization of
(C) 1 to 10 parts by mass of a rubber-like elastic body other than (B),
(D) Vinyl polymers 4 to 4 other than (B) having at least one selected from vinyl cyanide compounds, aromatic alkenyl compounds, and vinyl compounds other than vinyl cyanide compounds and aromatic alkenyl compounds as constituent units For 100 parts by mass of the resin composition consisting of 74 parts by mass,
(E) 0-50 parts by mass of filler,
(F) A thermoplastic polyester resin composition comprising 0 to 50 parts by mass of a flame retardant and 0 to 3 parts by mass of (G) an anti-dripping agent.   (A) The thermoplastic polyester resin composition according to claim 1, wherein the titanium atom content in the polybutylene naphthalate resin is 10 ppm or more and 60 ppm or less.   (G) The thermoplastic polyester resin composition according to claim 1 or 2, wherein the dripping inhibitor is polytetrafluoroethylene.   At least one monomer selected from vinyl compounds other than vinyl cyanide compounds and aromatic alkenyl compounds is a maleimide compound, an acrylate compound, an epoxy group-containing vinyl compound, vinyl acetate, maleic anhydride, and divinylbenzene. The thermoplastic polyester resin composition according to any one of claims 1 to 3, which is at least one monomer selected from the group consisting of:   A vinyl polymer having at least one selected from vinyl compounds other than vinyl cyanide compounds and aromatic alkenyl compounds as a structural unit is a maleimide compound, an acrylate compound, an epoxy group-containing vinyl compound, vinyl acetate, maleic anhydride The thermoplastic polyester resin composition according to any one of claims 1 to 4, which is a vinyl polymer obtained by polymerizing at least one compound selected from the group consisting of an acid and divinylbenzene.   The molded article obtained by shape | molding the thermoplastic polyester resin composition of any one of Claims 1-5.