JP2009292906A - Thermoplastic polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition that exhibits excellent impact resistant properties, particularly impact resistant properties at a lower temperature by employing a resin composition comprising PBN and a composite rubber-containing graft copolymer mixed therewith, based on wholehearted study on enhancement of impact resistant properties of PBN, particularly enhancement of impact resistant properties at a lower temperature. <P>SOLUTION: The thermoplastic polyester resin composition comprises (C) 5-50 pts.mass of a filler, (D) 1-50 pts.mass of a flame-retardant, and (E) 0-3 pts.mass of a drip inhibitor, based on 100 pts.mass of a resin composition comprising (A) 99-50 pts.mass of a polybutylene naphthalene resin having an intrinsic viscosity of 0.60-1.30 dL/g and a terminal carboxy group concentration of ≤30.0 eq/10<SP>3</SP>kg and (B) 1-50 pts.mass of the composite rubber-containing graft copolymer obtained by graft-polymerizing one or more vinyl monomers onto a composite rubber comprised of a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber mutually entangled inseparably to be integrated. <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 capable of improving impact resistance characteristics, particularly low temperature impact resistance characteristics, and obtaining good thermal stability, and the thermoplastic polyester resin composition. The present invention relates to a molded product formed by injection molding a 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. Among them, polybutylene naphthalate resin (hereinafter referred to as PBN or polybutylene naphthalate resin) has excellent mechanical and physical properties like other thermoplastic polyester resins. Compared to the above, it has excellent characteristics such as moisture and heat resistance, chemical resistance, gas barrier property, 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 is also in impact resistance like PBT. There is a need for improvement.

  Specifically, as a technique for improving impact resistance of PBN, a method of blending glycidyl methacrylate / anhydride / α-olefin with PBN (see, for example, Patent Document 1), and methyl methacrylate containing n-butyl acrylate rubber with PBN. A method of blending a graft copolymer (for example, see Patent Document 2), a method of blending glycidyl methacrylate / alkyl acrylate / α-olefin in PBN (for example, see Patent Document 3), and a PBN elastomer in PBN. Method (for example, see Patent Document 4), a method of blending styrene / ethylene / butylene / styrene block copolymer with PBN (for example, see Patent Document 5), and glycidyl methacrylate / α-olefin / vinyl acetate with PBN. A method of blending a polymer (for example, see Patent Document 6), A method of blending an olefinic elastomer BN (e.g., see Patent Document 7.) And the like is a relatively excellent method.

JP-A-5-339478 JP-A-6-145484 JP-A-6-157882 JP-A-6-172626 JP-A-6-240119 JP-A-9-104807 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.
Based on the background as in the prior art described above, the present inventor has conducted intensive studies on improving the impact resistance characteristics of PBN, particularly the impact resistance characteristics at low temperatures. As a result, a resin in which a composite rubber-based graft copolymer is blended with PBN. The present inventors have found that the composition is excellent in impact resistance characteristics, particularly impact resistance characteristics at low temperatures, and have reached the present invention.

That is, the present invention relates to (A) 99 to 50 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) A composite obtained by graft polymerization of one or two or more vinyl monomers to a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are intertwined and inseparably integrated. (C) 5 to 50 parts by mass of filler, (D) 1 to 50 parts by mass of flame retardant, and (E) dripping with respect to 100 parts by mass of the resin composition comprising 1 to 50 parts by mass of the rubber-containing graft copolymer. A thermoplastic polyester resin composition comprising 0 to 3 parts by weight of an inhibitor, and an injection-molded product formed by injection molding the thermoplastic polyester resin composition, and It can be solved.

  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.

  For the production of the (A) PBN resin constituting the thermoplastic polyester resin composition of the present invention, a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and / or an ester-forming derivative of naphthalenedicarboxylic acid, and 1,4-butane It can be obtained using a glycol component containing diol as a main component.

  The dicarboxylic acid component constituting (A) PBN used in the thermoplastic polyester resin composition of the present invention is mainly composed of 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. If it is a range which does not impair this, other dicarboxylic acid can be used together. 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 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 two 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. Further, 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 increased, which is not preferable.

  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-n-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 oxides 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 (B) composite rubber-containing graft copolymer used in the thermoplastic polyester resin composition of the present invention is a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are intertwined and inseparable from each other. In addition, one or two or more vinyl monomers are graft-polymerized.

  The characteristics of the thermoplastic polyester resin composition of the present invention can be obtained by using any one of polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber or a mixture thereof as a rubber source instead of the composite rubber. First, a thermoplastic polyester resin composition having excellent impact resistance, particularly impact resistance at low temperatures, is obtained only when the polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber are intertwined and integrated with each other. Obtainable.

  (B) As the polyorganosiloxane rubber component used for the composite rubber constituting the composite rubber-containing graft copolymer, Japanese Patent Nos. 2558126, 2567627, 2608439, and 2608469 are disclosed. JP-A-5-5055, JP-A-5-252288, JP-A-2003-261635, JP-A-2004-346271, JP-A-2004-359889, etc. Organosiloxanes, siloxane crosslinking agents, vinyl polymerizable functional group-containing siloxanes, and the like can be used.

  Examples of the organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. Siloxane etc. are mentioned, These can be used 1 type or in mixture of 2 or more types.

  As the siloxane-based crosslinking agent, trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane can be used.

  Examples of the vinyl polymerizable functional group-containing siloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ- Methacryloyloxysilane such as methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxy Methylsilane; γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. It can be used mercaptoethyloleates siloxane. These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

  (B) The polyorganosiloxane rubber constituting the composite rubber of the composite rubber-containing graft copolymer can be produced using the method described in US Pat. Nos. 2,891,920 and 3,294,725. . For example, a homogenized mixture of an organosiloxane and a vinyl polymerizable functional group-containing siloxane, or a latex obtained by further emulsifying a mixture containing a siloxane-based crosslinking agent with an emulsifier and water, if necessary, with a shearing force generated by high-speed rotation. It can be produced by using a mixer or a homogenizer that produces fine particles with a jet generated by a high-pressure generator and then polymerizing at high temperature using an acid catalyst and then neutralizing the acid with an alkaline substance. it can.

  Moreover, as an emulsifier used for manufacture of polyorganosiloxane rubber, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. In particular, sodium alkylbenzene sulfonate and sodium lauryl sulfate are preferred.

  Examples of the acid catalyst used for producing the polyorganosiloxane rubber include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts are used alone or in combination of two or more.

  In the production of polyorganosiloxane, the polymerization temperature of polyorganosiloxane is preferably 50 ° C. or more, and the polymerization time of polyorganosiloxane is preferably 2 hours or more.

  Next, as the polyalkyl (meth) acrylate rubber component which is the other component constituting the composite rubber of the composite rubber-containing graft copolymer (B), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, Examples include alkyl acrylates such as n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate, and alkyl methacrylates such as 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate. These may be used alone or in combination of two or more. Can be used. In particular, the use of n-butyl acrylate is preferred in consideration of the low-temperature impact characteristics and molded appearance of the resin composition containing the graft copolymer.

  At the time of alkyl (meth) acrylate polymerization, a polyfunctional alkyl (meth) acrylate can be used in combination. Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, Allyl isocyanurate etc. are mentioned, These can be used 1 type or in mixture of 2 or more types.

  The composite rubber used for the (B) composite rubber-containing graft copolymer, which is a constituent of the thermoplastic polyester resin composition of the present invention, is Japanese Patent Nos. 2558126, 2556727, 2608439, No. 2608469, JP-A-5-5055, JP-A-5-252288, JP-A-2003-261635, JP-A-2004-346271, JP-A-2004-359889. It can manufacture using the manufacturing method described in these.

  That is, after the polyorganosiloxane rubber is prepared by emulsion polymerization, the alkyl (meth) acrylate component monomer for synthesizing the alkyl (meth) acrylate rubber is then converted into the polyorganosiloxane rubber in the presence of the polyorganosiloxane rubber. It can be obtained by emulsion polymerization after impregnation.

  More specifically, the polymerization of the polyalkyl (meth) acrylate rubber component is carried out in the latex of the polyorganosiloxane rubber component neutralized by the addition of an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like. After adding (meth) acrylate, a crosslinking agent and a graft crossing agent and impregnating the polyorganosiloxane rubber particles, a normal radical polymerization initiator is allowed to act. As the polymerization proceeds, a cross-linked network of polyalkyl (meth) acrylate rubbers entangled with the cross-linked network of the polyorganosiloxane rubber is formed, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component that cannot be substantially separated are formed. A composite rubber latex is obtained. As the composite rubber, a composite rubber in which the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane and the main skeleton of the polyalkyl (meth) acrylate rubber component has a repetition of n-butyl acrylate is preferably used.

  The gel content measured by extracting the composite rubber produced by emulsion polymerization in this way with toluene at 90 ° C. for 12 hours is preferably 80% by mass or more. A composite rubber in which the polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber obtained as described above are intertwined and integrated with each other is 1 to 99% by mass of the polyorganosiloxane rubber component and the polyalkyl. It is preferably composed of 99 to 1% by mass of (meth) acrylate.

  The average particle size of the above composite rubber (excluding the composite rubber in which the polyorganosiloxane rubber component is a core and the polyalkyl (meth) acrylate component is a shell) is preferably 80 nm to 1500 nm. The particle size distribution may be a single distribution or one having a plurality of peaks of two or more.

  Examples of vinyl monomers to be graft polymerized to the composite rubber of polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber include aromatic alkenyl compounds such as styrene and α-methylstyrene; methyl methacrylate, 2-ethylhexyl. Methacrylic acid alkyl esters such as methacrylate; Methyl acrylate, ethyl acrylate, n-butyl acrylate and other acrylic acid alkyl esters; Acrylonitrile, methacrylonitrile and other vinyl cyanide compounds; Glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether , Glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl Epoxy group-containing vinyl monomer such as Ruitakoneto like. These may be used alone or in combination of two or more.

  The ratio of the composite rubber and the vinyl monomer in the composite rubber-containing graft copolymer (B) is preferably 30.0 based on the mass of the composite rubber-containing graft copolymer (B). ~ 95.0 mass%, vinyl monomer is 70.0-5.0 mass%, more preferably composite rubber is 40.0-90.0 mass%, vinyl monomer is 60.0. -10.0 mass%.

  (B) The composite rubber-containing graft copolymer is obtained by adding the vinyl monomer to the latex of the composite rubber and polymerizing it in one or more stages by radical polymerization. The thus obtained composite rubber-containing graft copolymer latex is put into hot water in which an acid such as sulfuric acid or hydrochloric acid, a metal salt such as calcium chloride, calcium acetate or magnesium sulfate is dissolved, and salted out and coagulated. Then, it is obtained as particles by separating and collecting. At this time, salts such as sodium carbonate and sodium sulfate may be used in combination. It can also be obtained by a direct drying method such as spray drying.

  Examples of the composite rubber-containing graft copolymer as described above include Metablene S-2001, S-2006, S-2030, S-2100, KS-4015, SX-006, and SRK- manufactured by Mitsubishi Rayon Co., Ltd. 200 (above, product name).

  The content of (A) PBN and (B) the composite rubber-containing graft copolymer in the thermoplastic polyester resin composition of the present invention is based on the total of 100 parts by mass of (A) and (B). It is preferable that the content of PBN is 99 to 50 parts by mass, and the content of (B) the composite rubber-containing graft copolymer is 1 to 50 parts by mass. (B) If the content of the composite rubber-containing graft copolymer is less than 1 part by mass, impact resistance characteristics cannot be obtained. If it exceeds 50 parts by mass, the molding processability and the molding appearance will deteriorate.

  Further, the filler (C) used in the thermoplastic polyester resin composition of the present invention includes metals, oxides, hydroxides, silicic acid or silicates, carbonates, silicon carbide, synthetic fibers, animal fibers, or vegetable matter. Specific examples of these include aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, hydroxide Examples thereof include aluminum, magnesium hydroxide, silica, clay, zeolite, talc, wollastonite, acetate powder, silk powder, aramid fiber, glass fiber, carbon fiber, metal fiber, carbon black, graphite, and glass beads. 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 used as the glass fiber, and HTA-C6-SR (trade name) manufactured by Toho Tenax Co., Ltd. can be used as the carbon fiber. .

  Furthermore, a regenerated filler material can also be used as the filler (C). 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 (C) 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 (C) fillers can be used alone or in admixture of two or more. Usually, it mix | blends in 5-50 mass parts with respect to 100 mass parts of thermoplastic polyester resin compositions which consist of (A) PBN and (B) composite rubber containing graft copolymer. (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 and the molded appearance may be deteriorated.

The thermoplastic polyester resin composition of the present invention preferably further comprises (D) a flame retardant.
Examples of the flame retardant (D) 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 (D) 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 monomeric or polymeric aromatic sulfide 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 or polyethylene earth terephthalate copolymer of 5-sulfoisophthalic acid copolymer, alkali metal salt or alkaline earth metal salt of aromatic carboxylic acid and ester sulfonic acid such as 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- Dimethylfe Lenoxide) polysulfonic acid or poly (2-fluoro-6-butylphenylene oxide) polysulfonic acid or other monomeric or polymeric aromatic ether sulfonic acid alkali metal salt or alkaline earth metal salt, benzene sulfonate sulfonic acid, etc. Sulfonic acid alkali metal salt or alkaline earth metal salt of benzene aromatic sulfonate, benzenesulfonic acid, p-benzenedisulfonic acid, naphthalene-2,6-disulfonic acid, biphenyl-3,3'-disulfonic acid, etc. Alternatively, an alkali metal salt or alkaline earth metal salt of a polymeric aromatic sulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid, diphenylsulfone-3,4′-disulfonic acid, etc. Monomeric or Polymeric aromatic sulfonesulfonic acid alkali metal salt or alkaline earth metal salt, sulfone of aromatic ketone such as 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 Acid ester, lauryl sulfate ester, hexadecyl sulfate ester, sulfate ester of polyoxyethylene alkylphenyl ether, mono-, di-, tri- or tetra-sulfate ester of pentaerythritol, sulfate ester of lauric acid monoglyceride, sulfate ester of palmitic acid monoglyceride, stearic acid Alkali metal salt or alkaline earth metal salt of monovalent and / or polyhydric alcohol sulfate such as sulfate of monoglyceride, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N Examples include alkali metal salts or alkaline earth metal salts of aromatic sulfonamides such as' -benzylaminocarbonyl) sulfanilimide and N- (phenylcarboxyl) sulfanilimide.

  These flame retardants (D) can be used alone or in admixture of two or more. Usually, it mix | blends in 1-50 mass parts with respect to 100 mass parts of thermoplastic polyester resin compositions which consist of (A) PBN and (B) composite rubber containing graft copolymer. (D) If the flame retardant is less than 1 part by mass, the flame retardancy is insufficient, and if it exceeds 50 parts by mass, the mechanical strength and thermal stability may be reduced.

The thermoplastic polyester resin composition of the present invention preferably further comprises (E) 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., BLENDEX B449 manufactured by GE Specialty Chemicals, manufactured by Pacific Interchem Corporation POLY TS AD001 (trade name) and the like.

  (E) The anti-dripping agent is blended in the range of 0 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin composition comprising (A) PBN and (B) the composite rubber-containing graft copolymer. 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.

  In the thermoplastic polyester resin composition of the present invention, as long as the characteristics of the present invention are not impaired, a rubber-containing graft copolymer or copolymer rubber other than the (B) composite rubber-containing graft copolymer is used in combination. You can also Examples of the rubber-containing graft copolymer and copolymer rubber other than the composite rubber-based graft copolymer include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer, methyl methacrylate-butadiene- Styrene copolymer, butadiene rubber-containing methyl methacrylate-styrene graft copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene rubber-containing acrylonitrile-styrene graft copolymer, 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 methacrylate Acid methyl graft copolymer, acrylic rubber-containing methyl methacrylate-styrene graft copolymer, acrylic rubber-containing acrylonitrile-styrene copolymer, silicone-containing acrylic rubber-containing methyl methacrylate graft copolymer, silicone-containing acrylic system Rubber-containing methyl methacrylate-styrene graft copolymer, Silicone-containing acrylic rubber-containing acrylonitrile-styrene graft copolymer, Silicone rubber-containing methyl methacrylate graft copolymer, Silicone rubber-containing acrylonitrile-styrene graft copolymer A polymer etc. are mentioned. 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.

  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 terminal 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) Extrudability measurement When the thermoplastic polyester resin composition blend of the present invention was pelletized by extrusion molding, ○ was easily pelletized, Δ was slightly difficult, and pelleting was not possible. What was possible 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 burning time after −0 and the burning time within 30 seconds and after 10 flame contact with 5 test pieces 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 1-7)
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) Composite rubber-containing graft copolymer <B-1> manufactured by Mitsubishi Rayon Co., Ltd., trade name: Metablen S-2100
<B-2> Made by Mitsubishi Rayon Co., Ltd., trade name: Metablen KS-4015
-(C) Filler <C-1> Glass fiber, Asahi Fiber Glass Co., Ltd., trade name: CS03JAFT792
<C-2> Carbon fiber manufactured by Toho Tenax Co., Ltd., trade name: HTA-C6-SR
(D) Flame retardant <D-1> Halogenated epoxy oligomer Bromine Compounds Ltd. Product name F2400
<D-2> Antimony trioxide manufactured by Nippon Seiko Co., Ltd., trade name Patox M
-(E) Anti-dripping agent <E-1> Polytetrafluoroethylene Daikin Co., Ltd., product name F201L

  From the results shown in Table 2, impact resistance characteristics, especially impact resistance characteristics at low temperatures, are improved by blending a composite rubber-containing graft copolymer using a composite rubber composed of polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber. Is recognized. It can also be seen that good thermal stability can be obtained by using PBN in which the titanium atom content and terminal carboxyl group concentration in the produced PBN are in the proper ranges.

  From Table 3, when the intrinsic viscosity, the titanium atom content in the produced PBN, and the terminal carboxyl group concentration deviate from the proper ranges even with the same type of blending, a decrease in impact resistance and thermal stability of the resin composition is observed.

  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 (4)

(A) 99-50 parts by mass of 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) polyorganosiloxane Composite rubber-containing graft copolymer in which one or more vinyl monomers are graft-polymerized into a composite rubber in which rubber and polyalkyl (meth) acrylate rubber are inseparably intertwined and integrated (C) 5 to 50 parts by weight of filler, (D) 1 to 50 parts by weight of flame retardant, and (E) 0 to 3 of anti-dripping agent for 100 parts by weight of the resin composition consisting of 1 to 50 parts by weight of coalescence. A thermoplastic polyester resin composition obtained by blending parts by mass.   (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.   (E) The dripping inhibitor is polytetrafluoroethylene, The thermoplastic polyester resin composition of any one of Claim 1 or 2.   The molded article formed by injection-molding the thermoplastic polyester resin composition of any one of Claims 1-3.