JP7206724B2 - Thermoplastic polyester resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition capable of suppressing an increase in viscosity during injection molding.

Thermoplastic polyester resins are used in a wide range of fields such as mechanical parts, electric/electronic parts, and automobile parts, taking advantage of their excellent mechanical properties.

Thermoplastic polyester resins are basically flammable, so in order to use them as industrial materials such as mechanical parts, electric/electronic parts, and automobile parts, they must be prepared against flames in addition to the general balance of chemical and physical properties. Safety, that is, flame retardancy is required, and in many cases, a high degree of flame retardancy indicating V-0 of the UL-94 standard is required.

As a method for imparting flame retardancy to a thermoplastic polyester resin, it is common to compound a resin with a halogenated epoxy compound as a flame retardant and antimony trioxide as a flame retardant aid. On the other hand, halogenated epoxy compounds tend to cause an increase in viscosity when melted during compounding or injection molding. I had a problem.

For example, Patent Documents 1 to 3 describe a method of adding a phosphorus compound to suppress thickening when using a halogenated epoxy compound.

JP 2014-118478 A Japanese Patent Application Laid-Open No. 2002-47400 JP-A-7-41651

However, in the methods of adding a phosphorus compound described in Patent Documents 1 to 3, the thickening-improving effect during melting was insufficient. Therefore, there is a problem that the viscosity increases during compounding, and the thickened thermoplastic resin remains in the cylinder to generate carbides. Furthermore, when the amount of the phosphorus compound added is increased with the aim of improving thickening, there is a problem that the amount of gas generated during molding increases, resulting in poor moldability.

As described above, there is a demand for a thermoplastic polyester resin composition that maintains a high level of flame retardancy and has excellent viscosity stability during melting during compounding or injection molding. could not be fully satisfied.

That is, the present invention provides a thermoplastic polyester resin composition that can suppress the generation of carbides during compounding, suppress the increase in viscosity during melting during injection molding, while maintaining high flame retardancy, and generates less gas during injection molding. It is to provide things.

That is, the present invention has the following configurations.
(1) (A) 100 parts by weight of thermoplastic polyester resin, (B) 25 to 40 parts by weight of halogenated epoxy compound, (C) 7 to 12 parts by weight of antimony trioxide, (D) 20 to 80 parts by weight of reinforcing fiber parts by weight, and (E) 0.1 to 1.0 parts by weight of an aliphatic alkyl acid phosphate, and the (B) halogenated epoxy compound is a terminal-blocked compound with tribromophenol, thermoplastic polyester resin Composition.
(2) The thermoplastic polyester resin composition according to (1), wherein the (E) aliphatic alkyl acid phosphate has a molecular weight of 200 or more and 2,000 or less.
(3) The thermoplastic polyester resin composition according to (1) or (2), wherein the (E) aliphatic alkyl acid phosphate is octadecyl acid phosphate.
(4) An electric/electronic component comprising the thermoplastic polyester resin composition according to any one of (1) to (3).

The present invention provides a thermoplastic polyester resin composition that suppresses the generation of carbides during compounding, exhibits excellent viscosity stability during injection molding, and generates a small amount of gas during injection molding while maintaining a high degree of flame retardancy. It provides.

The present invention will be described in detail below. The thermoplastic polyester resin composition of the present invention comprises (A) 100 parts by weight of the thermoplastic polyester resin, (B) 25 to 40 parts by weight of the halogenated epoxy compound, (C) 7 to 12 parts by weight of antimony trioxide, (D) 20 to 80 parts by weight of reinforcing fibers and (E) 0.1 to 1.0 parts by weight of aliphatic alkyl acid phosphate are blended. The polybutylene terephthalate composition of the present invention contains a reactant obtained by reacting individual components constituting the resin composition. There are circumstances in which it is impractical to specify a structure. Therefore, the present invention specifies the invention by the components to be blended.

The (A) thermoplastic polyester used in the present invention is a polymer or copolymer obtained by a polycondensation reaction containing a dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative) as main components. Can be used as a combination.

Terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3' as the dicarboxylic acid -biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid and the like, and terephthalic acid is preferably used.

These dicarboxylic acids may be used in combination of two or more. If the amount is small, these dicarboxylic acids may be mixed with one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. can.

Diol components include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl 1,3-propanediol, diethylene glycol and triethylene glycol, and 1,4-cyclohexane. Alicyclic diols such as dimethanol, mixtures thereof, and the like. One or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol and polytetramethylene glycol, may be copolymerized in small amounts.

Preferred examples of these polymers or copolymers include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyethylene naphthalate, polybutylene naphthalate (PBN), polyhexylene terephthalate ( PHT), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, polycyclohexane-1,4-dimethylol terephthalate, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate and copolyesters such as polybutylene terephthalate/decane dicarboxylate. Among these, polybutylene terephthalate can be preferably used. In addition, "/" means a copolymer here.

The amount of carboxyl terminal groups in (A) the thermoplastic polyester resin used in the present invention is not particularly limited, but in terms of fluidity, hydrolysis resistance and heat resistance, it is preferably 50 eq/t or less, and 30 eq/t. It is more preferably 20 eq/t or less, more preferably 20 eq/t or less. The lower limit of the amount of carboxyl terminal groups may be 0 eq/t. In the present invention, the carboxyl terminal group content of (A) the thermoplastic polyester resin is a value measured by dissolving the thermoplastic polyester resin in an o-cresol/chloroform solvent and titrating with ethanolic potassium hydroxide. .

The viscosity of (A) the thermoplastic polyester resin used in the present invention is not particularly limited as long as melt-kneading is possible, but in terms of moldability, the intrinsic viscosity of the o-chlorophenol solution measured at 25 ° C. It is preferably in the range of 0.36 to 1.60 dl/g, more preferably in the range of 0.50 to 1.50 dl/g.

The method for producing (A) the thermoplastic polyester resin used in the present invention is not particularly limited, and it can be produced by a known polycondensation method, ring-opening polymerization method, or the like, and either batch polymerization or continuous polymerization can be used. Also, both transesterification and direct polymerization reactions can be applied.

Moreover, (A) thermoplastic polyester resin used by this invention can be used in mixture of 2 or more types.

In order to effectively proceed with the esterification reaction, the transesterification reaction, and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanate, Organotitanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldistin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate , tin compounds such as diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, alkylstannoates such as methylstannoic acid, ethylstannoic acid, butylstannoic acid, zirconium tetra zirconia compounds such as -n-butoxide; antimony compounds such as antimony trioxide and antimony acetate; among these, organic titanium compounds and tin compounds are preferred; Tetra-n-butyl and tetraisopropyl esters are preferred, with tetra-n-butyl titanate being particularly preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The amount of the polymerization reaction catalyst to be added is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A), from the viewpoint of mechanical properties, moldability and color tone, and 0.01 part by weight. A range of ~0.2 parts by weight is more preferred.

The (B) halogenated epoxy compound used in the present invention is not particularly limited as long as it has an epoxy group in the molecule and at least one halogen atom. Brominated epoxy resins such as bisphenol-A-epoxy oligomers or polymers, brominated phenolic novolac epoxy are preferred.

(B) The halogenated epoxy compound may be terminal-blocked with tribromophenol or the like.

In addition, the amount of the halogenated epoxy compound (B) to be added is 25 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) of the present invention from the viewpoint of flame retardancy, hydrolyzability, and metal contamination. parts, preferably 27 to 38 parts by weight, more preferably 30 to 35 parts by weight. The above flame retardants may be used singly or in combination of two or more.

The antimony trioxide (C) used in the present invention can synergistically improve flame retardancy when used in combination with a halogenated epoxy compound. Antimony trioxide that has undergone surface treatment or the like can also be used.

In addition, the amount of (C) antimony trioxide to be added is 7 to 12 parts by weight with respect to 100 parts by weight of (A) thermoplastic polyester resin from the viewpoint of flame retardancy, hydrolyzability, and metal contamination. It is preferably 8 to 11 parts by weight, more preferably 9 to 10 parts by weight. Antimony trioxide may be used singly or in combination of two or more.

The (D) reinforcing fiber used in the present invention includes glass fiber, aramid fiber, carbon fiber, and the like. The above-mentioned glass fibers include chopped strand type and roving type glass fibers, and silane coupling agents such as aminosilane compounds and epoxysilane compounds, and/or urethane, vinyl acetate, bisphenol A diglycidyl ether, novolac epoxy compounds, etc. Glass fibers treated with a sizing agent containing one or more epoxy compounds, etc., are preferably used. Also, the silane coupling agent and/or sizing agent described above may be used in the emulsion.

In addition, the (D) reinforcing fiber has a great effect in improving the mechanical strength of the resin composition of the present invention, and the amount of the reinforcing fiber is determined in terms of fluidity during injection molding and durability of the injection molding machine and mold. Therefore, it is 20 to 80 parts by weight, preferably 20 to 70 parts by weight, and more preferably 20 to 60 parts by weight based on 100 parts by weight of the thermoplastic polyester resin (A).

The (E) aliphatic alkyl acid phosphate used in the present invention includes, for example, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, decyl acid phosphate, dodecyl acid phosphate, octadecyl and acid phosphate. A mixture containing one or more of these may be used. Particularly preferably used aliphatic alkyl acid phosphates include octadecyl acid phosphate. Among phosphorus-based stabilizers, (E) aliphatic alkyl acid phosphate can be used to suppress an increase in viscosity during melting during injection molding.

In the present invention, the molecular weight of (E) the aliphatic alkyl acid phosphate is preferably 200-2000, more preferably 300-1000, even more preferably 400-800. By making it 200 or more, the amount of gas generated during heating can be suppressed, and by making it 2000 or less, dispersibility in the resin composition is improved, so that retention stability is improved.

In the present invention, the blending amount of (E) the aliphatic alkyl acid phosphate is 0.1 to 1.0 parts by weight, and 0.03 to 0.8 parts by weight, per 100 parts by weight of the thermoplastic polyester resin (A). parts is more preferred, and 0.05 to 0.5 parts by weight is even more preferred. At 0.1 parts by weight or more, sufficient melt retention stability, inhibition of carbide formation, and reduction in the amount of gas generated during heating can be obtained, and good mechanical properties can be obtained at 1.0 parts by weight or less.

In addition, in the present invention, (D) an inorganic filler other than reinforcing fibers can be blended. This is intended to partially improve the crystallization properties, arc resistance, anisotropy, mechanical strength, flame retardancy, heat distortion temperature, etc. of the molded article of the present invention, and is particularly effective for anisotropy. Therefore, a molded product with less warpage can be obtained. Examples of inorganic fillers other than reinforcing fibers include, but are not limited to, needle-like, granular, powdery and layered inorganic fillers, and specific examples include glass beads, milled fibers, glass flakes, and titanium. acid potash whiskers, calcium sulfate whiskers, wollastonite, silica, kaolin, talc, smectite clay minerals (montmorillonite, hectorite), vermiculite, mica, fluorteniolite, zirconium phosphate, titanium phosphate, and dolomite, and more than one used in In particular, when gas beads, glass flakes, kaolin, talc and mica are used, moldings with little warpage can be obtained due to their anisotropic effects.

Inorganic fillers other than the above reinforcing fibers may be subjected to surface treatment such as coupling agent treatment, epoxy compound treatment, or ionization treatment. The average particle size of the granular, powdery and layered inorganic filler is preferably 0.1 to 20 μm, particularly preferably 5 to 15 μm, from the viewpoint of impact strength. In addition, the blending amount of the inorganic filler other than the reinforcing fiber, together with the blending amount of the reinforcing fiber in terms of the fluidity during molding and the durability of the molding machine and the mold, is (A) 100 parts by weight of the thermoplastic polyester resin. However, an amount not exceeding 20 to 80 parts by weight is preferred.

In the present invention, a hindered phenol-based compound and/or a phosphite-based compound may be used as a stabilizer to ensure that the resin composition of the present invention has extremely good heat aging resistance even when exposed to high temperatures for a long period of time. An inhibitor can be added. When the hindered phenol-based oxide compound and/or the phosphite-based compound are blended, the blending amount is from 0.01 to 0.01 per 100 parts by weight of the (A) thermoplastic polyester resin, from the viewpoint of heat aging resistance and flame retardancy. 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight.

Examples of the hindered phenol compounds include triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2, 2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene , bis or tris(3-t-butyl-6-methyl-4-hydroxyphenyl)propane, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) , N,N′-trimethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) and the like.

Examples of the phosphite compounds include tris(2,4-di-t-butylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylosphite, trisnonylphenyl phosphite, alkylallyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like.

In the present invention, it is possible to improve releasability during molding by adding one or more lubricants. Examples of such lubricants include metal soaps such as calcium stearate and barium stearate, fatty acid esters, salts of fatty acid esters (including partially salted products), fatty acid amides such as ethylenebisstearamide, ethylenediamine and stearic acid. and a polycondensate of sebacic acid, or a polycondensate of phenylenediamine, stearic acid and sebacic acid, a fatty acid amide, a polyalkylene wax, an acid anhydride-modified polyalkylene wax, and a mixture of the above-mentioned lubricants and fluorine-based resins or fluorine-based compounds Mixtures include, but are not limited to. When a lubricant is added, the amount added is 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight, per 100 parts by weight of the thermoplastic polyester resin (A). Department.

In the present invention, furthermore, carbon black, titanium oxide, and one or more kinds of pigments and dyes of various colors are blended to adjust the resin to various colors, thereby improving weather resistance (light) resistance and conductivity. The amount of the pigment or dye to be blended is 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin (A). .03 to 3 parts by weight.

Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, soot, pine soot, and graphite. Carbon black having an oil absorption of 50 to 400 cm ³ /100 g is preferably used, and may be treated with a treating agent such as aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, or silane coupling agent.

As the above titanium oxide, titanium oxide having a crystal form such as rutile or anatase and having an average particle size of 5 μm or less is preferably used. It may be treated with a polyol, a silane coupling agent, or the like. In addition, the carbon black, titanium oxide, and pigments and dyes of various colors are used in various thermoplastic resins in order to improve dispersibility with the flame-retardant resin composition of the present invention and to improve handling during production. It may be used as a mixed material that is melt blended or simply blended with. In particular, (A) a thermoplastic polyester resin is preferably used as the thermoplastic resin.

In the present invention, a resin other than (A) the thermoplastic polyester resin can be blended within a range that does not impair the effects of the present invention. As the resin other than the thermoplastic polyester resin (A) used in the present invention, both thermoplastic resins and thermosetting resins can be used, but thermoplastic resins are preferred from the standpoint of moldability. Specific examples of resins include polyolefin resins such as low-density polyethylene resins, high-density polyethylene resins, polypropylene resins, liquid crystal polyester resins, polyamide resins, vinyl resins, polyacetal resins, polyurethane resins, aromatic and aliphatic polyketone resins, Polyphenylene sulfide resin, polyetheretherketone resin, polyimide resin, thermoplastic starch resin, polyurethane resin, MS resin, aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly- 4-methylpentene-1, polyetherimide resin, cellulose acetate resin, polyvinyl alcohol resin, unsaturated polyester resin, melamine resin, urea resin and the like.

Others include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their alkali metal salts (so-called ionomers). , ethylene-glycidyl (meth)acrylate copolymer, ethylene-alkyl acrylate copolymer (e.g., ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer Coalescing, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, etc., and those with various degrees of cross-linking, various microstructures such as cis structure, One having a trans structure, etc., one having a vinyl group, etc., one having various average particle diameters (in the resin composition), a core layer and one or more shell layers covering it, and also adjacent to each other. A multi-layer structure polymer called a core-shell rubber in which the mating layers are composed of different polymers can also be used, and a core-shell rubber containing a silicone compound can also be used.

Further, the various (co)polymers listed in the above specific examples may be random copolymers, block copolymers, graft copolymers, or the like. Two or more of them may be used in combination.

The thermoplastic polyester resin composition of the present invention is generally produced by a known method. For example, (A) thermoplastic polyester resin, (B) halogenated epoxy compound, (C) antimony trioxide, (D) reinforcing fiber, and (E) aliphatic alkyl acid phosphate, and optionally other than reinforcing fiber Inorganic fillers, antioxidants, lubricants and, if necessary, other necessary additives and colorants such as pigments and dyes are premixed, or supplied to an extruder without premixing and sufficiently melted. The thermoplastic polyester resin composition of the present invention is prepared by kneading.

Examples of the above premixing include mixing using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer, although dry blending alone is possible. (D) Reinforcing fibers may be added by installing a side feeder in the middle between the main loading section and the vent section of a multi-screw extruder such as a twin-screw extruder. In the case of liquid additives, a method of installing a liquid addition nozzle in the middle of the main loading section and the vent section of a multi-screw extruder such as a twin-screw extruder and adding it using a plunger pump or the main loading section It may be a method of supplying with a metering pump from etc.

In addition, when producing a thermoplastic polyester resin composition, although not limited, for example, a single-screw extruder, a twin-screw extruder, a tri-screw extruder, equipped with a "unimelt" or "dulmage" type screw, A conical extruder, a kneader type kneader, and the like can be used.

The thermoplastic polyester resin composition thus obtained is injection molded by a conventionally known method to obtain the molded article of the present invention. As the injection molding method, gas assist method, two-color molding method, sandwich molding, in-mold molding, insert molding and injection press molding are known in addition to the usual injection molding method. Applicable.

Briefly speaking, the structure of an injection molding machine consists of a part that injects the molten plastic at high pressure after heating and melting and kneading the plastic, and a part that cools and solidifies the injected molten plastic into a predetermined shape (molded product). The mold temperature during injection molding of the specific thermoplastic polyester resin composition of the present invention is controlled at a constant temperature in the range of 30 ° C. to 90 ° C. to prevent defective products. It is preferable because less molded articles can be obtained.

The electric and electronic parts made of the thermoplastic polyester resin composition of the present invention are molded articles that take advantage of the excellent flame retardancy, mechanical properties, and injection moldability of the present invention, such as breakers, electromagnetic switches, and focus cases. , flyback transformers, moldings for copiers and printers, general home appliances, housings for OA equipment, variable capacitor case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors , relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, resistors, electrical and electronic parts with metal terminals and conductors, computer-related parts, audio parts voice parts, lighting parts, telegraph/telephone equipment parts, air conditioner parts, household appliance parts such as VTRs and televisions, copier parts, facsimile parts, and optical equipment parts.

EXAMPLES Hereinafter, the effects of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In addition, Example 8 is a reference example. Moreover, the measuring method of each characteristic is as follows.

[Reference example]
(A) Thermoplastic polyester resin <A-1> Polybutylene terephthalate resin, "1100S" manufactured by Toray Industries, Inc. was used. (hereinafter abbreviated as PBT).
<A-2> Polyethylene terephthalate resin, Mitsui PET “J005” manufactured by Mitsui Pet Resin Co., Ltd. PET having an intrinsic viscosity of 0.63 was used (hereinafter abbreviated as PET).

(B) Halogenated epoxy compound <B-1> Tetrabromobisphenol-A-epoxy oligomer, tribromophenol-terminated "SR-T3040" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used.
<B-2> Tetrabromobisphenol-A-epoxy polymer, “SR-T5000” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used.

(C) Antimony trioxide <C-1> Antimony trioxide, "PATOX-MK" manufactured by Nippon Seiko Co., Ltd. was used.

(D) Reinforcing fiber <D-1> A chopped strand glass fiber having a fiber diameter of about 13 μm, “T-187” manufactured by Nippon Electric Glass Co., Ltd. was used.

(E) Aliphatic alkyl acid phosphate <E-1> Octadecyl acid phosphate "AX-71" molecular weight 490 manufactured by Adeka Co., Ltd. was used.
<E-2>"Dodecyl acid phosphate" molecular weight 382 was used.
<E-3> Methyl acid phosphate with a molecular weight of 119 was used.

(E) Compounds not corresponding to aliphatic alkyl acid phosphates <E'-1> Sumitomo Chemical Co., Ltd. 6-t-butyl-4-[3-(2,4,8,10-tetra-t-butyldibenzo[d ,f][1,3,2]dioxaphosphepin-6-yloxy)propyl]-o-cresol “Sumilizer GP” was used.
<E'-2> Special grade reagent "trimethyl phosphate" manufactured by Yoneyama Chemical Co., Ltd. was used.
<E'-3> Special grade reagent “monosodium phosphate dihydrate” manufactured by Yoneyama Chemical Co., Ltd. was used.
<E'-4> 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane "PEP-8" manufactured by Adeka Corporation was used.

[Measurement method of each characteristic]
In the present examples and comparative examples, the properties were evaluated by the measurement methods described below.

(1) Flammability Using an IS55EPN injection molding machine manufactured by Toshiba Machine, the molding cycle conditions are a molding temperature of 270°C, a mold temperature of 80°C, a combined injection time and holding pressure time of 10 seconds, and a cooling time of 10 seconds. Using flame retardant evaluation test specimens having a thickness of 1/32 inch and 1/64 inch, flame retardancy was evaluated according to the evaluation criteria stipulated in the UL94 vertical test. Flame retardancy is ranked in the order of V-0>V-1>V-2. In the case of 1/64 inch V-0, it was judged as ⊚, in the case of 1/32 inch, it was judged as ◯, and in the case of 1/32 inch and V-1 or V-2, it was judged as x.

(2) Retention Stability Using a melt indexer (manufactured by Toyo Seiki Co., Ltd.), pellets dried in advance at 130° C. for 3 hours were measured according to ISO 1133 under conditions of a test temperature of 270° C. and a load of 1000 g. At that time, the MFR when staying for 20 minutes and the MFR when staying for 5 minutes were measured, and the thickening property was evaluated as follows.
Retention MFR change rate (%)
= (1-(MFR when staying for 20 minutes / MFR when staying for 5 minutes)) x 100
A rate of change of less than ±20% was evaluated as ◯, and a rate of change of ±20% or more was evaluated as x.

(3) Low gas properties Using the resin compositions obtained in each example and comparative example, heat treatment was performed at 270 ° C. for 0.5 hours using a perfect oven manufactured by TABAI ESPEC Co., Ltd., and heating was performed according to the following calculation formula. The weight reduction rate was determined by , and the low gas property was evaluated.
Weight reduction rate (%) = {1-(weight after heat treatment/weight before heat treatment)} x 100
If the weight reduction rate was less than 0.3%, it was judged to be ◯, and if it was 0.3% or more, it was judged to be x.

(4) Amount of carbide generated Using a J55AD injection molding machine manufactured by Japan Steel Works, the resin composition obtained in each example and comparative example is placed in a screw at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. After being plasticized and held for 15 minutes, a square plate of 80×80×1 mmt was obtained under the molding conditions of 10 seconds for the total injection and pressure holding time and 10 seconds for the cooling time. Using the obtained square plate, the number of carbides with a diameter of 0.5 mm or more that can be confirmed in a field of view at a magnification of 20 times or more was evaluated as the amount of generated carbides using a Shimadzu digital microscope VHX-500F.

[Examples 1 to 11], [Comparative Examples 1 to 9]
(A) thermoplastic polyester resin, (B) halogenated epoxy compound, (C) using a co-rotating vented twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX-30α) having a screw diameter of 30 mm and an L/D of 35. Antimony trioxide, (E) aliphatic alkyl acid phosphate, etc. were mixed according to the composition shown in Tables 1 to 4, and added from the main loading portion. The reinforcing fibers (D) were added by installing a side feeder between the main loading portion and the vent portion.

Further, melt-mixing was performed under the extrusion conditions of a kneading temperature of 270° C. and a screw rotation of 150 rpm, and the mixture was extruded in the form of strands, passed through a cooling bath, and pelletized with a strand cutter. After drying the obtained pellets in a hot air dryer at 130° C. for 3 hours, various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. Furthermore, various values were measured by the above measuring method, and the results are shown in Tables 1 and 2.

From Examples 1 to 11 in Table 1, the thermoplastic polyester resin composition of the present invention can be said to be a resin composition that is excellent in combustibility, retention stability, suppression of carbide generation, and low gas properties during injection molding.

From Comparative Examples 1 to 9 in Table 2, when a compound not corresponding to (E') aliphatic alkyl acid phosphate is blended, when any of the components (A) to (E) of the present invention is not blended, or ( When the blending amount of components A) to (E) is outside the specific range, it is clear that the resin composition has problems in combustibility, retention stability, suppression of carbide generation, and low gas properties. .

Claims (4)

(A) Per 100 parts by weight of the thermoplastic polyester resin, (B) 25 to 40 parts by weight of the halogenated epoxy compound, (C) 7 to 12 parts by weight of antimony trioxide, (D) 20 to 80 parts by weight of reinforcing fibers, and (E) 0.1 to 1.0 parts by weight of an aliphatic alkyl acid phosphate , wherein the (B) halogenated epoxy compound is a terminal-capped compound with tribromophenol, a thermoplastic polyester resin composition. 2. The thermoplastic polyester resin composition according to claim 1, wherein the (E) aliphatic alkyl acid phosphate has a molecular weight of 200 or more and 2,000 or less. 3. The thermoplastic polyester resin composition according to claim 1, wherein the (E) aliphatic alkyl acid phosphate is octadecyl acid phosphate. An electric/electronic component comprising the thermoplastic polyester resin composition according to any one of claims 1 to 3.