JP2013001772A - Flame-retardant thermoplastic polyester resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant thermoplastic polyester resin composition excellent in a tensile physical property, a weld physical property and thermal deformation temperature of a molding, while maintaining a high level of flame retaradancy, and the molding formed therewith.SOLUTION: The flame-retardant thermoplastic polyester resin composition is blended with (C) 1-40 pts.wt. of phosphorus flame retardant, (D) 1-50 pts.wt. of salt of a triazine compound and a cyanuric acid or isocyanuric acid, and (E) 0.01-5 pts.wt. of organic silane compound having an epoxy group or an isocyanate group, per 100 pts.wt. of total with (A) 60-95 wt.% of thermoplastic polyester resin, and (B) 5-40 wt.% of organic polycarbonate resin and/or polyphenylene ether resin.

Description

  The present invention relates to a flame retardant thermoplastic polyester resin composition and a molded product obtained by molding the same. In particular, a flame retardant thermoplastic polyester resin composition in which the tensile properties and weld properties of the molded product are greatly improved by blending an organosilane compound having an epoxy group or an isocyanate group, and a molded product obtained by molding the same. It is about.

  Thermoplastic polyester resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent properties such as injection moldability and mechanical properties. Since the thermoplastic polyester resin is a crystalline plastic having a high melting point, a high processing temperature is required for melt-kneading and injection molding of the thermoplastic polyester resin composition. In addition, since thermoplastic polyester resins are inherently flammable, they have general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical / electronic parts, and automotive parts. In addition to balance, flame safety, that is, flame retardancy is required, and high flame retardancy that indicates V-0 of the UL-94 standard is often required.

  As a method of imparting flame retardancy to a thermoplastic polyester resin, a method of blending a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary is generally used. There are moves to worry about the environmental impact of halogen-based flame retardant materials. Accordingly, it has been strongly desired to use a non-halogen flame retardant containing no halogen at all, and it has been proposed to add a phosphorus flame retardant to a thermoplastic resin.

  For example, it is disclosed that a phosphoric ester compound and melamine cyanurate are blended into a polyester resin composition containing a thermoplastic polyester resin and a polyphenylene ether resin and / or a polyphenylene sulfide resin (for example, Patent Document 1). However, the polyester resin composition disclosed in Patent Document 1 has a problem inferior to the tensile strength and elongation of the molded product.

  Further, in recent years, the shape of the molded product tends to be complicated, a weld part where the molten resin and the molten resin are joined in the molding die is generated, and there is a problem that the obtained molded product is easily broken from the weld part, A material having excellent weld properties such as weld strength and weld elongation has been desired. As a thermoplastic resin composition excellent in weld strength, a composition containing a thermoplastic polyester resin, an aromatic polycarbonate resin, and attapulgite (magnesium silicate clay mineral) in a rubber-modified styrene resin has been proposed (for example, However, in the flame-retardant thermoplastic polyester resin composition formed by blending a non-halogen flame retardant, further improvement in weld strength has been demanded.

JP-A-10-77396 (Claims) JP 2004-182827 A (Claims)

  The present invention is to obtain a flame retardant thermoplastic polyester resin composition excellent in tensile properties, weld properties and heat distortion temperature of a molded product while maintaining a high level of flame retardancy, and a molded product formed by molding the same. Let it be an issue.

As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a specific amount of (E) an organosilane compound having an epoxy group or an isocyanate group. The invention has been reached. That is, the present invention for solving such a problem is characterized by the following configuration.
(1) (C) Phosphorus-based difficulty with respect to a total of 100 parts by weight of (A) 60 to 95% by weight of thermoplastic polyester resin and (B) 5 to 40% by weight of aromatic polycarbonate resin and / or polyphenylene ether resin 1 to 40 parts by weight of a flame retardant, (D) 1 to 50 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, and (E) 0.01 to 5 parts by weight of an organosilane compound having an epoxy group or an isocyanate group A flame-retardant thermoplastic polyester resin composition obtained by blending.
(2) The flame retardancy according to (1), wherein the salt of (D) triazine compound and cyanuric acid or isocyanuric acid is blended in an amount of 15 to 25% by weight in the flame-retardant thermoplastic polyester resin composition. Thermoplastic polyester resin composition.
(3) The flame-retardant thermoplastic polyester resin composition according to (1) or (2), further comprising (F) 0.01 to 5 parts by weight of a transesterification inhibitor.
(4) A molded product obtained by molding the flame retardant thermoplastic polyester resin composition according to any one of (1) to (3).
(5) The molded product according to (4), which is used for an electric / electronic component or a housing obtained by a multipoint gate.
(6) The molded article according to (4) or (5), which passes the glow wire test of IEC60695-2-13 standard.

  According to the flame-retardant thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded article having excellent tensile properties such as tensile strength and elongation, weld properties, and heat distortion temperature while maintaining high flame retardancy. it can. The molded product comprising the flame-retardant thermoplastic polyester resin composition of the present invention is useful as a molded product for mechanical mechanism parts, electrical / electronic parts, automobile parts and the like.

  Hereinafter, the present invention will be described in detail.

  The (A) thermoplastic polyester resin in the present invention is composed of (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c) a lactone. It is a polymer or copolymer having one or more selected main structural units. Here, the main structural unit means that 50 mol% or more of at least one selected from (A) to (C) is included in all the structural units, and preferably 80 mol% or more.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, C2-C20 aliphatic glycols such as cyclohexanediol and dimer diol, long-chain glycols having a molecular weight of 200 to 100,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, 4,4′-dihydroxy Aromatic dioxy compounds such as biphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and ester-forming derivatives thereof. .

  Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate. , Polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, poly Tylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene Terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol , Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, poly Fragrances such as butylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Group polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, and aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  The hydroxycarboxylic acid or ester-forming derivative thereof includes glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2 -Naphthoic acid and ester-forming derivatives thereof. Moreover, as a polymer or copolymer having these as structural units, aliphatic polyester resins such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid, etc. Etc.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like. Examples of the polymer or copolymer having these as structural units include polycaprolactone, polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Among these, a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Alternatively, a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, and an aliphatic diol selected from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, propylene glycol, or butanediol or an ester-forming property thereof. A polymer or copolymer having a derivative as a main structural unit is more preferred. Among them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, Aromatic polyester resins such as polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate are particularly preferred, and polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene. One aromatic polyester resin selected from terephthalate is most preferred. Moreover, these can also be used by 2 or more types of arbitrary compounding quantities.

  In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.

  In the present invention, as the (A) thermoplastic polyester resin, a liquid crystalline polyester capable of forming anisotropy upon melting may be used. Examples of the structural unit of the liquid crystalline polyester include an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, and an aromatic iminooxy unit.

  The carboxyl end group amount of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or less, and preferably 30 eq / t or less, in terms of fluidity, hydrolysis resistance and heat resistance. More preferably, it is 20 eq / t or less, more preferably 10 eq / t or less. The lower limit is 0 eq / t.

  The amount of carboxyl end groups of the (A) thermoplastic polyester resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of hydroxy end groups of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or more, more preferably 80 eq / t or more, in terms of moldability and fluidity, and 100 eq / t is more preferably t or more, and particularly preferably 120 eq / t or more. The upper limit is 180 eq / t.

  The viscosity of the thermoplastic polyester resin (A) of the present invention is in the range of 0.50 to 1.50 dl / g in terms of moldability when the o-chlorophenol solution is measured at 25 ° C. Is preferred.

  The molecular weight of the thermoplastic polyester resin of component (A) used in the present invention is preferably in the range of more than 8,000 to 500,000 in terms of heat resistance, and more than 8,000 to 300,000 in terms of heat resistance. More preferably, it is more preferably in the range of more than 8000 and not more than 250,000. In the present invention, Mw of the polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The (A) thermoplastic polyester resin in the present invention can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization may be used, and any of transesterification and direct polymerization can be applied, but the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of this, continuous polymerization is preferable, and direct polymerization is preferable in terms of cost.

  When the thermoplastic polyester resin (A) of the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof The dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include titanic acid methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, Organic titanium compounds such as benzyl ester, tolyl ester, or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide , Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, Butyltin dichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, tin compounds such as methylstannic acid, ethylstannic acid, alkylstannic acid such as butylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, And antimony compounds such as antimony trioxide and antimony acetate. Among these, an organic titanium compound and a tin compound are preferable, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are more preferable, and tetra-n-butyl ester of titanic acid is particularly preferable. Two or more of these polymerization reaction catalysts can be used in combination. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin in terms of mechanical properties, moldability and color tone, and 0.01 to 0.00. A range of 2 parts by weight is more preferred.

  In the present invention, by blending (B) an aromatic polycarbonate resin and / or a polyphenylene ether resin, a molded product having a reduced molding shrinkage ratio at the time of injection molding and improved dimensional accuracy can be obtained. In addition, a molded product having excellent heat distortion temperature can be obtained. In addition, (C) there is an effect of suppressing bleeding out of the phosphorus-based flame retardant deposited on the surface of the molded product.

  Examples of the aromatic polycarbonate resin (B) in the present invention include aromatic homo- or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.

  Aromatic dihydric phenol compounds include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl- 1,1-bis (4-hydroxyphenyl) ethane and the like can be mentioned. Two or more of these can be used.

  (B) The aromatic polycarbonate resin preferably has a weight average molecular weight in the range of 10,000 to 1100000 and a glass transition temperature of about 150 ° C. Two or more aromatic polycarbonate resins may be used in combination. An aromatic polycarbonate resin having a weight average molecular weight in the range of 60000 to 1100000 is particularly preferably used. Here, the weight average molecular weight is a value obtained by measuring in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent.

  Further, those having a melt viscosity index (melt flow index) measured by a melt indexer according to ASTM D1238 at a temperature of 300 ° C. and a load of 1.2 kg are preferably in the range of 1 to 100 g / 10 min. From this point, an aromatic polycarbonate resin of 1 to 50 g / 10 min is preferably used.

  In addition, an aromatic polycarbonate resin oligomer may be used in combination as long as the amount does not impair the characteristics of the present invention. “Iupilon” (registered trademark) having a weight average molecular weight of about 4000 manufactured by Mitsubishi Gas Chemical Co., Ltd. ) AL etc. are commercially available.

  The polyphenylene ether resin (B) in the present invention is an amorphous polymer in which a benzene ring and oxygen are bonded, and is not limited, but preferably has a glass transition temperature of about 200 ° C., and has a molecular weight. Those of 5,000 to 30,000 are preferably used. Specific examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4). -Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1) , 4-phenylene) ether. Alternatively, the polyphenylene ether resin may be copolymerized with an alkyl trisubstituted phenol, a styrene compound may be graft copolymerized, and an acid anhydride may be graft copolymerized. Further, commercially available modified polyphenylene ether resins may be used, or two or more of these may be used in combination.

  The blending amount of (B) aromatic polycarbonate resin and / or polyphenylene ether resin in the present invention is 100% by weight in total of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin. 5 wt% or more and 40 wt% or less. (B) When the blending amount of the aromatic polycarbonate resin and / or polyphenylene ether resin is less than 5% by weight, the thermal deformation temperature of the molded product is lowered and the (C) phosphorus flame retardant bleed out occurs. It becomes easy. 10 weight% or more is preferable. On the other hand, when the blending amount of the blending amount of (B) aromatic polycarbonate resin and / or polyphenylene ether resin exceeds 40% by weight, the weld physical properties of the molded product are deteriorated. 35% by weight or less is more preferable.

  (C) Phosphorus flame retardant in the present invention is a flame retardant containing a phosphorus component, and is an aromatic phosphate ester compound, phosphazene compound, phosphaphenanthrene compound, phosphinic acid metal salt, ammonium polyphosphate, melamine polyphosphate, Examples thereof include phosphoric ester amide and red phosphorus. Among these, aromatic phosphate ester compounds, phosphazene compounds, phosphaphenanthrene compounds, and phosphinic acid metal salts are preferably used. Aromatic phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds are more preferred. Two or more of these may be blended.

  Examples of the aromatic phosphate compound include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, and biphenyl diphenyl phosphate. The commercially available products include PX-202, CR-741, PX-200, PX-201 manufactured by Daihachi Chemical Industry Co., Ltd., FP-500, FP-600, FP-700 and PFR manufactured by Adeka Co., Ltd. And so on.

  Examples of the phosphazene compound include a phosphonitrile linear polymer and / or a cyclic polymer, and a compound mainly composed of a linear phenoxyphosphazene is preferably used. The phosphazene compound can be synthesized by a known method described in the author Sugawara “Synthesis and Application of Phosphazene Compounds”, for example, phosphorus pentachloride or phosphorus trichloride as a phosphorus source, ammonium chloride or ammonia as a nitrogen source. It can be synthesized by reacting the gas by a known method (the cyclic product may be purified) and substituting the obtained substance with alcohol, phenol and amines. Further, as a commercially available product, “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.

  The phosphaphenanthrene compound is a phosphorus-based flame retardant having at least one phosphaphenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA, SANKO-220 manufactured by Sanko Co., Ltd. And M-Ester. In particular, M-Ester can be expected to react with a hydroxyl group at the terminal and the terminal of the thermoplastic polyester resin (A) at the time of melt kneading, and is effective in suppressing bleed out under high temperature and high humidity, and is preferably used.

  The phosphinic acid metal salt is a phosphinate and / or diphosphinate and / or a polymer thereof, and is a compound useful as a flame retardant for (A) a thermoplastic polyester resin. As said salt, salts, such as calcium, aluminum, and zinc, are mentioned. Commercially available phosphinic acid metal salts include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan.

  The phosphoric ester amide is an aromatic amide flame retardant containing a phosphorus atom and a nitrogen atom. Since it is a powdery substance at room temperature having a high melting point, it is excellent in handling at the time of blending, and the heat distortion temperature of the molded product can be further improved. As a commercial product of phosphoric ester amide, SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.

  Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium carbamyl polyphosphate. You may coat | cover with thermosetting resins, such as a phenol resin which shows thermosetting, a urethane resin, a melamine resin, a urea resin, an epoxy resin, and a urea resin.

  Examples of the melamine polyphosphate include melamine phosphate, melamine pyrophosphate, and melamine pyrophosphate such as melamine, melam, and phosphate with melem. “MPP-A” manufactured by Sanwa Chemical Co., Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Co., Ltd. are preferably used.

  Examples of the red phosphorus include not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of a thermosetting resin film, a metal hydroxide film, and a metal plating film. It can be preferably used. Examples of the thermosetting resin of the thermosetting resin film include phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin, and the like. Examples of the metal hydroxide of the metal hydroxide coating include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. The metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.

  The blending amount of the (C) phosphorus flame retardant in the present invention is 100 in total from (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin in terms of flame retardancy and bleed out. It is 1-40 weight part with respect to a weight part. (C) When the compounding quantity of a phosphorus flame retardant is less than 1 weight part, the flame retardance of a resin composition and a molded article will become inadequate. 3 parts by weight or more is preferable, and 10 parts by weight or more is more preferable. On the other hand, if the blending amount of (C) the phosphorus-based flame retardant exceeds 40 parts by weight, bleed-out in which the phosphorus-based flame retardant precipitates on the surface of the molded product tends to occur. 35 parts by weight or less is preferable.

  The salt of (D) triazine compound and cyanuric acid or isocyanuric acid in the present invention is a nitrogen-containing heterocyclic compound having a triazine skeleton, and melamine cyanurate and melamine isocyanurate are preferably used. By mix | blending this compound, the flame retardance of a resin composition and a molded article can be improved more according to the cooling effect. Two or more of these may be blended.

  As the melamine cyanurate or melamine isocyanurate, cyanuric acid or an adduct of isocyanuric acid and a triazine compound is preferable, and usually has a composition of 1: 1 (molar ratio), sometimes 1: 2 (molar ratio), etc. There may be mentioned adducts having Melamine cyanurate or melamine isocyanurate can be produced by a known method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry, mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried. . The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, you may process with well-known surface treatment agents, such as dispersing agents, such as a tris ((beta) -hydroxyethyl) isocyanurate, and metal oxides, such as polyvinyl alcohol and a silica, and can improve dispersibility. Further, the average particle diameter before and after blending with the resin of melamine cyanurate or melamine isocyanurate is preferably 0.1 to 100 μm, more preferably from the viewpoint of flame retardancy, mechanical strength and surface property of the molded product. Is 0.2 to 50 μm, more preferably 0.3 to 10 μm. An average particle diameter here is an average particle diameter measured by 50% of cumulative distribution particle diameter by a laser micron sizer method. Moreover, as a commercial item of the salt of (D) triazine compound and cyanuric acid or isocyanuric acid, MC-4000, MC-4250, MC-4500 and MC-6000 manufactured by Nissan Chemical Co., Ltd. are preferably used. .

  In the present invention, the blending amount of the salt of (D) triazine compound and cyanuric acid or isocyanuric acid is (A) a thermoplastic polyester resin, (B) an aromatic polycarbonate resin, from the viewpoint of flame retardancy and tensile properties. 1/50 parts by weight with respect to 100 parts by weight in total with the polyphenylene ether resin. (D) When the compounding quantity of the salt of a triazine type compound, cyanuric acid, or isocyanuric acid is less than 1 weight part, the flame retardance of a resin composition and a molded article will become inadequate. 3 parts by weight or more is preferable, and 10 parts by weight or more is more preferable. On the other hand, when the blending amount of the salt of (D) the triazine compound and cyanuric acid or isocyanuric acid exceeds 50 parts by weight, the tensile properties of the molded article are lowered. More preferred is 45 parts by weight or less.

  Further, the blending amount of the salt of (D) triazine compound and cyanuric acid or isocyanuric acid is more preferably 15 to 25% by weight in the flame retardant thermoplastic polyester resin composition, and flame retardant against direct fire In addition to the property, flame retardancy against electric fire can also be improved. For this reason, the molded product which passes the glow wire test of the safety standard IEC603335-1 standard 4th edition of an electric fire can be obtained easily.

  Here, the safety standard IEC603335-1 standard 4th edition is a fireproof safety standard revised in 2001 by the International Electrotechnical Commission (commonly known as IEC). This standard is a safety standard due to electrical ignition in contrast to the UL-94 standard due to direct fire established by UL (Underwriters Laboratories Inc). Applicable to electrical components of white goods that cannot be noticed by humans such as cautionable electrical components, air conditioners, refrigerators, washing machines, and televisions. For electrical components of white goods, it is required to pass a flame retardancy test (glow wire test) under severe conditions.

  To pass the above glow wire test, use a test piece with three recommended thicknesses of 0.75 mm, 1.5 mm, and 3 mm, and extinguish the fire within 30 seconds when a glow wire (red hot rod) at 850 ° C. is in contact. And after indirecting the glow wire (red hot rod) at 750 ° C. for 30 seconds, the fire is extinguished within 5 seconds.

  The organic silane compound (E) having an epoxy group or an isocyanate group in the present invention is an organic silane compound such as an alkoxysilane having at least one functional group of an epoxy group or an isocyanate group. In general, in a flame-retardant thermoplastic polyester resin composition containing a salt of (D) a triazine compound and cyanuric acid or isocyanuric acid, (A) a thermoplastic polyester resin, (D) a triazine compound and cyanuric acid Alternatively, the affinity with a salt with isocyanuric acid is considered to affect the tensile properties and weld properties of the molded product. In the present invention, it is presumed that the affinity of the (A) / (D) interface can be improved by blending (E) an organosilane compound having an epoxy group or an isocyanate group. As a result, the tensile properties and weld properties of the molded product can be dramatically improved. (E) Specific examples of the organosilane compound having an epoxy group or an isocyanate group include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples include diethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-isocyanatopropyltriethoxysilane. Two or more of these may be blended. Moreover, as a commercial item of the organosilane compound which has (E) epoxy group or an isocyanate group, Shin-Etsu Chemical Co., Ltd. epoxy modified organosilane compound KBM-303, isocyanate modified organosilane compound KBM-9007, etc. are used preferably. .

  In the present invention, (E) the compounding amount of the organosilane compound having an epoxy group or an isocyanate group is (A) a thermoplastic polyester resin, (B) an aromatic polycarbonate resin, and (B) an aromatic polycarbonate resin. It is 0.01-5 weight part with respect to a total of 100 weight part with / or polyphenylene ether resin. (E) When the compounding amount of the organosilane compound having an epoxy group or an isocyanate group is less than 0.01 parts by weight, the tensile physical properties and weld physical properties of the molded product are deteriorated. 0.1 weight part or more is preferable. On the other hand, when the compounding amount of the organosilane compound having (E) an epoxy group or an isocyanate group exceeds 5 parts by weight, the flame retardancy of the resin composition and the molded product is lowered. 1.0 parts by weight or less is more preferable.

  The (F) transesterification inhibitor in the present invention is a compound that deactivates the transesterification reaction catalyst, and a phosphate compound is preferably used. (F) By mix | blending a transesterification inhibitor, the heat-deformation temperature of a molded article can be improved more. The phosphate compound is a general term for partial ester compounds of alcohols and phosphoric acid. A low molecular weight compound is a colorless liquid, and a high molecular weight compound is a white waxy or flaky solid. Specific examples of the phosphate compound include monomethyl acid phosphate, monoethyl acid phosphate, monoisopropyl acid phosphate, monobutyl acid phosphate, monolauryl acid phosphate, monostearyl acid phosphate, monododecyl acid phosphate, monobehenyl acid phosphate, dimethyl acid Phosphate, diethyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, lauryl acid phosphate, distearyl acid phosphate, didodecyl acid phosphate, dibehenyl acid phosphate, trimethyl acid phosphate, triethyl acid phosphate, and mixtures of the above mono and di Mono, di Mixture of birds like and. Two or more of these may be blended. Preferred phosphate-based compounds include long chain alkyl acid phosphate compounds such as mixtures of mono and distearyl acid phosphates. Such a compound is, for example, commercially available from ADEKA Corporation under the name “Adeka Stub” (registered trademark) AX-71, and is a flaky solid having a melting point.

  The blending amount of the (F) transesterification inhibitor in the present invention is 0.01 wt. With respect to a total of 100 parts by weight of the (A) thermoplastic polyester resin and the (B) aromatic polycarbonate resin and / or polyphenylene ether resin. Part or more is preferable, and the thermal deformation temperature of the molded product can be further improved. 0.03 part by weight or more is preferable, and 0.1 part by weight or more is more preferable. On the other hand, the blending amount of the (F) transesterification inhibitor is preferably 5 parts by weight or less, and can maintain high flame retardancy of the resin composition and the molded product. In order to further improve the tensile physical properties, weld physical properties, and heat distortion temperature of the molded product, 4 parts by weight or less is more preferable.

  The flame-retardant thermoplastic polyester resin composition of the present invention preferably further contains a polyfunctional epoxy compound, and can improve hydrolyzability. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and excludes the (E) organosilane compound having an epoxy group or an isocyanate group. As the polyfunctional epoxy compound, a liquid or solid one can be used. For example, a copolymer of an α-olefin such as ethylene, propylene, and 1-butene and an α, β-unsaturated glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, having an unsaturated double bond Epoxy group-containing polymer compound obtained by epoxidizing the double bond part of the polymer, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyl Bisphenol-glycidyl ether type epoxy compounds such as dimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, phthalate Glycidyl ester type epoxy compounds such as glycidyl esters, N- glycidyl amine-based epoxy compound glycidyl aniline, novolac type phenolic resin novolak type epoxy resins obtained by reacting epichlorohydrin and the like. Two or more of these may be blended. Copolymer of α-olefin and α, β-unsaturated carboxylic acid glycidyl ester, novolak type epoxy resin obtained by reacting novolak type phenol resin with epichlorohydrin is preferable, and novolak type resin obtained by reacting novolak type phenol resin with epichlorohydrin. Epoxy resins are particularly preferred because they can further improve hydrolyzability and weld physical properties. The blending amount of the polyfunctional epoxy compound is 100 parts by weight in total of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin from the viewpoint of flame retardancy and hydrolyzability. Preferably it is 0.01-3 weight part, More preferably, it is 0.02-2.5 weight part, More preferably, it is 0.03-2 weight part. An effect of improving hydrolyzability is obtained at 0.01 parts by weight or more, and good flame retardancy is obtained at 5 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention preferably further contains a known polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, and is formed by molding such as injection molding. The fluidity of time can be improved. Here, the polyhydric alcohol refers to a compound having two or more hydroxyl groups. The polyhydric alcohol compound including one or more alkylene oxide units having three or more functional groups has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, and Any compound containing one or more alkylene oxide units is preferably used.

  The functional group of three or more functional groups is preferably at least one selected from a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, an ester group, and an amide group. It is more preferable to have three or more different functional groups, and it is more preferable that they are the same functional group in terms of fluidity, mechanical properties, durability, heat resistance and productivity.

  Examples of the alkylene oxide unit include aliphatic alkylene oxide units having 1 to 4 carbon atoms. Propylene oxide units are more preferred because of excellent fluidity, recyclability, durability, heat resistance, and mechanical properties. Moreover, since it is excellent in fluidity | liquidity and mechanical property, 1-5 are preferable for the alkylene oxide unit per functional group.

  The molecular weight or weight average molecular weight (Mw) of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is gel permeation chromatography using hexafluoroisopropanol as a solvent in terms of fluidity. The value measured by (GPC) and quantified in terms of polymethyl methacrylate (PMMA) is preferably in the range of 200 to 6000.

  The blending amount of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is the sum of (A) a thermoplastic polyester resin and (B) an aromatic polycarbonate resin and / or a polyphenylene ether resin. 0.1-1 weight part is preferable with respect to 100 weight part.

  In the flame-retardant thermoplastic polyester resin composition of the present invention, thermoplastic resins other than the components (A) and (B) can be blended in amounts that do not impair the characteristics of the present invention. Examples of such thermoplastic resins include vinyl resins, phenoxy resins, cellulose ester resins, polyamide resins, polyolefin copolymers, polyetherimide resins, ionomer resins, polyphenyl sulfide resins, phenol resins, and polyacetal resins. Is mentioned. From the viewpoint of flame retardancy, polyamide resins and polyphenyl sulfide resins are preferred. On the other hand, vinyl resins are preferred from the viewpoint of improving electrical characteristics such as tracking resistance, arc resistance and voltage resistance characteristics, and improving toughness such as impact strength.

  The vinyl resin is formed by polymerizing one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide monomers. A resin or a resin obtained by graft polymerization or copolymerization of these monomers with a rubber-based component such as a polybutadiene rubber, an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid alkyl ester, and Examples thereof include resins containing 50% by weight or more of one or more monomer components selected from the group consisting of maleimide monomers (hereinafter, these may be collectively referred to as “(co) polymers”).

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, and divinyl benzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the esters include (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. A copolymer of the above vinyl resin and a component capable of copolymerization can also be used in the present invention. Specific examples of components capable of such copolymerization include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.

  Examples of preferred (co) polymers of vinyl resins include polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, and styrene / N-phenyl. Maleimide resin, vinyl (co) polymers such as styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact -Styrenic resin modified with a rubbery polymer such as polystyrene resin, and styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene as block copolymers. / Styrene resins. In particular, polystyrene resin and acrylonitrile / styrene resin are preferable, and acrylonitrile / styrene copolymer, which is a copolymer obtained by copolymerizing acrylonitrile and styrene, is more preferable (/ indicates copolymerization). As the acrylonitrile / styrene resin, those containing 15% by weight or more and less than 35% by weight of acrylonitrile are particularly preferable.

  Further, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers may be graft-polymerized or copolymerized with the vinyl resin. Among these, a vinyl resin obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferable.

  The unsaturated acid anhydrides are compounds that share both a vinyl group capable of radical polymerization and an acid anhydride in one molecule, and preferred examples include maleic anhydride.

  In addition, the epoxy group-containing vinyl monomer is a compound that shares both radically polymerizable vinyl group and epoxy group in one molecule, and specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, Examples include glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. it can. Moreover, these can be used individually or in combination of 2 or more types.

  The amount used for graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is 0.05% by weight or more based on the vinyl resin. It is preferable that Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Further, a vinyl resin that is epoxy-modified with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid may be used. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like.

  Further, a vinyl resin in which an innermost layer (core layer) having a rubber layer and a vinyl resin covering the inner layer (shell layer) are used as one kind of outer layer (shell layer) is also preferably used, and has a so-called core-shell type structure. A core-shell type rubber is also preferably used.

  In addition, a vinyl resin containing a vinyl resin as a branched chain of the graft copolymer may be used, and examples of the resin serving as the main chain include polyolefin, acrylic resin, and polycarbonate resin. Either the chain or the main chain may be modified with glycidyl methacrylate or acid anhydride. Specific examples thereof include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g- PMMA), poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly (ethylene) -G-acrylonitrile / styrene (Eg-AS), polycarbonate-g- Examples thereof include acrylonitrile / styrene (PC-g-AS) ("-g-" represents a graft, and "-/-" represents a copolymerization). “Modiper” (registered trademark) manufactured by Nippon Oil & Fats Co., Ltd. may be used alone or in combination with other vinyl resins.

  Further, the compounding amount of the vinyl resin is 100 parts by weight in total of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin from the viewpoint of electrical characteristics, toughness and mechanical characteristics. On the other hand, it is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and still more preferably 1 to 6 parts by weight. When the content is 0.1 parts by weight or more, the electrical characteristics and toughness are improved, and when the content is 10 parts by weight or less, good mechanical properties are obtained.

  The flame retardant thermoplastic polyester resin composition of the present invention can further contain a known flame retardant such as a silicone flame retardant and an inorganic flame retardant within a range not impairing the effects of the present invention.

  In addition, the flame-retardant thermoplastic polyester resin composition of the present invention preferably further contains a fluorine-based resin, which suppresses melting and dropping of the resin composition at the time of combustion, and further improves flame retardancy. it can.

  The fluorine-based resin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra (Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Is mentioned. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferable. In particular, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymers are preferred.

  The blending amount of the fluorine-based resin is preferably 0.05 to 3 weights with respect to a total of 100 parts by weight of (A) the thermoplastic polyester resin and (B) the aromatic polycarbonate resin and / or the polyphenylene ether resin. Parts, more preferably 0.1 to 2 parts by weight, still more preferably 0.15 to 1.5 parts by weight. The effect of preventing melting and dropping during combustion is obtained at 0.05 part by weight or more, and good mechanical properties are obtained at 2 parts by weight or less.

  The flame retardant thermoplastic polyester resin composition of the present invention can further contain a resin that improves impact strength. Examples of resins that improve impact strength include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, natural rubber, thiocol rubber, polysulfide rubber, polyether rubber, Examples include chlorohydrin rubber and ethylene, an acid anhydride such as maleic anhydride, glycidyl methacrylate, and a modified olefin resin epoxy-modified with an epoxidizing agent. Further, those having various degrees of crosslinking and those having various microstructures such as a cis structure and a trans structure are exemplified. Examples of the modified olefin resin epoxy-modified with ethylene, such as acid anhydride such as maleic anhydride, glycidyl methacrylate and epoxidizing agent, include ethylene / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, ethylene / propylene / Specific examples include maleic anhydride, ethylene / maleic anhydride, and epoxidized olefin resin obtained by epoxidizing ethylene with a peroxide. Examples of commercially available products include “Bond First” (registered trademark) E (ethylene / glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd., MH-5010 and MH-5020 (ethylene / butene-1) manufactured by Mitsui Petrochemical Co., Ltd. / Maleic anhydride) and the like, and may or may not be combined with a vinyl resin. In particular, ethylene / butene-1 / maleic anhydride is preferably used because it greatly improves impact strength.

  The amount of the resin for improving the impact strength is preferably 0.1 to 100 parts by weight in total of (A) the thermoplastic polyester resin and (B) the aromatic polycarbonate resin and / or the polyphenylene ether resin. 10 parts by weight, more preferably 0.5 to 8 parts by weight, still more preferably 1 to 6 parts by weight. Impact strength is improved at 0.1 parts by weight or more, and good mechanical properties are obtained at 10 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention further comprises alkaline earth metal soaps such as calcium stearate, barium stearate and zinc stearate, fatty acid esters, fatty acid ester salts (partly salted products) Fatty acid amides such as ethylene bisstearyl amide, polycondensates composed of ethylenediamine and stearic acid and sebacic acid, or fatty acid amides composed of polycondensates of phenylenediamine and stearic acid and sebacic acid, polyalkylene waxes, acid anhydrides A known release agent for plastics such as a modified polyalkylene wax and a mixture of the above-described lubricant and a fluorine resin or a fluorine compound can be blended, and the mold release property at the time of injection molding can be improved. In particular, alkaline earth metal soaps such as zinc stearate and salts of fatty acid esters (including partially salted ones) contribute to retention stability in addition to improving mold release during injection molding. Preferably used.

  The compounding amount of the release agent is preferably 0.01 to 1 part by weight with respect to a total of 100 parts by weight of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin. More preferably, it is 0.02-0.8 weight part, More preferably, it is 0.03-0.6 weight part. When the amount is 0.01 parts by weight or more, a sufficient releasing effect is obtained, and when the amount is 1 part by weight or less, good mechanical properties are obtained.

  The flame-retardant thermoplastic polyester resin composition of the present invention preferably contains a fiber reinforcing material, and can further improve the mechanical strength and heat distortion temperature of the molded product. Specific examples of the fiber reinforcing material include glass fiber, aramid fiber, and carbon fiber. The above glass fiber is a chopped strand type or roving type glass fiber, such as a silane coupling agent such as an aminosilane compound or an epoxysilane compound, and / or urethane, vinyl acetate, bisphenol A diglycidyl ether, a novolac epoxy compound, or the like. Glass fibers treated with a sizing agent containing one or more epoxy compounds and the like are preferably used, and the silane coupling agent and / or sizing agent may be used by mixing with an emulsion liquid. The fiber diameter is usually 1 to 30 μm, preferably 5 to 15 μm. In addition, the fiber cross section is usually circular, but fiber reinforcing materials having an arbitrary cross section such as elliptical glass fiber, flat glass fiber, and eyebrow-shaped glass fiber having an arbitrary aspect ratio can be used, and injection molding can be used. It is characterized by improved fluidity at the time and a molded product with less warping.

  In addition, the blending amount of the fiber reinforcing material is such that (A) a thermoplastic polyester resin and (B) an aromatic polycarbonate resin and / or polyphenylene from the viewpoint of fluidity during injection molding and durability of the injection molding machine or mold. Preferably it is 1-100 weight part with respect to a total of 100 weight part with ether resin, More preferably, it is 2-95 weight part, More preferably, it is 3-90 weight part. If it is 1 part by weight or more, the effect of further improving the mechanical strength and the heat distortion temperature is obtained, and if it is 100 parts by weight or less, a good mechanical strength and heat distortion temperature can be obtained.

  In addition, the flame-retardant thermoplastic polyester resin composition of the present invention can further contain an inorganic filler other than the fiber reinforcement, and the crystallization characteristics of the molded product, arc resistance, anisotropy, mechanical strength, Part of flame retardancy or heat distortion temperature can be improved, and in particular, a molded product with less warpage can be obtained because of its effect on anisotropy. Examples of inorganic fillers other than the fiber reinforcing material include needle-like, granular, powdery and layered inorganic fillers. Specific examples include glass beads, milled fibers, glass flakes, california titanate, calcium sulfate. Whisker, Wollastonite, Silica, Kaolin, Talc, Calcium carbonate, Zinc oxide, Magnesium oxide, Aluminum oxide, Mixture of magnesium oxide and aluminum oxide, Fine silicate, Aluminum silicate, Silicon oxide, Smectite clay mineral (Montmorillonite, Hect Light), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, dolomite, and the like. In particular, when milled fiber, glass flake, kaolin, talc and mica are used, a molded product with less warpage can be obtained because of its effect on anisotropy. Further, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, a mixture of magnesium oxide and aluminum oxide, finely divided silicic acid, aluminum silicate and silicon oxide are converted into (A) a thermoplastic polyester resin, (B) an aromatic polycarbonate resin, and When blended in the range of 0.01 to 1 part by weight with respect to a total of 100 parts by weight with the polyphenylene ether resin, an effect on the retention stability was obtained.

  In addition, the inorganic filler other than the fiber reinforcing material may be subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. The average particle size of the granular, powdery and layered inorganic fillers is preferably 0.1 to 20 μm, particularly preferably 0.2 to 10 μm from the viewpoint of impact strength. In addition, the blending amount of the inorganic filler other than the fiber reinforcement is combined with the blending amount of the fiber reinforcement from the viewpoint of fluidity during molding and durability of the molding machine and the mold (A) thermoplastic polyester resin, From the viewpoint of fluidity at the time of molding, an amount not exceeding 100 parts by weight is preferable with respect to a total of 100 parts by weight of (B) aromatic polycarbonate resin and / or polyphenylene ether resin, and (A) a thermoplastic polyester resin and ( B) It is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and further preferably 3 to 30 parts by weight with respect to 100 parts by weight in total with the aromatic polycarbonate resin and / or polyphenylene ether resin. . An effect of improving sufficient anisotropy or residence stability is obtained at 1 part by weight or more, and a good mechanical strength is obtained at 50 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention may contain one or more of oxazoline compounds, carbodiimide-modified isocyanate compounds, carbodiimide compounds, etc. for the purpose of improving hydrolyzability.

  The blending amount of the oxazoline compound, carbodiimide-modified isocyanate compound and carbodiimide compound is preferably 100 parts by weight in total of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin. 0.01 to 3 parts by weight, more preferably 0.01 to 2.5 parts by weight, and still more preferably 0.01 to 2 parts by weight. In the case of 3 parts by weight or less, good mechanical strength can be obtained.

  The flame retardant thermoplastic polyester resin composition of the present invention can further contain a hindered phenolic antioxidant, a phosphite antioxidant, and a thioether antioxidant as stabilizers. Even if the resin composition is exposed to a high temperature for a long period of time, extremely good heat aging resistance can be provided. The blending amount is preferably 0.01 to 100 parts by weight with respect to a total of 100 parts by weight of (A) thermoplastic polyester resin and (B) aromatic polycarbonate resin and / or polyphenylene ether resin, from the viewpoint of improving heat aging resistance. 2 parts by weight, more preferably 0.02 to 1.5 parts by weight, still more preferably 0.03 to 1 part by weight. The effect of improving the heat aging resistance is obtained at 0.01 parts by weight or more, and good mechanical properties are obtained at 2 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention is further prepared by blending one or more types of carbon black, titanium oxide, and various colors of pigments and dyes to adjust the resin to various colors and weather resistance (light It is also possible to improve the property) and conductivity. The blending amount of the pigment or dye is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight in total of (A) the thermoplastic polyester resin and (B) the aromatic polycarbonate resin and / or the polyphenylene ether resin. More preferably, it is 0.02-2 weight part, More preferably, it is 0.03-1 weight part. 0.01 parts by weight is effective in toning, weather resistance (light), and conductivity, and good mechanical properties are obtained in 3 parts by weight or less.

As examples of the carbon black, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine, and, such as graphite and the like, average particle size below 500 nm, dibutyl phthalate absorption 50~400cm ³ / 100g The carbon black is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treating agent.

  Further, as the above titanium oxide, a titanium oxide having a crystal form such as a rutile form or anatase form and having an average particle size of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol are used as treatment agents. And may be treated with a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various ways to improve dispersibility with the flame-retardant thermoplastic polyester resin composition of the present invention and to improve handling during production. It may be used as a mixed material which is melt blended or simply blended with a thermoplastic resin.

  Furthermore, the flame-retardant thermoplastic polyester resin composition of the present invention contains 1 known additives such as ultraviolet absorbers, light stabilizers, plasticizers, and antistatic agents within a range that does not impair the object of the present invention. You may mix | blend a seed or more.

  A molded product obtained by molding the flame-retardant thermoplastic polyester resin composition of the present invention has high physical properties such as tensile strength and elongation, weld properties, and heat distortion temperature while maintaining high flame retardancy. Therefore, it can be suitably used as a molded product of a mechanical mechanism part, an electric / electronic part or an automobile part. Furthermore, (D) a flame retardant thermoplastic polyester resin composition obtained by blending a salt of triazine compound with cyanuric acid or isocyanuric acid in an amount of 15 to 25% by weight in the flame retardant thermoplastic polyester resin composition is molded. By doing, the molded article which is excellent in glow wire property and passes the glow wire test of the electrical fire safety standard IEC603335-1 standard 4th edition can be obtained easily. Such a molded article is particularly useful for parts and devices that come into contact with electricity, and is suitably used for electric / electronic parts or housings obtained by a multipoint gate.

  In addition, concrete molded products of mechanical mechanism parts, electrical / electronic parts and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, and general household 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 / electronic parts with built-in metal terminals and conductors, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, VTR, etc. Home appliance parts such as TV, parts for copiers, fax Use parts, parts for optical instruments, automotive ignition system parts, automotive connectors, and molded articles such as various electrical components for automobiles and the like. Among these, the molded article of the present invention is suitably used for an electric / electronic component or a housing obtained by a multipoint gate, where a weld portion is easily formed.

  The flame-retardant thermoplastic polyester resin composition of the present invention can be produced by a known method. For example, a method of premixing each of the components (A) to (E) and a blending material contained as necessary, supplying the mixture to an extruder, etc., and sufficiently melting and kneading, or a quantitative feeder such as a weight feeder The flame-retardant thermoplastic polyester resin composition of the present invention is produced by a method in which a predetermined amount of each component is supplied to an extruder or the like and sufficiently melt-kneaded.

  Examples of the premixing include a dry blending method and a mixing method using a mechanical mixing device such as a tumbler, ribbon mixer, and Henschel mixer. Further, the inorganic filler other than the fiber reinforcing material and the fiber reinforcing material may be added by installing a side feeder in the middle of the original loading part and the vent part of a multi-screw extruder such as a twin screw extruder. . In addition, in the case of liquid additives, a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part For example, a method of supplying with a metering pump may be used.

  In producing a flame-retardant thermoplastic polyester resin composition, for example, a single-screw extruder, twin-screw extruder, tri-screw extruder, conical extruder and kneader equipped with a “unimelt” or “dalmage” type screw. It can be obtained in the form of pellets by discharging into a strand using a kneader of the type and cutting with a strand cutter.

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

Hereinafter, the effects of the present invention will be described in more detail with reference to examples. The raw material used for an Example and a comparative example is shown below. Here, “%” and “part” represent “% by weight” and “part by weight”, and “/” in the resin name in the following Reference Examples means copolymerization.
(A) Thermoplastic polyester resin <A-1> Polybutylene terephthalate resin, “Toraycon” (registered trademark) 1401-X31 manufactured by Toray Industries, Inc. PBT having an intrinsic viscosity of 0.80 was used (hereinafter referred to as PBT resin and (Omitted).
(B) Aromatic polycarbonate resin <B-1> Aromatic polycarbonate resin, “A-1900” manufactured by Idemitsu Petrochemical Co., Ltd. was used (hereinafter abbreviated as PC resin).
<B-2> Polyphenylene ether resin, “YPX-100L” manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used (hereinafter abbreviated as PPE resin).
(C) Phosphorus flame retardant <C-1> Phosphate ester compound, condensed phosphate ester compound “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. was used (hereinafter abbreviated as PX-200).
<C-2> Phosphazene compound, “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. was used (hereinafter abbreviated as “phosphazene compound”).
<C-3> Phosphophenanthrene compound, M-Ester manufactured by Sanko Co., Ltd. was used (hereinafter abbreviated as “phosphaphenanthrene compound”).
(D) Salt of triazine compound and cyanuric acid or isocyanuric acid <D-1> Salt of triazine compound and cyanuric acid or isocyanuric acid, “MC-4000” manufactured by Nissan Chemical Co., Ltd. was used. (Hereinafter abbreviated as MC salt).
(E) Organosilane compound having epoxy group or isocyanate group <E-1> Epoxy-modified organosilane compound, KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter abbreviated as epoxysilane) was used.
<E-2> Isocyanate-modified organosilane compound, KBM-9007 manufactured by Shin-Etsu Chemical Co., Ltd. was used (hereinafter abbreviated as isocyanate silane).
(F) Transesterification inhibitor <F-1> A long-chain alkyl acid phosphate compound, “Adeka Stub” (registered trademark) AX-71 manufactured by Asahi Denka Co., Ltd. (hereinafter abbreviated as AX-71) was used.
(G) Furthermore, component <G-1> blended as necessary Polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, polyoxyethylene pentaerythritol, Nippon Emulsifier Co., Ltd. PNT-60U (molecular weight 400, alkylene oxide (ethylene oxide) unit number 1.5 per functional group was used (hereinafter abbreviated as polyhydric alcohol)).
<G-2> Vinyl resin, styrene / acrylonitrile / glycidyl methacrylate = 70 / 29.5 / 0.5 wt% epoxy-modified AS resin (hereinafter abbreviated as epoxidized AS).
<G-3> Resin for improving impact strength other than vinyl resin, ethylene / butene-1 / maleic anhydride copolymer, MH-5020 manufactured by Mitsui Petrochemical Co., Ltd. (hereinafter referred to as MH-5020) Abbreviated).
<G-4> Fluorine resin, polytetrafluoroethylene, “Teflon” (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., which acts as a melting and dropping (drip) inhibitor during combustion ( Hereinafter, abbreviated as fluororesin).
<G-5> Fiber reinforcing material, chopped strand glass fiber having a fiber diameter of about 10 μm, and “CS3J948” manufactured by Nitto Boseki Co., Ltd. (hereinafter abbreviated as GF) were used.
<G-6> hindered phenol antioxidant, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, “IRGANOX” manufactured by Ciba Geigy Corporation (Trademark) 1010 was used (hereinafter abbreviated as IR-1010).
<G-7> Mold release agent, fatty acid ester salt (including partly salted), montanic acid wax partial calcium salt, Rico wax OP manufactured by Clariant Japan Co., Ltd. (hereinafter Rico) (Abbreviated as -OP).

[Measurement method for each characteristic]
In Examples and Comparative Examples, the characteristics were evaluated by the measurement methods described below.

1. Tensile properties Test pieces using a Toshiba Machine IS55EPN injection molding machine under the molding conditions of a molding temperature of 260 ° C, a mold temperature of 80 ° C, a combined injection time and holding time of 10 seconds, and a cooling time of 10 seconds. A test piece for evaluation of tensile properties of ASTM No. 1 dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained. Tensile strength and elongation were measured in accordance with ASTM D638 (2005) using the test specimen for evaluation of tensile properties. In addition, the value was made into the average value of three measured values.

2. Weld properties Using IS55EPN injection molding machine manufactured by Toshiba Machine, using a mold with two gates (channels) at a molding temperature of 260 ° C and a mold temperature of 80 ° C, and a specimen thickness of 1/8 inch ( An injection molded product of ASTM No. 1 dumbbell of about 3.2 mm) was obtained. Two gate positions at this time were provided on the left and right in the longitudinal direction of the ASTM No. 1 dumbbell, and a molded product having a weld part at the center of the ASTM No. 1 dumbbell was obtained. Using this ASTM No. 1 dumbbell, a tensile test was performed according to ASTM D638 (2005), the tensile strength value was defined as weld strength, and the tensile elongation was defined as weld elongation. In addition, the value was made into the average value of three measured values.

3. Thermal deformation temperature Tested using a Toshiba Machine IS55EPN injection molding machine under molding temperature conditions of 260 ° C, mold temperature of 80 ° C, injection time and holding time of 10 seconds, and cooling cycle time of 10 seconds. A test piece having a thickness of 1/8 inch (about 3.2 mm) was obtained. Using the above test piece, the heat distortion temperature was measured under a test load of 1.82 MPa in accordance with ASTM D648 (2005). In addition, the value was made into the average value of three measured values.

4). Flame Retardancy Using a Toshiba Machine IS55EPN injection molding machine, a test specimen thickness of 1/32 inch (about 0.79 mm) was obtained under conditions of a molding temperature of 260 ° C. and a mold temperature of 80 ° C. Using the above-mentioned combustion test piece, flame retardancy was evaluated according to the evaluation criteria defined in the UL94 vertical test. Flame retardancy falls and ranks in the order of V-0>V-1> V-2. Moreover, the material which was inferior in combustibility, did not reach said V-2, and did not correspond to said flame retardance rank was made into the outside of specification.

  Also, during the combustion test, observe whether the test specimens after the first flame contact and the second flame contact are melted by heat and a part of the test piece falls or does not fall. It was evaluated.

5. Glow Wire Test Using a Toshiba Machine IS55EPN injection molding machine, three corners of 80mm x 80mm x 3mm thickness, 1.5mm, and 0.75mm were injection molded under conditions of molding temperature 260 ° C and mold temperature 80 ° C. Glow wire test using plate as sample, using test equipment of model HAT-214 manufactured by Nikka Techno Service Co., Ltd. conforming to IEC60695-2-10 standard, and conforming to test method of IEC60695-2-13 standard Went. After touching 850 ° C glow wire (red hot rod), extinguish within 30 seconds, and after passing 750 ° C glow wire (red hot rod) for 30 seconds, extinguish within 5 seconds, pass either If the fire was not extinguished under these conditions, the test was rejected.

6). Flowability In the flame retardancy of item 4, the molding lower limit pressure, which is the lowest pressure that can be filled in a molded product when a 1/32 inch (about 0.79 mm) thick combustion test piece is injection molded, was determined. The smaller the molding lower limit pressure is, the smaller the pressure can be obtained and the better the fluidity.

7). Color Tone The yellowness (YI value) of the color tone of the ASTM No. 1 dumbbell molded product used for the tensile properties described in item 1 above was measured using an SM color computer, model SM-3, manufactured by Suga Test Instruments Co., Ltd. The higher the value, the more yellowish, and the smaller the value, the closer to white.

8). Release property The release force at the time of injection molding was measured to determine the release property. The structure of the mold during injection molding consists of two plates on the fixed side and the working side that opens and closes the mold. It is released from the mold. In addition, a load cell for detecting a load is inserted into the protruding pin portion so that the releasing force at the time of releasing can be measured. The mold release force of 5 molded products was measured, and the average value of 5 mold release force values was used. In addition, it is excellent in the mold release property, so that the value of mold release force is small.

9. Bleed-out test ASTM No. 1 dumbbell is put into a constant temperature and high humidity tester of “Humiday cabinets” LHL-113 manufactured by Espec Co., Ltd., which is set to a temperature and humidity of 80 ° C. × 95% RH for 400 hours. The next bleed-out was determined by visual observation of the appearance of the molded product.

A molded product that bleeds out is a molded product that greatly impairs the value of the product.
X: A liquid or white powder-like bleed-out is observed in a part of the molded product or everywhere.
○: No liquid or white powder bleed out is observed in the molded product.

[Examples 1 to 24], [Comparative Examples 1 to 10]
Using a twin-screw extruder with a screw diameter of 30 mm and L / D35 and rotating in the same direction (manufactured by Nippon Steel Works, TEX-30α), (A) a thermoplastic polyester resin and (B) an aromatic polycarbonate resin and / or Polyphenylene ether resin, (C) phosphorus flame retardant, (D) salt of triazine compound with cyanuric acid or isocyanuric acid, (E) organosilane compound having epoxy group or isocyanate group, and other compounding as required The materials and the like were mixed at the blending compositions shown in Tables 1 to 3 and added from the former loading part of the twin screw extruder. In addition, the glass fiber <G-5> of the fiber reinforcing material among the components (G) was added by installing a side feeder in the middle of the original loading portion and the vent portion. Further, melt mixing was performed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, and the mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

  The obtained pellets were dried with a hot air dryer at 110 ° C. for 6 hours, and various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine. Various values were measured by the above measuring method, and the results are shown in Tables 1 to 3.

  From the comparison of Examples 1 to 13 in Table 1 and Comparative Examples 4 to 5 that do not contain the (E) component of the present invention in Table 3, (A) component, (B) component, (C) component of the present invention, ( A flame-retardant thermoplastic polyester resin composition comprising component D) and component (E) is a flame-retardant thermoplastic polyester resin exhibiting excellent UL-94 flame retardancy, tensile properties, weld properties, and heat distortion temperature. It can be said that it is a composition. In particular, the flame-retardant thermoplastic polyester resin compositions of Comparative Examples 4 to 5 have low weld strength, and therefore may be destroyed when a large force is applied to the molded product.

  From the comparison between Example 1 and Examples 5 and 7 in Table 1 and Example 3 and Example 6, (D) a salt of a triazine compound and cyanuric acid or isocyanuric acid was converted into a flame-retardant thermoplastic polyester resin composition. It can be seen that the flame-retardant thermoplastic polyester resin composition blended in an amount of 15 to 25% by weight is excellent in glow wire characteristics.

  Flame retardancy in which (G) known additives are blended with (A) component, (B) component, (C) component, (D) component, and (E) component of Examples 14 to 23 of Table 2 The heat-resistant thermoplastic polyester resin composition can be said to be a flame-retardant thermoplastic polyester resin composition exhibiting excellent UL-94 flame retardancy, tensile properties, weld properties, and heat distortion temperature. Specifically, the fluidity of the flame retardant thermoplastic polyester resin composition blended with the polyhydric alcohol of Example 14 shows a 28 MPa gauge pressure, which is much lower than the 38 MPa gauge pressure of Example 2, The fluidity was excellent. In addition, the flame-retardant thermoplastic polyester resin composition containing the epoxidized AS and MH-5020 of Examples 15 and 16 is characterized by excellent tensile properties and weld properties as compared with the corresponding Examples 3 and 2. Had. Moreover, the flame-retardant thermoplastic polyester resin composition containing the fluororesin of Example 17 had a non-drip performance during combustion in the flame-retardant test. Moreover, when the color tone of the flame-retardant thermoplastic polyester resin composition containing the antioxidant IR-1010 of Example 18 and the molded product of Example 2 was obtained, a value of 18 was obtained. It showed a low value. That is, it means that the yellowish color is lowered and whitened, and the color tone is improved. Moreover, when the release force when obtaining the molded article by the flame-retardant thermoplastic polyester resin composition containing the release agent Rico-OP of Example 19 and the injection molding of Example 2 was measured, it showed 12 MPa. The value was lower than 45 MPa in Example 2. That is, it had the performance that mold release property improved.

  Moreover, the flame-retardant thermoplastic polyester resin composition which mix | blended GF of Examples 20-23 had the performance in which the intensity | strength and the heat-deformation temperature were improved extremely.

  Next, the comparative example 1 which does not mix | blend (B) component in this invention has low heat deformation temperature, and bleed out generate | occur | produced. Moreover, when the bleed-out test was done about Examples 1-24 and Comparative Examples 2-10, bleed-out was recognized only in the comparative example 8 which mix | blends many (C) phosphorus flame retardants, and the molded article of an Example There was no bleed out. That is, the flame retardant thermoplastic polyester resin compositions of Comparative Examples 1 to 10 have one or more performances of bleed out, tensile physical properties, weld physical properties, heat distortion temperature, flame retardancy, and glow wire properties. It was extremely inferior.

Claims (6)

(C) Phosphoric flame retardant 1 to 100 parts by weight in total of 100 parts by weight of (A) thermoplastic polyester resin 60 to 95% by weight and (B) aromatic polycarbonate resin and / or polyphenylene ether resin 5 to 40% by weight. 40 parts by weight, (D) 1-50 parts by weight of a salt of triazine compound and cyanuric acid or isocyanuric acid, and (E) 0.01-5 parts by weight of an organosilane compound having an epoxy group or an isocyanate group A flame retardant thermoplastic polyester resin composition. The flame retardant thermoplastic polyester according to claim 1, wherein the salt of (D) triazine compound and cyanuric acid or isocyanuric acid is blended in an amount of 15 to 25% by weight in the flame retardant thermoplastic polyester resin composition. Resin composition. Furthermore, the flame-retardant thermoplastic polyester resin composition of Claim 1 or Claim 2 which mix | blends 0.01-5 weight part of (F) transesterification inhibitors. The molded article obtained by shape | molding the flame-retardant thermoplastic polyester resin composition in any one of Claims 1-3. The molded article according to claim 4, which is used for an electric / electronic part or a housing obtained by a multipoint gate. The molded article according to claim 4 or 5, which passes a glow wire test of IEC60695-2-13 standard.