JP5315683B2 - Flame retardant thermoplastic polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a material which hardly allows bleed-out to occur even in a high temperature atmosphere, has excellent flowability during injection molding, and is excellent in anisotropy which is a cause of warpage or strain when a fiber-reinforcing material is compounded; and to provide a molded article useful for a machine mechanical part, an electric or electronic part, and an automobile part. <P>SOLUTION: A flame-retardant thermoplastic polyester resin composition is provided, which is prepared by compounding (A) 100 pts.wt. thermoplastic polyester resin with (C) 1-100 pts.wt. flame retardant and (D) 0.01-10 pts.wt. polyhydric alcohol compound containing one or more alkylene oxide units each having three or more functional groups. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is a flame retardant thermoplastic polyester resin composition, which is excellent in fluidity, mechanical properties and flame retardancy at the time of injection molding, is also less likely to bleed out even in a high temperature atmosphere, and is fiber reinforced. The present invention relates to molded articles that are excellent in anisotropy that causes warping and distortion, which are problems when materials are blended, and are useful as mechanical mechanism parts, electrical / electronic parts, and automobile parts.

  Aromatic polyester resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent mechanical properties.

  Aromatic polyester resin is inherently flammable, so it can be used against industrial flames in addition to the balance of general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical / electronic parts, and automotive parts. 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 an aromatic polyester resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary is generally used. There was a problem that fluidity was lowered by the influence of the compound.

  In addition, due to increased environmental awareness, there is a concern about the environmental impact of halogen-based flame retardant materials. Therefore, in recent years, it has been strongly desired to use a non-halogen flame retardant containing no halogen.

  For example, Patent Document 1 discloses that an aromatic phosphate ester and melamine cyanurate are blended as a non-halogen flame retardant, but the molded product obtained by injection molding has a problem of poor fluidity. there were.

  Further, Patent Document 2 discloses that by adding a compound having a hydroxyl group such as pentaerythritol for improving flame retardancy to an aromatic phosphate ester and melamine cyanurate, it is possible to suppress corrosive gas and graphite, or at the time of molding or long-term use. Although a flame retardant resin composition in which a sublimation product or decomposition product does not occur has been disclosed, fluidity at the time of injection molding has not been studied.

Patent Document 3 discloses that an aromatic phosphate ester and melamine cyanurate are blended in a mixture of thermoplastic polyester, polyphenylene ether and polyphenylene sulfide. Polyphenylene ether and polyphenylene sulfide resins are known to have better flame retardancy than thermoplastic polyester resins, and are used as flame retardant aids for thermoplastic polyesters, providing high flame retardancy, and Although it has the effect of preventing bleeding out during heating, the mixture of polyphenylene ether and polyphenylene sulfide has a problem of poor fluidity. Further, when an aromatic polycarbonate resin is blended with a thermoplastic polyester, there is a problem in that it is excellent in flame retardancy but inferior in fluidity as described above.
JP-A-3-281652 (Claims) JP-A-8-73713 (Claims) Japanese Patent No. 3484803 (Claims)

  In other words, there is a need for a molded product that does not cause bleed-out even when heated while maintaining high flame retardancy and mechanical properties, and a flame-retardant thermoplastic polyester resin composition that has excellent fluidity during injection molding. It was.

  Moreover, the material which mix | blended fiber reinforcements, such as glass fiber, had a subject in anisotropy (the difference of the vertical and horizontal molding shrinkage rate of a molded product). For example, in the case of a thin molded product with large anisotropy, there is a problem that the molded product becomes a warped or strained molded product, and the flame retardant thermoplastic polyester resin composition is excellent in anisotropy causing warpage and strain Things were sought.

  That is, the present invention provides a resin composition that is less likely to bleed out even in a high-temperature atmosphere and that has excellent anisotropy that causes warping and distortion, which is a problem when a fiber reinforcing material is blended, It is another object of the present invention to provide a molded product useful for mechanical mechanism parts, electrical / electronic parts, and automobile parts.

That is, the present invention
(1) (A) 100 parts by weight of thermoplastic polyester resin (B) 1-100 parts by weight of resin other than thermoplastic polyester resin, (C) 1-100 parts by weight of flame retardant , (D) 3 or more 0.01 to 10 parts by weight of a polyhydric alcohol compound containing at least one alkylene oxide unit having a functional group and having 0.5 to 2.3 alkylene oxide units per functional group and (E) a fiber reinforcing material A flame retardant thermoplastic polyester resin composition comprising 1 to 150 parts by weight ,
(2) (C) One or more types of flame retardants selected from phosphorus flame retardants, nitrogen compound flame retardants, bromine flame retardants, chlorine flame retardants, silicone flame retardants, other inorganic flame retardants and phenolic resins The flame-retardant thermoplastic polyester resin composition according to (1), which is a flame retardant,
(3 ) ( B) The above (1) or ( B), wherein the resin other than the thermoplastic polyester resin comprises at least one thermoplastic resin selected from an amorphous polycarbonate resin, an aromatic polycarbonate resin, a polyphenylene ether resin, and a vinyl resin. 2) The flame-retardant thermoplastic polyester resin composition according to 2) ,
( 4 ) (A) The above (1) to ( 3 ), wherein the thermoplastic polyester resin is one or more aromatic polyester resins selected from polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate. A flame retardant thermoplastic polyester resin composition according to any one of
( 5 ) The flame retardant thermoplastic polyester resin composition according to any one of (1) to ( 4 ), further comprising (H) 0.05 to 10 parts by weight of a fluorine compound.
( 6 ) The flame retardant thermoplastic polyester resin composition according to any one of (1) to ( 5 ), further comprising (G) 0.1 to 10 parts by weight of an alkaline earth metal compound,
( 7 ) The flame retardant thermoplastic polyester resin composition according to any one of (1) to ( 6 ), further comprising (F) 0.1 to 10 parts by weight of an epoxy compound .
(8 ) The flame retardant thermoplastic polyester resin composition according to ( 3 ), wherein the vinyl resin is an epoxidized vinyl resin;
( 9 ) The flame retardant thermoplastic polyester resin composition according to any one of (1) to ( 8 ), wherein the carboxyl terminal group amount of the thermoplastic polyester resin is 50 eq / t or less,
( 10 ) A molded product selected from mechanical mechanism parts, electrical / electronic parts and automobile parts comprising the flame-retardant thermoplastic polyester resin composition according to any one of (1) to ( 9 ).

  The thermoplastic polyester resin composition according to the present invention is less likely to bleed out even in a high-temperature atmosphere, has excellent fluidity during injection molding, and has problems of warping and distortion, which are problems when a fiber reinforcing material is blended. Excellent molded anisotropy, and is a molded product useful for mechanical mechanism parts, electrical / electronic parts, and automotive parts.

  The present invention will be described in detail below.

  The (A) thermoplastic polyester resin used in the present invention includes (a) 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, ) A polymer or copolymer having at least one selected from lactone as a main structural unit.

  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 aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Group dioxy compounds, namely 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and these And ester forming derivatives thereof.

  (A) Polymers or copolymers having 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, poly Hexylene 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 Polyethylene 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, poly Lopylene 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 , Polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Aromatic polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene seba Kate, polypropylene cell Sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples of the polymer or copolymer having these as structural units include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β. -Aliphatic polyester resins such as hydroxyvaleric acid.

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

  Among these, (a) a polymer or copolymer having a main structural unit of a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof is preferable, and an aromatic dicarboxylic acid or an ester-forming derivative thereof A polymer or copolymer having an aliphatic diol or an ester-forming derivative thereof 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 the like. A polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, among which polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphtha. Aromatic polyesters such as poly (butylene terephthalate / naphthalate), poly (butylene terephthalate / naphthalate) Resins are particularly preferred, and one or more aromatic polyester resins selected from polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate are most preferred.

  In the present invention, terephthalic acid or its ester-forming derivative with respect to all the dicarboxylic acids in the polymer or copolymer having (i) the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit. Is preferably 30 mol% or more, and more preferably 40 mol% or more.

In the present invention, a liquid crystalline polyester capable of forming anisotropy when melted may be used as the thermoplastic polyester resin. 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. In view of fluidity and mechanical properties, it is preferable to use two or more kinds of polyester resins, and a combination of non-liquid crystalline polyester and liquid crystalline polyester is particularly preferable.

  The amount of carboxyl end groups of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 50 eq / t or less in terms of fluidity, hydrolysis resistance and heat resistance, and 30 eq / t. Or less, more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. It may be 0 eq / t. In the present invention, the carboxyl end group amount of (A) thermoplastic resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of hydroxyl terminal groups of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 50 eq / t or more, and 80 eq / t or more in terms of moldability and fluidity. More preferably, it is more preferably 100 eq / t or more, and particularly preferably 120 eq / t or more. The upper limit is not particularly limited, but is 180 eq / t.

  The viscosity of the (A) thermoplastic polyester resin used in the present invention is not particularly limited as long as it can be melt-kneaded. It is preferably in the range of .36 to 1.60 dl / g, and more preferably in the range of 0.50 to 1.50 dl / g.

  The molecular weight of the thermoplastic polyester resin (A) used in the present invention is preferably in the range of more than 8,000 and less than 500,000 in weight average molecular weight (Mw) in terms of heat resistance, and more than 8,000 and less than 300,000. Is more preferable, and more preferably in the range of more than 8000 and 250,000 or less. 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 method for producing the thermoplastic polyester resin (A) used in the present invention is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization can be used. Both can be applied both by transesterification and by direct polymerization, but continuous polymerization is preferred in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of cost, direct polymerization is preferable.

  The (A) thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. In some cases, it can be produced by subjecting a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative to an esterification reaction or a transesterification reaction, followed by a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexylditin oxide, Didodecyltin oxide, Triethyltin hydroxide, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid Tin compounds such as alkylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, etc. Among these, organic titanium compounds and tin compounds are preferred, Furthermore, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferred, and titanic acid is preferred. Tetra -n- butyl ester is particularly preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin in terms of mechanical properties, moldability, and color tone, The range of -0.2 weight part is more preferable.

  As the resin other than the thermoplastic polyester resin (B) used in the present invention, any of a thermoplastic resin other than the thermoplastic polyester resin and a thermosetting resin can be used. Thermoplastic resins are preferred. (B) Specific examples of resins other than thermoplastic polyester resins include low-density polyethylene resins, high-density polyethylene resins, polyolefin resins such as polypropylene resins, liquid crystal polyester resins, polyamide resins, vinyl resins, polyacetal resins, polyurethane resins. , Aromatic and aliphatic polyketone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, polyurethane resins, MS resins, aromatic polycarbonate resins, polyarylate resins, polysulfone resins, polyethersulfone resins, Phenoxy resin, polyphenylene ether resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, polyvinyl alcohol resin, unsaturated polyester resin, melamine Butter, and the like urea resins.

  In addition, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers) , Ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylic acid alkyl ester copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer Examples include coalesced rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like, and those having various degrees of crosslinking, various microstructures such as cis structure, Having a transformer structure, etc., having a vinyl group Or having various average particle sizes (in the resin composition), a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of different polymers. A so-called core-shell rubber called a multilayer structure polymer can be used, and a core-shell rubber containing a silicone compound can also be used.

  The various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers and graft copolymers, and may be used alone. Two or more types may be used in combination.

  Among resins other than the above (B) thermoplastic polyester resin, since the effect of improving the properties is high, polyamide resin, vinyl resin, polyurethane resin, aromatic polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, aromatic Aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, polyetherimide resin, polyamideimide resin, polyacetal resin, unsaturated polyester resin, urea resin, silicone compound-containing core-shell rubber are preferred Among these, an amorphous polycarbonate resin, a polyphenylene ether resin, and an amorphous thermoplastic resin such as a vinyl resin are particularly preferable, and one or more are used. The above-mentioned particularly preferred amorphous thermoplastic resins such as aromatic polycarbonate resin, polyphenylene ether resin and vinyl resin are amorphous thermoplastic resins having no crystal structure, and liquids are distilled from the molded product. This prevents the bleeding out phenomenon. Amorphous thermoplastic resins such as polyetherimide resin, polyamideimide resin, polyarylate resin, polyethersulfone resin, and polysulfone resin can be expected to have the same effect, and one or more of them may be used in combination.

  (B) The blending amount of the resin other than the thermoplastic polyester resin is 1 to 100 parts by weight, preferably 2 to 80 parts per 100 parts by weight of the (A) thermoplastic polyester resin, from the viewpoint of mechanical properties and bleed-out prevention effects. Part by weight, more preferably 3 to 60 parts by weight.

  As said aromatic polycarbonate resin, the aromatic homo or copolycarbonate obtained by making an aromatic dihydric phenol type compound, phosgene, or carbonic acid diester react is mentioned. The aromatic homo or copolycarbonate resin has a weight average molecular weight in the range of 10,000 to 1100000, a glass transition temperature of about 150 ° C., and a weight average molecular weight in the range of 10,000 to 1,000,000. Different 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. The weight average molecular weight is obtained by measuring in polystyrene conversion by gel permeation chromatography using tetrahydrofuran as a solvent. A weight average molecular weight of 10,000 or less is preferable because the excellent mechanical properties of the present invention are impaired. If the weight average molecular weight is 110,000 or more, the fluidity during molding is impaired, which is not preferable.

  In addition, the melt viscosity index (melt flow index) measured with a melt indexer according to ASTM D1238 under a load of 1.2 kg at a temperature of 300 ° C. is 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.

  Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 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 or the like can be used, and these can be used alone or as a mixture. However, blending the aromatic polycarbonate resin in an amount exceeding 100 parts by weight is not preferable because the fluidity during injection molding is greatly reduced. 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. ing.

  Further, when blending the above aromatic polycarbonate resin, it is useful for preventing transesterification of (A) thermoplastic polyester and aromatic polycarbonate resin by blending a small amount of acidic phosphoric acid ester. To prevent the loss of The acidic phosphoric acid ester is a general term for partial ester compounds of alcohols and phosphoric acid. The low molecular weight is a colorless liquid, the high molecular weight is a white waxy or flaky solid, and the hydrogen of phosphoric acid is an alkyl group. It is used separately from the phosphoric acid ester of the phosphorus flame retardant of the component (C) described later substituted with an allyl group or the like.

  Specific examples of the acid phosphate ester include, but are not limited to, 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 triphosphate And said Mixtures of mono- and di, mono, or a mixture of one or more thereof and the compounds of the di- and tri. Acid phosphates preferably used include long-chain alkyl acid phosphate compounds such as a mixture of mono and distearyl acid phosphates, which are commercially available from Asahi Denka Co., Ltd. under the name “Adekastab” AX-71, and have a melting point of It has a flaky solid.

  Moreover, the compounding quantity of the said acidic phosphoric acid ester is 0.01-5 weight part with respect to 100 weight part of (A) thermoplastic polyester resin from the point of a heat-deformation temperature and a mechanical characteristic, Preferably it is 0.02-4. Part by weight, more preferably 0.03 to 3 parts by weight.

  Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-1, 4-phenylene) ether, poly (2,6-dimethyl-1,4-2phenylene) ether, poly (2,6-dipropyl-1,4-2phenylene) ether, poly (2-ethyl-6-propyl-) 1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1, Specific examples include 4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether, and particularly poly (2,6-dipropyl-1,4-phenyl). Ylene) ether is preferably used, the copolymerizable components such as trimethylphenol may be copolymerized polyphenylene ether resin. Further, a modified polyphenylene ether resin may be used, and although not limited, a modified polyphenylene ether resin obtained by graft polymerization of high impact polystyrene is used.

A method for producing a polyphenylene ether resin is known. For example, a production method for oxidative coupling of 2,6-xylenol using a base metal salt as a catalyst can be used.
The viscosity of the polyphenylene ether resin is preferably in the range of an intrinsic viscosity of 0.15 to 0.7 dl / g measured at 30 ° C. using chloroform as a solvent. If the viscosity is less than 0.15 dl / g, the mechanical properties are greatly reduced. If it exceeds 0.7 dl / g, the fluidity is greatly impaired, which is not preferable. However, blending polyphenylene ether resin in an amount exceeding 100 parts by weight is not preferable because the fluidity during injection molding is greatly reduced.

  Examples of the vinyl resin include polystyrene, styrene / butadiene, ("-/-" represents copolymerization, the same applies hereinafter), styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butadiene / styrene. , High impact styrene, styrene / acrylonitrile (AS resin), styrene / acrylonitrile / styrene, polymethyl methacrylate acrylate (PMMA resin), acrylonitrile / butadiene / styrene, styrene / methyl methacrylate / butadiene / acrylonitrile, acrylonitrile / acrylic rubber / Core shellgo made of styrene, acrylonitrile / ethylene rubber / styrene and vinyl resin such as AS resin or PMMA resin as shell layer and rubber such as acrylic rubber as core layer And the like.

  Also, a vinyl resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer such as maleic anhydride or an epoxy group-containing vinyl monomer such as glycidyl methacrylate, or a vinyl resin epoxy-modified with an epoxidizing agent may be used. AS resin, epoxidized styrene / butadiene / styrene and epoxidized styrene / ethylene / butadiene / styrene, maleic anhydride / styrene, and the like. Especially, epoxidized vinyl resin epoxy-modified with glycidyl methacrylate or an epoxidizing agent is used. Preferably used.

  In addition, a polymer compound in which a vinyl resin unit such as an acrylic resin or a styrene resin is grafted on ethylene can also be used. As a specific example, polyethylene-g-polymethyl methacrylate (PE-g-PMMA) (“ -G- "represents a graft. The same applies hereinafter.), Polypropylene-g-polymethyl methacrylate (PP-g-PMMA), poly (ethylene / propylene) -g-polymethyl methacrylate (EPM-g-PMMA) ), Poly (ethylene / ethyl acrylate) -g-polymethyl methacrylate (EEA-g-PMMA), poly (ethylene / vinyl acetate) -g-polymethyl methacrylate (EVA-g-PMMA), poly (ethylene / Glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g-PMMA) Poly (ethyl acrylate / glycidyl methacrylate) -g-polymethyl methacrylate (EA / GMA-g-PMMA), polycarbonate-g-polymethyl methacrylate (PC-g-PMMA), polyethylene-g-polystyrene (PE-) g-PS), polypropylene-g-polystyrene (PP-g-PS), poly (ethylene / propylene) -g-polystyrene (EPM-g-PS), poly (ethylene / ethyl acrylate) -g-polystyrene (EEA) -G-PS), poly (ethylene / vinyl acetate) -g-polystyrene (EVA-g-PS), poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / Maleic anhydride) -g-polystyrene (E / MAH-g-PS), poly (acrylic Acid / glycidyl methacrylate) -g-polystyrene (EA / GMA-g-PS), poly (ethyl acrylate / maleic anhydride) -g-polystyrene (EA / MAH-g-PS), polycarbonate-g-polystyrene ( PC-g-PS), polyethylene-g-acrylonitrile / styrene (PE-g-AS), polypropylene-g-acrylonitrile / styrene (PP-g-AS), poly (ethylene / propylene) -g-acrylonitrile / styrene ( EPM-g-AS), poly (ethylene / ethyl acrylate) -g-acrylonitrile / styrene (EEA-g-AS), poly (ethylene / vinyl acetate) -g-acrylonitrile / styrene (EVA-g-AS), Poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / Styrene (E / GMA-g-AS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly (ethyl acrylate / maleic anhydride) -g-acrylonitrile / Styrene (EA / MAH-g-AS), polycarbonate-g-acrylonitrile / styrene (PC-g-AS), etc., especially 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 / maleic anhydride) -g-polystyrene (E MAH-g-PS) and the like are listed as preferred examples. Vinyl resins containing acrylic resins or vinyl resins such as styrene resins by grafting may be used alone or in combination of two or more. It may be a mixture of AS resin or PMMA resin, or it may be a single product. In particular, polymer compounds containing vinyl resin units such as acrylic resin or styrene resin by grafting on ethylene containing glycidyl methacrylate are epoxidized. It can be used as a vinyl resin.

  As a commercial product of vinyl resin containing vinyl resin such as acrylic resin or styrene resin by grafting to ethylene, for example, “Modiper” manufactured by NOF Corporation can be cited.

  In addition, since vinyl resin lowers flame retardancy compared to the above aromatic polycarbonate resin and polyphenylene ether resin, the blending amount of vinyl resin is (A) 100 weight of thermoplastic polyester resin from the viewpoint of flame retardancy. 1 to 100 parts by weight, preferably 2 to 45 parts by weight, and more preferably 3 to 40 parts by weight with respect to parts.

  The (C) flame retardant used in the present invention is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to a resin. Specifically, brominated flame retardants, chlorine-based flame retardants are used. Examples include flame retardants, phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and phenolic resins. At least one or more of these can be selected and used.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  Specific examples of the chlorinated flame retardant used in the present invention include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and generally used phosphorus-based flame retardants can be used. Typically, phosphoric acid esters, condensed phosphoric acid esters, polyphosphates, etc. Examples include organic phosphorus compounds and red phosphorus.

  Specific examples of the above phosphoric acid esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropyl). Phenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyl Oxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diph Nyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, etc. Can be mentioned.

  As said condensed phosphate ester, the condensed phosphate ester of following (1) Formula can be mentioned.

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is selected from the following formulas (2) to (4): In the following formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and k and m in the formula (1) are Each of them is an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.) In addition, such aromatic condensed phosphates are different n or aromatic condensed phosphates having different structures. It may be a mixture of

  In said Formula (1), n is an integer greater than or equal to 0, and an upper limit is 40 or less from the point of a flame retardance. Preferably it is 0-10, Most preferably, it is 0-5. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

Also in the above formula ^{(2) ~ (4),} R 1 ~R 8 denote the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a neopentyl group. However, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

  Of these, the following compounds (5) and (6) are preferable, and the compound (5) is particularly preferable.

  Moreover, as a commercial item of said condensed phosphate ester, Daihachi Chemical Industry Co., Ltd. PX-200, PX-201, PX-130, PX-202, CR-733S, TPP, CR-741, CR747 , TCP, TXP, CDP, SH-0890, AFRICA PFR, FP-500, FP-600, FP-700, T-1317F, etc. In particular, it is preferable from the viewpoint of the hydrolyzability and metal contamination of a molded product obtained by using PX-200, CR-741 manufactured by Daihachi Chemical Industry Co., Ltd., FP-600 manufactured by Adeka Co., Ltd., etc. Used.

  Moreover, phosphorus flame retardants having a phosphaphenanthrene skeleton can also be used, and examples of commercially available products include HCA, HCA-HQ, BCA, SANKO-220, and M-Ester-HP manufactured by Sanko Co., Ltd. It is done.

  Moreover, the polyphosphate which consists of a salt with phosphoric acid, polyphosphoric acid, a periodic table group IA-IVB group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts, etc. as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts, triazine salts, melamine salts, and ammonium salts.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof 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.

  Among the phosphorus-based flame retardants, condensed phosphate ester, polyphosphate, and red phosphorus are preferable, condensed phosphate ester and polyphosphate are particularly preferable, condensed phosphate ester is further preferable, and aromatic condensed phosphate ester is particularly preferable. preferable.

  Examples of the nitrogen compound flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides and aromatic amides, urea, thiourea, ammonium polyphosphate, melamine polyphosphate, and Examples thereof include phosphazene compounds.

  Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like.

  Examples of the aromatic amine include aniline and phenylenediamine.

  Examples of the nitrogen-containing heterocyclic compound include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and a triazine compound.

  Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide and aromatic amide include N, N-dimethylacetamide and N, N-diphenylacetamide, and further phosphoric ester amide having a structure containing a phosphorus atom and a nitrogen atom. Phosphoric ester amide is a powdery substance at room temperature with a high melting point, excellent handling properties at the time of blending, a flame retardant polyester resin having a high heat distortion temperature is obtained, and as a commercial product SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.

  Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, ammonium carbamyl polyphosphate, and the like, and phenol resins, urethane resins, melamine resins, urea resins, epoxy resins, and urea resins exhibiting thermosetting properties. It may be covered with a thermosetting resin such as, and may be used alone or in combination of two or more.

  Examples of the melamine polyphosphate include melamine polyphosphate such as melamine phosphate and melamine pyrophosphate, which may be used alone or in combination of two or more.

  The phosphazene compound is a phosphonitrile linear polymer and / or a cyclic polymer, and in particular, those mainly composed of a linear phenoxyphosphazene are preferably used, and the phosphonitrile linear polymer and / or the cyclic polymer are used. Can be synthesized by known methods 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 gas as a nitrogen source. It can be synthesized by reacting by a known method (the cyclic product may be purified) and substituting the obtained substance with alcohol, phenol and amines.

  The triazine compound exemplified in the nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound having a triazine skeleton, and includes triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, and triazine. Examples thereof include phenyltriazine, amelin, amelide, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine, and melamine cyanurate and melamine isocyanurate are preferably used. As the melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually has a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio). The adduct which has can be mentioned. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. When the dispersibility is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica may be used in combination. The average particle size before blending with the resin is preferably 100 to 0.1 μm, preferably 50 to 0.5 μm, more preferably from the viewpoint of flame retardancy, mechanical strength, and surface properties of the molded product. Is 10 to 1 μm, and the average particle diameter is an average particle diameter measured with a 50% cumulative distribution particle diameter by the laser micron sizer method.

  Among the nitrogen compound flame retardants described above, triazine compounds such as melamine polyphosphate, phosphazene compound and melamine cyanurate are preferable.

Examples of the silicone flame retardant include silicone resin and silicone oil. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

  Other inorganic flame retardants mentioned above include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, oxidation Tin, tin oxide salt, zinc sulfate, zinc oxide, calcium borate hydrate, zinc borate, zinc borate hydrate, zinc hydroxide ferrous oxide, ferric oxide, stannous oxide, stannic oxide, Ammonium borate, octamolybdate, metal salt of tungstic acid, complex oxide acid of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compound, guanidine compound, fluorine compound, graphite, swellable graphite And so on. Of these, magnesium hydroxide, fluorine-based compounds, and swellable graphite are preferable.

  The above-mentioned phenol resin is effective as a flame retardant aid that moves to the surface during combustion and assists the formation of a carbonized layer. The above phosphorus flame retardant, nitrogen compound flame retardant, silicone flame retardant, and other inorganic flame retardants It is preferably used in combination with at least one selected from flame retardants. The phenol resin is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and heat-reactive resins, and resins obtained by modifying these resins. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, novolak-type phenolic resins or melamine-modified novolak-type phenolic resins that are non-thermally reactive with no addition of a curing agent are preferred in terms of flame retardancy, mechanical properties, and economy.

  Further, the shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids, and the like can be used, and one or more can be used as necessary. The phenolic resin is not particularly limited, and commercially available ones are used. For example, in the case of a novolak type phenol resin, the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and further oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfone. After adding a catalyst such as an acid, the mixture is heated and refluxed for a predetermined time. In order to remove the produced water, it can be obtained by a method of vacuum dehydration or standing dehydration and further removing remaining water and unreacted phenols. These resins or co-condensed phenol resins obtained by using a plurality of raw material components can be used alone or in combination of two or more.

  In the case of a resol type phenol resin, the molar ratio of phenols to aldehydes is charged into the reaction vessel at a ratio of 1: 1 to 1: 2, and sodium hydroxide, aqueous ammonia, other basic substances, etc. After adding the catalyst, it can be obtained by the same reaction and treatment as the novolak type phenol resin.

  Here, as phenols, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy Examples include phenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols can be used singly or in combination. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can be used alone or in combination of two or more as required.

  The molecular weight of the phenol resin is not particularly limited, but is preferably 200 to 2,000 in terms of number average molecular weight. The molecular weight of the phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.

  Among the above flame retardants, it is preferable to use at least one selected from the group consisting of phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, other inorganic flame retardants, and phenolic resins. It is more preferable to use a combination of at least two selected from a nitrogen compound flame retardant, a silicone flame retardant, another inorganic flame retardant, and a phenol resin.

  The nitrogen compound flame retardant used in combination with the phosphorus flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and more preferably melamine cyanurate. A silicone resin is preferable as the silicone flame retardant used in combination with the phosphorus flame retardant. Further, as the other inorganic flame retardant used in combination with the phosphorus flame retardant, zinc borate or swellable graphite is preferable.

  Further, when a phosphorus flame retardant and a nitrogen compound flame retardant, a silicone flame retardant or other inorganic flame retardant are used in combination, a nitrogen compound flame retardant or a silicone flame retardant with respect to 100 parts by weight of the phosphorus flame retardant Alternatively, it is preferable to use 100 to 1 part by weight of another inorganic flame retardant.

  As the phosphorus-based flame retardant, any one or more of a condensed phosphate ester, a polyphosphate, and red phosphorus, and particularly any one or more of a condensed phosphate ester and a polyphosphate are preferable. Further, it is more preferable to use a condensed phosphate ester and a nitrogen compound-based flame retardant together, or it is more preferable to use a polyphosphate and a nitrogen compound-based flame retardant together. It is preferable to use a small amount because of its high flame retardant effect. As the nitrogen compound flame retardant, melamine cyanurate is preferable.

  Further, the amount of (C) flame retardant added is 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) of the present invention, in terms of flame retardancy, hydrolyzability, and metal contamination. Preferably it is 2-80 weight part, More preferably, it is 3-60 weight part. The above flame retardants may be used alone or in combination of two or more.

  The (D) polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups used in the present invention is necessary for improving the fluidity of the flame-retardant thermoplastic polyester resin of the present invention. It may be a low molecular compound or a polymer. Moreover, as a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, an alkylene having three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound is used. Any polyhydric alcohol compound containing one or more oxide units is preferably used. The functional groups of three or more functional groups are a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, It is preferably at least one selected from a silanol group and a silyl ether group, and preferably has three or more functional groups that are the same or different from these groups, particularly fluidity, mechanical properties, and durability. It is preferable that they are the same functional group from the viewpoint of the property, heat resistance and productivity.

  Further, (D) as a preferable example of the alkylene oxide unit of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective. Specific examples include methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units or isobutylene oxide units. In the present invention, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit, particularly in terms of excellent fluidity, recyclability, durability, heat resistance and mechanical properties. , Water resistant It is particularly preferable to use a compound containing a propylene oxide unit from the viewpoint of excellent properties and toughness (tensile elongation at break), and the number of alkylene oxide units is monofunctional in terms of excellent fluidity and mechanical properties. The number of alkylene oxide units per group is preferably from 0.1 to 20, more preferably from 0.5 to 10, and even more preferably from 1 to 5.

  (D) As a preferable example of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, when the functional group is a hydroxyl group, (poly) oxymethylene glycerol, (poly) oxyethylene glycerol, (Poly) oxytrimethylene glycerol, (Poly) oxypropylene glycerol, (Poly) oxyethylene- (Poly) oxypropylene glycerol, (Poly) oxytetramethylene glycerol, (Poly) oxymethylene diglycerol, (Poly) oxyethylene di- Glycerin, (poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, ( (I) oxypropylene trimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane , (Poly) oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene Pentaerythritol, (poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol , (Poly) oxymethylene dipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene Examples thereof include glucose, (poly) oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, and (poly) oxytetramethylene glucose.

  (D) As a preferred example of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, when the functional group is a carboxylic acid, propane-1,2 containing a (poly) methylene oxide unit , 3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, (poly) propylene oxide units Propane-1,2,3-tricarboxylic acid containing, propane-1,2,3-tricarboxylic acid containing (poly) tetramethylene oxide units, 2-methylpropane-1,2, containing (poly) methylene oxide units 3-triscarboxylic acid, 2-methylpropane-1,2,3-triscal containing (poly) ethylene oxide units Acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, Contains 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) tetramethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, and (poly) ethylene oxide units Butane-1,2,4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, Butane-1,2,4-tricarboxylic acid containing (poly) tetramethylene oxide units, containing (poly) methylene oxide units Butane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1,2, containing (poly) trimethylene oxide units 3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3,4-tetra containing (poly) tetramethylene oxide units Carboxylic acid, trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, trimellitic acid containing (poly) propylene oxide units , Trimellitic acid containing (poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units , Trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, (poly) methylene Hemimellitic acid containing oxide units, Hemimellitic acid containing (poly) ethylene oxide units, Hemimellitic acid containing (poly) trimethylene oxide units, Hemimellitic acid containing (poly) propylene oxide units, (Poly) tetramethylene oxide Hemimellitic acid containing units, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, (poly) propylene oxide units Including Piromel Tolic acid, pyromellitic acid containing (poly) tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-containing (poly) ethylene oxide units Tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing (poly) trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide units Examples thereof include cyclohexane-1,3,5-tricarboxylic acid.

  In addition, as a preferable example of the polyhydric alcohol compound including one or more alkylene oxide units having three or more functional groups as the component (D), when the functional group is an amino group, 2,3-triaminopropane, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, (poly) propylene oxide units 1,2,3-triaminopropane containing, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methyl containing (poly) methylene oxide units Propane, 1,2,3-triamino-2-methylpropane containing (poly) ethylene oxide units, (poly) trimethyleneoxy 1,2,3-triamino-2-methylpropane containing units, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2, containing (poly) tetramethylene oxide units 3-triamino-2-methylpropane, 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, (poly) trimethylene oxide 1,2,4-triaminobutane containing units, 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) methylene oxide units, 1,2,3 containing (poly) ethylene oxide units Tetraminobutane, 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, (poly) tetramethylene oxide units 1,2,3,4-tetraminobutane containing 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly ) 1,3,5-triaminocyclohexane containing trimethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-containing (poly) tetramethylene oxide units Triaminocyclohexane, 1,2,4-triaminosilane containing (poly) methylene oxide units Chlohexane, 1,2,4-triaminocyclohexane containing (poly) ethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2 containing (poly) propylene oxide units , 4-triaminocyclohexane, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) methylene oxide units, (poly) ethylene oxide units 1,2,4,5-tetraminocyclohexane containing 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetramino containing (poly) propylene oxide units Cyclohexane, 1 containing (poly) tetramethylene oxide units 2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, (poly) trimethylene oxide 1,3,5-triaminobenzene containing units, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, 1,2,4-triaminobenzene containing (poly) methylene oxide units, 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-containing (poly) trimethylene oxide units Triaminobenzene, 1,2,4-triaminobenzene containing (poly) propylene oxide units, (poly) tetra Including Chiren'okishido units 1,2,4-aminobenzene, and the like.

  (D) As a preferable example of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, when the functional group is an ester group, an aliphatic acid ester, an aromatic acid ester, an ester derivative, etc. Is mentioned.

  (D) As a preferable example of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, when the functional group is an amide group, an amide derivative or the like can be given.

  In addition, from the viewpoint of the fluidity of the flame-retardant polyester resin composition, (D) as a particularly preferred example of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, the functional group is a hydroxyl group. In case, (poly) oxyethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene diglycerol, (poly) oxypropylene diglycerol, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane , (Poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) Xylpropylene dipentaerythritol, and when the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing a (poly) ethylene oxide unit, propane-1,2, containing a (poly) propylene oxide unit 3-tricarboxylic acid, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, ( Examples thereof include cyclohexane-1,3,5-tricarboxylic acid containing a poly) ethylene oxide unit and cyclohexane-1,3,5-tricarboxylic acid containing a (poly) propylene oxide unit. When the functional group is an amino group, (poly) 1,2,3-tri containing ethylene oxide units Minopropane, 1,2,3-triaminopropane containing (poly) propylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5 containing (poly) propylene oxide units -Triaminocyclohexane, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, 1,3,5-triaminobenzene containing (poly) propylene oxide units.

  The (D) polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups used in the present invention reacts with (A) the thermoplastic polyester resin, and the main chain and side chain of the component (A) The structure at the time of blending may be maintained without reacting with the component (A).

  (D) The viscosity of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and has fluidity and mechanical properties. From the viewpoint, it is more preferably 5000 m · Pa or less, and particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property during molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or weight average molecular weight (Mw) of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups used in the present invention is determined by gel permeation chromatography using hexafluoroisopropanol as a solvent. The value measured by graphy (GPC) and quantified in terms of polymethyl methacrylate (PMMA) is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. More preferably, it is further in the range of 200 to 6000.

  The moisture content of the polyhydric alcohol compound (D) used in the present invention, which contains one or more alkylene oxide units having three or more functional groups, is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less. There is no particular lower limit on the moisture content of the component (B). A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, (D) the blending amount of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is in the range of 0.01 to 10 parts by weight per 100 parts by weight of component (A). From the viewpoint of fluidity and mechanical properties, it is preferably blended in the range of 0.05 to 8 parts by weight, more preferably blended in the range of 0.1 to 5 parts by weight, More preferably, it is blended in the range of 0.2 to 4 parts by weight.

  Examples of the (E) fiber reinforcement used in the present invention include glass fibers, aramid fibers, and carbon fibers. The 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 are preferably used. The silane coupling agent and / or sizing agent may be used as an emulsion.

  In addition, (E) fiber reinforcement has a great effect on improving the mechanical strength of the composition of the present invention, and its blending amount is from the viewpoint of fluidity during injection molding and durability of injection molding machines and molds. The amount of the thermoplastic polyester resin (A) of the present invention is 1 to 150 parts by weight, preferably 2 to 130 parts by weight, and more preferably 3 to 110 parts by weight.

  Further, in the present invention, an inorganic filler other than the fiber reinforcing material can be further blended, and the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy, or thermal deformation of the molded product of the present invention. This is to improve a part of the temperature and the like, and in particular, since it is effective in anisotropy, a molded product with less warping can be obtained. Examples of inorganic fillers other than the fiber reinforcement include, but are not limited to, needle-like, granular, powdery and layered inorganic fillers. Specific examples include glass beads, milled fibers, glass flakes, Potassium titanate whisker, calcium sulfate whisker, wollastonite, silica, kaolin, talc, smectite clay mineral (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, dolomite, etc. Used above. In particular, when gas beads, glass flakes, kaolin, talc, and mica are used, a molded product with less warpage can be obtained because of the effect of anisotropy.

  Moreover, surface treatments such as a coupling agent treatment, an epoxy compound, or an ionization treatment may be performed on the inorganic filler other than the above-described fiber reinforcement. 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. The amount of the inorganic filler other than the fiber reinforcing material is not more than 1 to 150 parts by weight in combination with the amount of the fiber reinforcing agent from the viewpoint of fluidity during molding and durability of the molding machine or mold. Is preferred.

  Examples of the (F) epoxy compound used in the present invention include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds, and these can be used singly or in combination.

  Further, the glycidyl ester compound is not limited, but as specific examples, glycidyl benzoate, glycidyl tBu-benzoate, glycidyl P-toluate, glycidyl cyclohexanecarboxylate, glycidyl pelargonate Ester, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl bersate, glycidyl oleate, glycidyl linoleate, glycidyl linoleate, glycidyl behenol, stearolic acid Glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester , Naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester , Succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the like. Two or more kinds can be used.

  The glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, P-phenylphenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy). ) Butane, 1,6-bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1 Others such as-(β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Examples include diglycidyl ether obtained by the reaction of bisphenol and epichlorohydrin. These can be used alone or in combination of two or more. .

  The (F) epoxy compound preferably used is an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination or a monofunctional glycidyl ester compound, and more preferably a composition from which a monofunctional glycidyl ester compound is obtained. Excellent balance between viscosity stability and hydrolysis resistance. Moreover, the epoxy equivalent of (F) epoxy compound is preferably an epoxy compound of less than 500, more preferably an epoxy compound of less than 400 epoxy equivalent. Here, the epoxy equivalent is an epoxy compound in which the number of grams of an epoxy compound containing 1 gram equivalent of an epoxy group is less than 500, and the epoxy equivalent is obtained by dissolving the epoxy compound in pyridine, adding 0.05N hydrochloric acid and adding 45N After heating, a mixture of thymol blue and cresol red is used as an indicator and back titration with 0.05N caustic soda can be used.

  In addition, (F) the epoxy compound has a great effect on improving the hydrolyzability of the flame retardant thermoplastic polyester resin composition of the present invention, and the compounding amount of (F) the epoxy compound is mechanical properties and hydrolysis resistance. From the surface, (A) 0.1 to 10 parts by weight, preferably 0.2 to 9 parts by weight, and more preferably 0.3 to 8 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin.

  In the present invention, for the purpose of further improving the hydrolysis resistance, an oxazoline compound, a carbodiimide compound, and the like can be blended and used in combination with the (F) epoxy compound in a blending amount not exceeding the (F) epoxy compound. It is preferable.

  The (G) alkaline earth metal compound used in the present invention is preferably an alkaline earth metal compound such as magnesium, calcium, and barium. Examples of the alkaline earth metal compounds include inorganic acid salts such as hydroxides, oxides, carbonates, sulfates, acetates, phosphates, acetates, lactates, oleic acids of alkaline earth metals. And organic acid salts such as palmitic acid, stearic acid and montanic acid. Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, Barium sulfate, magnesium phosphate, calcium phosphate, barium phosphate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid Examples include salts, calcium salts, and barium salts. Among these, hydroxides and carbonates of alkaline earth metals are preferably used. In particular, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. Such alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. Included in the invention. These alkaline earth metal compounds may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and the shape may be powder, plate or fiber. It is preferable from a dispersibility etc. to use in the powder form of 10 micrometers or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

In addition, as an effect of blending the (G) alkaline earth metal compound, when the phosphorus flame retardant in the (C) flame retardant effective as the non-halogen flame retardant is used, the component (A) is caused by the decomposed phosphoric acid. Although it is easily hydrolyzed, it has a disadvantage of poor hydrolysis resistance. (G) By adding an alkaline earth metal compound, the acid generated from the hydrolyzed phosphate ester bond is trapped. It is estimated that the hydrolyzability is improved. In general, it is known that hydrolysis of polyester is accelerated by acid or alkali as a catalyst. Addition of an alkali metal compound is not preferable because it often has alkalinity and usually promotes hydrolysis of the polyester. Accordingly, the alkaline earth metal compound of the present invention is hardly soluble in water in a neutral state, and when the phosphate ester decomposes and the system becomes acidic, it dissolves in an acidic environment and exhibits a neutralizing action. Preferably used. The solubility in the neutral state is described in, for example, the Handbook of Chemistry, published by Maruzen Co., Ltd. (Showa 41), and the solubility in water is preferably 1 g / 100 g or less, more preferably 10 ⁻¹ g / 100 g water or less, particularly preferably 10 ⁻² g / 100 g water or less. Incidentally, the solubility of calcium carbonate most preferably used in water is not more than 5.2 × 10 ⁻³ g / 100 g water.

  Furthermore, by using (F) the epoxy compound and (G) the alkaline earth metal compound in combination, extremely high hydrolysis resistance and metal contamination resistance can be obtained.

  Moreover, the compounding quantity of (G) alkaline-earth metal compound is 0.1-10 weight part with respect to 100 weight part of (A) thermoplastic polyester resin from a mechanical characteristic and a hydrolysis resistant point, Preferably it is 0. .2-9 parts by weight, more preferably 0.3-8 parts by weight.

  The (H) fluorine-based compound used in the present invention is a compound containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) Copolymer, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / Ethylene) copolymer, and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene) / Ethylene) copolymer, polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

  Moreover, (H) As an effect which mix | blends a fluorine-type compound, it can suppress that the flame-retardant resin composition at the time of combustion melts and falls, and can further improve a flame retardance. The blending amount when blending the (H) fluorine-based compound is 0.05 to 10 parts by weight, preferably 100 parts by weight of the (A) thermoplastic polyester resin, preferably from the viewpoint of flame retardancy and mechanical properties. 0.1 to 9 parts by weight, more preferably 0.2 to 8 parts by weight.

  In the present invention, a hindered phenolic antioxidant and / or a phosphite antioxidant can be added as a stabilizer that gives extremely good heat aging resistance even when the composition of the present invention is exposed to a high temperature for a long period of time. The blending amount in the case of blending a hindered phenol antioxidant and / or a phosphite antioxidant is (A) 100 parts by weight of the thermoplastic polyester resin from the viewpoint of heat aging resistance and flame retardancy. 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight.

  Specific examples of the hindered phenol antioxidant 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′-hexa Methylenebis (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 stabilizer include tris (2,4-di-t-butylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octyl male. Phyto, trisnonylphenyl phosphite, alkylallyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like can be mentioned.

  In the present invention, it is possible to improve the releasability during molding by further adding one or more lubricants. Such lubricants include metal soaps such as gallium stearate and barium stearate, fatty acid esters, fatty acid ester salts (including partially salted products), fatty acid amides such as ethylene bisstearoamide, ethylenediamine and stearic acid Fatty acid amides, polyalkylene waxes, acid anhydride-modified polyalkylene waxes composed of a polycondensate consisting of sebacic acid or polycondensates of phenylenediamine and stearic acid and sebacic acid, and the above-mentioned lubricants and fluororesins Examples include, but are not limited to, a mixture. The addition amount in the case of mix | blending a lubricant is 0.01-5 weight part with respect to 100 weight part of (A) thermoplastic polyester resins, Preferably it is 0.02-4 weight part, More preferably, it is 0.03-3 weight. Part.

  In the present invention, the resin is mixed in various colors, weather resistance (light), and electrical conductivity are improved by blending at least one kind of carbon black, titanium oxide, and various color pigments and dyes. The blending amount of the pigment or dye is 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, and more preferably 0.8 to 100 parts by weight of the (A) thermoplastic polyester resin. 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, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. carbon black oil absorption 50~400cm 3 ^/ 100g is preferably used, aluminum oxide treatment agent, silicon oxide, zinc oxide, zirconium oxide, polyol, may be treated with a silane coupling agent.

  Further, as the above titanium oxide, titanium oxide having a crystal form such as rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, 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 thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, as the thermoplastic resin, (A) a thermoplastic polyester resin is preferably used.

  Furthermore, sulfur-based antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, and the like are known as long as the object of the present invention is not impaired with respect to the flame-retardant thermoplastic polyester resin composition and molded article of the present invention. It is also possible to use a material in which one or more of these additives and one or more other thermoplastic resins are blended.

  The mechanical mechanism part, electrical / electronic part or automobile part molded article comprising the flame-retardant thermoplastic polyester resin composition of the present invention utilizes the characteristics of the present invention excellent in flame retardancy, mechanical characteristics and injection moldability. Molded products such as mechanical mechanism parts, electrical / electronic parts, automotive parts, breakers, electromagnetic switches, focus cases, flyback transformers, molded products for fixing machines for copying machines and printers, etc. Housing for home appliances, 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, motors Assembly of parts, sockets, plugs, capacitors, various cases, resistors, metal terminals and conductors Audio / electronic parts, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, home appliance parts such as VTR and TV, parts for copying machines, facsimile parts, optical equipment Moldings such as automobile parts, automobile ignition device parts, automobile connectors, and various automobile electrical parts.

  A molded article comprising the specific flame-retardant thermoplastic polyester resin composition of the present invention is usually produced by a known method. For example, (A) a thermoplastic polyester resin, and (B) one or more resins selected from aromatic polycarbonate resins, polyphenylene ether resins, and vinyl resins that are thermoplastic resins other than the component (A), (C) a flame retardant And (D) a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, and (E) a fiber reinforcing material, (F) an epoxy compound, (G) alkaline earth, if necessary Metal compounds, and (H) fluorine-based compounds, and if necessary, inorganic fillers other than fiber reinforcements, ethylene (co) polymers, hydrolysis resistance improving agents, hindered phenolic antioxidants and / or With or without premixing of phosphite antioxidants, lubricants and, if necessary, other necessary additives and colorants such as pigments and dyes Flame retardant thermoplastic polyester resin composition of the present invention is prepared by sufficiently kneading is supplied to an extrusion machine.

  As an example of the above-mentioned premixing, it is possible to perform dry blending alone, but mixing can be performed using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer. Further, (E) the fiber reinforcing material may be added by adding 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.

  Further, in producing a flame retardant thermoplastic polyester resin composition, for example, but not limited to, for example, a single screw extruder, a twin screw extruder, a three screw screw equipped with a “unimelt” or “dalmage” type screw. An extruder, a conical extruder, a kneader type kneader, or the like can be used.

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

  The structure of the injection molding machine is briefly described. After the plastics are heated and melted and kneaded, the part that injects the molten plastics at a high pressure and the gold that cools and solidifies the injected molten plastics into a predetermined shape (molded product). It is comprised from the type | mold, The mold temperature at the time of injection-molding the specific flame-retardant thermoplastic polyester resin composition of this invention is temperature-controlled at the fixed temperature of the range of 30 to 90 degreeC. It is preferable because a molded product with few defective products can be obtained.

  Hereinafter, the effects of the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Here, “%” and “part” represent “% by weight” and “part by weight”, and “/” in the resin name in the following Reference Examples means copolymerization. Moreover, the measuring method of each characteristic is as follows.

[Reference example]
(A) Thermoplastic polyester resin <A-1> Polyethylene terephthalate resin, Mitsui PET “J005” manufactured by Mitsui Pett Co., Ltd. PET having an intrinsic viscosity of 0.63 was used (hereinafter abbreviated as PET).
<A-2> Polybutylene terephthalate resin, “Toraycon” 1401-X31 PBT having an intrinsic viscosity of 0.80 manufactured by Toray Industries, Inc. was used (hereinafter abbreviated as PBT).

(B) Thermoplastic resin other than thermoplastic polyester resin <B-1> Aromatic polycarbonate resin, “A-1900” manufactured by Idemitsu Petrochemical Co., Ltd. (hereinafter abbreviated as PC) was used.
<B-2> Polyphenylene ether resin, “YPX-100L” manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used (hereinafter abbreviated as PPE).
<B-3> Epoxidized vinyl resin, styrene / acrylonitrile / glycidyl methacrylate = 70 / 29.5 / 0.5 wt% epoxy-modified AS resin (hereinafter abbreviated as epoxidized AS).
<B-4> Vinyl resin, acrylonitrile / butadiene / styrene (ABS resin), “Toyolac” T-500 manufactured by Toray Industries, Inc. (hereinafter abbreviated as ABS) were used.

(C) Flame retardant <C-1> An aromatic condensed phosphate ester of the following formula (7), “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. was used.

<C-2> An aromatic phosphate ester of the following formula (8), “FP-600” manufactured by Adeka Corporation was used.

<C-3> Triazine compound, salt of triazine compound and cyanuric acid or isocyanuric acid, “MC-440” manufactured by Nissan Chemical Co., Ltd. (hereinafter abbreviated as MC salt) was used.
<C-4> Melamine polyphosphate, “Melpua” 200 manufactured by DSM was used.
<C-5> Phosphazene compound, hexachlorocyclotriphosphazene (cyclic trimer) and phenol were reacted in THF in the presence of triethylamine. The resulting reaction solution was evaporated to dryness and washed with water to remove salts. Yield 95%. The phosphazene compound cyclic polymer thus obtained was recrystallized and purified from acetone. The number average polymerization degree n was not changed and n = 3.
<C-6> Tetrabromobisphenol-A-polycarbonate oligomer, “FG-7500” manufactured by Teijin Chemicals Ltd. was used.
<C-7> Antimony trioxide, “NA-1030” manufactured by Nissan Chemical Industries, Ltd. was used.

(D) a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups (hereinafter abbreviated as the polyhydric alcohol of the present invention).
<D-1> Polyoxyethylene diglycerin (molecular weight 410, alkylene oxide (ethylene oxide) unit number 1.5 per functional group, SC-E450 manufactured by Sakamoto Yakuhin Co., Ltd.)
<D-2> oxyethylenetrimethylolpropane (molecular weight 266, alkylene oxide (ethylene oxide) unit number 1 per functional group, Nippon Emulsifier Co., Ltd. TMP-30U)
<D-3> Polyoxyethylene pentaerythritol (molecular weight 400, number of alkylene oxide (ethylene oxide) units per functional group 1.5, Nippon Emulsifier Co., Ltd. PNT-60U)
<D-4> Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, SC-P750 manufactured by Sakamoto Yakuhin Co., Ltd.)
<D-5> Polyoxypropylene trimethylolpropane (molecular weight 308, alkylene oxide (propylene oxide) unit number 1 per functional group, Nippon Emulsifier Co., Ltd. TMP-F32)
<D-6> Polyoxypropylene pentaerythritol (molecular weight 452, one alkylene oxide (propylene oxide) unit per functional group, PNT-F40 manufactured by Nippon Emulsifier Co., Ltd.).

(D ′) Polyhydric alcohol compound not included in the present invention (hereinafter abbreviated as a polyhydric alcohol other than the present invention)
<D'-1> Glycerin (molecular weight 92, 0 alkylene oxide units per functional group, Tokyo Kasei)
<D'-2> Trimethylolpropane (molecular weight 134, number of alkylene oxide units 0 per functional group, ARDRICH)
<D′-3> pentaerythritol (molecular weight 136, number of alkylene oxide units 0 per functional group, Tokyo Kasei).

(E) Fiber reinforcing material <E-1> Chopped strand glass fiber having a fiber diameter of about 10 μm, “CS3J948” manufactured by Nitto Boseki Co., Ltd. (hereinafter abbreviated as GF) was used.

(F) Epoxy compound <F-1> Versatic acid glycidyl ester, “Cardura E10” manufactured by Japan Epoxy Resin Co., Ltd. was used.
<F-2> Versatic acid glycidyl ester, 30% by weight of Japan Epoxy Resin “Cardura E10” and bisphenol A diglycidyl ether, Japan Epoxy Resin “Epicoat 828” 70% by weight.

(G) Alkaline earth metal compound <G-1> Magnesium hydroxide, “Kisuma 6E” manufactured by Kyowa Chemical Industry Co., Ltd. was used.
<G-2> Calcium carbonate, “KSS1000” manufactured by Dowa Calfine Co., Ltd. was used.

(H) Fluorine compound <H-1> Polytetrafluoroethylene, “Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. was used.

(I) Other additives to be blended as necessary <I-1> Inorganic fillers other than fiber reinforcement, talc, and “LMS-100” manufactured by Fuji Talc were used.
<I-2> An ethylene (co) polymer, an ethylene (about 88 wt%) / glycidyl methacrylate (about 12 wt%) copolymer, “BF-E” manufactured by Sumitomo Chemical Co., Ltd. was used.

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

(1) Fluidity at the time of injection molding Using IS55EPN injection molding machine manufactured by Toshiba Machine, temperature conditions of molding temperature 270 ° C, mold temperature 80 ° C, injection time and pressure holding time 10 seconds in total, cooling time 10 seconds A molding gauge pressure (hereinafter referred to as a molding lower limit pressure) at which a test piece for flame retardance evaluation having a thickness of 1/32 inch (about 0.79 mm) is injection molded under the molding cycle conditions of Abbreviated). In addition, it is excellent in fluidity | liquidity, so that the value of a shaping | molding minimum pressure is low.

(2) Mechanical Properties Using a Toshiba Machine IS55EPN injection molding machine, 3 mm thick ASTM No. 1 dumbbell was injection molded under conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and the tensile strength was measured according to ASTM D638.

(3) Flame Retardancy Using the test piece for flame retardancy evaluation having a thickness of 1/32 inch (about 0.79 mm) obtained in the above (1), according to the evaluation standard defined in the UL94 vertical test, Flame retardancy was evaluated. 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.

(4) Bleed-out The ASTM No. 1 dumbbell obtained in (2) above was put into a pressure cooker tester set at 121 ° C. and 100% RH for 100 hours, subjected to wet heat treatment, and the appearance of the molded product was visually observed. The next bleed-out was determined.
X: A liquid or white powder bleed out is observed everywhere in the molded product.
(Triangle | delta): Liquid or white powder-like bleed-out is observed in a part of molded article.
○: No liquid or white powder bleed out is observed in the molded product.

(5) Hydrolyzability Tensile strength was measured according to ASTM D638 using the wet-heat treated ASTM No. 1 dumbbell (4), and the retention rate (%) relative to the tensile strength before treatment was determined.

(6) Anisotropy Using an IS55EPN injection molding machine manufactured by Toshiba Machine, injection molding of a square plate of 80 mm length, 80 mm width and 3 mm thickness under the conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. The molding shrinkage in the direction perpendicular to the flow direction and flow was measured. The value obtained by subtracting the molding shrinkage in the flow direction from the vertical molding shrinkage in the flow, that is, the difference in the molding shrinkage in different directions was defined as anisotropy. The flow direction of the molten resin and the method of measuring the mold shrinkage in the direction perpendicular to the flow are obtained by measuring the vertical (flow direction) and horizontal (perpendicular to flow) dimensions of the obtained square plate by Nikon Kogyo Co., Ltd. The profile shrinkage was measured with a profile projector V-12 universal projector, the molding shrinkage was determined from the vertical and horizontal mold dimensions of the square plate by the following formula, and then the anisotropy was determined. Mold shrinkage rate (%) = (Mold dimension-Molded product dimension) / Mold dimension x 100
Anisotropy = horizontal (flow direction perpendicular to molding) mold shrinkage ratio—longitudinal (flow direction) mold shrinkage ratio

[Reference Examples 1 to 19], [Examples 20 to 41], [Comparative Examples 1 to 14]
Thermoplastic other than (A) thermoplastic polyester resin and (B) component (A) using a twin screw extruder with a screw diameter of 30 mm and L / D35 (TEX-30α, manufactured by Nippon Steel) As the resin, one or more resins selected from aromatic polycarbonate resins, polyphenylene ether resins, and vinyl resins, (C) flame retardants, and (D) polyvalent compounds including one or more alkylene oxide units having three or more functional groups. Alcohol compound, further (E) fiber reinforcement, (F) epoxy compound, (G) alkaline earth metal compound, and (H) fluorine-based compound, and (I) fiber reinforcement as necessary Inorganic fillers other than the materials were mixed in the blending compositions shown in Tables 1 to 4 and added from the original filling portion. In addition, (E) Fiber reinforcement <E-1> GF was added by installing a side feeder in the middle of the original loading part and the vent part.

  Further, the mixture was melt-mixed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, discharged into 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 130 ° C. for 3 hours, and various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine. Furthermore, various values were measured by the above-described measurement method, and the results are also shown in Tables 1 to 4.

From Reference Example 1 to Reference Example 14 in Table 1, these flame-retardant thermoplastic polyester resin compositions are excellent in fluidity, mechanical properties and flame retardancy during injection molding, and bleed out even in a high-temperature and high-humidity atmosphere. It can be said that it is a resin composition which does not generate | occur | produce easily.

From Reference Example 15 to Reference Example 19 in Table 2, these flame retardant thermoplastic polyester resin compositions are excellent in fluidity, mechanical properties and flame retardancy during injection molding, and bleed out even in a high temperature and high humidity atmosphere. It can be said that it is a resin composition which does not generate | occur | produce easily.

  Further, from Example 20 to Example 24 in Table 2, (E) In the flame-retardant thermoplastic polyester resin composition containing GF as a fiber reinforcing material, fluidity, mechanical properties, and flame retardancy during injection molding It can be said to be a resin composition that is excellent in anisotropy that causes warping and distortion specifically, and hardly bleeds out even in a high temperature and high humidity atmosphere.

  From Comparative Example 1 to Comparative Example 14 in Table 3, when a polyhydric alcohol compound other than the present invention is blended, when any of the components of the present invention is not blended, or when the blending amount is outside the specific range, It is clear that the resin composition has a problem in one or more of fluidity, mechanical properties and flame retardancy, or occurrence of bleed-out in a high temperature and high humidity atmosphere.

  Moreover, it can be said that the resin composition of the comparative example 10-the comparative example 14 which mix | blended GF of the fiber reinforcement (E) is inferior in fluidity | liquidity, and is further inferior in the anisotropy causing a warp and distortion.

  From Example 25 to Example 35 in Table 4, the resin composition containing either (F) an epoxy compound or (G) an alkaline earth metal compound has fluidity, mechanical properties and flame retardancy, or high temperature and humidity. While maintaining excellent performance that does not cause bleed-out in an atmosphere, the hydrolyzability is further improved, and the resin composition containing both (F) an epoxy compound and (G) an alkaline earth metal compound is specific. It can be said that it is excellent in hydrolyzability.

(E) In the flame-retardant thermoplastic polyester resin composition containing GF as a fiber reinforcement, the same effect as described above can be obtained, and the resin composition having excellent anisotropy can be obtained. I can say that.
Moreover, although Table 4 Example 36 is a material which used PET and PBT for (A) component with respect to Example 31 only of PET component, it is excellent in the fluidity | liquidity at the time of injection molding, a mechanical characteristic, and a flame retardance. It can be said that the resin composition is less likely to bleed out even in a high-temperature and high-humidity atmosphere and has excellent anisotropy that specifically causes warping and distortion. Table 4 Examples 37 to 41 are materials using PET and PBT as the component (A), PC, epoxidized AS, combined use of PPE and epoxidized AS, and ABS as the component (B). It can be said that it is a resin composition having the performance of the present invention as described above. In particular, it can be said that the materials of Examples 38 and 39 using epoxidized AS as the component (B) are particularly excellent in the performance of the present invention. Moreover, it can be said that the material of Example 40 which used together PPE and epoxidized AS for (B) component has the mechanical property improved specifically with respect to Example 36 only of PPE in (B) component. The reason why the mechanical properties are improved is presumed that the epoxidized AS contributed to the improvement of the dispersibility of the component (A) and PPE.

Claims (10)

(A) With respect to 100 parts by weight of the thermoplastic polyester resin, (B) 1 to 100 parts by weight of a resin other than the thermoplastic polyester resin, (C) 1 to 100 parts by weight of a flame retardant , and (D) three or more functional groups. 1 or more alkylene oxide units, and the number of alkylene oxide units per functional group is 0.5-2 . A flame retardant thermoplastic polyester resin composition comprising 0.01 to 10 parts by weight of a polyhydric alcohol compound 3 and 1 to 150 parts by weight of (E) a fiber reinforcing material . (C) The flame retardant is one or more flame retardants selected from phosphorus flame retardants, nitrogen compound flame retardants, bromine flame retardants, chlorine flame retardants, silicone flame retardants, other inorganic flame retardants and phenolic resins. The flame-retardant thermoplastic polyester resin composition according to claim 1. (B) The difficulty according to claim 1 or 2, wherein the resin other than the thermoplastic polyester resin is one or more thermoplastic resins selected from the group consisting of an amorphous polycarbonate resin, an aromatic polycarbonate resin, a polyphenylene ether resin, and a vinyl resin. A flame-retardant thermoplastic polyester resin composition. The thermoplastic polyester resin (A) is one or more aromatic polyester resins selected from polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate. Flame retardant thermoplastic polyester resin composition. Furthermore, the flame-retardant thermoplastic polyester resin composition of any one of Claims 1-4 formed by mix | blending 0.05-10 weight part of (H) fluorine-type compounds. Furthermore, the flame-retardant thermoplastic polyester resin composition of any one of Claims 1-5 formed by mix | blending 0.1-10 weight part of (G) alkaline-earth metal compound. Furthermore, the flame-retardant thermoplastic polyester resin composition of any one of Claims 1-6 formed by mix | blending 0.1-10 weight part of (F) epoxy compounds. The flame retardant thermoplastic polyester resin composition according to claim 3, wherein the vinyl resin is an epoxidized vinyl resin. The flame retardant thermoplastic polyester resin composition according to any one of claims 1 to 8, wherein (A) the amount of carboxyl end groups of the thermoplastic polyester resin is 50 eq / t or less. A molded product selected from a mechanical mechanism part, an electrical / electronic part, and an automobile part, comprising the flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 9.