JP2019044037A - Thermoplastic polyester resin composition and molded article - Google Patents

Abstract

To provide a molded article which is excellent in flame retardancy and tracking resistance, has excellent mechanical properties and hydrolysis resistance, and hardly causes bleed out even under high temperature and high humidity environment.SOLUTION: A flame-retardant thermoplastic polyester resin composition is provided that is formed by blending into 100 pts.wt. of (A), a thermoplastic polyester resin, (B) 0.1-30 pts.wt. of a phosphorus flame retardant having an acid value of 10 KOHmg/g or less after being processed in a hot and humid condition of 121°C and 100% relative humidity for 40 hours, (C) 1-30 pts.wt. of a phosphorus flame retardant other then (B), (D) 0.1-20 pts.wt. of a nitrogen flame retardant, and (E) 0.01-1 pts.wt. of a drip prevention agent.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic polyester resin composition and a molded article obtained by molding the same.

  Thermoplastic polyester resins are utilized in a wide range of fields such as mechanical and mechanical parts, electric and electronic parts, and automotive parts, by taking advantage of various properties such as excellent injection moldability and mechanical properties. However, thermoplastic polyester resins are inherently flammable, and are therefore generally used in chemical and physical properties for use as industrial materials such as mechanical and mechanical parts, electric and electronic parts, and automobile parts. In addition to the balance, safety against flames, that is, flame retardancy is required, and a high degree of flame retardancy showing V-0 of the UL-94 standard is often required. In addition, when used in an environment where electricity flows, safety against tracking breakdown ignited by decomposition or carbonization of resin by discharge is required, that is, tracking resistance is required, and advanced tracking resistance showing CTI rank 0 of IEC60112 standard Sex is often required. In particular, electric vehicles have attracted attention in recent years due to rising environmental awareness, and even higher tracking resistance is required.

  As a method for improving flame retardancy and electrical characteristics, for example, base resin, a halogen-based flame retardant, an organic phosphinic acid or a salt thereof, a flame retardant aid, and an electrical property improvement aid such as melamine cyanurate The flame-retardant resin composition which is comprised and whose electric characteristic was improved is proposed (for example, refer to patent documents 1). However, there is a problem that the tracking resistance is still insufficient. Moreover, since the resin composition which mix | blends a halogen-type flame retardant may generate | occur | produce harmful dioxin at the time of combustion, the flame-retardant resin composition using a non-halogen-type flame retardant is calculated | required. .

  As a flame retardant resin composition using a non-halogen flame retardant, for example, a resin composition obtained by blending a thermoplastic resin such as a polybutylene terephthalate resin, a phosphoric ester compound and a methacrylic resin (see Patent Document 2) And polybutylene terephthalate resin, long-chain aliphatic polyamide resin, organophosphorus flame retardant such as phosphinate, and resin composition containing nitrogen-containing flame retardant auxiliary (see Patent Document 3), polyalkylene terephthalate Or a resin composition comprising a polycycloalkylene terephthalate, an organic phosphinate, an inorganic phosphate (Patent Document 4), a thermoplastic resin, an ethylene diamine phosphate, and an acid acceptor Patent document 5) is proposed.

International Publication No. 2006/090751 JP, 2014-196484, A JP 2011-231391 A JP, 2016-166358, A JP 2000-154324 A

  However, even in the techniques disclosed in Patent Documents 2 to 4, there are problems such as mechanical strength and impact resistance of a molded article, a large amount of gas at the time of molding of the molded article, and insufficient moldability. Further, the technology disclosed in Patent Document 5 has a problem that the flame retardancy and heat resistance of the molded article, and the retention stability at the time of melting of the resin composition are insufficient.

  Moreover, the polyester resin which mix | blended the flame retardant also had the problem of being easy to fall in intensity | strength by hydrolysis under high temperature and high humidity. An object of the present invention is to provide a thermoplastic polyester resin composition capable of obtaining a molded article excellent in flame retardancy while maintaining strength at high temperature and high humidity, and a molded article thereof.

As a result of repeating examinations in order to solve the above-mentioned subject, the inventors of the present invention, (A) thermoplastic polyester resin, (B) acid value after treatment for 40 hours under moist heat condition of 121 ° C-100% relative humidity 0.1 to 30 parts by weight of a phosphorus-based flame retardant having a content of 10 KOHmg / g or less, 0.1 to 30 parts by weight of a phosphorus-based flame retardant other than (C) and (B), and (D) a nitrogen-based flame retardant The present inventors have found that the above-mentioned problems can be solved by blending 20 parts by weight and (E) 0.01 to 1 part by weight of an anti-drip agent. That is, the present invention has the following configuration.
[1] A phosphorus-based flame retardant (A) having an acid value of 10 KOHmg / g or less after treated for 40 hours under moist heat conditions of (B) 121 ° C. to 100% relative humidity with respect to 100 parts by weight of (A) thermoplastic polyester resin B) 0.1 to 30 parts by weight, (C) 0.1 to 30 parts by weight of a phosphorus based flame retardant other than (B), (D) 0.1 to 20 parts by weight of a nitrogen based flame retardant, (E) drip prevention The thermoplastic polyester resin composition which mix | blends 0.01-1 weight part of agents.
[2] The thermoplasticity according to [1], wherein the phosphorus-based flame retardant having an acid value of 10 KOHmg / g or less after treated for 40 hours under the moist heat condition of (B) 121 ° C.-100% relative humidity is the diamine phosphate. Polyester resin composition.
[3] The thermoplastic polyester resin composition according to [1] or [2], wherein the phosphorus-based flame retardant other than the above (C) and (B) is a metal salt of phosphinate.
[4] The thermoplasticity according to any one of [1] to [3], wherein 0.1 to 10 parts by weight of the epoxy compound (F) is further blended with 100 parts by weight of the thermoplastic polyester resin (A) Polyester resin composition.
[5] The thermoplastic polyester resin composition according to [4], wherein the (F) epoxy compound is at least one selected from glycidyl ether compounds, epoxidized fatty acid ester compounds, and alicyclic epoxy compounds.
[6] The thermoplasticity according to any one of [1] to [5], wherein 0.01 to 1 part by weight of the (G) hindered amine compound is further blended with 100 parts by weight of the (A) thermoplastic polyester resin Polyester resin composition.
[7] The heat according to any one of [1] to [6], wherein 0.1 to 30 parts by weight of (H) a hydroxyl group-containing resin is further blended with 100 parts by weight of the (A) thermoplastic polyester resin Plastic polyester resin composition.
[8] The heat according to any one of [1] to [7], which further comprises (I) 1 to 100 parts by weight of a fibrous reinforcing material with respect to 100 parts by weight of (A) a thermoplastic polyester resin. Plastic polyester resin composition.
[9] The thermoplastic polyester resin composition according to any one of [1] to [8], wherein the thermoplastic polyester resin (A) is a polybutylene terephthalate resin.
[10] After subjecting a test piece for tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D 638 (2005) for 50 hours in an atmosphere with a relative humidity of 100% and a temperature of 121 ° C. The thermoplastic polyester resin composition according to any one of [1] to [9], wherein the tensile strength retention ratio of ((tensile strength after exposure / tensile strength before exposure) × 100) is 50% or more.
[11] A molded article obtained by melt-molding the thermoplastic polyester resin composition according to any one of [1] to [10].

  The thermoplastic polyester resin composition of the present invention is excellent in flame retardancy and tracking resistance, has excellent mechanical properties and hydrolysis resistance, and is a molded article which hardly bleeds out even under high temperature and high humidity environment. You can get it. Furthermore, the amount of gas generation at the time of melt processing is small and the moldability is excellent.

  Next, the thermoplastic polyester resin composition of the present invention will be described in detail.

  The thermoplastic polyester resin composition of the present invention is a phosphorus based (A) thermoplastic polyester resin having (B) an acid value of 10 KOH mg / g or less after treated for 40 hours under moist heat conditions of 121 ° C. to 100% relative humidity. 0.1-30 parts by weight of flame retardant, 0.1-30 parts by weight of phosphorus-based flame retardant other than (C) and (B), 0.1-20 parts by weight of (D) nitrogen-based flame retardant, and (E) drip It is the flame-retardant thermoplastic polyester resin composition which mix | blends 0.01-1 weight part of inhibiting agents. (A) Thermoplastic polyester resins are generally excellent in injection moldability and mechanical properties, but have a low limit oxygen index, so they burn when approaching a fire such as an open flame. In the present invention, as a method for enhancing the flame retardancy of the (A) thermoplastic polyester resin, (B) a phosphorus-based material having an acid value of 10 KOHmg / g or less after treatment for 40 hours under moist heat conditions of 121 ° C-100% relative humidity. A flame retardant, (C) a phosphorus-based flame retardant other than (B), (D) a nitrogen-based flame retardant, and (E) an anti-drip agent are blended. Generally, phosphorus flame retardants improve flame retardancy by promoting the formation of a carbonized layer during combustion of the (A) thermoplastic polyester resin, but at the same time decomposition of the phosphorus flame retardant under high temperature and high humidity environment It has been found that the strength and hydrolysis resistance of the (A) thermoplastic polyester resin are significantly impaired because an acidic component is produced by Therefore, the hydrolysis resistance of the thermoplastic polyester resin composition is suppressed by suppressing the generation of the acid component derived from the flame retardant when treated at a temperature of 121 ° C. and 100% relative humidity for 40 hours where the strength decrease of the thermoplastic polyester resin is remarkable. It is possible to improve the quality. Therefore, among the phosphorus-based flame retardants, the acid value of the phosphorus-based flame retardant after treatment at 121 ° C. and 100% relative humidity for 40 hours is 10 KOH mg / g or less as an index of the generation amount of the acidic component under wet heat environment B) Phosphorus-based flame retardants (hereinafter sometimes referred to as heat-resistant water-soluble phosphorus-based flame retardants), (C) Phosphorus-based flame retardants other than (B), (D) Nitrogen-based flame retardants, and (E) Anti-drip prevention By blending the agent, the flame retardancy, the strength and the hydrolysis resistance of the obtained resin composition can be highly compatible with each other.

  Here, the thermoplastic polyester resin composition of the present invention includes a reaction product in which the components (A), (B), (C), (D), and (E) are reacted, An object is produced by a complex reaction, and there are circumstances in which it is not practical to specify its structure. Therefore, the present invention specifies the invention by the components to be blended.

  The thermoplastic polyester resin (A) used in the present invention comprises (1) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (2) a hydroxycarboxylic acid or an ester-forming derivative thereof, ) Polymers or copolymers having as a main structural unit at least one residue selected from the group consisting of lactones. Here, "as a main structural unit" refers to having at least 50% by mole of at least one residue selected from the group consisting of (1) to (3) in all structural units, and those residues It is a preferable aspect to have 80 mol% or more. Among these, (1) polymers or copolymers having as a main structural unit a residue of a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof are preferable in that they are excellent in mechanical properties and heat resistance. .

  Examples of the above dicarboxylic acids or ester-forming derivatives thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene Aromatic acids such as dicarboxylic acids, 4,4'-diphenylether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedione Aliphatic dicarboxylic acids such as acid, malonic acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and their ester-forming derivatives . Two or more of these may be used.

  Moreover, as said diol or its ester formation derivative, ethylene glycol, propylene glycol, 1, 4- butanediol, neopentyl glycol, 1, 5- pentanediol, 1, 6- hexanediol, decamethylene glycol is mentioned, for example. Aliphatic or alicyclic glycols having 2 to 20 carbon atoms such as cyclohexanedimethanol, cyclohexanediol, dimer diol, etc., polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Molecular weights of 200 to 100,000 Aromatic dioxy compounds such as long-chain glycols of 4,4′-dihydroxybiphenyl, hydroquinone, t-butyl hydroquinone, bisphenol A, bisphenol S, bisphenol F and the like, Etc. Le forming derivatives thereof. Two or more of these may be used.

  As a polymer or copolymer which makes a dicarboxylic acid or its ester formation derivative and diol or its ester formation derivative a structural unit, For example, a polyethylene terephthalate, a polypropylene terephthalate, a polybutylene terephthalate, a polypropylene isophthalate, a polybutylene isophthalate , Polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decanedicarboxylate, polypropylene terephthalate / 5-sodium sulfoisophthalate, poly Butylene terephthalate / 5-sodium sulfoisophthalate, Polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / poly Tetramethylene glycol, polybutylene terephthalate / succinate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / Sofutareto / succinate, polybutylene terephthalate / isophthalate / adipate, and aromatic polyester resins such as polybutylene terephthalate / isophthalate / sebacate, and the like. Here, "/" represents a copolymer.

  Among these, from the viewpoint of further improving mechanical properties and heat resistance, a polymer having a residue of an aromatic dicarboxylic acid or an ester-forming derivative thereof and a residue of an aliphatic diol or an ester-forming derivative thereof as main structural units Or a copolymer is more preferable, mainly consisting of the residue of terephthalic acid, naphthalene dicarboxylic acid or an ester-forming derivative thereof and the residue of an aliphatic diol selected from propylene glycol and 1,4-butanediol or an ester-forming derivative thereof Further preferred are polymers or copolymers as structural units.

  Among them, aromatic polyester resins such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene naphthalate, polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate and polybutylene terephthalate / naphthalate In particular, polybutylene terephthalate, polypropylene terephthalate and polybutylene naphthalate are more preferable, and polybutylene terephthalate is more preferable in terms of excellent moldability and crystallinity. Moreover, these 2 or more types can also be used by arbitrary content.

  In the present invention, terephthalic acid or total dicarboxylic acid constituting a polymer or copolymer having as a main structural unit the residue of the above-described dicarboxylic acid or ester-forming derivative thereof and the residue of diol or ester-forming derivative thereof The proportion of the ester-forming derivative is preferably 30 mol% or more, more preferably 40 mol% or more.

  In the present invention, as the (A) thermoplastic polyester resin, a liquid crystalline polyester resin capable of forming anisotropy when melted can be used. As a structural unit of liquid crystalline polyester resin, an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylene dioxy unit, an aromatic imino oxy unit etc. are mentioned, for example.

  The carboxyl group content of the (A) thermoplastic polyester resin used in the present invention is preferably 50 eq / t or less in terms of flowability, hydrolysis resistance and heat resistance. If it exceeds 50 eq / t, hydrolysis resistance may be greatly reduced because the carboxyl group acts as an acid catalyst. More preferably, it is 40 eq / t or less, still more preferably 30 eq / t or less. The lower limit value of the amount of carboxyl groups is about 0 eq / t. Here, the carboxyl group content of the (A) thermoplastic polyester resin is a value measured by dissolving the (A) thermoplastic polyester resin in o-cresol / chloroform solvent and then titration with ethanolic potassium hydroxide.

  The thermoplastic polyester resin (A) used in the present invention preferably has a weight average molecular weight (Mw) of 8,000 or more from the viewpoint of further improving the mechanical properties. The upper limit value of the weight average molecular weight (Mw) is preferably 500,000 or less because the fluidity can be improved. More preferably, it is 300,000 or less, More preferably, it is 250,000 or less. In the present invention, Mw of the (A) thermoplastic polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The thermoplastic polyester resin (A) used in the present invention can be produced by a known polycondensation method or ring-opening polymerization method. The production method may be either batch polymerization or continuous polymerization, and any of transesterification reaction and reaction by direct polymerization can be applied, but from the viewpoint of productivity, continuous polymerization is preferable, and direct polymerization is also preferable. It is more preferably used.

  When the thermoplastic polyester resin (A) used in the present invention is a polymer or copolymer obtained by a condensation reaction comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components These compounds can be produced by subjecting a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof to an esterification reaction or a transesterification reaction and then a polycondensation reaction.

  In order to effectively promote the esterification reaction or the transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester of titanic acid Organotitanium compounds such as benzyl ester, tolyl ester or mixed ester thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexyhexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyl tin hydroxide, triisobutyl tin acetate, dibutyl tin diacetate, diphenyl tin dilaurate, monobutyl tin trichloride, di Tin compounds such as alkylstannonic acids such as chilltin dichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannonic acid, ethylstannonic acid, butylstannonic acid, and zirconia compounds such as zirconium tetra-n-butoxide And antimony compounds such as antimony trioxide and antimony acetate. Two or more of these may be used.

  Among these polymerization reaction catalysts, organic titanium compounds and tin compounds are preferable, and tetra-n-butyl ester of titanic acid is more preferably used. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin.

  The phosphorus-based flame retardant used in the present invention is a phosphorus-containing compound having a phosphorus atom content of 5% by weight or more. Among them, the (B) component is a phosphorus-based flame retardant having an acid value of 10 KOH mg / g or less after treated for 40 hours under moist heat conditions of 121 ° C. to 100% relative humidity and having high stability under high temperature and high humidity environment. (Heat resistant water-soluble phosphorus-based flame retardant). Here, the acid value after treatment for 40 hours under moist heat conditions of 121 ° C. to 100% relative humidity is a value obtained by dissolving the moist heat-treated phosphorus flame retardant in chloroform solvent and then titrating with ethanolic potassium hydroxide It is.

  In the present invention, examples of the (B) heat-resistant water-soluble phosphorus-based flame retardant include phosphazene compounds and diamine phosphates.

  As phosphazene compounds, mention may be made of phosphonitrile linear polymers and / or cyclic polymers, and in particular, those having a linear phenoxyphosphazene as a main component are preferably used. The phosphazene compounds can be synthesized by known methods described in “Synthesis and application of phosphazene compounds” (Naruaki Ashihara, CMC Publishing, 1986) and the like, and, for example, phosphorus pentachloride as a phosphorus source or Phosphorus trichloride, ammonium chloride as a nitrogen source or ammonia gas is reacted by a known method (the cyclic substance may be purified), and synthesis is performed by replacing the obtained substance with alcohol, phenol and amines. Can. Moreover, as a commercial item, "rabitol" (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.

As a diamine phosphate, a compound represented by the general formula M _m [P ₂ O ₈ C _n N ₂ H _{2 n + 6} ] (M is Zn and / or Mg, m = 1 to 2, n = 1 to 4) Examples thereof include composite salts obtained by mixing an aqueous solution of an amine metal salt such as a diamine zinc complex and an aqueous phosphoric acid solution. Specific examples include zinc ethylenediamine phosphate, 1,4-butanediamine phosphate, zinc magnesium ethylenediamine phosphate and the like. Moreover, as a commercial item, Suzuyu Chemical Co., Ltd. "fire cut" (registered trademark) ZPO-3 etc. are used preferably.

  In the present invention, the (B) heat-resistant water-soluble phosphorus-based flame retardant can improve flame retardancy by generating an amine-based decomposition product at the time of combustion and decomposition, and can further reduce the amount of gas generated during molding. Salts are preferred, and among these, zinc ethylenediamine phosphate is preferred because it can further improve the hydrolysis resistance.

  In the present invention, the compounding amount of the (B) heat resistant water-soluble phosphorus-based flame retardant is 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount of the component (B) is less than 0.1 parts by weight, the flame retardancy decreases. More preferably, it is 1 part by weight or more, still more preferably 2 parts by weight or more. On the other hand, if the compounding amount of the component (B) exceeds 30 parts by weight, there is a concern that the impact resistance may decrease and the component (B) may bleed out. More preferably, it is 20 parts by weight or less, still more preferably 15 parts by weight or less.

  The phosphorus-based flame retardants other than (C) and (B) used in the present invention promote formation of a carbonized layer of the thermoplastic polyester resin (A) at the time of combustion with the component (B) to further improve the flame retardancy. Can.

  In the present invention, phosphorus-based flame retardants other than (C) and (B) include aromatic phosphoric acid ester compounds, phosphaphenanthrene compounds, metal salts of phosphinates, ammonium polyphosphates, melamine polyphosphates, phosphoric acid ester amides, red phosphorus, etc. Can be mentioned. Among these, metal phosphinates generate an acidic phosphorus compound at the time of combustion decomposition, and the acidic phosphorus compound remains in the resin for a long time by the neutralization reaction with the amine decomposition product generated at the time of decomposition of the component (B), By promoting the formation of the carbonized layer, the flame retardancy can be further improved, which is preferably used. Two or more of these may be blended.

  Examples of the aromatic phosphoric acid ester compounds include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, biphenyl diphenyl phosphate and the like. As a commercial item, Daihachi Chemical Industry Co., Ltd. product PX-202, CR-741, PX-200, PX-201, ADEKA company FP-500, FP-600, FP-700 and PFR And the like.

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

  The metal phosphinate described above is a phosphinate and / or diphosphinate and / or a polymer thereof, and is a compound useful as a flame retardant for (A) thermoplastic polyester resin. Said salts include salts such as calcium, aluminum and zinc. Examples of commercially available products of metal phosphinate include "Exolit" (registered trademark) OP 1230 and OP 1240 manufactured by Clariant Japan.

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

  Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine modified ammonium polyphosphate and ammonium carbamyl polyphosphate. It may be coated with a thermosetting resin such as a thermosetting phenolic resin, a urethane resin, a melamine resin, a urea resin, an epoxy resin, and a urea resin.

  Examples of the above-mentioned melamine polyphosphate include melamine phosphate, melamine pyrophosphate and melamine polyphosphate such as melamine, melamine and phosphate with Melem. Sanwa Chemical Co., Ltd. "MPP-A, Nissan Chemical Co., Ltd. PMP-100, PMP-200 etc. are used preferably.

  The red phosphorus is not only untreated red phosphorus but also red phosphorus treated with at least one compound coating selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. Can be preferably used. Examples of the thermosetting resin used for the thermosetting resin film include phenol-formalin resins, urea-formalin resins, melamine-formalin resins, alkyd resins and the like. As a metal hydroxide used for a metal hydroxide film, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide etc. can be mentioned, for example. The metal used for 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 films may be laminated in combination of two or more, or in two or more.

  The compounding amount of the phosphorus-based flame retardant other than (C) and (B) in the present invention is 0.1 to 30 with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of flame retardancy and hydrolysis resistance. It is a weight part. When the blending amount of the component (C) is less than 0.1 parts by weight, the flame retardancy decreases. More preferably, it is 1 part by weight or more, still more preferably 2 parts by weight or more. On the other hand, when the compounding quantity of (C) component exceeds 30 weight part, mechanical strength and hydrolysis resistance will fall. More preferably, it is 25 parts by weight or less, still more preferably 20 parts by weight or less.

  The thermoplastic polyester resin composition in the present invention improves the flame retardancy by blending the (D) nitrogen-based flame retardant. Examples of the (D) nitrogen-based flame retardant in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyan compounds, aliphatic amide compounds, aromatic amide compounds, urea and thiourea, etc. It can be mentioned. Two or more of these may be blended. Among these, nitrogen-containing heterocyclic compounds are preferably used. However, the thing applicable also to (B) component of this invention is handled as (B) component, and the thing applicable to (C) component is handled as (C) component.

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

  An aniline, phenylenediamine, etc. can be mentioned as said aromatic amine compound.

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

  Examples of the above-mentioned cyan compounds include dicyandiamide.

  Examples of the aliphatic amide compound and the aromatic amide compound include N, N-dimethylacetamide and N, N-diphenylacetamide.

  The triazine compound exemplified in the above nitrogen-containing heterocyclic compound is a compound having a triazine skeleton. For example, triazine, melamine, benzoguanamine, methyl guanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyl triazine, triphenyl triazine, amelin, amelide, thiocyanuric acid, diamino mercapto triazine, diamino methyl triazine, diamino phenyl triazine, diamino iso Examples thereof include propoxy triazine and melamine polyphosphate, and melamine cyanurate, melamine isocyanurate and melamine polyphosphate are preferably used.

  As the above-mentioned melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually a composition of 1 to 1 (molar ratio), optionally 1 to 2 (molar ratio) The adduct which it has can be mentioned. These are produced by a known method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry, mixed well to form fine salts of both salts, and then this slurry is filtered and dried. Generally, it is obtained in powder form. In addition, the above-mentioned salts do not have to be completely pure, and some unreacted melamine to 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 polyvinyl alcohol and a metal oxide such as silica may be used in combination. Moreover, as for the average particle diameter before and after mix | blending with resin of melamine cyanurate or melamine isocyanurate, as for the flame retardance of a molded article, mechanical strength, and the point of surface property, 0.1-100 micrometers is preferable. Here, the average particle diameter is an average particle diameter measured by a 50% particle diameter of a cumulative distribution by a laser micron sizer method. As commercially available products of melamine cyanurate or melamine isocyanurate, MC-4000, MC-4500, MC-6000, etc. manufactured by Nissan Chemical Industries, Ltd. are preferably used.

  Moreover, the compounding quantity of (D) component is 0.1-20 weight part with respect to 100 weight part of (A) thermoplastic polyester resin from the point of the balance of a flame retardance and toughness. If the amount of the component (D) is less than 0.1 parts by weight, the flame retardancy is insufficient. 1 weight part or more is preferable and 2 weight part or more is more preferable. On the other hand, when the compounding amount of the component (D) exceeds 20 parts by weight, the toughness is lowered. 18 parts by weight or less is preferable, and 16 parts by weight or less is more preferable.

  Moreover, in this invention, (E) anti-drip agent is a compound which can suppress the melt fall of the resin composition at the time of a combustion, and can improve a flame retardance more, and a fluorine resin is mentioned.

  The above-mentioned fluorine-based resin is a resin containing fluorine in substance molecules, and specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Can be mentioned. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, polyvinylidene fluoride are preferable. In particular, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer are preferable.

  Moreover, the compounding quantity of (E) component is 0.01-1 weight part with respect to 100 weight part of (A) thermoplastic polyester resin from the point of the balance of a flame retardance and mechanical strength. Flame retardancy will become inadequate that the compounding quantity of (E) component is less than 0.01 weight part. 0.03 parts by weight or more is preferable, and 0.05 parts by weight or more is more preferable. On the other hand, when the compounding amount of the component (E) exceeds 1 part by weight, the fluidity is lowered. 0.8 parts by weight or less is preferable, and 0.6 parts by weight or less is more preferable.

  In the flame-retardant thermoplastic polyester resin composition of the present invention, in order to improve hydrolysis resistance, it is preferable to further add (F) an epoxy compound. By blending the epoxy compound, the carboxyl group of the (A) thermoplastic polyester resin can be blocked, and the hydrolysis reaction in a moist and heat environment can be suppressed.

  The epoxy compound (F) used in the present invention is a compound having an epoxy group in the molecule, and is not particularly limited, but glycidyl ester compound, glycidyl ether compound, epoxidized fatty acid ester compound, glycidyl imide compound, Alicyclic epoxy compounds may be mentioned. Two or more of these may be used in combination.

  The glycidyl ether compound is a compound having a glycidyl ether structure, and examples thereof include a condensate of a phenol compound and epichlorohydrin, a novolac epoxy, a glycidyl ether of a polyvalent hydroxyl compound, and the like.

  Specific examples of condensates of phenol compounds and epichlorohydrin include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, bisphenol S, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, 1,4- Dihydroanthracene-9,10-diol, 6-hydroxy-2-naphthoic acid, 1,1-methylenebis-2,7-dihydroxynaphthalene, 1,1,2,2-tetrakis-4-hydroxyphenylethane, cashew phenol and the like And condensates obtained by condensation of epichlorohydrin with a phenol compound of

  Specific examples of novolac type epoxy include phenol novolac type epoxy, cresol novolac type epoxy, naphthol novolac type epoxy, bisphenol A novolac type epoxy, dicyclopentadiene-phenol added novolac type epoxy, dimethylene phenylene-phenol added novolak type epoxy, diphenol Methylene biphenylene-phenol addition novolac type epoxy etc. are mentioned.

  In the present invention, the polyvalent hydroxyl compound is an aliphatic compound having two or more hydroxyl groups, and specifically, glycol having 2 to 20 carbon atoms, glycerin, polyglycerin, dipentaerythritol, tripentaerythritol, xylitol, Examples include mannitol, sorbitol, galactose, maltitol, lactitol, isomalt, inositol, glucose, fructose and the like.

  In the present invention, the epoxidized fatty acid ester compound is a compound obtained by epoxidizing unsaturated bond of unsaturated fatty acid ester such as soybean oil and linseed oil, and specifically, epoxidized fatty acid octyl ester, epoxidized soybean oil, Examples thereof include epoxidized linseed oil.

  Specific examples of the glycidyl imide compound include N-glycidyl phthalimide, N-glycidyl-4-methyl phthalimide, N-glycidyl-4,5-dimethyl phthalimide, N-glycidyl-3-methyl phthalimide, N-glycidyl-3,6 -Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidylsuccinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N -Glycidyl-α, β-dime Chilsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, triglycidyl isocyanurate, N-glycidyl benzamide, N-glycidyl-p-methyl benzamide, N-glycidyl naphthamide or N -Glycidyl stearamide etc. are mentioned.

  Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4 5-epoxycyclohexane-1,2-dicarboximide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboximide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid Imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboximide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboximide and the like can be mentioned.

  (F) The epoxy compound is at least one selected from a glycidyl ether compound, an epoxidized fatty acid ester compound, and an alicyclic epoxy compound because it can suppress the reaction between the epoxy and suppress the deterioration of the retention stability. Among them, glycidyl ether compounds and epoxidized fatty acid ester compounds are more preferable, and among them, glycidyl ether compounds are more preferable because hydrolysis resistance can be further improved. Among the glycidyl ether compounds, novolac type epoxy is preferable because heat resistance can be improved.

  Moreover, the epoxy compound whose epoxy equivalent is 100-3000 g / eq is preferable as (F) epoxy compound. (F) When the epoxy equivalent of an epoxy compound is 100 g / eq or more, the gas amount at the time of melt processing can be suppressed. 150 g / eq or more is more preferable. Moreover, when the epoxy equivalent of (F) epoxy compound is 3000 g / eq or less, long-term hydrolysis resistance and high temperature melt retention stability can be compatible at a higher level. 2000 g / eq or less is more preferable.

  In the present invention, the compounding amount of the (F) epoxy compound is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the blending amount of the component (F) is 0.1 parts by weight or more, long-term hydrolysis resistance is improved. More preferably, it is 0.3 parts by weight or more. On the other hand, if the compounding quantity of (F) component is 10 weight part or less, heat resistance and retention stability will improve. More preferably, it is 8 parts by weight or less, still more preferably 5 parts by weight or less.

  Moreover, in this invention, the preferable range of the compounding quantity of (F) epoxy compound can be set according to the epoxy equivalent of the (F) epoxy compound. For example, the ratio of the amount of epoxy groups derived from the epoxy compound (F) compounded into the thermoplastic polyester resin composition to the amount of carboxyl groups derived from the thermoplastic polyester resin (A) compounded into the thermoplastic polyester resin composition (epoxy As for group compounding quantity (eq / g) / carboxyl group compounding quantity (eq / g), 0.5-8 are preferable. When the (epoxy group blending amount (eq / g) / carboxyl group blending amount (eq / g)) is 0.5 or more, the long-term hydrolysis resistance can be further improved. 1 or more is preferable and 2 or more is more preferable. Moreover, when (the epoxy-group compounding quantity (eq / g) / carboxyl-group compounding quantity (eq / g)) is eight or less, retention stability, heat resistance, and mechanical physical property can be compatible on a higher level. Seven or less are preferable and six or less are more preferable.

  In the present invention, the amount of the carboxyl group derived from the thermoplastic polyester resin (A) to be added to the thermoplastic polyester resin composition is the carboxyl group concentration of the component (A) and the amount of the carboxyl group in the entire thermoplastic polyester resin composition (A And the mixing ratio of the components). (A) The carboxyl group concentration of the thermoplastic polyester resin is obtained by dissolving a solution of the thermoplastic polyester resin in o-cresol / chloroform (2/1, vol / vol) mixed solution, 1% bromophenol blue It can be calculated by titration with 0.05 mol / L ethanolic potassium hydroxide as an indicator.

  In the thermoplastic polyester resin composition of the present invention, in order to accelerate the reaction of the carboxyl group of (A) thermoplastic polyester resin and (F) epoxy compound, and to improve hydrolysis resistance, (G) hindered amine compound is further added It is preferable to mix | blend.

  The (G) hindered amine compound used in the present invention is a compound having a structure having at least one 2,2,6,6-tetramethylpiperidine derivative in the molecule.

  (G) Specific examples of the hindered amine compound include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis- (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis- (2,2,6,6-tetramethyl-4-piperidyl) suberate, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (2,2,6,6-tetra Methyl-4-piperidyl) phthalate, bis- (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis -(1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) isophthalamide N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) adipamide, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5,1,1 11,2] henicosan 21-one, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl (3,5-di-t-butyl-4-hydroxybenzyl) malonate Bis- (2,2,6,6-tetramethyl-4-piperidyl) -n-butyl (3,5-di-t-butyl-4-hydroxybenzyl) malonate, tetra- (2 of butanetetracarboxylic acid) 2,2,6,6-Tetramethyl-4-piperidyl) ester, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3 -(3,5-di-t-butyl) -4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2 2,4-diyl] [(2,2,6,6-tetramethyl piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], tetrakis (1,2,2,6 2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4- Butane tetracarboxylate, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] Condensates with undecane) diethanol, 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ', β'-tetramethyl- Examples thereof include condensates with 3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol.

  The blending amount of the (G) hindered amine compound is 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A). (G) The hydrolysis resistance can be improved as the compounding quantity of a hindered amine compound is 0.01 weight part or more. More preferably, it is 0.03 parts by weight or more. On the other hand, if the blending amount of the (G) hindered amine compound is 1 part by weight or less, the retention stability is improved. More preferably, it is 0.8 parts by weight or less, still more preferably 0.5 parts by weight or less.

  In the thermoplastic polyester resin composition of the present invention, in order to improve the heat aging resistance under long-term exposure in a dry heat environment, it is preferable to further add a (H) hydroxyl group-containing resin. (A) The thermoplastic polyester resin has its molecular weight reduced by thermal decomposition under dry heat environment and its carboxyl group increases, but by blending a hydroxyl group containing resin, the carboxyl terminal group derived from the polyester resin and the hydroxyl group of the hydroxyl group containing resin Can react to improve the heat aging resistance by suppressing the decrease in molecular weight.

  In the present invention, the (H) hydroxyl group-containing resin is a compound having a hydroxyl group-containing number average molecular weight of 2,000 to 500,000. Here, the number average molecular weight of the hydroxyl group-containing resin is a value in terms of polystyrene or poly (methyl methacrylate), which is measured using gel permeation chromatography (GPC). The solvent for GPC can be selected appropriately depending on the structure of the (H) hydroxyl group-containing resin, but generally it is hexafluoroisopropanol, chloroform, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide Etc. can be illustrated.

  When the number average molecular weight of the (H) hydroxyl group-containing resin used in the present invention is less than 2,000, the molecular weight is likely to decrease due to the progress of transesterification with the (A) thermoplastic polyester resin when exposed to dry heat. Poor in heat aging resistance. If the number average molecular weight exceeds 500,000, the retention stability at the time of melting tends to deteriorate, which is not preferable. Preferably it is 3,000-200,000, More preferably, it is 4,000-100,000, More preferably, it is 5,000-50,000.

  The hydroxyl value of the (H) hydroxyl group-containing resin used in the present invention is preferably 3 to 20 eq / kg. Here, the hydroxyl value (eq / kg) of the (H) hydroxyl group-containing resin is acetylated with the acetylation reagent of the hydroxyl group of the (H) hydroxyl group-containing resin according to JIS K 0070 and JIS K 1557-1, and a phenolphthalein solution as an indicator And titrated with potassium hydroxide ethanol solution. The thermoplastic polyester resin composition containing a hydroxyl group-containing resin (H) having a hydroxyl value of 3 to 20 eq / kg can exhibit excellent heat aging resistance and retention stability at the time of melting. (H) By setting the hydroxyl value of the hydroxyl group-containing resin to 3 eq / kg or more, the reaction with the carboxy group terminal of the (A) thermoplastic polyester resin is promoted to be excellent in heat aging resistance, and the hydroxyl value is 20 eq / kg or less. By doing this, retention stability at the time of melting can be maintained. It is preferably 3 to 17 eq / kg, more preferably 3 to 15 eq / kg.

  (H) The structure of the hydroxyl group-containing resin is not particularly limited. For example, polyhydroxy polyethers such as phenoxy resin, acrylic resin containing hydroxyalkyl (meth) acrylate in the structural unit, ethylene-vinyl alcohol copolymer And EVOH resin, paravinyl phenol resin, carbinol modified or diol modified silicone oil, polycarbonate diol and the like. Among them, phenoxy resins or acrylic resins containing at least hydroxyalkyl (meth) acrylate as a structural unit are preferable from the viewpoint of the heat resistance of the hydroxy group-containing resin itself and the dispersibility in (A) the thermoplastic polyester resin. By using these hydroxyl group-containing resins, the compatibility and dispersibility with the thermoplastic polyester resin are improved. As a result, in the use of a molded article obtained by melt-molding a thermoplastic polyester resin composition in a dry heat environment, it is possible to achieve both heat aging resistance and hydrolysis resistance at a high level. In addition, while suppressing the thermal deterioration of the hydroxy group-containing resin itself, effects such as improvement of retention stability at the time of melt processing, deterioration of moldability, suppression of mold deposit, suppression of bleed out to the surface of a molded article, etc. are obtained. Be

  Specific examples of polyhydroxy polyethers include hydroquinone, resorcine, 2,2'-biphenol, 4,4-biphenol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, bis (hydroxyaryl) ) Aromatic dihydroxys such as alkanes, bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, and 2,6-dihydroxynaphthalene The phenoxy resin obtained by condensing a compound and epichlorohydrin can be illustrated. As bis (hydroxyaryl) alkanes, bis (4-hydroxyphenyl) methane: bisphenol F, 2,2-bis (4-hydroxyphenylpropane): bisphenol A, 1,1-bis (4-hydroxyphenylethane): Bisphenol AD, 2, 2-bis (4-hydroxyphenyl) butane etc. can be illustrated, and as bis (hydroxy aryl) cycloalkane, 1, 1-bis (hydroxyphenyl) pentane, 1, 1-bis (4-hydroxy) Examples include phenyl) hexane, 1,1-bis (hydroxyphenyl) heptane and the like. These phenoxy resins having a bisphenol skeleton can be used alone or in combination of two or more.

  As hydroxyalkyl (meth) acrylate in an acrylic resin containing hydroxyalkyl (meth) acrylate in a structural unit, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate and the like can be exemplified. Further, alkyl or aryl esters such as acrylic acid and methacrylic acid other than the above, olefin compounds such as ethylene, propylene, 1-butene and butadiene, vinyl aromatic compounds such as styrene, homopolymers such as acrylonitrile, acrylamide and methacrylamide, Copolymers and the like can be included in the hydroxy group-containing acrylic resin of the present invention. These hydroxy group-containing acrylic resins can be used alone or in combination of two or more.

  The compounding amount of the (H) hydroxyl group-containing resin is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the thermoplastic polyester resin (A). (H) The heat aging resistance improvement effect can be improved as the compounding quantity of hydroxyl-containing resin is 0.1 weight part or more. More preferably, it is 0.5 parts by weight or more, still more preferably 1 part by weight or more. On the other hand, when the compounding amount of the (H) hydroxyl group-containing resin is 10 parts by weight or less, retention stability and fluidity can be improved. More preferably, it is 8 parts by weight or less.

  It is preferable to further mix | blend (I) fibrous reinforcement with the thermoplastic polyester resin composition of this invention. (I) The fibrous reinforcing material can further improve mechanical strength and heat resistance.

  Specific examples of the (I) fibrous reinforcing material include glass fibers, aramid fibers, and carbon fibers. The above glass fiber is a chopped strand type or roving type glass fiber, and is a co-made of a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or an acrylic acid such as urethane or acrylic acid / styrene copolymer. Polymer, copolymer consisting of maleic anhydride such as methyl acrylate / methyl methacrylate / maleic anhydride copolymer, and one or more epoxy compounds such as vinyl acetate, bisphenol A diglycidyl ether, novolac epoxy compound, etc. Glass fibers treated with a contained sizing agent are preferably used. A glass fiber treated with a convergent agent containing a copolymer of maleic anhydride is more preferable because the hydrolysis resistance can be further improved. The silane coupling agent and / or the sizing agent may be used by being mixed with the emulsion liquid. Moreover, as for the fiber diameter of glass fiber, the range of 1-30 micrometers is preferable normally. From the viewpoint of the dispersibility of the glass fiber in the resin, the lower limit thereof is preferably 5 μm. The upper limit is preferably 15 μm from the viewpoint of mechanical strength. In addition, although the fiber cross section described above is usually circular, it is also possible to use a fibrous reinforcing material having an arbitrary cross section such as oval glass fiber, flat glass fiber, and cocoon-shaped glass fiber of any aspect ratio. It is characterized in that the flowability at the time of molding is improved, and a molded product with less warpage can be obtained.

  Moreover, the compounding quantity of the (I) fibrous reinforcement is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The mechanical strength and the heat resistance can be further improved by blending the fibrous reinforcing material in an amount of 1 part by weight or more. 2 parts by weight or more is more preferable, and 3 parts by weight or more is more preferable. On the other hand, mechanical strength and fluidity can be further improved by blending (I) the fibrous reinforcing material in an amount of 100 parts by weight or less. 95 parts by weight or less is more preferable, and 90 parts by weight or less is more preferable.

  The preferable range of the compounding amount of the fibrous reinforcing material (I) can also be set as the content in the thermoplastic polyester resin composition. The content of the fibrous reinforcing material in the thermoplastic polyester resin composition is preferably 1 to 70 parts by weight based on 100 parts by weight of the thermoplastic polyester resin composition. (I) Mechanical strength and heat resistance can be further improved by blending 1 part by weight or more when the fibrous reinforcing material is 100 parts by weight of the thermoplastic polyester resin composition. 3 parts by weight or more is more preferable, and 5 parts by weight or more is more preferable. On the other hand, mechanical strength and fluidity can be further improved by blending 70 parts by weight or less of (I) fibrous reinforcing material with 100 parts by weight of the thermoplastic polyester resin composition. 60 parts by weight or less is more preferable, and 50 parts by weight or less is more preferable.

  In the thermoplastic polyester resin composition of the present invention, a reinforcing material other than the fibrous reinforcing material can be blended within a range not impairing the effects of the present invention, and for example, an inorganic filler can be blended. By blending the inorganic filler, it is possible to improve part of the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or heat distortion temperature etc. of the molded article, in particular, the anisotropy The molded product with less warpage can be obtained.

  Examples of reinforcing materials other than the above-mentioned fibrous reinforcing materials include needle-like, granular, powdery and layered inorganic fillers, and specific examples include glass beads, milled fibers, glass flakes, potassium titanate whiskers, sulfuric acid Calcium whiskers, warastenite, silica, kaolin, talc, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, a mixture of magnesium oxide and aluminum oxide, finely powdered silica, aluminum silicate, silicon oxide, smectite clay mineral (montmorillonite, Hectorite), vermiculite, mica, fluoroteniolite, zirconium phosphate, titanium phosphate, and dolomite. Two or more of these may be blended. When milled fibers, glass flakes, kaolin, talc and mica are used, molded articles with less warpage can be obtained because they have an anisotropy effect. In addition, at least one selected from the group consisting of calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, a mixture of magnesium oxide and aluminum oxide, finely divided silicic acid, aluminum silicate and silicon oxide (A) a thermoplastic polyester resin When it mix | blends in the range of 0.01-1 weight part with respect to 100 weight part, retention stability can be improved more.

  Moreover, surface treatment by coupling agent treatment, an epoxy compound, or ionization treatment etc. may be performed to reinforcements other than said fibrous reinforcement. The average particle diameter of the granular, powdery and layered inorganic fillers is preferably 0.1 to 20 μm in terms of impact strength. From the viewpoint of the dispersibility of the inorganic filler in the resin, it is particularly preferably 0.2 μm or more, and from the viewpoint of mechanical strength, preferably 10 μm or less. In addition, the blending amount of the inorganic filler other than the fibrous reinforcing material is combined with the blending amount of the fibrous reinforcing material from the viewpoint of the fluidity at the time of molding and the durability of the molding machine and the mold (A) thermoplastic polyester 100 parts by weight or less is preferable with respect to 100 parts by weight of the resin. Moreover, the compounding quantity of inorganic fillers other than fibrous reinforcement is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the compounding quantity of inorganic fillers other than fibrous reinforcement is 1 weight part or more, anisotropy can be reduced and retention stability can be improved more. 2 parts by weight or more is more preferable, and 3 parts by weight or more is more preferable. On the other hand, if the compounding quantity of inorganic fillers other than a fibrous reinforcement is 50 weight part or less, mechanical strength can be improved.

  In the resin composition of the present invention, one or more optional additives such as an ultraviolet light absorber, a light stabilizer, a plasticizer and an antistatic agent may be blended within a range not to impair the object of the present invention.

  The resin composition of the present invention may be blended with a thermoplastic resin other than the component (A) within the range that does not impair the object of the present invention, and improves moldability, dimensional accuracy, molding shrinkage, toughness and the like. Can. Examples of thermoplastic resins other than the component (A) include olefin resins, vinyl resins, polyamide resins, polyacetal resins, polyurethane resins, aromatic or aliphatic polyketone resins, polyphenylene sulfide resins, polyetheretherketone resins, polyimides Resin, thermoplastic starch resin, polyurethane resin, aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, polyvinyl Alcohol resin etc. can be mentioned. Specific examples of the olefin resin include ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene-butene-1 copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / butene-1 / Maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, ethylene / maleic anhydride copolymer and the like. Further, specific examples of the vinyl resin include methyl methacrylate / styrene resin (MS resin), methyl methacrylate / acrylonitrile resin, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, styrene / N- Phenylmaleimide resin, vinyl (co) polymer such as styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high Impact-Styrene resin modified with rubbery polymer such as polystyrene resin, styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin Block copolymers, etc., and as core-shell rubbers, dimethylsiloxane / butyl acrylate polymer (core layer) and methyl methacrylate polymer (shell layer) multilayer structure, dimethylsiloxane / butyl acrylate polymer (core layer) And acrylonitrile / styrene copolymer (shell layer) multilayer structure, multilayer structure of butanediene / styrene polymer (core layer) and methyl methacrylate polymer (shell layer), butanediene / styrene polymer (core layer) and acrylonitrile And a multilayer structure of styrene / styrene copolymer (shell layer).

  Among them, from the viewpoint of improving the toughness and hydrolysis resistance of the resin composition, it is preferable to add an olefin resin having high hydrolysis resistance.

  Moreover, as for the compounding quantity of olefin resin, 0.1-30 weight parts is preferable with respect to 100 weight parts of (A) thermoplastic polyester resin. When the amount is 0.1 parts by weight or more, the toughness and the hydrolysis resistance are further improved. As for a compounding quantity, 0.5 weight part or more is more preferable, More preferably, it is 1 weight part or more. On the other hand, when the compounding amount is 30 parts by weight or less, mechanical physical properties are further improved. The blending amount is more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

  The resin composition of the present invention contains a polyhydric alcohol compound having three or four functional groups and containing one or more alkylene oxide units (hereinafter sometimes referred to as "polyhydric alcohol compound"). can do. By blending such a compound, the flowability at the time of molding processing such as injection molding can be improved. The polyhydric alcohol compound may be a low molecular weight compound or a polymer. Moreover, as a functional group, a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, an isocyanate group, a carbodiimide group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, a silyl ether group etc. are mentioned. . Among them, it is preferable to have three or four functional groups which are the same or different, and particularly three or more identical functional groups in that flowability, mechanical properties, durability, heat resistance and productivity are further improved. It is more preferable to have four.

  Moreover, the aliphatic alkylene oxide unit which is a C1-C4 as a preferable example of an alkylene oxide unit is mentioned. 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, isobutylene oxide units, etc. it can.

  In the present invention, in particular, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit, from the viewpoint of being more excellent in fluidity, recyclability, durability, heat resistance and mechanical properties. In addition, it is particularly preferable to use a compound containing a propylene oxide unit in that it is excellent in long-term hydrolysis resistance and toughness (tensile breaking elongation). The number of alkylene oxide units is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1 or more, from the viewpoint of being more excellent in fluidity. is there. On the other hand, the alkylene oxide unit per one functional group is preferably 20 or less, more preferably 10 or less, and still more preferably 5 or less, in terms of more excellent mechanical properties.

  In addition, the polyhydric alcohol compound may be reacted with the (A) thermoplastic polyester resin, and may be introduced into the main chain and / or side chain of the (A) component, without reacting with the (A) component. The composition at the time of compounding may be maintained in the composition.

  In the resin composition of the present invention, a mold release agent can be blended, and mold releasability from the mold can be improved during melt processing. As a mold release agent, higher fatty acid ester-based waxes such as montanic acid and stearic acid, polyolefin-based waxes, ethylene bis stearoamide-based waxes and the like can be mentioned.

  Moreover, as for the compounding quantity of a mold release agent, 0.01-1 weight part is preferable with respect to 100 weight part of (A) thermoplastic polyester resin. From the viewpoint of releasability, 0.03 parts by weight or more is more preferable, and from the viewpoint of heat resistance, 0.6 parts by weight or less is more preferable.

The resin composition of the present invention may further contain one or more of carbon black, titanium oxide, and pigments and dyes of various colors, toning to various colors, weatherability (light) resistance and conductivity. It is also possible to improve the sex. Examples of carbon black include channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. Carbon black has an average particle diameter of at 500nm or less, and dibutyl phthalate oil absorption is 50~400cm ³ / 100g is preferably used. As titanium oxide, titanium oxide having a crystal form such as rutile type or anatase type and having an average particle diameter of 5 μm or less is preferably used.

  These carbon black, titanium oxide and pigments and dyes of various colors may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, and a silane coupling agent. Further, in order to improve the dispersibility of the resin composition of the present invention and the handling property at the time of production, it may be used as a mixed material which is melt-blended or simply blended with various thermoplastic resins.

  The blending amount of the pigment and the dye is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. From the viewpoint of preventing uneven coloring, 0.03 parts by weight or more is more preferable, and from the viewpoint of mechanical strength, 1 part by weight or less is more preferable.

  As an indicator of hydrolysis resistance of a molded article made of a polyester resin composition, a test piece for tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D 638 (2005), relative humidity 100 %, Tensile strength retention after exposure for 50 hours in an atmosphere at a temperature of 121 ° C .: Attention is paid to a value of (tensile strength after exposure / tensile strength before exposure) × 100. The molded article according to the embodiment of the present invention has a tensile strength retention of 50% or more after exposure for 50 hours under an atmosphere of a relative humidity of 100% and a temperature of 121 ° C. to suppress a decrease in molecular weight due to hydrolysis of the polyester resin. It is. When the tensile strength retention after exposure for 50 hours under the conditions is less than 50%, it means that the carboxyl end group is increased by the hydrolysis of the polyester resin and the decrease in molecular weight is progressing. By the increase of the carboxy terminal group due to the hydrolysis of the main chain, the molecular weight reduction of the polyester resin is further promoted and the mechanical properties are reduced. 55% or more is preferable and 60% or more of the said tensile strength retention is more preferable. It shows that the decrease in molecular weight due to the progress of hydrolysis of the polyester resin is suppressed as the value of tensile strength retention after exposure for 50 hours under an atmosphere of relative humidity 100% and temperature 121 ° C. is closer to 100%, It shows that hydrolysis resistance is high.

  The thermoplastic polyester resin composition of the present invention can be obtained, for example, by melt-kneading the components (A) to (E) and, if necessary, other components.

  As a method of melt-kneading, for example, (A) component, (B) component, (C) component, (D) component, (E) component, if necessary, (F) component, (G) component, (H) ) Method of pre-mixing components, various additives, etc. and supplying them to an extruder etc. for sufficient melt-kneading, or supplying each component to an extruder etc. using a quantitative feeder such as a weight finder The method of carrying out sufficient melt-kneading etc. are mentioned.

  Examples of the above-mentioned pre-mixing include a method of dry blending and a method of mixing using a mechanical mixing device such as a tumbler, a ribbon mixer and a Henschel mixer. In addition, (I) inorganic fillers other than fibrous reinforcing materials and fibrous reinforcing materials are added by installing a side feeder in the middle of the loading portion and the vent portion of a multi-screw extruder such as a twin-screw extruder. It is also good. Also, in the case of a liquid additive, a method of installing a liquidation nozzle in the middle of the loading and unloading parts of a multi-screw extruder such as a twin-screw extruder and adding using a plunger pump, or loading It is also possible to use a method of supplying a metering pump from a part or the like.

  The thermoplastic polyester resin composition of the present invention is preferably pelletized and then molded. As a method of pelletization, for example, using a single screw extruder equipped with a screw of “unimelt” or “dalmage” type, a twin screw extruder, a triple screw extruder, a conical extruder, a kneader type kneader, etc. It is discharged in a shape and cut by a strand cutter.

  By melt-molding the thermoplastic polyester resin composition of the present invention, molded articles of films, fibers and other various shapes can be obtained. Examples of the melt molding method include injection molding, extrusion molding and blow molding, and injection molding is particularly preferably used.

  As a method of injection molding, gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding, injection press molding, etc. are known besides the usual injection molding method, but any molding method is applied. it can.

  The molded article of the present invention can be used as a molded article of mechanical and mechanical parts, electrical parts, electronic parts and automobile parts that make use of the features of excellent flame retardancy, tracking resistance, and long-term hydrolysis resistance. The molded article of the present invention is particularly useful for electric and electronic parts for automobiles because it is excellent in flame retardancy, tracking resistance, and long-term hydrolysis resistance.

  Specific examples of mechanical parts, electrical parts, electronic parts and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded articles for fixing machines for copying machines and printers, general household appliances, OA Housings for equipment, Varicon case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, socket parts, motor parts, sockets, plugs , Capacitors, various cases, resistors, electric / electronic parts incorporating metal terminals and wires, computer parts, audio parts such as acoustic parts, lighting parts, telegraph equipment parts, telephone equipment parts, air conditioner parts, VTR Home appliance parts such as TVs, etc., parts for copying machines, Shimiri parts, parts for optical instruments, automotive ignition system parts, automotive connectors, and various electrical components for automobiles and the like.

  Next, the effects of the thermoplastic polyester resin composition of the present invention will be specifically described by way of examples. The raw material used for an Example and a comparative example is shown next. Here, “%” and “parts” mean all by weight and parts by weight, and “/” in the following resin names means copolymerization.

(A) Thermoplastic Polyester Resin <A-1> Polybutylene Terephthalate Resin: A polybutylene terephthalate resin having a carboxyl group weight of 30 eq / t was used.
<A-2> Polyethylene terephthalate resin: A polyethylene terephthalate resin having a carboxyl group weight of 40 eq / t, manufactured by Toray Industries, Inc., was used.

(B) Heat resistant water-soluble phosphorus-based flame retardant <B-1> Diamine phosphate: Zinc ethylenediamine phosphate, "Firecut" (registered trademark) ZPO-3 (manufactured by Suzuyu Kagaku Co., Ltd.) acid value 3HOH mg / g after wet heat treatment , Phosphorus atom content 16%).
<B-2> Phosphazene compound: Phenoxyphosphazene compound, SPB-100 (manufactured by Otsuka Chemical Co., Ltd.) having an acid value of 1 KOH mg / g and a phosphorus atom content of 18% after wet heat treatment.

(C) Phosphorus-based flame retardant other than (B) <C-1> Organic phosphinic acid metal salt: "Exolit" (registered trademark) OP-1240 (manufactured by Clariant Japan KK) (acid value 31 KOH mg / g after wet heat treatment, phosphorus 22% atomic content)
<C-2> Condensed phosphoric acid ester: 4,4 bis (diphenyl phosphoryl) 1, 1 biphenyl, "ADEKA STAB" (trademark registration) FP-800 (made by ADEKA Co., Ltd.) acid value 57 KOHmg / g after wet heat treatment, phosphorus atom The content was 8%).

(D) Nitrogen flame retardant <D-1> Melamine cyanurate, Nissan Chemical Industries Ltd. MC-4000 (average particle diameter 10 micrometers white powder) was used.

(E) Anti-Drip Agent <E-1> A fluorine-based resin, polytetrafluoroethylene, "Teflon" (registered trademark) 6-J manufactured by Dupont Fluorochemicals Co., Ltd. was used.

(F) Epoxy compound <F-1> Condensation product with bisphenol A epichlorohydrin having an epoxy equivalent weight of 190 g / eq: “jER” (registered trademark) 819 manufactured by Mitsubishi Chemical Corporation.
<F-2> Cresol novolac epoxy having an epoxy equivalent of 211 g / eq: EOKN-102S manufactured by Nippon Kayaku Co., Ltd. was used.
<F-3> Dicyclopentadiene-phenol addition novolac type epoxy of epoxy equivalent 253 g / eq: XD-1000 made from Nippon Kayaku Co., Ltd. was used.

(G) Hindered amine compound <G-1> Bis- (2,2,6,6-tetramethyl-4-piperidyl) terephthalate: "ADEKA STAB" (registered trademark) LA57 manufactured by ADEKA CORPORATION was used.

(H) Hydroxyl Group-Containing Resin <H-1> Bisphenol A Type Phenoxy Resin: Using “jER” (registered trademark) 1010 manufactured by Mitsubishi Chemical Corporation (hydroxy group number: 3.3 eq / kg, number average molecular weight: 5,5000)
<H-2> Hydroxy group-containing acrylic polymer: “ARUFON” (registered trademark) UH-2170 manufactured by Toagosei Co., Ltd. (hydroxy group value: 7.7 eq / kg, number average molecular weight: 6, 500).

(I) Fibrous Reinforcing Material <I-1> Glass fiber treated with a bundling agent containing an epoxy compound: Glass fiber ECS 03T-187 manufactured by Nippon Electric Glass Co., Ltd., diameter 13 μm in cross section, fiber length 3 mm .

[Method of measuring each characteristic]
In the examples and comparative examples, the characteristics were evaluated by the measurement method described below.

(1) ESPEC after setting the acid value (B) component or (C) component of the phosphorus-based flame retardant ((B) component or (C) component) to a temperature and humidity of 121 ° C. × 100% RH It was put into an advanced accelerated life test apparatus EHS-411 manufactured by Co., Ltd., and was subjected to wet heat treatment for 40 hours. After that, a solution of the phosphorus-based flame retardant treated with wet heat treatment in chloroform was titrated with 0.05 mol / L ethanolic potassium hydroxide using 1% bromophenol blue as an indicator, and the acid value was calculated by the following formula . The end point of the titration was blue (color tone D55-80 (Dpockettype Japan Paint Industry Association 2007)).
Acid value [KOH mg / g] = (It took for titration of 0.05 mol / L ethanolic potassium hydroxide [ml]-chloroform solution required for titration of chloroform solution in which (B) component or (C) component was dissolved 0.05 mol / L ethanolic potassium hydroxide [ml] × 0.05 mol / L ethanolic potassium hydroxide concentration [mol / ml] × 56.1 / (B) component or (C) component used for titration Collection amount of [g].

(2) Mechanical properties (tensile strength and tensile elongation)
When polybutylene terephthalate resin is used as the component (A) using NEX 1000 injection molding machine manufactured by Nissei Resin Industries, the molding temperature is 250 ° C., the mold temperature is 80 ° C., and the component (A) is used. When a polyethylene terephthalate resin is used, ASTM D 638 (2005) is formed at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and a molding cycle of 10 seconds in total for injection time and pressure holding time and 10 seconds for cooling time. Test pieces for tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) and Izod test pieces with a mold notch, which were formed according to The tensile maximum point strength (tensile strength) and the tensile maximum point elongation (tensile elongation) were measured according to ASTMD 638 (2005) using the obtained test pieces for tensile property evaluation. The value was an average value of three measured values. It was judged that a material having a large tensile strength value is excellent in mechanical strength, and a material having a large tensile elongation value is judged to be excellent in toughness.

(3) Flame retardancy (combustion rank)
A combustion test piece of 1/32 inch (about 0.79 mm) in thickness was obtained using the NEX 1000 injection molding machine manufactured by Nissei Plastic Industry under the same injection molding conditions as the tensile properties in item (2) above. The flame retardancy was evaluated using the obtained combustion test pieces in accordance with the evaluation standard set forth in the UL 94 vertical test. The flame retardancy decreases in the order of V-0>V-1> V-2 and is ranked. Moreover, the material which was inferior to combustibility and did not reach said V-2 and did not correspond to said flame-retardant rank was made out of specification.

(4) Tracking resistance (comparative tracking index)
A square plate of 80 mm × 80 mm × thickness 3 mm was obtained by injection molding under the same injection molding conditions as in (2) above, using a NEX 1000 injection molding machine manufactured by Nissei Resin Industries. The comparative tracking index was measured using the 0.1% ammonium chloride aqueous solution as an electrolyte solution according to the measuring method of the comparative tracking index of IEC60112: 2003 using the obtained square plate.

(5) Long-term hydrolysis resistance (tensile strength retention rate)
Evaluation of tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D 638 (2005) under the same injection molding conditions as the above (2) using a Niseki resin industrial NEX 1000 injection molding machine A test piece was obtained. The obtained ASTM No. 1 dumbbell was put into an advanced accelerated life tester EHS-411 manufactured by ESPEC Co., Ltd. set to a temperature and humidity of 121 ° C. × 100% RH, and wet heat treatment was performed for 50 hours. With respect to the molded article after the wet heat treatment, the tensile maximum point strength was measured under the same conditions as the tensile test in the above (2), and the average value of the three measured values was determined. From the tensile maximum point strength after the wet heat treatment and the tensile maximum point strength before the wet heat treatment, the tensile strength retention was determined by the following equation.
Tensile strength retention (%) = (Tension maximum point strength after wet heat treatment / maximum tensile point strength before wet heat treatment) × 100

  The material having a tensile strength retention of less than 50% was judged to be inferior in hydrolysis resistance, and it was judged that the material having a higher tensile strength retention rate had a higher resistance to hydrolysis.

(6) Residence stability (rate of change of melt viscosity index)
The melt viscosity index (melt flow index) of the thermoplastic polyester resin composition was measured according to ASTM D1238 (1999) under conditions of a temperature of 270 ° C. and a load of 2.6 kg using C501 DOS manufactured by Toyo Seiki Co., Ltd. .

  Furthermore, after the thermoplastic polyester resin composition is allowed to stay in the cylinder for 30 minutes, the melt viscosity index is measured under the same conditions, and the difference between the melt viscosity index before and after the melt viscosity index before change (rate of change (%) Asked for). The change rate (%) calculated here is an absolute value and was calculated as a positive value. When the change rate of the melt viscosity index exceeded 50%, it was judged that the retention stability was poor, and it was judged that the retention stability was excellent as the difference was smaller.

(7) Gas content 10 g of the resin composition was weighed in an aluminum cup, placed in a hot air oven at 270 ° C. under atmospheric pressure using a hot air oven PHH 202 made by ESPEC, and heat treated for 2 hours; The weight was determined. The rate of change was determined from the difference in weight before and after heat treatment (gas amount (%)) relative to the weight before heat treatment, and the weight of the resin composition. When the amount of gas exceeded 3%, it was judged that the amount of generated gas was large, and it was judged that the formability was excellent. It was judged that the smaller the amount of gas, the better the formability.

(8) Bleed out ASTM No. 1 dumbbell bleed of 1/8 inch (about 3.2 mm) in thickness using the NEX 1000 injection molding machine manufactured by Nissei Plastic Industry under the same injection molding conditions as in (2) above. A test piece for out evaluation was obtained. The obtained ASTM No. 1 dumbbell was introduced into an advanced accelerated life tester EHS-411 manufactured by ESPEC Co., Ltd. set at a temperature and humidity of 121 ° C. × 100% RH for 96 hours (4 days) to perform wet heat treatment. The appearance of the molded article after the wet heat treatment was visually observed, and the bleed out was determined according to the following criteria.
A: Liquid or white powder bleed out is not observed in the molded article.
B: A liquid or white powder bleed out is observed in a part or everywhere of the molded article.

(9) Heat resistance (heat distortion temperature)
A test piece for heat distortion temperature evaluation of a 1/8 inch (about 3.2 mm) thick dumbbell was obtained under the same injection molding conditions as in (2) above using a Niseki Plastics NEX 1000 injection molding machine. Using the obtained test piece for thermal deformation temperature evaluation, the thermal deformation temperature was measured under the condition of a measurement load of 1.82 MPa according to ASTM D 648 (2005). The value was an average value of three measured values. It was judged that the material whose heat distortion temperature is less than 50 ° C. is inferior to the heat resistance, and it is judged that the material whose heat distortion temperature is larger is more excellent in the heat resistance.

(10) Long-term heat aging resistance (tensile strength retention)
Evaluation of tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D 638 (2005) under the same injection molding conditions as the above (2) using a Niseki resin industrial NEX 1000 injection molding machine A test piece was obtained. The obtained test piece for evaluation was placed in a hot air oven at 190 ° C. under atmospheric pressure, and heat treatment was performed for 2000 hours. The tensile maximum point strength of the test piece for evaluation after heat treatment was measured under the same conditions as in item (2) above. The value was an average value of three measured values. With respect to the tensile maximum point strength of the test piece for evaluation after heat treatment, the tensile strength retention was calculated from the following formula. It was judged that the higher the tensile strength retention, the better the heat aging resistance, and the particularly excellent at 75% or more. The maximum tensile strength retention is 100%.
Tensile strength retention (%) = (Tensic maximum point strength after heat treatment / Tensic maximum point strength before heat treatment) × 100

[Examples 1 to 17], [Comparative Examples 1 to 7]
(A) Thermoplastic polyester resin, (B) Heat-resistant water-soluble phosphorus-based flame retardant, using a twin screw extruder with a screw diameter of 30 mm and L / D 35 and a co-rotational vent (made by Japan Steel Works, TEX-30α) C) Phosphorus-based flame retardants other than (B), (D) Nitrogen-based flame retardants, (E) anti-drip agent, if necessary, (F) epoxy compound, (G) hindered amine compound, (H) hydroxyl group-containing resin And other materials were mixed with the compositions shown in Tables 1 to 3 and added from the backfill of the twin-screw extruder. In addition, the side-feeder was installed and added to the middle of the main loading part and the vent part of (I) fibrous reinforcement. Furthermore, melt mixing was performed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, and the mixture was discharged in strands, passed through a cooling bath, and pelletized by a strand cutter.

  The obtained pellet was dried by a hot air drier at a temperature of 110 ° C. for 6 hours, evaluated by the above method, and the results are shown in Tables 1 to 3. The compounding amount of the (I) fibrous reinforcing material in 100 parts by weight of the flame retardant thermoplastic polyester resin composition was described as "the content of (I) fibrous reinforcing material in the thermoplastic polyester resin composition".

  From the comparison of Examples 1 to 11 and Comparative Examples 1 to 7, it is possible to blend the components (B), (C), (D), and (E) with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The material was excellent in the balance of the mechanical physical property, the flame retardance, the tracking resistance, and the long-term hydrolysis resistance in a specific amount range.

  According to a comparison between Example 9 and Example 10, (B) using a diamine phosphate as a phosphorus-based flame retardant having an acid value of 10 KOH mg / g or less after treatment for 40 hours under moist heat conditions of 121 ° C.-100% relative humidity Thus, a material is obtained which is more excellent in the balance of mechanical properties, flame retardancy, tracking resistance, and long-term hydrolysis resistance.

  From the comparison of Example 8 and Example 9, by using a metal salt of phosphinate as the phosphorus-based flame retardant other than the above (C) and (B), the long-term hydrolysis resistance is more excellent, and the amount of gas is reduced. A material excellent in moldability was obtained.

  From the comparison of Examples 12 to 14 and Example 3, when 0.1 to 10 parts by weight of the (F) epoxy compound was blended, a material excellent in long-term hydrolysis resistance and excellent in retention stability was obtained. .

  From the comparison of Example 15 and Example 13, when 0.01 to 1 part by weight of (G) hindered amine compound is blended, while being excellent in long-term hydrolysis resistance, the amount of gas is reduced and the formability is excellent. The material was obtained.

  According to the comparison of Examples 16 and 17 with Example 3, when 0.1 to 10 parts by weight of (H) hydroxyl group-containing resin is blended, a material which is more excellent in balance of mechanical properties, long-term hydrolysis resistance and heat aging resistance was gotten.

  From the comparison of Example 11 and Example 9, when polybutylene terephthalate resin is used as the component (A), a material which is more excellent in the balance between mechanical strength and flame retardancy, tracking resistance, and long-term hydrolysis resistance can be obtained. The

Claims (11)

(A) Phosphorus-based flame retardant 0.1 having an acid value of 10 KOH mg / g or less after treated for 40 hours under moist heat conditions of (B) 121 ° C. to 100% relative humidity with respect to 100 parts by weight of the thermoplastic polyester resin 30 parts by weight, 0.1 to 30 parts by weight of phosphorus based flame retardant other than (C) and (B), 0.1 to 20 parts by weight of (D) nitrogen based flame retardant, and (E) anti-drip agent 0.01 The thermoplastic polyester resin composition which mix | blends 1 weight part. The thermoplastic polyester resin composition according to claim 1, wherein the phosphorus-based flame retardant having an acid value of 10 KOHmg / g or less after treated for 40 hours under moist heat conditions of (B) 121 ° C-100% relative humidity is a diamine phosphate. object. The thermoplastic polyester resin composition according to claim 1 or 2, wherein the phosphorus-based flame retardant other than (C) and (B) is a metal salt of phosphinate. The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein 0.1 to 10 parts by weight of the epoxy compound (F) is further blended with 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to claim 4, wherein the (F) epoxy compound is at least one selected from a glycidyl ether compound, an epoxidized fatty acid ester compound, and an alicyclic epoxy compound. The thermoplastic polyester resin composition according to any one of claims 1 to 5, wherein 0.01 to 1 part by weight of the (G) hindered amine compound is further blended with 100 parts by weight of the (A) thermoplastic polyester resin. The thermoplastic polyester resin composition according to any one of claims 1 to 6, wherein 0.1 to 10 parts by weight of (H) a hydroxyl group-containing resin is further blended with 100 parts by weight of the (A) thermoplastic polyester resin. . The thermoplastic polyester resin composition according to any one of claims 1 to 7, wherein 1 to 100 parts by weight of the fibrous reinforcement (I) is further blended with 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to any one of claims 1 to 8, wherein the (A) thermoplastic polyester resin is a polybutylene terephthalate resin. Tensile strength after exposing test pieces for tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D 638 (2005) for 50 hours in an atmosphere with a relative humidity of 100% and a temperature of 121 ° C. The thermoplastic polyester resin composition according to any one of claims 1 to 9, wherein the retention ((tensile strength after exposure / tensile strength before exposure) x 100) is 50% or more. The molded article formed by melt-molding the thermoplastic polyester resin composition in any one of Claims 1-10.