JP6904173B2 - Thermoplastic polyester resin compositions and articles - Google Patents

Description

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

Thermoplastic polyester resins are used in a wide range of fields such as mechanical mechanical parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent injection moldability and mechanical characteristics. However, since thermoplastic polyester resin is flammable in nature, it has general chemical and physical properties for use as an industrial material such as mechanical mechanical parts, electrical / electronic parts, and automobile parts. In addition to balance, flame safety, that is, flame retardancy, is required, and in many cases, a high degree of flame retardancy indicating V-0 of the UL-94 standard is required. Further, when used in an environment where electricity flows, safety against tracking destruction ignited by decomposition or carbonization of the resin due to electric discharge, that is, tracking resistance is required, and a high degree of tracking resistance indicating CTI rank 0 of the IEC60112 standard is required. Sex is often required. In particular, in recent years, electric vehicles have been attracting attention due to heightened environmental awareness, and even higher tracking resistance is required.

As a method for improving flame retardancy and electrical properties, for example, a base resin, a halogen-based flame retardant, organic phosphinic acid or a salt thereof, a flame retardant aid, and an electrical property improving aid such as melamine cyanurate are used. A flame-retardant resin composition that is configured and has improved electrical characteristics has been proposed (see, for example, Patent Document 1). However, there is a problem that the tracking resistance is still insufficient. Further, since a resin composition containing a halogen-based flame retardant may generate harmful dioxins during combustion, a flame-retardant resin composition using a non-halogen flame retardant is required. ..

Examples of the flame-retardant resin composition using a non-halogen flame-retardant agent include a resin composition containing a thermoplastic resin such as a polybutylene terephthalate resin, a phosphoric acid ester compound, and a methacrylic resin (see Patent Document 2). ), Polybutylene terephthalate resin, long-chain aliphatic polyamide resin, organic phosphorus-based flame retardant such as phosphinate, resin composition containing nitrogen-containing flame retardant aid (see Patent Document 3), polyalkylene terephthalate. Alternatively, a resin composition containing polycycloalkylene terephthalate, an organic phosphinate, and an inorganic phosphate (Patent Document 4), a thermoplastic resin, zinc ethylenediamine phosphate, and a resin composition containing an acid receiving agent (Patent Document 4). Patent Document 5) has been proposed.

International Publication No. 2006/090751 Japanese Unexamined Patent Publication No. 2014-196484 Japanese Unexamined Patent Publication No. 2011-213391 Japanese Unexamined Patent Publication No. 2016-166358 Japanese Unexamined Patent Publication No. 2000-154324

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

In addition, the polyester resin containing a flame retardant has a problem that its strength tends to decrease due to hydrolysis under high temperature and high humidity. An object of the present invention is to provide a thermoplastic polyester resin composition and a molded product thereof, which can obtain a molded product having excellent flame retardancy while maintaining strength under high temperature and high humidity.

As a result of repeated studies to solve the above-mentioned problems, the present inventors have made (A) a thermoplastic polyester resin and (B) an acid value after 40 hours of treatment under moist heat conditions of 121 ° C.-100% relative humidity. 0.1 to 30 parts by weight of the phosphorus-based flame retardant having a value of 10 KOH mg / g or less, 0.1 to 30 parts by weight of the phosphorus-based flame retardant other than (C) and (B), (D) 0.1 to 30 parts by weight of the nitrogen-based flame retardant. We have found that the above problems can be solved by blending 20 parts by weight and 0.01 to 1 part by weight of the (E) anti-drip agent, and have reached the present invention. That is, the present invention has the following configuration.
[1] (A) Phosphor-based flame retardant 0 having an acid value of 10 KOH mg / g or less after 40 hours of treatment under moist heat conditions of 121 ° C.-100% relative humidity with respect to 100 parts by weight of the thermoplastic polyester resin. .1 to 30 parts by weight, phosphorus-based flame retardants other than (C) and (B) 0.1 to 30 parts by weight, (D) nitrogen-based flame retardants 0.1 to 20 parts by weight, and (E) anti-drip agent 0 A thermoplastic polyester resin composition containing 1.01 to 1 part by weight of phosphorus having an acid value of 10 KOH mg / g or less after treatment for 40 hours under moist heat conditions of (B) 121 ° C.-100% relative humidity. A thermoplastic polyester resin composition in which the flame retardant is diamine phosphate.
[2] The thermoplastic polyester resin composition according to [1] , wherein the phosphorus-based flame retardant other than the above (C) and (B) is a phosphinic acid metal salt.
[3] The thermoplastic polyester resin composition according to [1] or [2] , which is obtained by further blending 0.1 to 10 parts by weight of the (F) epoxy compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin. Stuff.
[4] The thermoplastic polyester resin composition according to [3] , 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.
[5] The thermoplastic according to any one of [1] to [4] , which is obtained by further blending 0.01 to 1 part by weight of the (G) hindered amine compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin. Polyester resin composition.
[6] The heat according to any one of [1] to [5] , which is obtained by further blending 0.1 to 10 parts by weight of (H) hydroxyl group-containing resin with 100 parts by weight of (A) thermoplastic polyester resin. Plastic polyester resin composition.
[7] The thermoplastic according to any one of [1] to [6] , which is obtained by further blending 1 to 100 parts by weight of (I) a fibrous reinforcing material with respect to 100 parts by weight of (A) thermoplastic polyester resin. Polyester resin composition.
[8] The thermoplastic polyester resin composition according to any one of [1] to [7] , wherein the (A) thermoplastic polyester resin is a polybutylene terephthalate resin.
[9] A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of [1] to [8].

The thermoplastic polyester resin composition of the present invention is excellent in flame retardancy and tracking resistance, and also has excellent mechanical properties and hydrolysis resistance, and a molded product in which bleed-out is unlikely to occur even in a high temperature and high humidity environment. Obtainable. Furthermore, the amount of gas generated during melt processing is small and the molding processability 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 composition obtained by treating (A) a thermoplastic polyester resin with (B) an acid value of 10 KOHmg / g or less after 40 hours of treatment under moist heat conditions of 121 ° C.-100% relative humidity. 0.1 to 30 parts by weight of flame retardant, 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) drip. A flame-retardant thermoplastic polyester resin composition containing 0.01 to 1 part by weight of an inhibitor. (A) The thermoplastic polyester resin is generally excellent in injection moldability and mechanical properties, but has a low critical oxygen index, so that it burns when it is close to a fire source such as an open flame. In the present invention, as a method for increasing 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 40 hours of treatment under moist heat conditions of 121 ° C.-100% relative humidity. A flame retardant, a phosphorus-based flame retardant other than (C) and (B), (D) a nitrogen-based flame retardant, and (E) an anti-drip agent are blended. In general, phosphorus-based flame retardants improve flame retardancy by promoting the formation of a carbide layer during combustion of (A) thermoplastic polyester resin, but at the same time, decomposition of phosphorus-based flame retardants under high temperature and high humidity environments. It has been found that (A) the strength and hydrolysis resistance of the thermoplastic polyester resin are significantly impaired due to the formation of an acidic component. Therefore, the hydrolysis resistance of the thermoplastic polyester resin composition is suppressed by suppressing the generation of the acidic component derived from the flame retardant during the treatment at 121 ° C.-100% relative humidity for 40 hours at 121 ° C.-100% relative humidity where the strength of the thermoplastic polyester resin is remarkably lowered. The sex can be improved. Therefore, among the phosphorus-based flame retardants, the acid value of the phosphorus-based flame retardant after treatment at 121 ° C.-100% relative humidity for 40 hours is 10 KOHmg / g or less as an index of the amount of acidic components generated in a moist heat environment ( B) Phosphorus-based flame retardants (hereinafter sometimes referred to as heat-resistant water-based phosphorus-based flame retardants), phosphorus-based flame retardants other than (C) and (B), (D) nitrogen-based flame retardants, and (E) drip prevention. By blending the agent, the flame retardancy, strength and hydrolysis resistance of the obtained resin composition can be highly compatible.

Here, the thermoplastic polyester resin composition of the present invention contains a reaction product obtained by reacting the component (A), the component (B), the component (C), the component (D), and the component (E). A thing is produced by a complicated 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 (A) thermoplastic polyester resin used in the present invention includes (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, and (3). ) A polymer or copolymer having at least one residue selected from the group consisting of lactones as a main structural unit. Here, "to be the main structural unit" means having at least 50 mol% or more of at least one residue selected from the group consisting of (1) to (3) in all the structural units, and those residues. It is a preferable embodiment to have 80 mol% or more of. Among these, (1) a polymer or copolymer having a residue of (1) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a main structural unit is preferable in that it is superior in mechanical properties and heat resistance. ..

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

Examples of the above-mentioned diol or ester-forming derivative thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene glycol. , Cyclohexanedimethanol, cyclohexanediol, dimerdiol and other aliphatic or alicyclic glycols having 2 to 20 carbon atoms, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like having a molecular weight of 200 to 100,000. Long-chain glycols, 4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and other aromatic dioxy compounds and ester-forming derivatives thereof. Two or more of these may be used.

Examples of the polymer or copolymer having a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a structural unit include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene isophthalate, and polybutylene isophthalate. , Polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decandicarboxylate, 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 / polytetramethylene glycol, polybutylene terephthalate / succinate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polypropylene terephthalate / isophthalate / adipate, poly Examples thereof include aromatic polyester resins such as butylene terephthalate / isophthalate / succinate, polypropylene terephthalate / isophthalate / adipate, and polypropylene terephthalate / isophthalate / sebacate. 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 a main structural unit. Alternatively, a copolymer is more preferable, and the residue of terephthalic acid, naphthalenedicarboxylic 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 are mainly used. A polymer or copolymer as a structural unit is more preferable.

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. Is particularly preferable, polybutylene terephthalate, polypropylene terephthalate and polybutylene naphthalate are more preferable, and polybutylene terephthalate is further preferable in terms of excellent moldability and crystallinity. Further, these two or more kinds can be used at an arbitrary content.

In the present invention, terephthalic acid or terephthalic acid or terephthalic acid with respect to all dicarboxylic acids constituting the polymer or copolymer having the residue of the above dicarboxylic acid or its ester-forming derivative and the residue of the diol or its ester-forming derivative as the main structural unit. 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 crystal polyester resin capable of forming anisotropy at the time of melting can be used. Examples of the structural unit of the liquid crystal polyester resin include aromatic oxycarbonyl unit, aromatic dioxy unit, aromatic and / or aliphatic dicarbonyl unit, alkylenedioxy unit and aromatic iminooxy unit.

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

The (A) thermoplastic polyester resin used in the present invention preferably has a weight average molecular weight (Mw) of 8,000 or more in terms of further improving mechanical properties. Further, when the upper limit of the weight average molecular weight (Mw) is 500,000 or less, the fluidity can be improved, which is preferable. It is more preferably 300,000 or less, still more preferably 250,000 or less. In the present invention, Mw of the (A) thermoplastic polyester resin is a value in terms of polymethylmethacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

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

When the (A) thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction containing a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components. 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 an ester exchange reaction, and then a polycondensation reaction.

In order to effectively proceed with 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 of titanium acid, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, and phenyl ester. Organic titanium compounds such as benzyl esters, trill esters or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldistin oxide, cyclohexahexyl distin oxide, didodecyltin oxide, triethyltin hydrooxide, Triphenyltin Hydrooxide, Triisobutyltin Acetate, Dibutyltin Diacetate, Diphenyltin Dilaurate, Monobutyltin Trichloride, Dibutyltin Dichloride, Tributyltin Chloride, Dibutyltin Sulfide, Butylhydroxytin Oxide, Methylstannoic Acid, Ethylstannoic Acid, Butylstannon Examples thereof include tin compounds such as alkylstannonic acid such as acids, zirconia compounds such as zirconiumtetra-n-butoxide, and antimony compounds such as antimony trioxide and antimonate acetate. Two or more of these may be used.

Among these polymerization reaction catalysts, an organic titanium compound and a tin compound are preferable, and a tetra-n-butyl ester of titanium acid is more preferably used. The amount of the polymerization reaction catalyst added 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 component (B) is a phosphorus-based flame retardant 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 and having high stability in a high temperature and high humidity environment. (Heat-resistant water-based phosphorus flame retardant). Here, the acid value after treatment for 40 hours under a moist heat condition of 121 ° C.-100% relative humidity is a value measured by dissolving a phosphorus-based flame retardant that has undergone moist heat treatment in a chloroform solvent and then titrating it with ethanolic potassium hydroxide. Is.

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

Examples of the phosphazene compound include a phosphonitrile linear polymer and / or a cyclic polymer, and those containing linear phenoxyphosphazene as a main component are particularly preferably used. The phosphazene compound can be synthesized by a known method described in "Synthesis and Application of Phosphazene Compound" (Meisetsu Kajiwara, CMC Publishing, 1986), for example, phosphorus pentachloride as a phosphorus source or It is synthesized by reacting phosphorus trichloride, ammonium chloride or ammonia gas as a nitrogen source by a known method (the cyclic substance may be purified), and substituting the obtained substance with alcohol, phenol and amines. Can be done. Further, as a commercially available product, "Ravitor" (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.

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

In the present invention, the (B) heat-resistant water-based phosphorus-based flame retardant can improve flame retardancy by producing an amine-based decomposition product during combustion decomposition, and can further reduce the amount of gas generated during molding. Therefore, diamine phosphoric acid. A salt is preferable, and zinc ethylenediamine phosphate is preferable because the hydrolysis resistance can be further improved.

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

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

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

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

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

The phosphinic acid metal salt is a phosphinate and / or a diphosphanate and / or a polymer thereof, and is a compound useful as a flame retardant for (A) a thermoplastic polyester resin. Examples of the salt include salts such as calcium, aluminum, and zinc. Examples of commercially available phosphinic acid metal salts include "Exolit" (trademark registration) OP1230 and OP1240 manufactured by Clariant Japan.

The phosphate ester amide is an aromatic amide-based flame retardant containing a phosphorus atom and a nitrogen atom. Since it is a powdery substance at room temperature having a high melting point, it is excellent in handleability at the time of compounding, and the thermal deformation temperature of the molded product can be further improved. As a commercially available product of phosphoric acid ester amide, SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.

Examples of the above-mentioned ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium carbamil polyphosphate. It may be coated with a thermosetting resin such as a phenol resin, a urethane resin, a melamine resin, a urea resin, an epoxy resin, or a urea resin which exhibits thermosetting property.

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

The red phosphorus is not only untreated red phosphorus, but also red phosphorus treated with one or more compound coatings selected from the group consisting of a thermosetting resin coating, a metal hydroxide coating, and a metal plating coating. Can be preferably used. Examples of the thermosetting resin used for the thermosetting resin coating include phenol-formalin resin, urea-formalin resin, melamine-formalin resin, and alkyd resin. Examples of the metal hydroxide used for the metal hydroxide film include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. 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. Further, these coatings may be combined in two or more types, or may be laminated in two or more types.

The blending 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 part by weight. When the blending amount of the component (C) is less than 0.1 parts by weight, the flame retardancy is lowered. It is more preferably 1 part by weight or more, and further preferably 2 parts by weight or more. On the other hand, when the blending amount of the component (C) exceeds 30 parts by weight, the mechanical strength and the hydrolysis resistance are lowered. It is more preferably 25 parts by weight or less, still more preferably 20 parts by weight or less.

The thermoplastic polyester resin composition in the present invention has improved flame retardancy by blending (D) a 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, cyanide compounds, aliphatic amide compounds, aromatic amide compounds, urea and thiourea. Can be mentioned. Two or more of these may be blended. Among these, nitrogen-containing heterocyclic compounds are preferably used. However, those corresponding to the component (B) of the present invention are treated as the component (B), and those corresponding to the component (C) are treated as the component (C).

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

Examples of the aromatic amine compound include aniline and phenylenediamine.

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

Examples of the cyanide compound include dicyandiamide and the like.

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-mentioned nitrogen-containing heterocyclic compound is a compound having a triazine skeleton. For example, triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amerin, ameride, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoiso Examples thereof include propoxytriazine and melamine polyphosphate, and melamine cyanurate, melamine isocyanurate, and melamine polyphosphate are preferably used.

As the melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and the composition is usually 1: 1 (molar ratio), and in some cases 1: 2 (molar ratio). Additives to have can be mentioned. These are produced by a known method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is used as an aqueous slurry, and the slurry is mixed well to form fine particles of salts of both, and then the slurry is filtered and dried. By doing so, it is generally obtained in the form of powder. Further, the above salt does not have to be completely pure, and some unreacted melamine, cyanuric acid, or isocyanuric acid may remain. When the dispersibility is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica may be used in combination. The average particle size before and after blending with the resin of melamine cyanurate or melamine isocyanurate is preferably 0.1 to 100 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product. Here, the average particle size is the average particle size measured by the laser micron sizer method with a cumulative distribution of 50% particle size. As commercially available products of melamine cyanurate or melamine isocyanurate, MC-4000, MC-4500, MC-6000 and the like manufactured by Nissan Chemical Industries, Ltd. are preferably used.

The amount of the component (D) blended is 0.1 to 20 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of the balance between flame retardancy and toughness. If the blending amount of the component (D) is less than 0.1 parts by weight, the flame retardancy becomes insufficient. 1 part by weight or more is preferable, and 2 parts by weight or more is more preferable. On the other hand, if the blending amount of the component (D) exceeds 20 parts by weight, the toughness decreases. 18 parts by weight or less is preferable, and 16 parts by weight or less is more preferable.

Further, in the present invention, the (E) drip inhibitor is a compound capable of suppressing melt-dropping of the resin composition during combustion and further improving flame retardancy, and examples thereof include fluororesins.

The fluororesin is a resin containing fluorine in a substance molecule, 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. Of these, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferable. In particular, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymers are preferable.

The amount of the component (E) blended is 0.01 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of the balance between flame retardancy and mechanical strength. If the blending amount of the component (E) is less than 0.01 parts by weight, the flame retardancy becomes insufficient. 0.03 parts by weight or more is preferable, and 0.05 parts by weight or more is more preferable. On the other hand, if the blending amount of the component (E) exceeds 1 part by weight, the fluidity decreases. 0.8 parts by weight or less is preferable, and 0.6 parts by weight or less is more preferable.

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

The (F) epoxy compound used in the present invention is a compound having an epoxy group in the molecule, and is not particularly limited, but is a glycidyl ester compound, a glycidyl ether compound, an epoxidized fatty acid ester compound, a glycidylimide compound, and the like. An alicyclic epoxy compound can 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 type epoxy, and a polyvalent hydroxyl compound glycidyl ether.

Specific examples of the condensate of the phenol compound 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, etc. Examples thereof include a condensate obtained by condensing the phenol compound of the above with epichlorohydrin.

Specific examples of novolac type epoxies include phenol novolac type epoxy, cresol novolac type epoxy, naphthol novolac type epoxy, bisphenol A novolac type epoxy, dicyclopentadiene-phenol-added novolac type epoxy, dimethylenephenylene-phenol-added novolac type epoxy, and di. Examples thereof include methylene biphenylene-phenol-added novolac type epoxy.

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

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

Specific examples of the glycidylimide compound include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, and N-glycidyl-3,6. -Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromphthalimide, N-glycidyl-4-n-butyl-5-bromphthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleinimide, N -Glysidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, triglycidyl isocyanurate, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, Examples thereof include N-glycidyl naphthamide and N-glycidyl stellamid.

Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenediepoxide, and N-methyl-4. , 5-Epoxycyclohexane-1,2-dicarboxylic acid imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid Examples thereof include imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide or N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide.

The epoxy compound (F) 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 epoxys and suppress the deterioration of retention stability. Of these, the glycidyl ether compound and the epoxidized fatty acid ester compound are more preferable, and among them, the glycidyl ether compound is further preferable because the hydrolysis resistance can be further improved. Further, among the glycidyl ether compounds, the novolak type epoxy is preferable because the heat resistance can be improved.

The epoxy compound (F) is preferably an epoxy compound having an epoxy equivalent of 100 to 3000 g / eq. When the epoxy equivalent of the epoxy compound (F) is 100 g / eq or more, the amount of gas during melt processing can be suppressed. More preferably, it is 150 g / eq or more. Further, when the epoxy equivalent of the epoxy compound (F) is 3000 g / eq or less, both long-term hydrolysis resistance and melt retention stability at high temperature can be achieved at a higher level. 2000 g / eq or less is more preferable.

In the present invention, the blending 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, the long-term hydrolysis resistance is improved. More preferably, it is 0.3 parts by weight or more. On the other hand, when the blending amount of the component (F) is 10 parts by weight or less, the heat resistance and the retention stability are improved. It is more preferably 8 parts by weight or less, and further preferably 5 parts by weight or less.

Further, in the present invention, the preferable range of the blending amount of the (F) epoxy compound can be set according to the epoxy equivalent of the (F) epoxy compound. For example, the ratio of the amount of (F) epoxy group-derived epoxy group to be blended in the thermoplastic polyester resin composition to the amount of (A) carboxyl group derived from the thermoplastic polyester resin blended in the thermoplastic polyester resin composition (epoxy). The group compounding amount (eq / g) / carboxyl group compounding amount (eq / g)) is preferably 0.5 to 8. When the (epoxy group compounding amount (eq / g) / carboxyl group compounding 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. Further, when (epoxy group compounding amount (eq / g) / carboxyl group compounding amount (eq / g)) is 8 or less, retention stability, heat resistance, and mechanical properties can be compatible at a higher level. 7 or less is preferable, and 6 or less is more preferable.

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

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

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.

Specific examples of the (G) hindered amine compound include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis- (2,2,6,6-tetramethyl-4-piperidyl) adipate, and bis-. (2,2,6,6-tetramethyl-4-piperidyl) Svelate, 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 [5,1,11,2] 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-(2,2,6) butanetetracarboxylic acid , 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-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] , Tetrakiss (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, Tetrakiss (2,2,6,6-tetramethyl-4-piperidyl) 1 , 2,3,4-butanetetracarboxylate, dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1,2,3,4-butane Tetracarboxylic acid And 2,2,6,6-tetramethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9- (2,4,5,10-tetraoxaspiro [5,5] Undecane) Condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl- Examples thereof include a condensate 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). When the blending amount of the (G) hindered amine compound is 0.01 parts by weight or more, the hydrolysis resistance can be improved. More preferably, it is 0.03 part by weight or more. On the other hand, when the blending amount of the (G) hindered amine compound is 1 part by weight or less, the retention stability is improved. It is more preferably 0.8 parts by weight or less, still more preferably 0.5 parts by weight or less.

It is preferable that the thermoplastic polyester resin composition of the present invention further contains a (H) hydroxyl group-containing resin in order to improve heat aging resistance under long-term exposure in a dry heat environment. (A) The molecular weight of the thermoplastic polyester resin decreases due to thermal decomposition in a dry heat environment, and the carboxyl group increases. However, by blending the hydroxyl group-containing resin, the carboxyl terminal group derived from the polyester resin and the hydroxyl group of the hydroxyl group-containing resin are added. Reacts and suppresses the decrease in molecular weight, so that heat aging resistance can be improved.

In the present invention, the (H) hydroxyl group-containing resin is a compound containing a hydroxyl group and having a 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 polymethyl methacrylate measured by gel permeation chromatography (GPC). An appropriate solvent for GPC can be selected depending on the structure of the (H) hydroxyl group-containing resin, but in general, hexafluoroisopropanol, chloroform, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide. Etc. can be exemplified.

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 tends to decrease due to the progress of transesterification with the (A) thermoplastic polyester resin when exposed in a dry heat environment. , Inferior in heat aging resistance. Further, if the number average molecular weight exceeds 500,000, the retention stability at the time of melting tends to deteriorate, which is not preferable. It is preferably 3,000 to 200,000, more preferably 4,000 to 100,000, and even more preferably 5,000 to 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 determined by acetylating the hydroxyl group of the (H) hydroxyl group-containing resin with an acetylating reagent according to JIS K0070 and JIS K1557-1, and a phenolphthalein solution as an indicator. It is a value measured by adding and titrating with a potassium hydroxide ethanol solution. The thermoplastic polyester resin composition containing the (H) hydroxyl group-containing resin having a hydroxyl value of 3 to 20 eq / kg can exhibit excellent heat aging resistance and retention stability at the time of melting. By setting the hydroxyl value of the (H) hydroxyl group-containing resin to 3 eq / kg or more, the reaction of the (A) thermoplastic polyester resin with the carboxy group terminal is promoted and the heat aging property is excellent, and the hydroxyl value is set to 20 eq / kg or less. By doing so, the 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.

The structure of the hydroxyl group-containing resin (H) is not particularly limited, but for example, polyhydroxypolyethers such as phenoxy resin, acrylic resin containing hydroxyalkyl (meth) acrylate as a structural unit, and ethylene-vinyl alcohol copolymer. Examples thereof include EVOH resin, paravinylphenol resin, carbinol-modified or diol-modified silicone oil, and polycarbonate diol. Among them, from the viewpoint of heat resistance of the hydroxy group-containing resin itself and (A) dispersibility in the thermoplastic polyester resin, a phenoxy resin or an acrylic resin containing at least hydroxyalkyl (meth) acrylate as a structural unit is preferable. By using these hydroxyl group-containing resins, the compatibility and dispersibility with the thermoplastic polyester resin are improved. As a result, when the molded product obtained by melt-molding the thermoplastic polyester resin composition is used in a dry heat environment, both heat aging resistance and hydrolysis resistance can be achieved at a high level. Further, while suppressing the thermal deterioration of the hydroxy group-containing resin itself, the effects of improving the retention stability during melt processing, suppressing the deterioration of moldability, suppressing the mold deposit, and suppressing the bleed-out to the surface of the molded product can be obtained. Be done.

Specific examples of the polyhydroxypolyethers include hydroquinone, sulforcin, 2,2'-biphenol, 4,4-biphenol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and bis (hydroxyaryl). ) Aromatic dihydroxy such as alkane, bis (hydroxyaryl) cycloalkane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, and 2,6-dihydroxynaphthalene. An example is a phenoxy resin obtained by condensing a compound with epichlorohydrin. As the bis (hydroxyaryl) alkane, 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 and the like can be exemplified, and examples of the bis (hydroxyaryl) cycloalkane include 1,1-bis (hydroxyphenyl) pentane and 1,1-bis (4-hydroxy). Examples thereof include phenyl) hexane and 1,1-bis (hydroxyphenyl) heptane. Phenoxy resins having these bisphenol skeletons can be used alone or in combination of two or more.

Examples of the hydroxyalkyl (meth) acrylate in the acrylic resin containing hydroxyalkyl (meth) acrylate as a structural unit include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate. In addition, other than the above, alkyl or aryl esters such as acrylic acid and methacrylic acid, olefin compounds such as ethylene, propylene, 1-butene and butadiene, vinyl aromatic compounds such as styrene, homopolymers such as acrylonitrile, acrylamide and methacrylamide, or Copolymers and the like can be contained 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 blending amount of the hydroxyl group-containing resin (H) is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the thermoplastic polyester resin (A). When the blending amount of the hydroxyl group-containing resin (H) is 0.1 parts by weight or more, the effect of improving heat aging resistance can be improved. It is more preferably 0.5 parts by weight or more, and further preferably 1 part by weight or more. On the other hand, when the blending amount of the (H) hydroxyl group-containing resin is 10 parts by weight or less, the retention stability and fluidity can be improved. More preferably, it is 8 parts by weight or less.

It is preferable that the thermoplastic polyester resin composition of the present invention further contains (I) a fibrous reinforcing material. (I) The fibrous reinforcing material can further improve the mechanical strength and heat resistance.

Specific examples of the fibrous reinforcing material (I) include glass fibers, aramid fibers, and carbon fibers. The above-mentioned glass fibers are chopped strand type and roving type glass fibers, and are composed of a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or an acrylic acid such as a urethane or an acrylic acid / styrene copolymer. Polymers, copolymers composed of maleic anhydride such as methyl acrylate / methyl methacrylate / maleic anhydride copolymers, vinyl acetate, bisphenol A diglycidyl ether, one or more epoxy compounds such as novolak epoxy compounds, etc. Glass fibers treated with the contained sizing agent are preferably used. Glass fibers treated with a converging agent containing a copolymer composed of maleic anhydride are more preferable because they can further improve hydrolysis resistance. The silane coupling agent and / or the sizing agent may be mixed with the emulsion liquid and used. The fiber diameter of the glass fiber is usually preferably in the range of 1 to 30 μm. From the viewpoint of dispersibility of the glass fiber in the resin, the lower limit is preferably 5 μm. From the viewpoint of mechanical strength, the upper limit is preferably 15 μm. Further, although the fiber cross section is usually circular, a fibrous reinforcing material having an arbitrary cross section such as an elliptical glass fiber having an arbitrary aspect ratio, a flat glass fiber, and an eyebrows-shaped glass fiber can be used for injection. It has the characteristics of improving fluidity during molding and obtaining a molded product with less warpage.

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

The preferable range of the blending 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 when the thermoplastic polyester resin composition is 100 parts by weight. (I) When the fibrous reinforcing material is 100 parts by weight of the thermoplastic polyester resin composition, the mechanical strength and heat resistance can be further improved by blending 1 part by weight or more. 3 parts by weight or more is more preferable, and 5 parts by weight or more is further preferable. On the other hand, when the fibrous reinforcing material (I) is 100 parts by weight of the thermoplastic polyester resin composition and 70 parts by weight or less is blended, the mechanical strength and fluidity can be further improved. 60 parts by weight or less is more preferable, and 50 parts by weight or less is further preferable.

In the thermoplastic polyester resin composition of the present invention, a reinforcing material other than the fibrous reinforcing material can be blended as long as the effects of the present invention are not impaired, and for example, an inorganic filler can be blended. By blending an inorganic filler, some parts such as crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or thermal deformation temperature of the molded product can be improved, and in particular, anisotropy. Since it is effective in, a molded product with less warpage can be obtained.

Examples of the reinforcing material other than the above-mentioned fibrous reinforcing material include needle-like, granular, powder-like and layered inorganic fillers, and specific examples thereof include glass beads, milled fibers, glass flakes, potassium titanate whiskers and sulfuric acid. Calcium whisker, wallastenite, silica, kaolin, talc, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, a mixture of magnesium oxide and aluminum oxide, fine silicic acid, aluminum silicate, silicon oxide, smectite clay minerals (montmorillonite, Hectrite), vermiculite, mica, fluoroteniolite, zirconium phosphate, titanium phosphate, and dolomite. Two or more of these may be blended. When milled fiber, glass flakes, kaolin, talc and mica are used, a molded product with less warpage can be obtained because it has an effect on anisotropy. Further, 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, fine silicic acid, aluminum silicate and silicon oxide (A) thermoplastic polyester resin. When blended in the range of 0.01 to 1 part by weight with respect to 100 parts by weight, the retention stability can be further improved.

Further, the reinforcing material other than the above-mentioned fibrous reinforcing material may be surface-treated by a coupling agent treatment, an epoxy compound, an ionization treatment or the like. The average particle size of the granular, powdery and layered inorganic filler is preferably 0.1 to 20 μm from the viewpoint of impact strength. From the viewpoint of dispersibility of the inorganic filler in the resin, it is particularly preferably 0.2 μm or more, and from the viewpoint of mechanical strength, it is preferably 10 μm or less. In addition, the blending amount of the inorganic filler other than the fibrous reinforcing material is the same as the blending amount of the fibrous reinforcing material from the viewpoint of fluidity at the time of molding and durability of the molding machine and the mold (A) thermoplastic polyester. It is preferably 100 parts by weight or less with respect to 100 parts by weight of the resin. The amount of the inorganic filler other than the fibrous reinforcing material is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the blending amount of the inorganic filler other than the fibrous reinforcing material is 1 part by weight or more, the anisotropy can be reduced and the retention stability can be further improved. 2 parts by weight or more is more preferable, and 3 parts by weight or more is further preferable. On the other hand, if the blending amount of the inorganic filler other than the fibrous reinforcing material is 50 parts by weight or less, the mechanical strength can be improved.

The resin composition of the present invention may contain one or more arbitrary additives such as an ultraviolet absorber, a light stabilizer, a plasticizer and an antistatic agent as long as the object of the present invention is not impaired.

The resin composition of the present invention may contain a thermoplastic resin other than the component (A) as long as the object of the present invention is not impaired, and may improve moldability, dimensional accuracy, molding shrinkage, toughness, and the like. Can be done. Examples of the thermoplastic resin other than the component (A) include olefin resin, vinyl resin, polyamide resin, polyacetal resin, polyurethane resin, aromatic or aliphatic polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, and polyimide. 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 and the like can be mentioned. Specific examples of the olefin-based resin include ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene-butene-1 copolymer, ethylene / glycidyl methacrylate copolymer, and ethylene / butene-1. / Maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, ethylene / maleic anhydride copolymer and the like can be mentioned. Specific examples of the vinyl-based resin include methyl methacrylate / styrene resin (MS resin), methyl methacrylate / acrylonitrile resin, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, and styrene / N-. Vinyl-based (co) polymers such as phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high Impact-A styrene resin modified with a rubber polymer such as polystyrene resin, a block copolymer such as styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin, and core shell rubber. As a multi-layer structure of dimethylsiloxane / butyl acrylate polymer (core layer) and methyl methacrylate polymer (shell layer), dimethylsiloxane / butyl acrylate polymer (core layer) and acrylonitrile / styrene copolymer (shell layer). ) Multi-layer structure, multi-layer structure of butandien / styrene polymer (core layer) and methyl methacrylate polymer (shell layer), butandien / styrene polymer (core layer) and acrylonitrile / styrene copolymer (shell layer) Examples include a multilayer structure.

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

The blending amount of the olefin resin is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the blending amount is 0.1 parts by weight or more, the toughness and hydrolysis resistance are further improved. The blending amount is more preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more. On the other hand, when the blending amount is 30 parts by weight or less, the mechanical 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, may be referred to as "polyhydric alcohol compound"). can do. By blending such a compound, the fluidity during molding processing such as injection molding can be improved. The polyhydric alcohol compound may be a low molecular weight compound or a polymer. Examples of the functional group include a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group and a silyl ether group. .. Among these, it is preferable to have the same or different 3 or 4 functional groups, and particularly in terms of further improving fluidity, mechanical properties, durability, heat resistance and productivity, 3 or 4 identical functional groups are used. It is more preferable to have four.

Moreover, a preferred example of the alkylene oxide unit is an aliphatic alkylene oxide unit having 1 to 4 carbon atoms. Specific examples include methylene oxide unit, ethylene oxide unit, trimethylene oxide unit, propylene oxide unit, tetramethylene oxide unit, 1,2-butylene oxide unit, 2,3-butylene oxide unit, isobutylene oxide unit and the like. it can.

In the present invention, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as the alkylene oxide unit, particularly from the viewpoint of being excellent in fluidity, recyclability, durability, heat resistance and mechanical properties. Further, 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 elongation at break). Regarding the number of alkylene oxide units, the number of alkylene oxide units per functional group is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, in terms of being more excellent in fluidity. is there. On the other hand, in terms of being more excellent in mechanical properties, the alkylene oxide unit per functional group is preferably 20 or less, more preferably 10 or less, and further preferably 5 or less.

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

A mold release agent can be blended in the resin composition of the present invention, and the mold release property from the mold can be improved at the time of melt processing. Examples of the release agent include higher fatty acid ester waxes such as montanic acid and stearic acid, polyolefin waxes, and ethylene bisstearoamide waxes.

The amount of the release agent compounded is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the (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 can further contain one or more of carbon black, titanium oxide and pigments and dyes of various colors, and can be toned to various colors, and has weather resistance (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 the titanium oxide, titanium oxide having a crystal form such as rutile type or anatase type and having an average particle size of 5 μm or less is preferably used.

These carbon blacks, titanium oxides and pigments and dyes of various colors may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyols, silane coupling agents and the like. Further, in order to improve the dispersibility of the resin composition of the present invention and the handleability at the time of production, it may be used as a melt-blended or simply blended mixed material with various thermoplastic resins.

The blending amount of the pigment or 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 index of hydrolysis resistance of a molded product made of a polyester resin composition, a test piece for evaluating tensile strength of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) was used at a relative humidity of 100. %, Tension strength retention after exposure for 50 hours in an atmosphere with a temperature of 121 ° C.: (Tensile strength after exposure / Tension strength before exposure) × 100. The molded product according to the embodiment of the present invention has a tensile strength retention rate of 50% or more after being exposed for 50 hours in an atmosphere of 100% relative humidity and 121 ° C. in order to suppress a decrease in molecular weight due to hydrolysis of the polyester resin. Is. When the tensile strength retention rate after exposure for 50 hours under these conditions is less than 50%, it means that the carboxy-terminal group is increased by the hydrolysis of the polyester resin and the molecular weight is gradually decreased. By increasing the number of carboxy-terminal groups due to the hydrolysis of the main chain, the decrease in the molecular weight of the polyester resin is further promoted, and the mechanical properties are deteriorated. The tensile strength retention rate is preferably 55% or more, more preferably 60% or more. It was shown that the closer the value of the tensile strength retention rate after exposure to 100% relative humidity and 121 ° C. for 50 hours was to 100%, the more the decrease in molecular weight due to the progress of hydrolysis of the polyester resin was suppressed. It shows that it has high hydrolysis resistance.

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

Examples of the melt-kneading method include (A) component, (B) component, (C) component, (D) component, (E) component, and if necessary, (F) component, (G) component, and (H). ) Ingredients and various additives are premixed and supplied to an extruder or the like for sufficient melt-kneading, or each component is supplied to a predetermined amount extruder or the like using a quantitative feeder such as a weight feeder. Examples thereof include a method of sufficiently melting and kneading.

Examples of the above-mentioned premixing 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. Further, (I) the fibrous reinforcing material and the inorganic filler other than the fibrous reinforcing material are added by installing a side feeder in the middle of the main filling portion and the vent portion of the multi-screw extruder such as the twin-screw extruder. May be good. In the case of liquid additives, a method of adding a liquid addition nozzle in the middle of the breech loader and vent of a multi-screw extruder such as a twin-screw extruder and using a plunger pump, or the breech loader A method of supplying from a unit or the like with a metering pump may be used.

The thermoplastic polyester resin composition of the present invention is preferably pelletized and then molded. Strands can be pelletized using, for example, single-screw extruders, twin-screw extruders, triple-screw extruders, conical extruders and kneader-type kneaders equipped with "unimelt" or "dalmage" type screws. A method of discharging in a shape and cutting with a strand cutter can be mentioned.

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

As the injection molding method, gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding, injection press molding and the like are known in addition to the usual injection molding method, but any molding method can be applied. it can.

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

Specific examples of mechanical mechanical parts, electrical parts, electronic parts and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for fixing machines of copiers and printers, general household appliances, and OA. Equipment housings, variable condenser case parts, various terminal boards, metamorphosers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs , Condenser, various cases, resistors, electrical / electronic parts incorporating metal terminals and conductors, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph equipment-related parts, telephone equipment-related parts, air conditioner parts, VTR Examples include home appliances such as televisions, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various electric parts for automobiles.

Next, the effect of the thermoplastic polyester resin composition of the present invention will be specifically described with reference to Examples. The raw materials used in Examples and Comparative Examples are shown below. Here,% and parts all represent% by weight and parts by weight, and "/" in the resin name below means copolymerization. Example 10 is a reference example.

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

(B) Heat-resistant water-based phosphorus flame retardant <B-1> Diamine phosphate: Zinc ethylenediamine phosphate, "Firecut" (registered trademark) manufactured by Suzuhiro Chemical Co., Ltd. ZPO-3 (acid value after wet heat treatment 3KOHmg / g) , Phosphorus atom content 16%) was used.
<B-2> Phosphazene compound: A phenoxyphosphazene compound, SPB-100 manufactured by Otsuka Chemical Co., Ltd. (acid value after wet heat treatment 1 KOHmg / g, phosphorus atom content 18%) was used.

Phosphorus-based flame retardants other than (C) and (B) <C-1> Organic phosphinic acid metal salt: "Exolit" (registered trademark) OP-1240 (acid value after moist heat treatment 31 KOHmg / g, phosphorus) manufactured by Clariant Japan Co., Ltd. Atomic content 22%)
<C-2> Condensed phosphate ester: 4,4 bis (diphenylphosphoryl) 1,1 biphenyl, "ADEKA STAB" (registered trademark) manufactured by ADEKA Corporation (registered trademark) FP-800 (acid value after wet heat treatment 57 KOHmg / g, phosphorus atom Content 8%) was used.

(D) Nitrogen-based flame retardant <D-1> melamine cyanurate, MC-4000 manufactured by Nissan Chemical Industries, Ltd. (white powder with an average particle size of 10 μm) was used.

(E) Drip inhibitor <E-1> Fluorine-based resin, polytetrafluoroethylene, and "Teflon" (registered trademark) 6-J manufactured by Mitsui-DuPont Fluorochemical Co., Ltd. were used.

(F) Epoxy compound <F-1> Condensate with bisphenol A epichlorohydrin having an epoxy equivalent of 190 g / eq: “jER” (registered trademark) 819 manufactured by Mitsubishi Chemical Corporation was used.
<F-2> Cresol novolac type epoxy having an epoxy equivalent of 211 g / eq: EOCN-102S manufactured by Nippon Kayaku Co., Ltd. was used.
<F-3> Dicyclopentadiene-phenol-added novolac type epoxy having an epoxy equivalent of 253 g / eq: XD-1000 manufactured by 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) Hydroxy group-containing resin <H-1> Bisphenol A type phenoxy resin: “jER” (registered trademark) 1010 manufactured by Mitsubishi Chemical Corporation was used (hydroxy group value: 3.3 eq / kg, number average molecular weight: 5,5000)
<H-2> Hydroxy group-containing acrylic polymer: “ARUFON” (registered trademark) UH-2170 manufactured by Toa Synthetic Co., Ltd. was used (hydroxy group value: 7.7 eq / kg, number average molecular weight: 6,500).

(I) Fiber-like reinforcing material <I-1> Glass fiber treated with a sizing agent containing an epoxy compound: Glass fiber ECS03T-187 manufactured by Nippon Electric Glass Co., Ltd., having a cross-sectional diameter of 13 μm and a fiber length of 3 mm was used. ..

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

(1) Acid value of phosphorus-based flame retardant (component (B) or component (C)) after moist heat treatment ESPEC (component (B) or component (C) set to a temperature and humidity of 121 ° C. × 100% RH) It was put into the highly accelerated life test apparatus EHS-411 manufactured by Co., Ltd. and subjected to a wet heat treatment for 40 hours. Then, a solution of a heat-treated phosphorus-based flame retardant dissolved 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 (2007 Dpackettype Japan Paint Manufacturers Association)).
Acid value [KOHmg / g] = (required for titration of 0.05 mol / L ethanolic potassium hydroxide [ml] -chloroform solution required for titration of chloroform solution in which component (B) or component (C) was dissolved. 0.05 mol / L ethanolic potassium hydroxide [ml]) × 0.05 mol / L Concentration of ethanolic potassium hydroxide [mol / ml] × 56.1 / Component (B) or component (C) used for titration Collection amount [g].

(2) Mechanical properties (tensile strength and tensile elongation)
When polybutylene terephthalate resin is used as the component (A) using the NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., the molding temperature is 250 ° C. and the mold temperature is 80 ° C., and as the component (A). When polyethylene terephthalate resin is used, the molding temperature is 270 ° C., the mold temperature is 80 ° C., the injection time and the holding pressure time are 10 seconds in total, and the cooling time is 10 seconds. A test piece for evaluating tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) and an eyezot test piece with a mold notch were obtained, which were molded according to the above year. Using the obtained test piece for evaluating tensile physical characteristics, the maximum tensile strength (tensile strength) and the maximum tensile elongation (tensile elongation) were measured according to ASTMD638 (2005). The value was the average value of the three measured values. A material having a large tensile strength value was judged to have excellent mechanical strength, and a material having a large tensile elongation value was judged to have excellent toughness.

(3) Flame retardant (combustion rank)
Using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a combustion test piece having a thickness of 1/32 inch (about 0.79 mm) was obtained under the same injection molding conditions as the tensile physical characteristics of the above item (2). Using the obtained combustion test piece, flame retardancy was evaluated according to the evaluation criteria defined in the UL94 vertical test. Flame retardancy decreases in the order of V-0>V-1> V-2 and is ranked. In addition, materials that were inferior in flammability, did not reach the above V-2, and did not correspond to the above flame retardancy rank were excluded from the standard.

(4) Tracking resistance (comparative tracking index)
Using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., an 80 mm × 80 mm × 3 mm thick square plate was injection-molded under the same injection-molding conditions as in item (2) above. Using the obtained square plate, the comparative tracking index was measured using a 0.1% ammonium chloride aqueous solution as the electrolyte solution according to the method for measuring the comparative tracking index of IEC60112: 2003.

(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 D638 (2005) under the same injection molding conditions as in item (2) above using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd. A test piece was obtained. The obtained ASTM No. 1 dumbbell was put into an advanced accelerated life test device EHS-411 manufactured by ESPEC Co., Ltd., which was set to a temperature and humidity of 121 ° C. × 100% RH, and subjected to moist heat treatment for 50 hours. With respect to the molded product after the wet heat treatment, the maximum tensile strength was measured under the same conditions as the tensile test in item (2) above, and the average value of the three measured values was obtained. From the maximum tensile strength after the wet heat treatment and the maximum tensile strength without the wet heat treatment, the tensile strength retention rate was calculated by the following formula.
Tensile strength retention rate (%) = (Maximum tensile strength after wet heat treatment ÷ Maximum tensile strength before wet heat treatment) x 100

It was judged that the material having a tensile strength retention rate of less than 50% was inferior in hydrolysis resistance, and that the material having a larger number of tensile strength retention rate was judged to be superior in hydrolysis resistance.

(6) Retention stability (rate of change in melt viscosity index)
Using C501DOS manufactured by Toyo Seiki Co., Ltd., the melt viscosity index (melt flow index) of the thermoplastic polyester resin composition was measured according to ASTM D1238 (1999) under the conditions of a temperature of 270 ° C. and a load of 2.6 kg. ..

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

(7) Amount of gas Weigh 10 g of the resin composition in an aluminum cup, place it in a hot air oven at 270 ° C. under atmospheric pressure using an ESPEC hot air oven PHH202, heat-treat for 2 hours, and then heat the resin composition. I asked for the weight. The rate of change was determined from the difference in weight before and after the heat treatment (gas amount (%)) with respect to the weight before the heat treatment and the weight of the resin composition. When the amount of gas exceeds 3%, it is judged that the amount of generated gas is large and the moldability is excellent. It was judged that the smaller the amount of gas, the better the moldability.

(8) Bleed-out Using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., under the same injection molding conditions as in item (2) above, bleeding of ASTM No. 1 dumbbell with a test piece thickness of 1/8 inch (about 3.2 mm). A test piece for out evaluation was obtained. The obtained ASTM No. 1 dumbbell was put into an advanced accelerated life test device EHS-411 manufactured by ESPEC CO., LTD., Which was set to a temperature and humidity of 121 ° C. × 100% RH, and subjected to moist heat treatment for 96 hours (4 days). The appearance of the molded product after the wet heat treatment was visually observed, and the bleed-out was determined according to the following criteria.
A: No liquid or white powder bleed-out is observed in the molded product.
B: Liquid or white powder bleed-out is observed in a part or everywhere of the molded product.

(9) Heat resistance (thermal deformation temperature)
Using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a test piece for evaluating the thermal deformation temperature of a dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained under the same injection molding conditions as in item (2) above. Using the obtained test piece for evaluating the thermal deformation temperature, the thermal deformation temperature was measured under the condition of a measurement load of 1.82 MPa according to ASTMD648 (2005). The value was the average value of the three measured values. It was judged that the material having a thermal deformation temperature of less than 50 ° C. was inferior in heat resistance, and the material having a larger number of thermal deformation temperatures was judged to have excellent heat resistance.

(10) Long-term heat aging resistance (tensile strength retention rate)
Evaluation of tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) under the same injection molding conditions as in item (2) above using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd. A test piece was obtained. The obtained evaluation test piece was placed in a hot air oven at 190 ° C. under atmospheric pressure and heat-treated for 2000 hours. The maximum tensile strength of the evaluation test piece after the heat treatment was measured under the same conditions as in item (2) above. The value was the average value of the three measured values. The tensile strength retention rate was calculated from the following formula with respect to the maximum tensile strength of the evaluation test piece after the heat treatment. It was judged that the larger the tensile strength retention rate, the more excellent the heat-resistant aging property, and 75% or more, which is particularly excellent. The maximum tensile strength retention rate is 100%.
Tensile strength retention rate (%) = (maximum tensile strength after heat treatment / maximum tensile strength before heat treatment) x 100

[Examples 1 to 17], [Comparative Examples 1 to 7]
Using a twin-screw extruder (manufactured by Japan Steel Works, TEX-30α) with a screw diameter of 30 mm and L / D35 in the same direction, (A) thermoplastic polyester resin, (B) heat-resistant water-based phosphorus flame retardant, ( C) Phosphor-based flame retardants other than (B), (D) Nitrogen-based flame retardants, (E) Drip inhibitor, (F) Epoxy compound, (G) Hindered amine compound, (H) hydroxyl group-containing resin, if necessary. , And other materials were mixed in the compositions shown in Tables 1 to 3 and added from the loading part of the twin-screw extruder. The fibrous reinforcing material (I) was added by installing a side feeder in the middle of the filling portion and the vent portion. Further, melt mixing was performed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, the mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

The obtained pellets were dried in a hot air dryer 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 blending amount of the (I) fibrous reinforcing material in 100 parts by weight of the flame-retardant thermoplastic polyester resin composition is described as "the content of the (I) fibrous reinforcing material in the thermoplastic polyester resin composition".

From the comparison between Examples 1 to 11 and Comparative Examples 1 to 7, the components (B), (C), (D), and (E) were blended with respect to 100 parts by weight of the (A) thermoplastic polyester resin. A material having an excellent balance of mechanical properties, flame retardancy, tracking resistance, and long-term hydrolysis resistance within a specific range was obtained.

Comparing Example 9 and Example 10, (B) Diamine phosphate is used as a phosphorus-based flame retardant 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. As a result, a material having a better balance of mechanical properties, flame retardancy, tracking resistance, and long-term hydrolysis resistance was obtained.

From the comparison between Examples 8 and 9, by using the phosphinic acid metal salt as the phosphorus-based flame retardant other than the above (C) and (B), the long-term hydrolysis resistance is improved and the amount of gas is reduced. A material having excellent moldability was obtained.

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

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

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

From the comparison between Examples 11 and 9, when polybutylene terephthalate resin is used as the component (A), a material having a better balance between mechanical strength, flame retardancy, tracking resistance, and long-term hydrolysis resistance can be obtained. It was.

Claims (9)

(A) A phosphorus-based flame retardant 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 with respect to 100 parts by weight of the thermoplastic polyester resin 0.1. 30 parts by weight, phosphorus-based flame retardants other than (C) and (B) 0.1 to 30 parts by weight, (D) nitrogen-based flame retardants 0.1 to 20 parts by weight, and (E) anti-drip agent 0.01 to A thermoplastic polyester resin composition containing 1 part by weight of 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 (B) 121 ° C.-100% relative humidity. A thermoplastic polyester resin composition in which is a diamine phosphate . The thermoplastic polyester resin composition according to claim 1 , wherein the phosphorus-based flame retardant other than the above (C) and (B) is a phosphinic acid metal salt. The thermoplastic polyester resin composition according to claim 1 or 2 , wherein 0.1 to 10 parts by weight of the epoxy compound (F) is further added to 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to claim 3 , wherein the epoxy compound (F) 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 4 , wherein 0.01 to 1 part by weight of the (G) hindered amine compound is further blended with respect to 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to any one of claims 1 to 5 , wherein 0.1 to 10 parts by weight of the (H) hydroxyl group-containing resin is further mixed with 100 parts by weight of the thermoplastic polyester resin (A). .. The thermoplastic polyester resin composition according to any one of claims 1 to 6 , further comprising (I) 1 to 100 parts by weight of a fibrous reinforcing material with respect to 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to any one of claims 1 to 7 , wherein the thermoplastic polyester resin (A) is a polybutylene terephthalate resin. A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of claims 1 to 8.