JP2021014478A - Thermoplastic polyester resin composition and molded article - Google Patents

Abstract

To provide a molded article which is excellent in flame retardancy and tracking resistance, has excellent mechanical properties and hydrolysis resistance, and hardly causes bleed-out even under a high-temperature and high-humidity environment.SOLUTION: A thermoplastic polyester resin composition is obtained by blending (A) 100 pts.wt. of a thermoplastic polyester resin with (B) 0.1-30 pts.wt. of a phosphorus-based flame retardant, (C) 0.1-30 pts.wt. of a nitrogen-based flame retardant, (D) 0.01-10 pts.wt. of nanotubes containing aluminum atoms and silicon atoms and having a tubular shape, a tube average outer diameter of 1-100 nm and a tube average length of 100-3,000 nm, and (E) 0.1-10 pts.wt. of a polyfunctional epoxy compound.SELECTED DRAWING: None

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 physical 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 high 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 the non-halogen flame retardant include a thermoplastic polyester resin, an aromatic polycarbonate, a phosphorus flame retardant, a nitrogen-containing flame retardant, and an epoxy group-containing organic silane compound (see Patent Document 2). , Polybutylene terephthalate resin, long-chain aliphatic polyamide resin, organic phosphorus flame retardant such as phosphinate, resin composition containing a nitrogen-containing flame retardant (see Patent Document 3), polyalkylene terephthalate or A resin composition containing a polycycloalkylene terephthalate, an organic phosphinate, and an inorganic phosphate (Patent Document 4), a thermoplastic resin, a zinc ethylenediamine phosphate, and a resin composition containing an acid receiving agent (Patent). Reference 5), Thermoplastic polyester resin, polystyrene-based resin, compatibilizer, fibrous reinforcing material, and resin made by blending a combination of phosphorus-based, nitrogen-based, boric acid-based flame retardant, and layered silicate as a drip preventive. A resin composition containing a composition (Patent Document 6), a thermoplastic resin, dialkylphosphinic acid, an alkylphosphonic acid, and a flame retardant synergist (Patent Document 7), a polyester resin, a phosphate, a nitrogen-containing flame retardant, A resin composition containing a combination of silicon-containing compounds as a flame retardant aid is disclosed (Patent Document 8).

Patent Document 9 discloses a resin composition containing a thermoplastic polyester resin, a metal salt of phosphinic acid, a melamine compound, an epoxidized natural linseed oil or a fatty acid ester.

Further, Patent Document 10 proposes a polymeric nanoparticle composite material containing a polymer matrix and a filler composed of inorganic nanotubes.

International Publication No. 2006/090751 Japanese Unexamined Patent Publication No. 2013-1772 Japanese Unexamined Patent Publication No. 2011-231191 JP-A-2016-166358 Japanese Unexamined Patent Publication No. 2000-154324 JP-A-2010-024324 Special Table 2015-504862 Japanese Unexamined Patent Publication No. 2007-070615 Special Table 2016-591193 Special Table 2009-507945

However, in the techniques disclosed in Patent Documents 2 to 8, the polyester resin containing a non-halogen flame retardant such as a phosphorus compound tends to deteriorate in initial physical properties, and is strong due to hydrolysis at high temperature and high humidity. There was also a problem that it was easy to decrease. Although the technique disclosed in Patent Document 9 has improved hydrolysis resistance, it has been difficult to achieve both flame retardancy, tracking resistance, and bleed-out resistance at a high level. With the technique disclosed in Patent Document 10, it has been difficult to achieve both flame retardancy, tracking resistance, and initial physical properties at a high level.

In the present invention, a thermoplastic that does not contain a halogen-based flame retardant such as a bromine-containing resin and can obtain a molded product having excellent initial physical properties, flame retardancy and tracking resistance while maintaining strength under high temperature and high humidity. An object of the present invention is to provide a polyester resin composition and a molded product thereof.

As a result of repeated studies to solve the above-mentioned problems, the present inventors have obtained 0.1 to 30 parts by weight of (B) a phosphorus-based flame retardant with respect to 100 parts by weight of (A) thermoplastic polyester resin. ) A nitrogen-based flame retardant containing 0.1 to 30 parts by weight, (D) aluminum atoms and silicon atoms, having a tubular shape, having an average outer diameter of 1 to 100 nm, and an average length of the tube. 0.01 to 10 parts by weight of nanotubes having a size of 100 nm to 3,000 nm (hereinafter, may be referred to as “(D) nanotubes”), and 0.1 to 10 parts by weight of the (E) thermoplastic epoxy compound. By doing so, it has been found that the above-mentioned problems can be solved, and the present invention has been reached. That is, the present invention has the following configuration.
[1] 0.1 to 30 parts by weight of (B) phosphorus-based flame retardant, 0.1 to 30 parts by weight of (C) nitrogen-based flame retardant, (D) with respect to 100 parts by weight of (A) thermoplastic polyester resin. 0.01-10 parts by weight of nanotubes containing aluminum and silicon atoms, having a tubular morphology, with an average outer diameter of the tube of 1 to 100 nm and an average length of the tube of 100 nm to 3,000 nm. , And (E) a thermoplastic polyester resin composition comprising 0.1 to 10 parts by weight of a polyfunctional epoxy compound.
[2] The thermoplastic polyester resin composition according to [1], wherein the (D) nanotube is a halloysite nanotube.
[3] The ratio (%) of the weight part of the (D) nanotube to the total amount of the weight part of the (B) phosphorus-based flame retardant and the weight part of the (D) nanotube (((A) component 100 parts by weight ( D) Part by weight of component) ÷ ((A) Part by weight of component (B) with respect to 100 parts by weight of component + (A) Part by weight of component (D) with respect to 100 parts by weight of component)) × 100) is 0.5 The thermoplastic polyester resin composition according to [1] or [2], which is ~ 20%.
[4] The thermoplastic polyester resin composition according to any one of [1] to [3], wherein the acid point inside the tube of the (D) nanotube is coated with a basic compound.
[5] The thermoplastic polyester resin composition according to any one of [1] to [4], wherein the pH of the (D) nanotube is 6 to 8.
[6] Described in any one of [1] to [5], wherein the phosphorus-based flame retardant (B) is at least one selected from a condensed phosphoric acid ester compound, phosphinic acid and a metal salt thereof, and a phosphazene compound. Thermoplastic polyester resin composition.
[7] The thermoplastic polyester resin composition according to any one of [1] to [6], wherein the (E) polyfunctional epoxy compound is a novolak type epoxy.
[8] The method according to any one of [1] to [7], wherein 0.1 to 20 parts by weight of (F) thermoplastic elastomer resin is further blended with 100 parts by weight of (A) thermoplastic polyester resin. Thermoplastic polyester resin composition.
[9] The method according to any one of [1] to [8], wherein 0.001 to 1 part by weight of (G) reaction accelerator is further added to 100 parts by weight of (A) thermoplastic polyester resin. Thermoplastic polyester resin composition.
[10] The method according to any one of [1] to [9], wherein 0.01 to 1 part by weight of (H) drip inhibitor is further added to 100 parts by weight of (A) thermoplastic polyester resin. Thermoplastic polyester resin composition.
[11] The heat according to any one of [1] to [10], which is obtained by further blending 0.01 to 30 parts by weight of (I) barium sulfate with respect to 100 parts by weight of (A) thermoplastic polyester resin. Plastic polyester resin composition.
[12] With respect to 100 parts by weight of (A) thermoplastic polyester resin, (J) hydroxy group-containing resin 0.1 having a number average molecular weight of 2,000 to 500,000 and a halogen element content of 1,000 ppm or less. The thermoplastic polyester resin composition according to any one of [1] to [11], which comprises 20 parts by weight.
[13] The heat according to any one of [1] to [12], which comprises adding 1 to 100 parts by weight of (K) fibrous reinforcing material to 100 parts by weight of (A) thermoplastic polyester resin. Plastic polyester resin composition.
[14] The thermoplastic polyester resin composition according to any one of [1] to [13], wherein the thermoplastic polyester resin (A) is a polybutylene terephthalate resin.
[15] After exposing a test piece for evaluating tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) for 50 hours in an atmosphere of 100% relative humidity and 121 ° C. The thermoplastic polyester resin composition according to any one of [1] to [14], wherein the tensile strength retention rate (%) ((tensile strength after exposure / tensile strength before exposure) × 100) is 50% or more.
[16] A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of [1] to [15].

The thermoplastic polyester resin composition of the present invention does not contain a halogen-based flame retardant such as a bromine-containing resin, has excellent flame retardancy and tracking resistance, and has excellent mechanical properties and hydrolysis resistance at high temperatures. It is possible to obtain a molded product in which bleed-out is unlikely to occur even in a high humidity environment.

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

The thermoplastic polyester resin composition of the present invention comprises 0.1 to 30 parts by weight of (B) a phosphorus-based flame retardant and 0.1 to 0 parts by weight of a nitrogen-based flame retardant with respect to 100 parts by weight of (A) thermoplastic polyester resin. A nanotube containing 30 parts by weight, (D) aluminum atom and silicon atom, having a tubular shape, having an average outer diameter of 1 to 100 nm, and an average length of 100 nm to 3,000 nm. A flame-retardant thermoplastic polyester resin composition comprising 0.01 to 10 parts by weight and 0.1 to 10 parts by weight of the (E) polyfunctional epoxy compound. (A) Thermoplastic polyester resin is generally excellent in injection moldability and mechanical properties, but has a low critical oxygen index, so 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) 0.1 to 30 parts by weight of a phosphorus-based flame retardant, (C) 0.1 to 30 parts by weight of a nitrogen-based flame retardant, (D) Nanotubes 0.01 to 10 containing aluminum atoms and silicon atoms, having a tubular shape, having an average outer shape of the tube of 1 to 100 nm, and an average length of the tube of 100 nm to 3,000 nm. The parts by weight and (E) the polyfunctional epoxy compound 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, by using the (D) nanotube and the (E) thermoplastic epoxy compound in combination with the phosphorus-based flame retardant, it was generated by hydrolysis while suppressing the formation of acidic components generated by the decomposition of the phosphorus-based flame retardant (). A) By reaction-sealing and repairing the terminal of the carboxyl group derived from the thermoplastic polyester resin, both strength, hydrolysis resistance, flame retardancy, and tracking resistance can be achieved at a high level.

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 where 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, "referred to as a 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 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, polybutylene 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 copolymer 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, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate 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 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, the Mw of the (A) thermoplastic polyester resin is a value converted to 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 (B) phosphorus-based flame retardant used in the present invention is a phosphorus-containing compound containing at least one phosphorus atom in the molecule and having a content of 5% by weight or more.

The (B) phosphorus-based flame retardant used in the present invention can promote the formation of a carbonized layer of (A) a thermoplastic polyester resin during combustion, and can further improve the flame retardancy.

In the present invention, the phosphorus-based flame retardant is a condensed phosphate ester compound, a phosphaphenanthrene compound, phosphinic acid and a metal salt thereof, ammonium polyphosphate, melamine polyphosphate, phosphate esteramide, phosphazene compound, diamine phosphate and Red phosphorus and the like can be mentioned. Among these, condensed phosphoric acid ester compounds, phosphinic acid and metal salts thereof, and phosphazene compounds are preferably used because they have a good balance between flame retardancy and physical properties. Two or more of these may be combined and blended.

Examples of the condensed 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 and its metal salt are phosphinate and / or diphosphinate and / or a polymer thereof, and are useful compounds as (A) a flame retardant for 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 aluminum hypophosphate "Phoslite" (registered trademark) IP-A manufactured by Italych Chemicals, and "Exolit" (registered trademark) OP1230 and OP1240 manufactured by Clarant Japan.

The above-mentioned 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 Chemicals Corporation is preferably used.

Examples of the above-mentioned ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl ammonium 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.

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, "Rabbitl" (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.

As the diamine phosphate, the 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). Examples of the compound 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-butanediol 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.

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 in the present invention is 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of flame retardancy and hydrolysis resistance. 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, when the blending amount of the component (B) exceeds 30 parts by weight, the mechanical strength and the hydrolysis resistance are lowered. It is more preferably 25 parts by weight or less, and further preferably 22 parts by weight or less.

The thermoplastic resin composition in the present invention has improved flame retardancy by blending (C) a nitrogen-based flame retardant. Examples of the (C) 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. At this time, in the case of a flame retardant containing both a nitrogen atom and a phosphorus atom, if the phosphorus atom content is 5% by weight or more, it is treated as (B) a phosphorus-based flame retardant.

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. In addition, the above salts do 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 (C) blended is 0.1 to 30 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 (C) is less than 1 part 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 (C) exceeds 30 parts by weight, the toughness decreases. It is preferably 25 parts by weight or less, and more preferably 22 parts by weight or less.

The flame-retardant thermoplastic polyester resin composition of the present invention contains (D) aluminum atoms and silicon atoms, has a tubular shape, has an average outer diameter of 1 to 100 nm, and has an average tube length. It is made by blending nanotubes having a size of 100 nm to 3,000 nm. By blending (D) nanotubes, it is possible to suppress the decrease in strength derived from (B) phosphorus-based flame retardant, and to suppress the decrease in hydrolysis resistance due to the synergistic effect with (E) polyfunctional epoxy compound described later. ..

(D) The nanotube has a tubular shape, and the average outer diameter of the tube is 1 to 100 nm, the average length is 100 nm to 3,000 nm, and the inside is a hollow cylinder / tube. For the average outer diameter and average length of the tubes, 10 (D) nanotubes were arbitrarily selected from the images obtained by observing the component (D) with a scanning electron microscope, and the outer diameter and length of each tube structure were obtained. Is obtained by calculating the arithmetic mean value after measuring. If the average outer diameter of the nanotube (D) is less than 1 nm, the effect of suppressing the decrease in strength becomes insufficient, and if it exceeds 100 nm, the dispersibility in the resin deteriorates. The average outer diameter of the nanotube (D) is preferably 10 to 90 nm, more preferably 30 to 80 nm. If the average length of the nanotubes (D) is less than 100 nm, the strength becomes insufficient, and if it exceeds 3,000, the dispersibility in the resin deteriorates. The average length of the nanotubes (D) is preferably 100 to 2,500 nm, more preferably 150 to 2,000 nm.

Specific examples of the (D) nanotubes include halloysite nanotubes (composition formula: Al ₂ Si ₂ O ₅ (OH) ₄ ) and imogolite nanotubes (composition formula: Al ₂ SiO ₃ (OH) ₄ ). Above all, it is preferable to use halloysite nanotubes as the component (D) because the decrease in hydrolysis resistance of the resin is further suppressed.

The acid points inside the (D) nanotubes are preferably coated with a basic compound. Since the acid spots are coated, the decrease in hydrolysis resistance is further suppressed. The acid point referred to here is the Al (OH) structure of the (D) nanotube. The acid point coating of halloysite is as follows. Am. Chem. Soc. 2012, 134, 1853-1859, J. Mol. Am. Chem. Soc. 2012, 134, 12134-12137, Chem. Lett. 2013, 42, 121123, J. Mol. Chil. Chem. Soc. vol. 63 no. 3 Methods described in academic papers such as Concepcion 2018, methods for coating inorganic fillers described in JP-A-7-300568, JP-A-2001-26666, JP-A-2005-48034, and other known methods. It can be done by the method. As specific examples of the basic compound, ammonium polyacrylate and sodium tripolyphosphate are preferably used.

The pH of the (D) nanotube is preferably 6 to 8. By setting the pH to 6 to 8, it is possible to suppress the decrease in hydrolysis resistance due to the blending of the component (D). The pH of the (D) nanotube is obtained by preparing a 20 wt% slurry aqueous solution of the (D) nanotube and measuring the pH of the aqueous solution using an electrode pH meter. If the acid point is not coated with the basic compound, the pH will be 6 or less (for example, the pH value will be about 5), and then the pH value will increase depending on the coverage. In the present invention, when the pH value becomes 6 to 8, it is determined that the internal acid point is covered with a 100% basic compound.

In the present invention, the blending amount of (D) nanotubes is 0.01 to 10 parts by weight with respect to 100 parts by weight of (A) thermoplastic polyester resin. If it is less than 0.01 parts by weight, the effect of suppressing the decrease in strength and the decrease in hydrolysis resistance derived from the phosphorus-based flame retardant (B) becomes insufficient. On the other hand, if it exceeds 10 parts by weight, the strength decreases due to the acid point derived from the (D) nanotube.

The ratio (%) of the weight portion of the (D) nanotube to the total amount of the weight portion of the (B) phosphorus-based flame retardant and the weight portion of the (D) nanotube (((A) component (D) component with respect to 100 parts by weight) (Parts by weight) ÷ (parts by weight of component (B) with respect to 100 parts by weight of component (A) + parts by weight of component (D) with respect to 100 parts by weight of component (A)) × 100) is 0.5 to 20% It is preferable to mix so as to be. When the compounding ratio of the (B) phosphorus-based flame retardant and the (D) nanotube takes the above-mentioned specific value, the effect of suppressing the decrease in strength and the decrease in hydrolysis resistance derived from the (B) phosphorus-based flame retardant becomes higher. The ratio of the parts by weight of the (D) nanotubes to the total amount of the parts by weight of the (B) phosphorus-based flame retardant and the parts by weight of the (D) nanotubes is more preferably 0.8 to 12%, still more preferably 0. It is 9.9 to 8%, most preferably 1.0 to 5.0%.

The flame-retardant thermoplastic polyester resin composition of the present invention is further blended with (E) a polyfunctional epoxy compound in order to improve hydrolysis resistance. By blending the (E) polyfunctional 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 (E) polyfunctional epoxy compound used in the present invention is a compound having two or more epoxy groups in one molecule and does not contain a bromine atom. Examples thereof include, but are not limited to, glycidyl ester compounds, glycidyl ether compounds, epoxidized fatty acid ester compounds, glycidylimide compounds, and alicyclic epoxy compounds. 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 phenolic compound of 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 linseed 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-Epoxide cyclohexane-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 polyfunctional epoxy compound (E) 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. Among them, 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 polyfunctional epoxy compound (E) is preferably an epoxy compound having an epoxy equivalent of 100 to 3000 g / eq. When the epoxy equivalent of the polyfunctional epoxy compound (E) 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 polyfunctional epoxy compound (E) 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. It is more preferably 2000 g / eq or less.

In the present invention, the blending amount of the (E) polyfunctional epoxy compound is 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 (E) is 0.1 parts by weight or more, the long-term hydrolysis resistance is improved. It is more preferably 0.3 parts by weight or more, and further preferably 0.5 parts by weight or more. On the other hand, when the blending amount of the component (E) 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 (E) polyfunctional epoxy compound can be set according to the epoxy equivalent of the (E) polyfunctional epoxy compound. For example, the ratio of the amount of (A) the amount of the epoxy group derived from the polyfunctional epoxy compound (E) to be blended in the thermoplastic polyester resin composition to the amount of the carboxyl group derived from the thermoplastic polyester resin (A) blended in the thermoplastic polyester resin composition. (Epoxide 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 determined by adding 1% bromophenol blue to a solution obtained by dissolving (A) the thermoplastic polyester resin in an o-cresol / chloroform (2/1, vol / vol) mixed solution. It can be calculated by titrating with 0.05 mol / L ethanolic potassium hydroxide as an indicator.

The thermoplastic polyester resin composition of the present invention is preferably further blended with (F) a thermoplastic elastomer resin. By blending the (F) thermoplastic elastomer resin, the tracking resistance can be further enhanced.

Specific examples of the (F) thermoplastic elastomer resin include an olefin resin, a vinyl resin, a polyamide resin, a polyurethane resin, and a polyester resin other than the component (A), which may be used alone or in combination of two types. The above can be used in combination.

The olefin-based resin is a thermoplastic resin obtained by polymerizing or copolymerizing olefins such as ethylene, propylene, butene, isoprene, and penten, and specific examples thereof include polyethylene, polypropylene, polystyrene, poly1-butene, and poly. Homopolymers such as 1-pentene and polymethylpentene, ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene-butene-1 copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / Buten-1 / glycidyl methacrylate copolymer, ethylene / propylene / glycidyl methacrylate copolymer, ethylene / octene-1 / glycidyl methacrylate copolymer, ethylene / acrylic acid ester / glycidyl methacrylate copolymer, ethylene / maleic anhydride Examples thereof include a polymer, an ethylene / butene-1 / maleic anhydride copolymer, an ethylene / propylene / maleic anhydride copolymer, and an ethylene / acrylic acid ester / maleic anhydride copolymer.

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-phenylmaleimide. Resin, vinyl-based (co) polymers such as styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact- A styrene resin modified with a rubbery polymer such as a polystyrene resin; a block copolymer such as styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin; and dimethylsiloxane / Butyl acrylate polymer (core layer) and methyl methacrylate polymer (shell layer) multilayer structure, dimethylsiloxane / butyl acrylate polymer (core layer) and acrylonitrile / styrene copolymer (shell layer) multilayer structure, Multilayer structure of butandien / styrene polymer (core layer) and methyl methacrylate polymer (shell layer), core-shell rubber of butandien / styrene polymer (core layer) and acrylonitrile / styrene copolymer (shell layer), etc. Be done.

The blending amount of the (F) thermoplastic elastomer resin is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. In this range, it is possible to improve heat aging resistance, hydrolysis resistance and tracking resistance. When the blending amount is 0.1 part by weight or more, the tracking resistance improving effect can be sufficiently obtained. It is more preferably 1 part by weight or more, further preferably 2 parts by weight or more, and particularly preferably 3 parts by weight or more. On the other hand, it is preferable that the blending amount is 20 parts by weight or less because the flame retardancy and the deterioration of the mechanical properties tend to be suppressed. It is more preferably 16 parts by weight or less, still more preferably 12 parts by weight or less.

In the thermoplastic polyester resin composition of the present invention, the reaction of (A) the carboxyl group of the thermoplastic polyester resin and (E) the polyfunctional epoxy compound is promoted, and (G) reaction is further carried out in order to improve the hydrolysis resistance. It is preferable to add an accelerator.

Specific examples of the (G) reaction accelerator include tertiary amines, hindered amine compounds, amidine compounds, organometallic compounds, organic phosphine and salts thereof, imidazoles, and boron compounds, and hindered amine compounds are preferably used.

Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris. Examples thereof include salts of (diaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and tri-2-ethylhexylic acid.

The hindered amine compound is, for example, a compound having a structure having at least one 2,2,6,6-tetramethylpiperidine derivative in the molecule, and specific examples thereof include 4-benzoyloxy-2,2,6,6. -Tetramethylpiperidin, bis- (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis- (2,2,6,6-tetramethyl-4-piperidyl) svelate, bis- (2,2) 2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (2,2,6,6-tetramethyl-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-) Piperidine) -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- (2,2,6,6-tetramethyl-4-piperidyl) ester of butanetetracarboxylic acid, 1- [2- [3- (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-tetra) Methylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2, 3,4-Butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, dimethyl-1- (2-hydroki) succinate Siethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidin, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β , Β', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) Condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid Acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9- (2,4,5,10-tetraoxaspiro [5, 5] Undecane) Examples thereof include a condensate with diethanol.

Examples of the amidine compound include 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5,5,6-dibutylamino-1,8 diazabicyclo. Examples thereof include (5,4,0) undecene-7, 7-methyl-1,5,7-triazabicyclo (4,4,0) decene-5. The amidine compound can also be used in the form of a salt with an inorganic acid or an organic acid such as 1,8-diazabicyclo (5,4,0) undecene-7 or tetraphenylborate.

Examples of organic phosphine and salts thereof include triphenylphosphine, trioltotrilphosphine, trimethatrilphosphine, triparatrilphosphine, tri-4-methoxyphenylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, and triterchary. Butylphosphine, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane , Triphenylphosphine 1,4-benzoquinone adduct and the like.

Examples of the imidazole include 2-methylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-undecylimidazole. , 1-allyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimerite, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolium isocyanurate, 2-phenyl Imidazole isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)] ethyl S-triazine, 1,3-dibenzyl-2-methylimidazolium chloride, 1,3-diaza-2,4 -Cyclopentadiene, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, Examples thereof include 2,4-diamino-6- [2-undecylimidazolyl- (1)] ethyl-S-triazine.

Examples of the boron compound include boron trifluoride-n-hexylamine, boron trifluoride-monoethylamine, boron trifluoride-benzylamine, boron trifluoride-diethylamine, boron trifluoride-piperidin, and trifluoride. Boron-Triethylamine, Boron Trifluoride-Aniline, Boron Trifluoride-n-Hexylamine, Boron Trifluoride-Monoethylamine, Boron Trifluoride-benzylamine, Boron Trifluoride-Diethylamine, Boron Trifluoride-Piperidine , Boron trifluoride-triethylamine, boron trifluoride-aniline and the like.

As the (G) reaction accelerator used in the present invention, two or more of these may be blended.

The blending amount of the reaction accelerator (G) is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A). When the blending amount of the reaction accelerator (G) is 0.001 part by weight or more, the hydrolysis resistance can be improved. It is more preferably 0.01 parts by weight or more, and further preferably 0.03 parts by weight or more. On the other hand, when the blending amount of the reaction accelerator (G) 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 (H) an inhibitor of drip. In the present invention, the (H) 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.

Further, the blending amount of the component (H) 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 the balance between flame retardancy and mechanical strength. Flame retardancy can be ensured by setting the blending amount of the component (H) to 0.01 parts by weight or more. 0.03 parts by weight or more is preferable, and 0.05 parts by weight or more is more preferable. On the other hand, the fluidity of the thermoplastic resin composition can be maintained by setting the blending amount of the component (H) to 1 part by weight or less. It is preferably 0.8 parts by weight or less, and more preferably 0.6 parts by weight or less.

It is preferable to further add (I) barium sulfate to the thermoplastic polyester resin composition of the present invention. In the present invention, by adding (I) barium sulfate, it is a compound capable of further improving the tracking resistance without lowering the flame retardancy.

The blending amount of the component (I) is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of the balance between tracking resistance and mechanical strength. When it is 0.01 parts by weight or more, a sufficient tracking resistance improving effect can be obtained. Further, by setting the amount to 30 parts by weight or less, it is possible to suppress a decrease in mechanical strength. It is preferably 0.05 to 20 parts by weight, more preferably 0.08 to 15 parts by weight, and most preferably 1.0 to 10 parts by weight.

The thermoplastic polyester resin composition of the present invention further has a (J) number average molecular weight of 2,000 to 500,000 and a halogen element in order to improve heat aging resistance under long-term exposure to dry heat. It is preferable to blend a hydroxy group-containing resin having a content of 1,000 ppm or less (hereinafter, may be referred to as (J) hydroxy group-containing resin). The molecular weight of the (A) thermoplastic polyester resin decreases due to thermal decomposition in a dry heat environment, and the carboxyl group increases. However, by blending the (J) hydroxy group-containing resin, the carboxyl terminal group derived from the polyester resin and hydroxy The hydroxyl group of the group-containing resin reacts to suppress the decrease in molecular weight, so that the heat aging property can be improved.

In the present invention, the (J) hydroxy 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). As the solvent for GPC, an appropriate solvent can be selected depending on the structure of the (J) hydroxy group-containing resin, but in general, hexafluoroisopropanol, chloroform, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethyl Examples thereof include formamide.

When the number average molecular weight of the (J) hydroxy group-containing resin used in the present invention is 2,000 or more, the molecular weight caused by the progress of ester exchange with the (A) thermoplastic polyester resin during exposure in a dry heat environment. It can be said that it does not easily decrease and has excellent heat aging resistance. Further, when the number average molecular weight is 500,000, the retention stability at the time of melting can be maintained. 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 (J) hydroxy group-containing resin used in the present invention is preferably 3 to 20 eq / kg. Here, the hydroxyl value (eq / kg) of the (J) hydroxy group-containing resin is determined by acetylating the hydroxyl group of the (J) hydroxy group-containing resin with an acetylating reagent according to JIS K0070 and JIS K1557-1, and phenolphthalein as an indicator. It is a value measured by adding a rain solution and titrating with a potassium hydroxide ethanol solution. A thermoplastic polyester resin composition containing a (J) hydroxy group-containing resin having a hydroxyl value of 3 to 20 eq / kg can exhibit excellent heat aging resistance and retention stability during melting. By setting the hydroxyl value of the (J) hydroxy 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 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 (J) hydroxy group-containing resin 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 co-weight. Examples thereof include EVOH resin, paravinylphenol resin, carbinol-modified or diol-modified silicone oil, and polycarbonate diol which are coalesced. Among them, an acrylic resin containing a phenoxy resin or at least a hydroxyalkyl (meth) acrylate as a structural unit is preferable from the viewpoint of the heat resistance of the hydroxy group-containing resin itself and the dispersibility in the (A) thermoplastic polyester resin. By using these hydroxy group-containing resins, the compatibility and dispersibility with the thermoplastic polyester resin are improved. As a result, when a molded product obtained by melt-molding a 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, resorcin, 2,2'-biphenol, 4,4-biphenol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and bis (hydroxyaryl). ) Aromatic dihydroxys 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): Examples thereof include bisphenol AD and 2,2-bis (4-hydroxyphenyl) butane. 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, and 4-hydroxybutyl (meth) acrylate. Examples thereof include 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate. In addition, acrylic acids other than the above, alkyl or aryl esters such as methacrylic acid, olefin compounds such as ethylene, propylene, 1-butene and butadiene, vinyl aromatic compounds such as styrene, homopolymers such as acrylonitrile, acrylamide and methacrylic acid, 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 (J) hydroxy group-containing resin is preferably 0.1 to 20 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 (J) hydroxy group-containing resin 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 (J) hydroxy group-containing resin is 20 parts by weight or less, the retention stability and fluidity can be improved. It is more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less.

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

Specific examples of the (K) fibrous reinforcing material include glass fiber, aramid fiber, carbon fiber and the like. The above 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 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 focusing agent may be mixed with the emulsion solution and used. The fiber diameter of the glass fiber is usually preferably in the range of 1 to 30 μm. From the viewpoint of the 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 (K) fibrous reinforcing material to be blended is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. By blending 1 part by weight or more of the fibrous reinforcing material (K), the 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 100 parts by weight or less of the (K) fibrous reinforcing material, the mechanical strength and fluidity can be further improved. It is more preferably 95 parts by weight or less, and further preferably 90 parts by weight or less.

The preferable range of the blending amount of the (K) fibrous reinforcing material 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. When the fibrous reinforcing material (K) 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 (K) is 100 parts by weight of the thermoplastic polyester resin composition, 70 parts by weight or less is blended, so that the mechanical strength and fluidity can be further improved. 60 parts by weight or less is more preferable, and 55 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.

The reinforcing material other than the above-mentioned fibrous reinforcing material may be subjected to surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. The average particle size of the granular, powdery and layered inorganic 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 components (A), (F) and (J) as long as the object of the present invention is not impaired, and may contain moldability and dimensional accuracy. , Molding shrinkage and toughness can be improved. Examples of the thermoplastic resin other than the component (A) include polyamide resin, polyacetal resin, polyurethane resin, aromatic or aliphatic polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, and polyurethane. Examples thereof include resins, aromatic polycarbonate resins, polyarylate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, poly-4-methylpentene-1, polyetherimide resins, cellulose acetate resins, polyvinyl alcohol resins and the like. ..

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. Here, the polyhydric alcohol compound refers to a molecule having a molecular weight smaller than 2,000, and a polyhydric alcohol compound having a molecular weight of 2,000 or more is treated as a (J) hydroxy group-containing resin. 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 particularly preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as the alkylene oxide unit in that it is excellent in fluidity, recyclability, durability, heat resistance and mechanical properties. In addition, it is particularly preferable to use a compound containing a propylene oxide unit in that it is excellent in long-term hydrolysis resistance and toughness (tensile 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 number of alkylene oxide units per functional group is preferably 20 or less, more preferably 10 or less, still more 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 a 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 thermoplastic polyester resin composition, the thermoplastic polyester resin composition of the present invention is molded according to ASTM D638 (2005), and the ATM No. 1 dumbbell (1/8 inch thickness) is formed. ) Tensile strength retention after exposure to 100% relative humidity and 121 ° C. temperature for 50 hours: (Tensile strength after exposure / Tensile strength before exposure) x 100 (%) ) Pay attention to the numerical value. The molded product according to the embodiment of the present invention has a tensile strength retention rate of 50 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 thermoplastic polyester resin. % Or more is preferable. 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 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). ) Component, (I) component, (J) component, (K) component, various additives, etc. are premixed and supplied to an extruder or the like for sufficient melt-kneading, or a quantitative feeder such as a weight feeder. Examples thereof include a method in which a predetermined amount of each component is supplied to an extruder or the like and sufficiently melt-kneaded.

Examples of the 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, (K) inorganic fillers other than the fibrous reinforcing material and the fibrous reinforcing material are added by installing a side feeder in the middle of the feeding part and the vent part of the multi-screw extruder such as the twin-screw extruder. May be good. In the case of liquid additives, a method of installing a liquid addition nozzle in the middle of the breech loader and the vent of a multi-screw extruder such as a twin-screw extruder and adding it 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. There is a method of discharging in a shape and cutting with a strand cutter.

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. In addition, 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 copying machines and printers, general household appliances, and OA. Housing for equipment, variable condenser case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs , 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 appliance parts such as televisions, copying machine 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.

(A) Thermoplastic Polyester Resin <A-1> Polybutylene terephthalate resin: A polybutylene terephthalate resin manufactured by Toray Corporation 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) Phosphorus-based flame retardant <B-1> Organic phosphinic acid metal salt: "Exolit" (registered trademark) OP-1240 manufactured by Clariant Japan Co., Ltd. was used.
<B-2> Phosphazene compound: “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. was used.
<B-3> Condensed phosphoric acid ester: 1,3 phenylenebis (di2,6 xylenyl phosphate), "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. was used.

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

(D) Nanotube <D-1> Halloysite nanotube: "DRAGONITE" (registered trademark) manufactured by Fimatec Co., Ltd.-HP (average outer diameter 60 nm, average length 1,500 nm, no internal acid point coating, pH value 5. 0, Composition formula Al ₂ Si ₂ O ₅ (OH) ₄ )
<D-2> Halloysite nanotubes: "DRAGONITE" (registered trademark) manufactured by Phymatec Co., Ltd.-APA: M (average outer diameter 50 nm, average length 900 nm, internal acid point coated with ammonium polyacrylate, pH value 7. 0, Composition formula Al ₂ Si ₂ O ₅ (OH) ₄ )

(D') Aluminum and / or silicon-containing compound <D'-1> that does not have a tubular form other than the above (D): Talc: "Talcan powder" (registered trademark) manufactured by Hayashi Kasei Co., Ltd. PK-C (Composition formula 3MgO · 4SiO ₂ )
<D'-2> Hydrotalcite: Kyowa Chemical Industry Co., Ltd .: KW-1100 (composition formula Mg _0.7 Al _0.3 O _1.15 )
<D'-3> Mica: Yamaguchi Mica Co., Ltd. "Mikaretto" 21PU (composition formula _{K 2 O · 3Al 2 O 3} · 6SiO 2)

(E) Polyfunctional Epoxy Compound <E-1> Dicyclopentadiene-type Novolac Epoxy: “EPICLON” HP-7200H manufactured by DIC Corporation was used (epoxy equivalent: 275 g / eq).
<E-2> Bisphenol A type epoxy: “jER” (registered trademark) 1004K manufactured by Mitsubishi Chemical Corporation was used (epoxy equivalent: 926 g / eq).
<E-3> Epoxy linseed oil: “ADEKA Sizer” (registered trademark) O-180A manufactured by ADEKA Corporation was used (epoxy equivalent 176 g / eq).

(F) Thermoplastic Elastomer Resin <F-1> Acrylic Core-Shell Elastomer: "Paraloid" (registered trademark) manufactured by Dow Chemical Co., Ltd., which is a core-shell elastomer with an acrylic rubber core layer and a vinyl polymer shell layer. ) EXL2314 was used.

(G) Reaction accelerator <G-1> Bis- (2,2,6,6-tetramethyl-4-piperidyl) terephthalate: "ADEKA STAB" (registered trademark) LA57 manufactured by ADEKA Corporation was used.

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

(I) Barium Sulfate <I-1> Barium Sulfate: B-55 manufactured by Sakai Chemical Industry Co., Ltd. was used.

(J) Hydroxy group-containing resin <J-1> Bisphenol A type phenoxy resin: PKHB manufactured by Gabriel was used (hydroxy group value: 3.6 eq / kg, number average molecular weight: 10,000).
<J-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).
The halogen element content of <J-1> and <J-2> was 1000 ppm or less.

(K) Fiber-like reinforcing material <K-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) 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, and the molding cycle condition is ASTM D638 (2005). 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 year). Using the obtained test piece for evaluating tensile properties, 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.

(2) 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 1/16 inch (about 1.6 mm) was obtained under the same injection molding conditions as the mechanical properties of the above item (1). 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 and did not reach the above V-2 and did not correspond to the above flame retardancy rank were excluded from the standard.

(3) 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 (1) 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.

(4) Long-term hydrolysis resistance (tensile strength retention rate)
Tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) under the same injection molding conditions as in item (1) 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 acceleration 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 (1) 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 a material having a tensile strength retention rate of less than 50% was inferior in hydrolysis resistance, and a material having a larger tensile strength retention rate was judged to be superior in hydrolysis resistance.

(5) Bleed-out Using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., under the same injection molding conditions as in (1) 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, for 96 hours (4 days) and subjected to moist heat treatment. 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.

(6) Long-term heat aging resistance (tensile strength retention rate)
Tensile property evaluation of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) under the same injection molding conditions as in item (1) above using a NEX1000 injection molding machine manufactured by Nissei Resin Industry Co., Ltd. A test piece was obtained. Using the obtained evaluation test piece, it was placed in a hot air oven at 210 ° C. under atmospheric pressure and heat-treated for 500 hours. For the evaluation test piece after the heat treatment, the maximum tensile strength was measured under the same conditions as in the above item (2). 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. The larger the tensile strength retention rate, the better the heat aging resistance. It was judged to be particularly excellent at 45% or more. 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 21], [Comparative Examples 1 to 16]
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) phosphorus-based flame retardant, (C) Nitrogen-based flame retardant, (D) nanotube, (E) polyfunctional epoxy compound, (F) thermoplastic elastomer resin, (G) reaction accelerator, (H) drip inhibitor, (I) barium sulfate, if necessary. , (J) hydroxy group-containing resin, and other materials were mixed in the compositions shown in Tables 1 to 4, and added from the main filling portion of the twin-screw extruder. The fibrous reinforcing material (K) was added by installing a side feeder in the middle of the filling portion and the vent portion. Further, when polybutylene terephthalate resin is used as the component (A), the kneading temperature is 250 ° C., and when polyethylene terephthalate resin is used as the component (A), the kneading temperature is 270 ° C. and the screw rotation is 200 rpm. The mixture was melt-mixed in, discharged into a strand, passed through a cooling bath, and pelletized with 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 4. The blending amount of the (K) fibrous reinforcing material in 100 parts by weight of the thermoplastic polyester resin composition is described as "the content of the (K) fibrous reinforcing material in the thermoplastic polyester resin composition".

From the comparison of Examples 1 to 14 and Comparative Examples 1 to 13, and Examples 15 to 22 and Comparative Examples 14 to 17, (A) component (B) and (C) component with respect to 100 parts by weight of the thermoplastic polyester resin. A material having an excellent balance of mechanical characteristics, flame retardancy, tracking resistance, and long-term hydrolysis resistance was obtained in a specific range of the amounts of the component (D) and the component (E).

By comparing Example 1 and Comparative Examples 10 to 12, mechanical properties and tracking resistance are obtained by blending the component (D), which contains aluminum atoms and silicon atoms and has a tube shape. Excellent material was obtained.

Claims (16)

With respect to 100 parts by weight of (A) thermoplastic polyester resin, (B) 0.1 to 30 parts by weight of phosphorus-based flame retardant, (C) 0.1 to 30 parts by weight of nitrogen-based flame retardant, (D) aluminum atom and 0.01-10 parts by weight of nanotubes containing silicon atoms, having a tubular morphology, an average outer diameter of the tube of 1 to 100 nm, and an average length of the tube of 100 nm to 3,000 nm, and ( E) A thermoplastic polyester resin composition containing 0.1 to 10 parts by weight of a polyfunctional epoxy compound. The thermoplastic polyester resin composition according to claim 1, wherein the nanotube (D) is a halloysite nanotube. The ratio (%) of the weight portion of the (D) nanotube to the total amount of the weight portion of the (B) phosphorus-based flame retardant and the weight portion of the (D) nanotube (((A) component (D) component with respect to 100 parts by weight) (Parts by weight) ÷ (parts by weight of component (B) with respect to 100 parts by weight of component (A) + parts by weight of component (D) with respect to 100 parts by weight of component (A)) × 100) is 0.5 to 20% The thermoplastic polyester resin composition according to claim 1 or 2. The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein the acid point inside the tube of the nanotube (D) is coated with a basic compound. The thermoplastic polyester resin composition according to any one of claims 1 to 4, wherein the pH of the nanotube (D) is 6 to 8. The thermoplastic polyester resin according to any one of claims 1 to 5, wherein the phosphorus-based flame retardant is at least one selected from a condensed phosphoric acid ester compound, a phosphinic acid and a metal salt thereof, and a phosphazene compound. Composition. The thermoplastic polyester resin composition according to any one of claims 1 to 6, wherein the polyfunctional epoxy compound (E) is a novolak type epoxy. The thermoplastic polyester resin composition according to any one of claims 1 to 7, wherein 0.1 to 20 parts by weight of (F) thermoplastic elastomer resin is further blended with 100 parts by weight of (A) thermoplastic polyester resin. Stuff. The thermoplastic polyester resin composition according to any one of claims 1 to 8, wherein 0.001 to 1 part by weight of the reaction accelerator (G) is further added to 100 parts by weight of the thermoplastic polyester resin (A). Stuff. The thermoplastic polyester resin composition according to any one of claims 1 to 9, wherein 0.01 to 1 part by weight of (H) drip inhibitor is further added to 100 parts by weight of (A) thermoplastic polyester resin. Stuff. The thermoplastic polyester resin composition according to any one of claims 1 to 10, wherein 0.01 to 30 parts by weight of (I) barium sulfate is further blended with respect to 100 parts by weight of the thermoplastic polyester resin (A). .. (A) 0.1 to 20 weight by weight of (J) hydroxy group-containing resin having a number average molecular weight of 2,000 to 500,000 and a halogen element content of 1,000 ppm or less with respect to 100 parts by weight of the thermoplastic polyester resin. The thermoplastic polyester resin composition according to any one of claims 1 to 11, wherein the parts are blended. The thermoplastic polyester resin composition according to any one of claims 1 to 12, wherein 1 to 100 parts by weight of (K) fibrous reinforcing material is further blended with respect to 100 parts by weight of (A) thermoplastic polyester resin. .. The thermoplastic polyester resin composition according to any one of claims 1 to 13, wherein the thermoplastic polyester resin (A) is a polybutylene terephthalate resin. Tensile strength after exposing a test piece for evaluating tensile properties of ASTM No. 1 dumbbell (1/8 inch thickness) molded according to ASTM D638 (2005) for 50 hours in an atmosphere of 100% relative humidity and 121 ° C. The thermoplastic polyester resin composition according to any one of claims 1 to 14, wherein the retention rate (%) ((tensile strength after exposure / tensile strength before exposure) × 100) is 50% or more. A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of claims 1 to 15.