WO2020100727A1

WO2020100727A1 - Flame-retardant polybutylene terephthalate resin composition

Info

Publication number: WO2020100727A1
Application number: PCT/JP2019/043788
Authority: WO
Inventors: 一也五島
Original assignee: ポリプラスチックス株式会社
Priority date: 2018-11-13
Filing date: 2019-11-08
Publication date: 2020-05-22
Also published as: JP7256822B2; JPWO2020100727A1

Abstract

[Problem] To suppress corrosion of metal members in contact with a molded article composed of a polybutylene terephthalate resin composition in which a halogenated benzyl-acrylate-based flame retardant is used as a flame retardant, and to improve the heat shock resistance of the molded article. [Solution] The problem is solved by suppressing the amount of halogenated aromatic compounds such as chlorobenzene derived from the halogenated benzyl-acrylate-based flame retardant used as a flame retardant in a polybutylene terephthalate resin composition to which a heat shock resistance improver and a flame retardant are added.

Description

Flame-retardant polybutylene terephthalate resin composition

The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a method for producing the same.

Polybutylene terephthalate resin (PBT resin) is widely used as an engineering plastic for various purposes such as automobile parts and electric / electronic equipment parts because of its excellent mechanical properties, electrical properties, and heat resistance. Of these, in electrical and electronic equipment parts applications, the materials used are required to be flame-retardant in order to prevent ignition due to tracking, etc. Since various electric and electronic parts are mounted, the demand for flame-retardant materials is expanding. Here, since the polybutylene terephthalate resin itself lacks in flame retardancy, it is used as a flame retardant resin composition to which a flame retardant is added.

A halogenated benzyl acrylate flame retardant is one of the flame retardants added to such a polybutylene terephthalate resin, and an example thereof is polypentabromobenzyl acrylate (PBBPA) introduced in Patent Document 1. .. As a method for producing this flame retardant, paragraph [0004] of Patent Document 1 describes that a monomer, pentabromobenzyl acrylate, is polymerized in ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether, or in chlorobenzene. The method is illustrated.

Among these, when chlorobenzene, which is a halogenated aromatic compound, is used as a solvent for polymerization, a small amount of chlorobenzene will eventually exist as an impurity in PBBPA. The flame-retardant polybutylene terephthalate resin composition added with this also contains chlorobenzene.

This chlorobenzene is generally a stable compound, but when it comes into contact with a metal such as a metal oxide or an alkali metal compound in a high temperature environment, dechlorination occurs and a compound such as hydrogen chloride is generated. Sometimes. Therefore, when a composition containing the same is used in a molded product that comes into contact with a metal member such as insert molding or terminal press-fitting, a problem may occur in which the metal member is corroded. Here, in the above-mentioned electric / electronic component application, since a molded article made of the polybutylene terephthalate resin composition is used as an electrically insulating member in combination with a metal member which is a conductive portion, the metal member may not be corroded. Required. Further, not only when the molded product is used in combination with a metal member, but also in the process of molding the molded product itself, from the viewpoint of corrosion of a metal member such as a screw or a cylinder of a molding machine, or a metal mold, this is suppressed Required to do so.

By the way, since polybutylene terephthalate resin is a crystalline thermoplastic resin, mold shrinkage due to crystallization after molding and post-shrinkage in the usage environment are likely to occur. Further, since the linear expansion coefficient is larger than that of a metal, a molded article made of the polybutylene terephthalate resin composition used in combination with the metal member as described above is a resin when exposed to an environment where heating and cooling are repeated. Molding shrinkage and post-shrinkage occur together with the strain caused by the difference in linear expansion coefficient between metal and resin, and the molded product is apt to be damaged by cracks (so-called heat shock destruction). .. Therefore, in Patent Document 2, as a technique for improving the heat shock resistance of the polybutylene terephthalate resin, in order to improve the heat shock resistance of the insert-molded product using polybutylene terephthalate or the like, in the vicinity of the fragile portion of the molded product. A technique of providing a stress concentration part is disclosed.

Japanese Patent Publication No. 2015-532350 JP, 2013-103472, A

The present invention, in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant, suppresses damage due to heat shock when a molded article made of the composition is used in an environment where heating and cooling are repeated. In addition, it is an object to suppress corrosion of a metal member that comes into contact with the molded product.

The present inventor, in the course of research to solve the above problems, uses a halogenated benzyl acrylate flame retardant as a flame retardant, and in a polybutylene terephthalate resin composition containing a specific heat shock resistance improver, the polybutylene terephthalate It is possible to solve the above problems by suppressing the amount of halogenated aromatic compounds such as chlorobenzene contained in the resin composition, particularly by suppressing the amount of halogenated aromatic compounds derived from the manufacturing process of the flame retardant. Heading out, the present invention has been completed.

That is, the present invention relates to the following (1) to (12).
(1) 100 parts by weight of (A) polybutylene terephthalate resin, (B) 3 to 50 parts by weight of halogenated benzyl acrylate flame retardant, (C) 5 to 100 parts by weight of resin for improving heat shock resistance, D) Heat-shock resistance-improving filler 10 to 200 parts by mass and (E) Heat shock resistance-improving additive 0.1 to 30 parts by mass are contained, and headspace gas chromatography (150 ° C., 1 Is a flame-retardant polybutylene terephthalate resin composition having a halogenated aromatic compound content other than the flame retardant content of less than 0.5 ppm as measured by time heating), wherein the heat shock resistance improving additive is A flame-retardant polybutylene terephthalate resin composition comprising one or more selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, an aromatic polycarboxylic acid ester, and a combination thereof.
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate flame retardant (B) contains a brominated acrylic polymer represented by the general formula (I).

(In the formula, X is a hydrogen atom or a bromine atom, at least one or more X is a bromine atom, and m is a number of 10 to 2000.)
(3) The flame-retardant polybutylene terephthalate resin composition according to (1) or (2), wherein the halogenated benzyl acrylate flame retardant (B) contains polypentabromobenzyl acrylate.
(4) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (3), wherein the halogenated aromatic compound other than the flame retardant contains halogenated benzene.
(5) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (4), wherein the halogenated aromatic compound other than the flame retardant contains chlorobenzene.
(6) Containing a polybutylene terephthalate resin and a halogenated benzyl acrylate flame retardant having a protic compound content of 10 to 1000 ppm as measured by a headspace gas chromatographic method (180 ° C., heating for 1 hour), The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5).
(7) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (6), wherein the polybutylene terephthalate resin contains a linear low molecular weight substance in an amount of 50 to 1000 ppm.
(8) The flame-retardant polybutylene terephthalate resin composition according to (6), wherein the protic compound is derived from a polymerization solvent for a halogenated benzyl acrylate-based flame retardant.
(9) The flame-retardant polybutylene terephthalate resin composition according to (6) or (8), wherein the protic compound is an alkoxy alcohol.
(10) A method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (9), which comprises a step (B) for producing a halogenated benzyl acrylate flame retardant, The production method, wherein the content of the halogenated aromatic compound in the solvent used in the step is 1000 ppm or less.
(11) The production method according to (10), wherein the halogenated aromatic compound is not used as a solvent in the production process of the halogenated benzyl acrylate flame retardant (B).
(12) In the step of producing the halogenated benzyl acrylate-based flame retardant (B), one or more solvents selected from the group consisting of ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are used as a solvent, (10) or The production method according to (11).

According to the present invention, in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant, by suppressing the amount of halogenated aromatic compounds such as chlorobenzene in the production process of the flame retardant, Corrosion of a metal member combined with a molded article using the butylene terephthalate resin composition can be suppressed, and heat shock destruction in an environment in which the molded article is repeatedly heated and cooled can be suppressed.

It is a figure which shows the test piece used for the heat shock resistance test, Comprising: (A) is a perspective view and (B) is a top view. It is a figure which shows the insert member of the test piece shown in FIG. 1, (A) is a perspective view, (B) is a top view. It is the figure which showed the example of the molded article used when measuring melt fluidity in this invention.

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention. In the present invention, A to B means A or more and B or less.

[Flame Retardant Polybutylene Terephthalate Resin Composition]
Hereinafter, details of each component of the flame-retardant polybutylene terephthalate resin composition of the present embodiment will be described with examples.

((A) Polybutylene terephthalate resin)
The (A) polybutylene terephthalate resin (PBT resin) is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as a C _1-6 alkyl ester or acid halide) and an alkylene having at least 4 carbon atoms. It is a polybutylene terephthalate resin obtained by polycondensing a glycol component containing glycol (1,4-butanediol) or its ester-forming derivative (acetylated product, etc.). In the present embodiment, the (A) polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin, but may be a copolymer containing 60 mol% or more of butylene terephthalate units.

The amount of the terminal carboxyl group of the (A) polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, more preferably 25 meq / kg or less.

The intrinsic viscosity of the (A) polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 0.60 dL / g or more and 1.5 dL / g or less, and 0.65 dL / g or more 1 More preferably, it is not more than 0.2 dL / g. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the polybutylene terephthalate resin composition obtained has particularly excellent moldability. Also, the intrinsic viscosity can be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. You can The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.

In the preparation of the (A) polybutylene terephthalate resin, when an aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4, C _8-14 aromatic dicarboxylic acid such as 4′-dicarboxydiphenyl ether; C _4-16 alkanedicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid; C _5-10 such as cyclohexanedicarboxylic acid Cycloalkanedicarboxylic acids; ester-forming derivatives of these dicarboxylic acid components (C _1-6 alkyl ester derivatives, acid halides, etc.) can be used. These dicarboxylic acid components can be used alone or in combination of two or more.

Among these dicarboxylic acid components, C _8-12 aromatic dicarboxylic acids such as isophthalic acid, and C _6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.

In the preparation of the (A) polybutylene terephthalate resin, when a glycol component other than 1,4-butanediol is used as a comonomer component, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol , C _2-10 alkylene glycols such as neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; cycloaliphatic compounds such as cyclohexanedimethanol and hydrogenated bisphenol A Diol; aromatic diol such as bisphenol A, 4,4'-dihydroxybiphenyl; C _2-4 alkylene oxide of bisphenol A such as bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct Adducts; or ester-forming derivatives of these glycols (acetylated products etc.) can be used. These glycol components can be used alone or in combination of two or more.

Among these glycol components, C _2-6 alkylene glycols such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, and alicyclic diols such as cyclohexanedimethanol are more preferable.

Examples of comonomer components that can be used in addition to the dicarboxylic acid component and the glycol component include, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl and the like. Aromatic hydroxycarboxylic acids; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components Formable derivatives (C _1-6 alkyl ester derivatives, acid halides, acetylated compounds, etc.) can be mentioned.

The content of the (A) polybutylene terephthalate resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 70% by mass based on the total mass of the resin composition. Is more preferable.

((B) Halogenated benzyl acrylate flame retardant)
Examples of the (B) halogenated benzyl acrylate flame retardant used in the present invention include a brominated acrylic polymer represented by the following general formula (I).

X in the formula is a hydrogen atom or a bromine atom, and at least one or more is a bromine atom. The number of X is 1 to 5 in one structural unit, but it is preferably 3 to 5 from the effect of flame retardancy. The average degree of polymerization m is 10 to 2000, preferably 15 to 1000. When the average degree of polymerization is lower than 10, the thermal stability deteriorates, and when it exceeds 2000, the moldability of the added polybutylene terephthalate resin deteriorates. The above-mentioned brominated acrylic polymers may be used alone or in combination of two or more.

The (B) halogenated benzyl acrylate-based flame retardant used in the present invention is, in addition to the above-mentioned brominated acrylic polymer which is the flame retardant itself, an impurity such as a solvent at the time of polymerization or a decomposed product of the brominated acrylic polymer. Although it may contain a halogenated aromatic compound derived from it, the content of the halogenated aromatic compound other than the flame retardant, which is such an impurity, is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 30 ppm or less. , Particularly preferably 10 ppm or less. The content of the halogenated aromatic compound other than the flame retardant is measured by, for example, a gas chromatograph of a gas generated when a sample obtained by pulverizing the (B) halogenated benzyl acrylate flame retardant is heat-treated in the head space. It can be determined from the amount of gas generated from the halogenated aromatic compound.

The brominated acrylic polymer represented by the general formula (I) is obtained by polymerizing benzyl acrylate containing bromine alone, but benzyl methacrylate having a similar structure may be copolymerized. Bromine-containing benzyl acrylates include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, or mixtures thereof. Of these, pentabromobenzyl acrylate is preferable. Examples of benzyl methacrylate that is a copolymerizable component include methacrylates corresponding to the above-mentioned acrylates. Furthermore, it is possible to copolymerize with vinyl monomers, acrylic acid, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate. Examples thereof include methacrylic acid esters, styrene, acrylonitrile, fumaric acid, unsaturated carboxylic acids such as fumaric acid or anhydrides thereof, vinyl acetate, vinyl chloride and the like. Further, crosslinkable vinyl monomers, xylylene diacrylate, xylylene dimethacrylate, tetrabromoxylylene diacrylate, tetrabromoxylylene dimethacrylate, butadiene, isoprene, and divinylbenzene can also be used. These are used in an equimolar amount or less, preferably 0.5 times or less the molar amount of benzyl acrylate or benzyl methacrylate.

As an example of the method for producing the above-mentioned brominated acrylic polymer as a method for producing the halogenated benzyl acrylate-based flame retardant (B), the brominated acrylic monomer is solution-polymerized or bulk-polymerized to a predetermined degree of polymerization. A method of reacting can be mentioned. In the case of solution polymerization, the content of the halogenated aromatic compound in the solvent is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, and particularly preferably 100 ppm or less. preferable. It is more preferable not to use halogenated benzene or a halogenated aromatic compound such as chlorobenzene as the solvent. Further, as the solvent in the solution polymerization, aprotic solvents such as ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are preferable. However, in the present invention, as will be described later, since the resin composition contains a protic compound, a polymerization solvent containing a protic compound can be used.

The (B) halogenated benzyl acrylate-based flame retardant such as the brominated acrylic polymer described above contains water and / or an alkaline (earth) metal ion in order to remove reaction by-products such as residual sodium polyacrylate. It is preferable to wash with the contained aqueous solution. In the present specification, “containing an alkali (earth) metal ion” means containing an alkali metal ion and / or an alkaline earth metal ion. An aqueous solution containing an alkali (earth) metal ion can be easily obtained by adding an alkali (earth) metal salt to water, but an alkali (earth) metal containing no chloride ion, phosphate ion, etc. Certain hydroxides (eg calcium hydroxide) are optimal. When calcium hydroxide is used as the alkali (earth) metal salt, calcium hydroxide is generally soluble in about 0.126 g in 100 g of water at 20 ° C., and the concentration of the aqueous solution is not particularly limited as long as the solubility is reached. .. In addition, the method of washing with water and / or an aqueous solution containing an alkali (earth) metal ion is not particularly limited, and the brominated acrylic polymer may contain water and / or an alkali (earth) metal ion for an appropriate time. A method such as immersing in an aqueous solution may be used. The brominated acrylic polymer that has been washed with an aqueous solution containing water and / or an alkaline (earth) metal ion generally has a dry solid content of 100 ppm or less in the hot water extract. When such a brominated acrylic polymer is used, almost no foreign matter is generated on the surface of the molded product.

The flame-retardant polybutylene terephthalate resin composition of the present invention has a content of halogenated aromatic compound other than the flame retardant, which is the above-mentioned impurity, is less than 0.5 ppm, preferably 0.3 ppm or less, more preferably Is 0.1 ppm or less. In the flame-retardant polybutylene terephthalate resin composition, the content of the halogenated aromatic compound other than the flame retardant is in the above range, in the molded article using the polybutylene terephthalate resin composition, in combination with a metal member When used as well, corrosion of the metal member can be suppressed, and heat shock destruction when the molded product is exposed to an environment in which heating and cooling are repeated can be suppressed. The content of the halogenated aromatic compound other than such a flame retardant, for example, a sample obtained by pulverizing the polybutylene terephthalate resin composition, the generated gas at the time of heat treatment in the head space, measured by gas chromatography, It can be determined from the amount of gas generated from the halogenated aromatic compound.

▽ In making the above resin flame-retardant, it is preferable to use an antimony-based flame retardant auxiliary together. Typical examples of the flame retardant aid include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate and the like. In the polybutylene terephthalate resin composition of the present invention, it is preferable to use antimony pentoxide and sodium antimonate from the viewpoint of further improving the heat shock resistance. The addition amount of the antimony-based flame retardant auxiliary may be appropriately set in consideration of heat shock resistance, mechanical properties and fluidity, but 1 part by mass or more and 30 parts by mass or more with respect to 100 parts by mass of the polybutylene terephthalate resin. The following is preferable. Further, it is also preferable to use an anti-dripping agent such as polytetrafluoroethylene together for the purpose of preventing the fire from spreading due to the dropping of the burned resin.

The range of addition of the halogenated benzyl acrylate flame retardant and antimony flame retardant aid (B) to the resin is 3 to 50 parts by mass of the polymer with respect to 100 parts by mass of the polybutylene terephthalate resin, and 5 to 40 parts by mass. It is preferably 10 parts by mass and more preferably 10 to 35 parts by mass. The antimony flame retardant aid is preferably in the range of 1 to 40 parts by mass. If the amounts of the brominated acrylic polymer and antimony flame retardant aid added are too small, sufficient flame retardancy cannot be imparted, and if the amounts are too large, the physical properties of the molded product may deteriorate.

(Protic compound) In the present invention, the protic compound means a compound having a proton (hydrogen ion) donating property. In the present invention, examples of the protic compound include compounds derived from a polymerization solvent for a halogenated benzyl acrylate flame retardant, an alkoxy alcohol is preferable, and a C1 to C20 alkoxy C1 to C20 alcohol is more preferable. As the C1-C20 alkoxy C1-C20 alcohol, methoxy C1-C20 alcohol and C1-C20 alkoxy ethanol are more preferable, and methoxy ethanol is still more preferable.

The C1 to C20 dialkoxy C1 to C20 alcohol is also preferable as the protic compound, and 3,3-diethoxypropanol is preferable as the C1 to C20 dialkoxy C1 to C20 alcohol.

In the present invention, examples of the protic compound include compounds derived from a raw material of a halogenated benzyl acrylate flame retardant, an aromatic carboxylic acid is preferable, and benzoic acid is more preferable. In the present invention, the protic compound is preferably derived from the polymerization solvent rather than derived from the halogenated benzyl acrylate flame retardant raw material.

In the present invention, the amount of the protic compound contained in the halogenated benzyl acrylate flame retardant is preferably 10 to 1000 ppm, more preferably 100 to 800 ppm, in the halogenated benzyl acrylate flame retardant. More preferably, it is 300 to 500 ppm. When the amount of the protic compound contained in the halogenated benzyl acrylate flame retardant is less than 10 ppm, it becomes difficult to obtain the effect of improving the fluidity of the flame retardant polybutylene terephthalate resin composition. When the amount of the protic compound contained in the halogenated benzyl acrylate flame retardant exceeds 1000 ppm, the amount of gas generated during compounding increases, and strand breakage easily occurs during pelletization.

(Linear low molecular weight compounds)
In the flame-retardant polybutylene terephthalate resin composition of the present invention, the protic compound contained in the halogenated benzyl acrylate flame retardant is a linear product which is a reaction product with a linear low molecular weight substance (oligomer) of the polybutylene terephthalate resin. It is presumed that a compound is produced, which brings about the same effect as that of the plasticizer and improves the fluidity of the flame-retardant polybutylene terephthalate resin composition. For this reason, the polybutylene terephthalate resin preferably contains a linear low molecular weight substance. The amount of the linear low molecular weight substance contained in the polybutylene terephthalate resin is preferably 50 to 1000 ppm, more preferably 70 to 700 ppm, and further preferably 100 to 200 ppm. When the amount of the linear low molecular weight substance is less than 50 ppm, it is difficult to obtain the effect of improving the fluidity of the flame-retardant polybutylene terephthalate resin composition, and when it exceeds 1000 ppm, Mold Deposition (die deposit) is likely to occur. Therefore, it is not preferable.

((C) Resin for improving heat shock resistance)
The resin for improving heat shock resistance (C) used in the present invention is required when a molded article made of the flame-retardant polybutylene terephthalate resin composition of the present invention is used in an environment in which heating and cooling are repeated. It is added to improve heat shock resistance.

As the resin (C) for improving heat shock resistance, an elastic body such as rubber or elastomer is used in the sense that by imparting toughness to the polybutylene terephthalate resin composition, the strain generated in the molded article can be absorbed. It is preferable to use, specifically, an olefin elastomer, a core shell elastomer, a diene elastomer, a polyester elastomer, a urethane elastomer, a silicone elastomer, a styrene elastomer, a polyamide elastomer, and the like. Or, two or more kinds can be used in combination.

Examples of the olefin elastomer include ethylene-propylene copolymer (EP copolymer), ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-diene copolymer (EPD copolymer), Copolymer containing at least one unit selected from ethylene-propylene-butene copolymer, ethylene-vinyl acetate copolymer, EP copolymer and EPD copolymer, olefin and (meth) acrylic monomer With ethylene, ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, α-olefin / α, β-unsaturated carboxylic acid (ester) / α, β-unsaturated carboxylic acid glycidyl ester An original copolymer, an ethylene-based copolymer obtained by copolymerizing an ethylene (co) polymer with maleic anhydride or glycidyl methacrylate, and the like are included. Preferred olefin elastomers include EP copolymers, EPD copolymers, and copolymers of olefins and (meth) acrylic monomers, with ethylene ethyl acrylate being particularly preferred. These olefinic elastomers can be used alone or in combination of two or more.

The core-shell elastomer is a polymer in which the core layer is composed of a rubber component (soft component) and the shell layer is composed of a hard component, and it is preferable to use acrylic rubber or the like as the rubber component of the core layer. The rubber component used in the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (eg −10 ° C. or lower), and −20 ° C. or lower (eg −180 ° C. or higher and −25 ° C. or lower). It is more preferably −30 ° C. or lower (eg −150 ° C. or higher and −40 ° C. or lower).

When an acrylic rubber is used as the rubber component, a polymer obtained by polymerizing an acrylic monomer such as an alkyl acrylate as a main component is preferable. The alkyl acrylate used as the monomer of the acrylic rubber is preferably a C ₁ to C ₁₂ alkyl ester of acrylic acid such as butyl acrylate, and more preferably a C ₂ to C ₆ alkyl ester of acrylic acid.

The acrylic rubber may be a homopolymer or a copolymer of acrylic monomers. When the acrylic rubber is a copolymer of acrylic monomers, it may be a copolymer of acrylic monomers or a copolymer of acrylic monomers and another unsaturated bond-containing monomer. When the acrylic rubber is a copolymer, the acrylic rubber may be a copolymer of a crosslinkable monomer.

A vinyl polymer is preferably used for the shell layer. The vinyl polymer is, for example, at least one monomer selected from aromatic vinyl monomers, vinyl cyanide monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. It can be obtained by polymerization or copolymerization. The core layer and the shell layer of the core-shell type elastomer may be bonded by graft copolymerization. This graft copolymerization is obtained by adding a graft cross-linking agent that reacts with the shell layer during the polymerization of the core layer, if necessary, to give a reactive group to the core layer, and then to form the shell layer. When a silicone rubber is used as the graft crossing agent, an organosiloxane having a vinyl bond or an organosiloxane having a thiol is used, and preferably acryloxysiloxane, methacryloxysiloxane or vinylsiloxane.

As the polyester-based elastomer, both an ester-ester type in which the hard segment and the soft segment have a polyester-based unit structure and an ester-ether type in which the soft segment has a polyether-based unit structure can be preferably used. The former is more preferable in terms of heat resistance and the latter is more preferable in terms of dimensional accuracy. An aromatic polyester unit such as polybutylene terephthalate or polyethylene terephthalate can be preferably used as the polyester unit structure of the heart segment, and an aliphatic polyester unit such as polyethylene adipate, polybutylene adipate, or polycaprolactone is preferably used as the polyester unit of the soft segment. As the polyether unit of the soft segment, polyethylene glycol or polytetramethylene glycol can be preferably used, but the soft segment polyether unit is not limited thereto.

Examples of urethane elastomers include reacting diisocyanates such as 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, tolylene diisocyanate and hexamethylene diisocyanate with glycols such as ethylene glycol and tetramethylene glycol. A block copolymer having polyurethane as a hard segment and polyether or polyethylene adipate such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polyethylene adipate, polybutylene adipate, aliphatic polyester such as polycaprolactone as a soft segment can be mentioned. However, it is not limited to this.

Examples of the styrene elastomer include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene. -Butadiene-styrene copolymer, acrylonitrile-styrene-epoxy group-containing vinyl copolymer, and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

Examples of polyamide elastomers include, but are not limited to, block copolymers having nylon 6, nylon 66, nylon 11, nylon 12, etc. as the hard segment and polyether or aliphatic polyester as the soft segment. Not a thing. Although not strictly classified as an elastomer, an aliphatic polyamide can also be used as the polyamide elastomer in the present invention.

The amount of the (C) resin for improving heat shock resistance added is 5 to 100 parts by mass, or 10 to 90 parts by mass or 20 to 80 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin. However, in the case of a resin having low flame retardance, the content of the resin for improving heat shock resistance is the flame-retardant polybutylene of the present invention because the combustibility of the composition may be deteriorated by adding a large amount thereof. It is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, based on the entire terephthalate resin composition.

(D) As a filler for improving heat shock resistance, by reducing the shrinkage rate or linear expansion coefficient of the polybutylene terephthalate resin, it is possible to reduce the strain generated in the molded product, thereby reducing the processing temperature range of the resin molded product. Inorganic fillers and metal fillers, which have a small shrinkage ratio and linear expansion coefficient in the operating temperature range, are preferable, and in a molded product used as an insulating member to be combined with a metal member, an inorganic filler is used in order to ensure insulation. Is particularly preferably used.

The shape of the filler (D) for improving heat shock resistance may be any of fibrous filler, plate-like filler, spherical filler, powdery filler, curved filler, amorphous filler and combinations thereof. Although it is also possible to use, it is preferable to reduce the anisotropy of shrinkage and linear expansion in order to suppress the destruction due to heat shock. Therefore, it is desirable that the filler itself has small anisotropy, It is more preferable to use a plate-like filler, a spherical filler, a powdery filler, or the like, particularly a filler having an aspect ratio close to 1. On the other hand, when a fibrous filler such as glass fiber is used, the effect of improving mechanical properties such as tensile strength is great, but the anisotropy of shrinkage tends to increase due to the orientation of the fibrous filler. Therefore, as fibrous fillers, short fibers such as milled fibers and whiskers, and flat shapes such as cocoon-shaped or elliptical / oval cross-sections (for example, ratio of cross-section long diameter / short diameter is 1.3 to 10) It is more preferable to use a fiber having a relatively small aspect ratio, such as a fiber. In particular, it is preferable to use glass fibers having a flat cross section because both heat shock resistance and mechanical properties can be improved.

Specific examples of the plate-like filler include plate-like talc, mica, glass flakes, metal pieces and combinations thereof, and specific examples of the spherical filler include glass beads, glass balloons, spherical silica and Examples of the powdery filler include glass powder, talc powder, quartz powder, quartz powder, kaolin, clay, diatomaceous earth, wollastonite, silicon carbide, silicon nitride, metal powder, and inorganic acid metal. Powder of salt (calcium carbonate, zinc borate, calcium borate, zinc stannate, calcium sulfate, barium sulfate, etc.), powder of metal oxide (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.), metal Powders of hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (boehmite), etc.), metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.), and combinations thereof. Can be mentioned. From the viewpoint of metal corrosiveness, the content of the free inorganic acid contained in the filler (D) for improving heat shock resistance is preferably 0.5% by mass or less.

(D) The size of the heat shock resistance-improving filler can be appropriately selected in consideration of the balance between the warp reduction effect and the mechanical characteristics, fluidity and the like. For example, as talc, talc having a volume average particle size of 1 to 10 μm or compressed fine powder talc having a bulk specific gravity of 0.4 to 1.5 can be suitably used, and as mica, a volume average particle size of 10 to Mica of 60 μm can be preferably used.

These (D) fillers for improving heat shock resistance may be surface-treated (surface-coated) with an inorganic compound and / or an organic compound. As the inorganic compound used for the surface treatment, for example, aluminum hydroxide, alumina, silica, zirconia, zirconium hydroxide, zirconia hydrate, cerium oxide, cerium oxide hydrate, aluminum such as cerium hydroxide, silicon, zirconium. Preferred are inorganic oxides such as cerium and cerium, and hydroxides. Further, these inorganic compounds may be hydrates. Among these, aluminum hydroxide and silica are preferable, and when silica is used, a silica hydrate represented by SiO ₂ .nH ₂ O is particularly preferable. The organic compound used for the surface treatment is preferably an epoxy compound or an amine compound, and an epoxy compound such as bisphenol A type epoxy or novolac type epoxy and an amine compound such as monoethanolamine, diethanolamine, triethanolamine or dichlorohexylamine. Can be exemplified as a more preferable compound.

The addition amount of the (D) filler for improving heat shock resistance is 10 to 200 parts by mass, or 20 to 180 parts by mass or 30 to 150 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin. .. The addition amount of the (D) filler for improving heat shock resistance can be appropriately selected in consideration of the balance between the effect of improving heat shock resistance and mechanical properties, fluidity and the like.

Examples of the additive (E) for improving heat shock resistance include a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, and an aromatic polycarboxylic acid ester, and one kind or a combination of two or more kinds thereof is used. Can be used.

As the carbodiimide compound, a compound having at least one carbodiimide group represented by (-N = C = N-) in the molecule can be used. Such a carbodiimide compound can be used, for example, in the presence of a suitable catalyst. It can be produced by heating an organic isocyanate and performing a decarboxylation reaction.

Examples of the carbodiimide compound include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6 ′ -Tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-di-cyclohexylcarbodiimide, N, N′-di-o-triylcarbodiimide, N, N′-diphenyl Carbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide , N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di- p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-toluylcarbodiimide, N, N'-benzylcarbodiimide, N -Octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N -Benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di-o-isopropylphenylcarbodiimid N, N'-di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2, 6-diethylphenylcarbodiimide, N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4 , 6-trimethylphenylcarbodiimide, N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide and other mono- or dicarbodiimide compounds, Poly (1,6-hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4, 4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly ( And polycarbodiimides such as poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), and poly (triisopropylphenylenecarbodiimide). As the polycarbodiimide, a xylylene-based polycarbodiimide synthesized from m-xylylene diisocyanate, p-xylene diisocyanate, m-tetramethyl xylylene diisocyanate, p-tetramethyl xylene diisocyanate, or the like can be used. Further, a carbodiimide compound obtained by reacting a diisocyanate compound with a diol compound such as a polyether polyol, a polyester polyol, a polycarbonate polyol, a silicone diol, a polyolefin polyol, a polyurethane polyol, and an alkylene (21 to 22 carbon atoms) diol can also be used. Among these, aromatic carbodiimides such as N, N′-di-2,6-diisopropylphenylcarbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable from the viewpoint of heat resistance, and Carbodiimides are preferred.

The epoxy compound may be any compound containing an epoxy group in its molecular structure, and glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, and alicyclic epoxy compounds can be preferably used.

Examples of the glycidyl ether compound include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, Of epichlorohydrin with pentaerythritol polyglycidyl ether, bisphenols such as 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane and bis (4-hydroxyphenyl) sulfone Examples thereof include bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, and bisphenol S diglycidyl ether type epoxy resin obtained from the condensation reaction. Among them, bisphenol A diglycidyl ether type epoxy resin is preferable.

Examples of the glycidyl ester compound include glycidyl benzoate, glycidyl p-toluate, glycidyl cyclohexanecarboxylic acid, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl oleate, and glycidyl oleate. Ester, glycidyl linoleate, glycidyl linolenate, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl phthalate, naphthalene dicarboxylic acid diglycidyl ester, diglycidyl bibenzoate, diglycidyl methyl terephthalate , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecane dicarboxylic acid Examples thereof include acid diglycidyl ester, trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidyl ester. Of these, glycidyl benzoate and glycidyl versatate are preferable.

Examples of the glycidyl amine compound include tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl metaxylenediamine, diglycidyl tribromoaniline, tetra Examples thereof include glycidyl bisaminomethylcyclohexane, triglycidyl cyanurate and triglycidyl isocyanurate.

Examples of the glycidyl imide compound include N-glycidyl phthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, Examples thereof include N-glycidyl steramide. Of these, N-glycidyl phthalimide is preferable.

Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, 5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide , N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide and the like.

As other epoxy compounds, epoxidized soybean oil, epoxidized linseed oil, epoxy-modified fatty acid glyceride such as epoxidized whale oil, phenol novolac type epoxy resin, cresol nozolac type epoxy resin, etc. can be used.

Further, as the epoxy compound, an epoxy compound such as a glycidyl ester of an α, β-unsaturated acid, for example, a glycidyl acrylic acid ester, a glycidyl methacrylic acid ester, a glycidyl ethacrylic acid glycidyl ester, etc. may be added to another monomer by random, block or graft copolymerization. Epoxy-modified resin or epoxy-modified elastomer copolymerized with, specifically, a glycidyl group-containing copolymer composed of α-olefin and a glycidyl ester of an α, β-unsaturated acid, or an epoxy group-containing vinyl-based copolymer. A polyorganosiloxane / polyalkyl (meth) acrylate composite rubber graft copolymer obtained by graft-polymerizing a monomer, a styrene / butadiene copolymer elastomer having an epoxy group in its main chain, etc. can also be used. It is also possible to use a brominated epoxy compound (which does not have an epoxy group sealed) used as a flame retardant.

Examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-pentyloxy-2-oxazoline, 2- Hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline , 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2-m-propyl Phenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2 -Pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-cyclopentyl -2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethyl Phenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4 ' -Dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis ( 4-propyl-2-oxazoline), 2, 2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2 ' -Bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m- Phenylene bis (2-oxazoline), 2,2'-o-phenylene bis (2-oxazoline), 2,2'-p-phenylene bis (4-methyl-2-oxazoline), 2,2'-p-phenylene Bis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylene bis (4-methyl-2-oxazoline), 2,2'-m-phenylene bis (4,4'-dimethyl-) 2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2,2 ′ -Octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis ( 4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethane bis (2-oxazoline), 2,2'-cyclohexylene bis (2-oxazoline), 2,2 ' -Diphenylene bis (2-oxazoline) and the like. Further, a polyoxazoline compound containing the above-mentioned compound as a monomer unit can also be mentioned.

Examples of the oxazine compound include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro-4H-1,3-oxazine, 2-propoxy-5,6. -Dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy-5,6-dihydro-4H-1,3-oxazine, 2- Hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3-oxazine, 2-octyloxy-5,6-dihydro-4H-1 , 3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-5,6- Dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-meta Examples include allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine, and further 2,2′-bis (5 , 6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-ethylenebis (5,6-dihydro-) 4H-1,3-oxazine), 2,2′-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-butylenebis (5,6-dihydro-4H-1,3) -Oxazine), 2,2'-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (5,6-dihydro-4H-1,3- Oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-P, P'-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned. Furthermore, the polyoxazine compound etc. which contain the above-mentioned compound as a monomer unit are mentioned.

Among the above oxazoline compounds and oxazine compounds, 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferable.

As the aromatic polyvalent carboxylic acid ester, for example, trimellitic acid ester and pyromellitic acid ester are mentioned as preferable examples, and alkyl ester is particularly preferable. Examples of the alkyl group constituting the alkyl ester include a trioctyl group, a triisodecyl group, a tris (2-ethylhexyl) group, a tributyl group, and the like, and any one or a combination of two or more thereof may be used. These aromatic polycarboxylic acid esters can be used alone or in combination of two or more.

The addition amount of the (E) heat shock resistance improving additive is 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass, and 0 to 100 parts by mass of the polybutylene terephthalate resin. It is more preferably from 0.3 to 10 parts by mass.

The amount of the (E) additive for improving heat shock resistance is the total of carbodiimide group, epoxy group, oxazoline group, oxazine ring, and ester group, with the amount of terminal carboxyl group in the polybutylene terephthalate resin composition being 1. The functional group content may be set to 0.3 to 5 equivalents. The preferred total functional group content is 0.5 to 3 equivalents, more preferably 0.8 to 2 equivalents.

(Additive) Improve the heat shock resistance, which is generally added to a thermoplastic resin or the like in order to impart desired properties other than flame retardancy and heat shock resistance to the composition of the present invention as necessary. Known substances other than those corresponding to the additives for use can be added and used in combination. For example, antioxidants, ultraviolet absorbers, stabilizers such as light stabilizers, antistatic agents, lubricants, release agents, colorants such as dyes and pigments, plasticizers, fluidity improvers, toughness improvers, impact resistance. It is possible to mix any of improvers, resins other than those corresponding to the heat shock resistance improving resin, fillers other than those corresponding to the heat shock resistance improving filler, and the like.

When an inorganic pigment such as carbon black is used as the colorant, it is preferable to use one having an average primary particle diameter of 10 to 100 nm, and one having an average primary particle diameter of 25 to 50 nm, from the viewpoint that the reduction of heat shock resistance can be suppressed. Is more preferable. The average primary particle diameter here is an arithmetic average particle diameter obtained by observing 1000 colorants before being mixed in the resin composition with an electron microscope.

When the colorant is added, it is melt-kneaded with (A) a resin used as a polybutylene terephthalate resin or (C) a resin for improving heat shock resistance, or another resin having a high compatibility with the polybutylene terephthalate resin. Addition in the state of a masterbatch is preferable in that the decrease in heat shock resistance can be further suppressed.

[Method for producing flame-retardant polybutylene terephthalate resin composition]
The form of the flame-retardant polybutylene terephthalate resin composition of the present invention may be a mixture of powder or granules or a melt mixture (melt-kneaded product) such as pellets. A method for producing a polybutylene terephthalate resin composition according to an embodiment of the present invention has a step of producing (B) a halogenated benzyl acrylate flame retardant. Since the process is as described above, the description is omitted here.
The method for producing the polybutylene terephthalate resin composition is not particularly limited, and the polybutylene terephthalate resin composition can be produced using equipment and methods known in the art. For example, necessary components can be mixed and kneaded using a single-screw or twin-screw extruder or another melt-kneading device to prepare pellets for molding. Plural extruders or other melt-kneading devices may be used. Further, all the components may be charged simultaneously from the hopper, or some of the components may be charged from the side feed port.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. The characteristic evaluation was performed by the following methods.

(1) Content of Halogenated Aromatic Compound The materials shown in Table 1 and dry-blended with the composition (parts by mass) were supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ. A sample was prepared by melt-kneading at 260 ° C. and crushing the obtained pellet of the polybutylene terephthalate resin composition. After taking 5 g of the sample and leaving it in a head space of 20 ml for 1 hour at 150 ° C., a device: HP5890A manufactured by Yokogawa Hewlett-Packard Co., and a column: HR-1701 (0.32 mm diameter × 30 m) at 50 ° C. After holding for 1 minute, the temperature was raised at 5 ° C./min, the amount of gas generated from the halogenated aromatic compound was measured by gas chromatography, and the content of the halogenated aromatic compound was shown in ppm. The results are shown in Table 1.

(2) Metal Corrosion The materials dry-blended with the components and composition (parts by mass) shown in Table 1 are supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. 50 g of pellets of the polybutylene terephthalate resin composition obtained by kneading were put in a 300 ml glass stopper bottle together with a silver plate of 1 cm × 1 cm and capped, and the mixture was allowed to stand in a gear oven at 150 ° C. for 500 hours. After that, the surface of the silver plate was visually confirmed, and those without corrosion were evaluated as ◯, and those with corrosion were evaluated as x. The results are shown in Table 1.

(3) Flame retardance The materials dry-blended with the components and composition (parts by mass) shown in Table 1 are supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. The pellets of the polybutylene terephthalate resin composition obtained by kneading and drying are dried at 140 ° C. for 3 hours, and then injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. according to UL94, 125 mm × 13 mm × A strip-shaped test piece having a thickness of 1/32 inch was prepared and evaluated for flammability. The results are shown in Table 1.

(4) Heat shock resistance The materials dry-blended with the components and composition (parts by mass) shown in Table 1 were supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ at 260 ° C. The pellets of the polybutylene terephthalate resin composition obtained by melt-kneading were dried at 140 ° C. for 3 hours, injection-molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and a test piece shown in FIGS. Was insert-molded and the heat shock resistance was evaluated. FIG. 1 is a view showing a test piece 10 that has been insert-molded, and FIG. 2 is a view showing an insert member 2. As shown in FIG. 1, the test piece 10 has a rectangular columnar insert member 2 made of a metal embedded in a rectangular columnar resin member 1 made of a thermoplastic aromatic polyester resin composition. The resin member 1 is molded using the resin composition pellets obtained as described above. As shown in FIG. 2, the insert member 2 is configured to include an upper portion 2a having a quadrangular prism shape, a lower portion 2b having a quadrangular prism shape, and a columnar constricted portion 2c connecting the two between them. In the insert member 2, the lower portion 2b and the constricted portion 2c are embedded in the resin member 1, and the upper portion 2a is exposed from the upper surface of the resin member 1 (see FIG. 1A). Furthermore, as shown in FIG. 1 (B), the corners of the resin member 1 and the insert member 2 are arranged so as to be positioned in mutually different directions. That is, the corner portion of the insert member 2 is arranged so as to face the side surface of the resin member 1. The distance between the tip of the corner of the insert member 2 and the side surface of the resin member 1 is about 1 mm. In the resin member 1, the vicinity of the tip of the corner (sharp corner) of the insert member 2 is a thin portion. Using the thermal shock tester (manufactured by ESPEC Co., Ltd.) for the above-mentioned test piece 10, a cycle of cooling at −40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours was repeated, 20 cycles. The weld part was observed every time. The number of cycles when cracks were generated in the weld portion was used as an index of heat shock resistance, and 200 cycles or more were evaluated as ⊚, 100 cycles or more were evaluated as ◯, and less than 100 cycles was evaluated as x. The results are shown in Table 1.

(5) Strand break The materials dry-blended with the components and composition (parts by mass) shown in Table 1 were supplied to a twin-screw extruder (TEX-30 manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ, and the cylinder temperature was supplied. When the pellets of the polybutylene terephthalate resin composition are obtained by melting and kneading under the conditions of 260 ° C., screw rotation speed 120 rpm, and extrusion rate 15 kg / hr and extruding from a die in a strand shape, strand breakage occurs The generation state was confirmed, and the one in which strand breakage hardly occurred was evaluated as ◯, and the one that occurred frequently was evaluated as x. The results are shown in Table 1.

(6) Melt fluidity After the pellets obtained by the method of (5) were dried at 140 ° C for 3 hours, the box-shaped molded product shown in Fig. 3 (the thickness of the four side walls and the bottom was 0.7 mm) was obtained. ) Was injected at a resin temperature of 260 ° C., a mold temperature of 60 ° C., an injection speed of 100 mm / s, and a holding pressure of 50 MPa, and was completely filled with ◯, and those that could not be filled to the end due to insufficient fluidity were marked with x. evaluated.

(7) Die deposits The strip-shaped test pieces used in the evaluation of (3) above were continuously molded for 6000 shots, and then the surface of the mold cavity was evaluated by visual observation. The case where no metal deposit was observed was evaluated as ◯, and the one where adhesion was observed was evaluated as x.

N. in the table. D. Indicates that it is below the detection limit (0.1 ppm).
The unit of content is parts by mass.

Details of each component shown in Table 1 are as follows. The amount of linear low molecular weight PBT resin was measured by SEC (size exclusion chromatography), and the amount of the protic compound in the flame retardant was measured by headspace gas chromatography (180 ° C., 1 hour heating).
(A-1) PBT resin 1: manufactured by Polyplastics Co., Ltd., a polybutylene terephthalate resin (A-2) PBT resin having a terminal carboxyl group concentration of 20 meq / kg, an intrinsic viscosity of 0.7 dL / g, and a linear low molecular weight substance of 50 ppm. 2: Polyplastics Co., Ltd., terminal carboxyl group concentration 20 meq / kg, intrinsic viscosity 0.7 dL / g, linear low molecular weight polymer 150 ppm polybutylene terephthalate resin (A-3) PBT resin 3: Polyplastics Co., Ltd. Polybutylene terephthalate resin (A-4) PBT resin having a terminal carboxyl group concentration of 20 meq / kg, an intrinsic viscosity of 0.7 dL / g, and a linear low molecular weight substance of 30 ppm: manufactured by Polyplastics Co., Ltd., a terminal carboxyl group concentration of 20 meq. / Kg, intrinsic viscosity 0.7 dL / g, linear low molecular weight substance 1200 ppm polybutylene terephthalate resin (B-1) PBBPA1: polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (other than flame retardant Containing 8 ppm of halogenated aromatic compound and containing 20 ppm of methoxyethanol as a protic compound)
(B-2) PBBPA2: Polypentabromobenzyl acrylate polymerized by using chlorobenzene as a solvent (containing 150 ppm of halogenated aromatic compound other than flame retardant and 20 ppm of methoxyethanol as a protic compound)
(B-3) PBBPA3: Polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (content of halogenated aromatic compound other than flame retardant 8 ppm, methoxyethanol 300 ppm as protic compound)
(B-4) PBBPA4: Polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (containing 8 ppm of halogenated aromatic compound other than flame retardant, and 800 ppm of methoxyethanol as a protic compound)
(B-5) PBBPA5: Polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (content of halogenated aromatic compound other than flame retardant 8 ppm, protic compound 3,3-diethoxypropanol 100 ppm Contained)
(B-6) PBBPA6: Polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (content of halogenated aromatic compound other than flame retardant: 8 ppm, methoxyethanol: 5 ppm as protic compound)
(B-7) PBBPA7: Polypentabromobenzyl acrylate polymerized by using ethylene glycol monomethyl ether as a solvent (content of halogenated aromatic compound other than flame retardant 8 ppm, methoxyethanol 1200 ppm as protic compound)
(C) Resin for improving heat shock resistance EEA: ethylene ethyl acrylate copolymer NUC-6570 manufactured by NUC
EEA-g-BAMMA: NOF CORPORATION graft copolymer of ethylene ethyl acrylate and butyl acrylate-methyl methacrylate Modiper A5300
Core shell: Rohm and Haas Japan Co., glycidyl group-containing acrylic core shell elastomer Paraloid EXL2314
(D) Filler for improving heat shock resistance Circular cross section GF: ECS03T-127 manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 13 μm, average fiber length 3 mm)
Flat cross section GF: manufactured by Nitto Boseki Co., Ltd., CSG3PA830 (oval cross section with major axis 28 μm, minor axis 7 μm (major axis / minor axis ratio = 4), oval circular section glass fiber with average fiber length of 3 mm)
(E) Additive for improving heat shock resistance Carboxylic acid ester: pyromellitic acid ester ADEKAIZER UL100 manufactured by ADEKA
Carbodiimide: Aromatic polycarbodiimide STABAXOL P manufactured by Rhein Chemie Japan
Antimony trioxide: PATOX-M manufactured by Nippon Seiko Co., Ltd.
Antimony pentoxide: manufactured by Nippon Chemical Industry Co., Ltd., Sun Epoch NA1030
Anti-drip agent: Polytetrafluoroethylene resin

Claims

(A) 100 parts by mass of polybutylene terephthalate resin,
(B) 3 to 50 parts by mass of halogenated benzyl acrylate flame retardant,
(C) 5 to 100 parts by mass of resin for improving heat shock resistance,
(D) 10 to 200 parts by mass of a filler for improving heat shock resistance,
(E) 0.1 to 30 parts by mass of an additive for improving heat shock resistance,
A flame-retardant polybutylene terephthalate resin composition containing less than 0.5 ppm of a halogenated aromatic compound other than the flame retardant, as measured by headspace gas chromatography (150 ° C., 1 hour heating), The heat shock resistance improving additive contains one or more selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, an aromatic polycarboxylic acid ester, and a combination thereof. Flame-retardant polybutylene terephthalate resin composition.
The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated benzyl acrylate-based flame retardant (B) contains a brominated acrylic polymer represented by the general formula (I).

(In the formula, X is a hydrogen atom or a bromine atom, at least one or more X is a bromine atom, and m is a number of 10 to 2000.)
The flame-retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the (B) halogenated benzyl acrylate flame retardant contains polypentabromobenzyl acrylate.
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the halogenated aromatic compound other than the flame retardant contains halogenated benzene.
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, wherein the halogenated aromatic compound other than the flame retardant contains chlorobenzene.
A polybutylene terephthalate resin and a halogenated benzyl acrylate flame retardant having a protic compound content of 10 to 1000 ppm as measured by a headspace gas chromatographic method (180 ° C., 1 hour heating). 5. The flame-retardant polybutylene terephthalate resin composition according to any one of items 1 to 5.
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 6, wherein the polybutylene terephthalate resin contains a linear low molecular weight substance in an amount of 50 to 1000 ppm.
The flame-retardant polybutylene terephthalate resin composition according to claim 6, wherein the protic compound is derived from a polymerization solvent for a halogenated benzyl acrylate flame retardant.
The flame-retardant polybutylene terephthalate resin composition according to claim 6 or 8, wherein the protic compound is an alkoxy alcohol.
A method for producing the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 9,
(B) A process for producing a halogenated benzyl acrylate flame retardant, wherein the content of the halogenated aromatic compound in the solvent used in the process is 1000 ppm or less.
11. The production method according to claim 10, wherein a halogenated aromatic compound is not used as a solvent in the production process of (B) a halogenated benzyl acrylate flame retardant.
(B) In the step of producing a halogenated benzyl acrylate flame retardant, one or more solvents selected from the group consisting of ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are used as a solvent. Manufacturing method.