JPWO2020100727A1 - Flame-retardant polybutylene terephthalate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress corrosion of a metal member in contact with a molded product made of a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant, and to improve heat shock resistance of the molded product. And. SOLUTION: In a polybutylene terephthalate resin composition to which a heat shock resistance improver and a flame retardant are added, the amount of a halogenated aromatic compound such as chlorobenzene derived from a halogenated benzyl acrylate flame retardant used as a flame retardant is suppressed. By doing so, the above problem is solved. [Selection diagram] None

Description

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

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

Of these, when chlorobenzene, which is a halogenated aromatic compound, is polymerized as a solvent, a trace amount of chlorobenzene is finally present as an impurity in PBBPA. Then, the polybutylene terephthalate resin composition to which this is added to make it flame-retardant also contains chlorobenzene.

This chlorobenzene is generally a stable compound, but in a high temperature environment, especially when it comes into contact with a metal such as a metal oxide or an alkali metal compound, dechlorination occurs and a compound such as hydrogen chloride is generated. Sometimes. Therefore, when a composition containing this is used for a molded product that comes into contact with a metal member such as insert molding or terminal press fitting, there may be a problem that the metal member is corroded. Here, in the above-mentioned electric / electronic component applications, since a molded product made of a 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 the metal member, but also from the viewpoint of corrosion of the metal member such as the screw, cylinder, or mold of the molding machine in the process of molding the molded product itself, this is suppressed. Is required to do.

By the way, since polybutylene terephthalate resin is a crystalline thermoplastic resin, molding shrinkage due to crystallization after molding and post-shrinkage in the usage environment are likely to occur. Further, since the coefficient of linear expansion is larger than that of metal, when a molded product made of a polybutylene terephthalate resin composition used in combination with the above-mentioned metal member is exposed to an environment where heating and cooling are repeated, the resin is used. Combined with the occurrence of molding shrinkage and post-shrinkage of the molded product and the strain generated due to the difference in linear expansion coefficient between metal and resin, the molded product is liable to be damaged such as cracks (so-called heat shock failure). .. Therefore, as a technique for improving the heat shock resistance of the polybutylene terephthalate resin, in Patent Document 2, 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 for providing a stress concentration portion is disclosed.

Special Table 2015-532350 Japanese Unexamined Patent Publication No. 2013-103472

The present invention suppresses destruction of a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant due to heat shock when a molded product composed of the composition is used in an environment where heating and cooling are repeated. At the same time, it is an object to suppress the corrosion of the metal member in contact with the molded product.

The present inventor uses a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research subject to the above, and in a polybutylene terephthalate resin composition containing a specific heat shock resistance improving agent, the polybutylene terephthalate is used. The above problems can be solved 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. We have found and completed the present invention.

（式中、Ｘは、水素原子または臭素原子であり、少なくとも１つ以上のＸは臭素原子であり、ｍは１０〜２０００の数である。）
（３）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤が、ポリペンタブロモベンジルアクリレートを含有する、（１）または（２）に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（４）前記難燃剤以外のハロゲン化芳香族化合物が、ハロゲン化ベンゼンを含有する、（１）から（３）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（５）前記難燃剤以外のハロゲン化芳香族化合物が、クロロベンゼンを含有する、（１）から（４）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（６）ポリブチレンテレフタレート樹脂と、ヘッドスペースガスクロマトグラフ法（１８０℃、１時間加熱）により測定される、プロトン性化合物の含有量が１０〜１０００ｐｐｍであるハロゲン化ベンジルアクリレート系難燃剤を含有する、（１）から（５）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（７）ポリブチレンテレフタレート樹脂が、線状低分子量体を５０〜１０００ｐｐｍ含有する、（１）から（６）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（８）プロトン性化合物が、ハロゲン化ベンジルアクリレート系難燃剤の重合溶媒に由来する、（６）に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（９）プロトン性化合物が、アルコキシアルコールである、（６）または（８）に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（１０）（１）から（９）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物の製造方法であって、（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程を有し、該工程で用いる溶媒中のハロゲン化芳香族化合物の含有量が１０００ｐｐｍ以下であることを特徴とする、製造方法。
（１１）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてハロゲン化芳香族化合物を用いない、（１０）に記載の製造方法。
（１２）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてエチレングリコールモノメチルエーテル、メチルエチルケトン、エチレングリコールジメチルエーテルおよびジオキサンからなる群から選択される一以上の溶媒を用いる、（１０）又は（１１）に記載の製造方法。That is, the present invention relates to the following (1) to (12).
(1) 100 parts by mass of (A) polybutylene terephthalate resin, (B) 3 to 50 parts by mass of flame retardant based on halogenated benzyl acrylate, (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 and (E) 0.1 to 30 parts by mass of an additive for improving heat shock resistance are contained, and a headspace gas chromatograph method (150 ° C., 1) is contained. A flame-retardant polybutylene terephthalate resin composition having a content of a halogenated aromatic compound other than the flame retardant of less than 0.5 ppm, which is measured by time heating). A flame-retardant polybutylene terephthalate resin composition, which comprises one or more selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, an aromatic polyvalent carboxylic acid ester, and a combination thereof.
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate-based flame retardant 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 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-based flame retardant 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 benzene halide.
(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) Contains a polybutylene terephthalate resin and a halogenated benzyl acrylate-based flame retardant having a protonic compound content of 10 to 1000 ppm, which is measured by a headspace gas chromatograph method (heating at 180 ° C. 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 50 to 1000 ppm of a linear low molecular weight substance.
(8) The flame-retardant polybutylene terephthalate resin composition according to (6), wherein the protonic compound is derived from a polymerization solvent of a halogenated benzyl acrylate-based flame retardant.
(9) The flame-retardant polybutylene terephthalate resin composition according to (6) or (8), wherein the protonic compound is an alkoxy alcohol.
(10) The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (9), which comprises (B) a step for producing a halogenated benzyl acrylate-based flame retardant. A production method, characterized in that 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 process of producing the halogenated benzyl acrylate flame retardant.
(12) In the process of producing the 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 the solvent, (10) or The manufacturing 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, the amount of a halogenated aromatic compound such as chlorobenzene in the production process of the flame retardant is suppressed, thereby suppressing the poly. Corrosion of the metal member combined with the molded product using the butylene terephthalate resin composition can be suppressed, and heat shock destruction in an environment where the molded product is repeatedly heated and cooled can be suppressed.

It is a figure which shows the test piece used in the heat shock resistance test, (A) is a perspective view, (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 a figure which showed the example of the molded article used when measuring the melt fluidity in this invention.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. 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 reference to examples.

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

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

The intrinsic viscosity of the polybutylene terephthalate resin (A) is not particularly limited as long as it does not impair the object of the present invention, but 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 2 dL / g or less. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. It is also possible to adjust the intrinsic viscosity by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be 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. Can be done. The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol under the condition of a temperature of 35 ° C.

When an aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component in the preparation of the polybutylene terephthalate resin (A), 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} alcandicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic _{acid; C 5-10} such as cyclohexanedicarboxylic acid Cycloalkanedicarboxylic acid; an ester-forming derivative of these dicarboxylic acid components (C _1-6 alkyl ester derivative, acid halide, 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} alcandicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferable.

When a glycol component other than 1,4-butanediol is used as the comonomer component in the preparation of the polybutylene terephthalate resin (A), for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol , Neopentyl glycol, C _2-10 alkylene glycol such as 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol, dipropylene glycol; alicyclic type such as cyclohexanedimethanol, hydride bisphenol A, etc. Diols; aromatic diols such as bisphenol A, 4,4'-dihydroxybiphenyl; alkylene oxides _{of C 2-4} of bisphenol A such as 2 mol adducts of ethylene oxide of bisphenol A and 3 mol adducts of propylene oxide of bisphenol A. Additives; or ester-forming derivatives of these glycols (acetylates, 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 the comonomer component that can be used in addition to the dicarboxylic acid component and the glycol component include 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 Examples thereof include formable derivatives (C _1-6 alkyl ester derivatives, acid halides, acetylates, etc.).

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

式中のＸは、水素原子または臭素原子であり、少なくとも１つ以上が臭素原子である。Ｘの数は、一構成単位中１〜５であるが、難燃化の効果から３〜５であることが好ましい。平均重合度ｍは１０〜２０００であり、好ましくは１５〜１０００の範囲である。平均重合度が１０より低いものは、熱安定性が悪化し、２０００を超えると添加したポリブチレンテレフタレート樹脂の成形加工性を悪化させる。また、上記ブロム化アクリル重合体は１種又は２種以上混合使用してもよい。((B) Halogenated benzyl acrylate flame retardant)
Examples of the (B) halogenated benzyl acrylate-based 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 constituent unit, but it is preferably 3 to 5 from the viewpoint of flame retardancy. The average degree of polymerization m is 10 to 2000, preferably in the range of 15 to 1000. If the average degree of polymerization is lower than 10, the thermal stability is deteriorated, and if it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated. Further, the brominated acrylic polymer may be used alone or in combination of two or more.

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

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

(B) As an example of the method for producing a brominated acrylic polymer as a method for producing a halogenated benzyl acrylate-based flame retardant, the brominated acrylic monomer is subjected to solution polymerization or bulk polymerization 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 for 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 described later, since the resin composition contains a protic compound, a polymer solvent containing a protic compound can be used.

The (B) halogenated benzyl acrylate flame retardant such as the above brominated acrylic polymer uses water and / or alkaline (earth) metal ions in order to remove reaction by-products such as residual sodium polyacrylate. It is preferable to wash with the contained aqueous solution. In addition, in this 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, for example, 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 specified as long as it is soluble. .. Further, the method of cleaning with an aqueous solution containing water and / or alkaline (earth) metal ions is not particularly limited, and the brominated acrylic polymer contains water and / or alkaline (earth) metal ions 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 alkaline (earth) metal ions generally has a dry solid content of 100 ppm or less in the hot water extract. When a brominated acrylic polymer is used, foreign matter is hardly generated on the surface of the molded product.

The flame-retardant polybutylene terephthalate resin composition of the present invention contains the above-mentioned impurities, a halogenated aromatic compound other than the flame retardant, of less than 0.5 ppm, preferably 0.3 ppm or less, more preferably. Is 0.1 ppm or less. When the content of the halogenated aromatic compound other than the flame retardant in the flame-retardant polybutylene terephthalate resin composition is within the above range, it is combined with the metal member in the molded product using the polybutylene terephthalate resin composition. In addition, it is possible to suppress corrosion of the metal member, and it is also possible to suppress heat shock destruction when the molded product is exposed to an environment in which heating and cooling are repeated. The content of the halogenated aromatic compound other than the flame retardant is determined by, for example, measuring the gas generated when the sample obtained by crushing the polybutylene terephthalate resin composition is heat-treated in the headspace by a gas chromatograph. It can be obtained from the amount of gas generated from the halogenated aromatic compound.

In making the resin flame-retardant, it is preferable to use an antimony-based flame-retardant aid together. Typical flame-retardant aids 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 enhancing heat shock resistance. The amount of the antimony flame retardant added may be appropriately set in consideration of heat shock resistance, mechanical properties and fluidity, but is 1 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin. The following is preferable. Further, for the purpose of preventing the spread of fire due to the dripping of the burned resin, it is also preferable to use a dripping inhibitor such as polytetrafluoroethylene together.

(B) The range of addition of the halogenated benzyl acrylate flame retardant and the antimon flame retardant 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, more preferably 10 to 35 parts by mass. The antimony-based flame retardant aid is preferably in the range of 1 to 40 parts by mass. If the amount of the brominated acrylic polymer and the antimony-based flame retardant aid added is too small, sufficient flame retardancy cannot be imparted, and if it is too large, the physical properties of the molded product may be deteriorated.

(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 protonic compound include those derived from the polymerization solvent of the halogenated benzyl acrylate flame retardant, and alkoxy alcohol is preferable, and C1 to C20 alkoxy C1 to C20 alcohol is more preferable. As the C1 to C20 alkoxy C1 to C20 alcohol, methoxy C1 to C20 alcohol, C1 to C20 alkoxyethanol are more preferable, and methoxyethanol is further preferable.

Further, the protonic compound is preferably C1 to C20 dialkoxy C1 to C20 alcohol, and the C1 to C20 dialkoxy C1 to C20 alcohol is preferably 3,3-diethoxypropanol.

Further, in the present invention, examples of the protonic compound include those derived from the raw material of the halogenated benzyl acrylate-based flame retardant, and aromatic carboxylic acids are preferable, and benzoic acid is more preferable. In the present invention, the protonic compound is preferably derived from a polymerization solvent rather than the raw material of the halogenated benzyl acrylate flame retardant.

In the present invention, the amount of the protonic compound contained in the halogenated benzyl acrylate-based flame retardant is preferably 10 to 1000 ppm, more preferably 100 to 800 ppm in the halogenated benzyl acrylate-based flame retardant. It is more preferably 300 to 500 ppm. If 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. Further, if the amount of the protonic compound contained in the halogenated benzyl acrylate flame retardant exceeds 1000 ppm, the amount of gas generated during compounding increases, and strand breakage is likely to occur during pelletization.

(Linear low molecular weight body)
In the flame-retardant polybutylene terephthalate resin composition of the present invention, the protonic compound contained in the halogenated benzyl acrylate flame retardant is a linear reaction product of the polybutylene terephthalate resin with a linear low molecular weight substance (oligomer). It is speculated that it produces a compound, which has the same effect as a plasticizer and improves the fluidity of the flame retardant polybutylene terephthalate resin composition. Therefore, the polybutylene terephthalate resin preferably contains a linear low molecular weight substance. The amount of the linear low molecular weight substance contained is preferably 50 to 1000 ppm, more preferably 70 to 700 ppm, and even more preferably 100 to 200 ppm in the polybutylene terephthalate resin. If 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 if it exceeds 1000 ppm, Mold Deposit (mold deposits) is likely to occur. Therefore, it is not preferable.

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

(C) As the resin for improving heat shock resistance, an elastic body such as rubber or an elastomer is used in the sense that by imparting toughness to the polybutylene terephthalate resin composition, it is possible to absorb the strain generated in the molded product. It is preferable to use, and specific examples thereof include olefin-based elastomer, core-shell-based elastomer, diene-based elastomer, polyester-based elastomer, urethane-based elastomer, silicone-based elastomer, styrene-based elastomer, and polyamide-based elastomer, and one of them. , Or two or more types can be used in combination.

Examples of the olefin-based elastoma include an ethylene-propylene copolymer (EP copolymer), an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene-propylene-diene copolymer (EPD copolymer), and the like. Copolymers containing at least one unit selected from ethylene-propylene-butene copolymers, ethylene-vinyl acetate copolymers, EP copolymers and EPD copolymers, olefins and (meth) acrylic monomers Copolymer with, ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, α-olefin / α, β-unsaturated carboxylic acid (ester) / α, β-unsaturated carboxylic acid glycidyl ester-based three Includes an ethylene-based copolymer obtained by copolymerizing a former copolymer or an ethylene (co) polymer with maleic anhydride or glycidyl methacrylate. Preferred olefin-based elastomas include EP copolymers, EPD copolymers, and copolymers of olefins and (meth) acrylic monomers, with ethylene ethyl acrylate being particularly preferred. These olefin-based 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 an acrylic rubber or the like as the rubber component of the core layer. The rubber component used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (for example, -10 ° C. or lower), and preferably -20 ° C. or lower (for example, −180 ° C. or higher and -25 ° C. or lower). More preferably, it is −30 ° C. or lower (for example, −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 alkyl acrylate as a main component is preferable. As the alkyl acrylate used as the monomer of the acrylic rubber, _{the alkyl ester of acrylic acid C 1 to} C ₁₂ such as butyl acrylate is preferable, and the alkyl ester of acrylic acid C _{2 to} C ₆ is more preferable.

The acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer. When the acrylic rubber is a copolymer of an acrylic monomer, it may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer 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-based polymer may be, for example, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, a methacrylic acid ester-based monomer, and an acrylic acid ester monomer. Obtained by polymerization or copolymerization. The core layer and the shell layer of such a core-shell elastomer may be bonded by graft copolymerization. This graft copolymerization is obtained by adding a graft crossover that reacts with the shell layer at the time of polymerization of the core layer, giving a reactive group to the core layer, and then forming the shell layer, if necessary. When a silicone-based rubber is used as the graft crossing agent, an organosiloxane having a vinyl bond or an organosiloxane having a thiol is used, and acroxisiloxane, methacryoxysiloxane, and vinylsiloxane are preferably used.

As the polyester-based elastoma, either an ester-ester type having a polyester-based unit structure in both the hard segment and the soft segment and an ester-ester type having a soft segment having 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. As the polyester unit structure of the heart segment, aromatic polyester units such as polybutylene terephthalate and polyethylene terephthalate can be preferably used, and as the polyester unit of the soft segment, aliphatic polyester units such as polyethylene adipate, polybutylene adipate and polycaprolactone are preferably used. Therefore, as the polyester unit of the soft segment, those such as polyethylene glycol and polytetramethylene glycol can be preferably used, but the present invention is not limited thereto.

Examples of urethane-based elastomas 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. Examples thereof include block copolymers having polyurethane as a hard segment and an aliphatic polyester such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like or an aliphatic polyester such as polyethylene adipate, polybutylene adipate or polycaprolactone as a soft segment. However, it is not limited to this.

Examples of styrene-based elastomas include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, and styrene-ethylene. Examples thereof include a-butadiene-styrene copolymer and an acrylonitrile-styrene-epoxy group-containing vinyl-based copolymer, and these can be used alone or in combination of two or more.

Examples of polyamide-based elastoma include, but are limited to, block copolymers having nylon 6, nylon 66, nylon 11, nylon 12 and the like as hard segments and polyether or aliphatic polyester as soft segments. It's not a thing. Further, although not strictly classified as an elastomer, an aliphatic polyamide can also be used as the polyamide-based elastomer in the present invention.

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

(D) As the filler for improving heat shock resistance, the processing temperature range of the resin molded product is meant to reduce the strain generated in the molded product by reducing the shrinkage rate and the coefficient of linear expansion of the polybutylene terephthalate resin. Inorganic fillers and metal fillers, which have a small coefficient of thermal expansion and linear expansion coefficient in the operating temperature range, are preferable, and in molded products used as insulating members to be combined with metal members, inorganic fillers are used to ensure insulating properties. Is particularly preferable.

(D) The shape of the filler for improving heat shock resistance includes a fibrous filler, a plate-shaped filler, a spherical filler, a powder-like filler, a curved-shaped filler, an amorphous filler, or a combination thereof. However, in order to suppress destruction due to heat shock, it is preferable to reduce the anisotropy of shrinkage and linear expansion, so it is desirable that the filler itself has a small anisotropy. It is more preferable to use a filler having an aspect ratio close to 1, such as a plate filler, a spherical filler, and a powder filler. 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 large, but the anisotropy of shrinkage tends to increase due to the orientation of the fibrous filler. Therefore, the fibrous filler includes short fibers such as milled fibers and whiskers, and flat shapes such as cocoon-shaped, oval-shaped, and elliptical cross-sections (for example, the ratio of the major axis to the minor axis of the cross section is 1.3 to 10). It is more preferable to use fibers having a relatively small aspect ratio. In particular, when a glass fiber having a flat cross section is used, both heat shock resistance and mechanical properties can be improved, which is preferable.

Specific examples of the plate-shaped filler include plate-shaped talc, mica, glass flakes, metal pieces and combinations thereof, and specific examples of the spherical filler include glass beads, glass balloons, spherical silica and the like. Combinations of these can be mentioned, and examples of the powder 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. Salt (calcium carbonate, zinc borate, calcium borate, zinc nitrate, calcium sulfate, barium sulfate, etc.) powder, metal oxide (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.) powder, metal Powders of hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (bemite), etc.), powders of metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.), and combinations thereof, etc. Can be mentioned. From the viewpoint of metal corrosiveness, it is preferable that the content of the free inorganic acid contained in these (D) fillers for improving heat shock resistance is 0.5% by mass or less.

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

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

The amount of the filler for improving heat shock resistance (D) added is 10 to 200 parts by mass, and may be 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. .. (D) The amount of the filler for improving heat shock resistance to be added can be appropriately selected in consideration of the balance between the heat shock resistance improving effect and the mechanical properties, fluidity and the like.

Examples of the (E) additive for improving heat shock resistance include carbodiimide compounds, epoxy compounds, oxazoline compounds, oxazine compounds, aromatic polyvalent carboxylic acid esters, and the like, and one or a combination of two or more of these may be mentioned. 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, and such a carbodiimide compound can be used, for example, in the presence of a suitable catalyst. , Organic isocyanate can be heated and produced by decarbonation reaction.

Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluyl carbodiimide, di-p-toluyl carbodiimide, 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-toluyl carbodiimide, 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-toluyl carbodiimide, N, N'-benzyl carbodiimide, N -Octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecil-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-isopropylphenylcarbodiimide , 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 Mono or dicarbodiimide compounds such as 6-trimethylphenylcarbodiimide, N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6-hexamethylene carbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4 ′ -Diphenylmethane carbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethane carbodiimide), poly (naphthylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (trill) Examples thereof include polycarbodiimides such as carbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), and poly (triisopropylphenylene carbodiimide). Further, as the polycarbodiimide, xylene-based polycarbodiimide synthesized from m-xylene diisocyanate, p-xylene diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate and the like can also 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, or an alkylene (21 to 21 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 poly Carbodiimide is preferred.

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

Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxidephenol 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, Bisphenols such as pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone and epichlorohydrin Examples thereof include bisphenol A diglycidyl ether type epoxy resin obtained from the condensation reaction, bisphenol F diglycidyl ether type epoxy resin, and bisphenol S diglycidyl ether type epoxy resin. Of these, bisphenol A diglycidyl ether type epoxy resin is preferable.

Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearate glycidyl ester, laurate glycidyl ester, palmitate glycidyl ester, versatic acid glycidyl ester, and oleate glycidyl ester. Esters, linoleic acid glycidyl esters, linolenic acid glycidyl esters, terephthalic acid diglycidyl esters, isophthalic acid diglycidyl esters, phthalic acid diglycidyl esters, naphthalenedicarboxylic acid diglycidyl esters, bibenzoic acid diglycidyl esters, methylterephthalic acid diglycidyl esters , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipate diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecandioic acid diglycidyl ester, octadecandicarboxylic Examples thereof include acid diglycidyl ester, trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidyl ester. Of these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyl toluidine, tetraglycidyl metaxylylenediamine, diglycidyl tribromoaniline, tetra. Examples thereof include glycidyl bisaminomethylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

Examples of glycidylimide compounds include N-glycidylphthalimide, 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-tetrabromphthalimide, N -Glysidyl-4-n-butyl-5-bromphthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleinimide, N- Glycidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide and the like can be mentioned. Of these, N-glycidyl phthalimide is preferable.

Examples of alicyclic epoxy compounds 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.

Further, as other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resin, cresol nozolac type epoxy resin, and the like can be used.

Further, as the epoxy compound, an epoxy compound such as an α, β-unsaturated acid glycidyl ester, for example, an acrylic acid glycidyl ester, a methacrylic acid glycidyl ester, or an etacrylic acid glycidyl ester is used by random, block or graft copolymerization with other monomers. Epoxide-modified resin or epoxy-modified elastoma copolymerized with, specifically, a glycidyl group-containing copolymer composed of α-olefin and glycidyl ester of α, β-unsaturated acid, or epoxy group-containing vinyl-based single polymer. A polyorganosiloxane / polyalkyl (meth) acrylate composite rubber graft copolymer obtained by graft-polymerizing a polymer, a styrene / butadiene copolymer having an epoxy group in the main chain, and the like can also be used, and are generally used. A brominated epoxy compound (one in which an epoxy group is not sealed) used as a flame retardant can also be used.

Examples of oxazoline compounds 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 (4,4'-diethyl-2-oxazoline) 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-phenylene bis (2-oxazoline), 2,2'-m-phenylene Bis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (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'-diphenoxyetambis (2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'- Examples thereof include diphenylenebis (2-oxazoline). Further, a polyoxazoline compound containing the above-mentioned compound as a monomer unit can also be mentioned.

Examples of oxazine compounds are 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-Deciloxy-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-metha Examples thereof 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'-propylene bis (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-xazine) 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. Further, a polyoxazine compound containing the above-mentioned compound as a monomer unit and the like can be mentioned.

Among the 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, a trimellitic acid ester and a pyromellitic acid ester are preferable examples, and an alkyl ester is particularly preferable. Examples of the alkyl group constituting this 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 of these may be used. Such aromatic polyvalent carboxylic acid esters can be used alone or in combination of two or more.

The amount of the additive for improving heat shock resistance (E) added is 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass, with respect to 100 parts by mass of the polybutylene terephthalate resin, and is 0. More preferably, it is 3 to 10 parts by mass.

The amount of the additive for improving heat shock resistance (E) is the total of the carbodiimide group, the epoxy group, the oxazoline group, the oxazine ring, and the ester group, with the amount of the terminal carboxyl group in the polybutylene terephthalate resin composition as 1. The functional group content may be set to be 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) The composition of the present invention is generally added to a thermoplastic resin or the like in order to impart desired properties other than flame retardancy and heat shock resistance, as needed, to improve heat shock resistance. Known substances other than those corresponding to the additives for use can be added and used in combination. For example, stabilizers such as antioxidants, ultraviolet absorbers and light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, plasticizers, fluidity improvers, toughness improvers, impact resistance. It is possible to blend any of an improver, a resin other than the one corresponding to the heat shock resistance improving resin, a filler other than the one 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 size of 10 to 100 nm, and one having an average primary particle size of 25 to 50 nm is used because it is possible to suppress a decrease in heat shock resistance. Is more preferable. The average primary particle size referred to here is an arithmetic average particle size obtained by electron microscope observation of 1000 colorants before being blended in the resin composition.

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

[Manufacturing method of flame-retardant polybutylene terephthalate resin composition]
The form of the flame-retardant polybutylene terephthalate resin composition of the present invention may be a powder or granular material mixture or a melt mixture (melt kneaded product) such as pellets. The method for producing a polybutylene terephthalate resin composition according to an embodiment of the present invention includes (B) a step for producing a halogenated benzyl acrylate-based flame retardant. Since the process is as described above, the description thereof 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, the required components can be mixed and kneaded using a single-screw or twin-screw extruder or other melt-kneading device to prepare pellets for molding. Multiple extruders or other melt kneaders may be used. Further, all the components may be input from the hopper at the same time, or some components may be input from the side feed port.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The characteristic evaluation was performed by the following method.

(1) Content of Halogenated Aromatic Compounds The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ. The pellets of the obtained polybutylene terephthalate resin composition obtained by melt-kneading at 260 ° C. were crushed and used as a sample. After taking 5 g of a sample and leaving it in a head space of 20 ml at 150 ° C. for 1 hour, the apparatus: HP5890A manufactured by Yokogawa Hulett Packard Co., Ltd., column: HR-1701 (0.32 mm diameter × 30 m) was used 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 a gas chromatograph, and the content of the halogenated aromatic compound was shown in ppm. The results are shown in Table 1.

(2) Metal Corrosiveness The material dry-blended with the components and composition (parts by mass) shown in Table 1 is 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 obtained polybutylene terephthalate resin composition after kneading was placed in a 300 ml glass stopper bottle together with a 1 cm × 1 cm silver plate, stoppered, and 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 the one without corrosion was evaluated as ◯, and the one with corrosion was evaluated as ×. The results are shown in Table 1.

(3) Flame retardancy The material dry-blended with the components and composition (parts by mass) shown in Table 1 is 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 were 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., conforming to UL94, 125 mm × 13 mm. × A strip-shaped test piece having a thickness of 1/32 inch was prepared and its flammability was evaluated. The results are shown in Table 1.

(4) Heat shock resistance The material dry-blended with the components and composition (parts by mass) shown in Table 1 is 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, then injection-molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and the test pieces shown in FIGS. Was insert-molded and the heat shock resistance was evaluated. FIG. 1 is a diagram showing an insert-molded test piece 10, and FIG. 2 is a diagram showing an insert member 2. As shown in FIG. 1, the test piece 10 has a square columnar insert member 2 made of metal embedded in a square columnar resin member 1 made of a thermoplastic aromatic polyester resin composition. The resin member 1 is formed by using the resin composition pellets obtained as described above. As shown in FIG. 2, the insert member 2 is configured to include a square columnar upper part 2a, a square columnar lower part 2b, and a columnar constriction 2c connecting the two. 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. 1 (A)). Further, as shown in FIG. 1B, the corners of the resin member 1 and the corners of the insert member 2 are arranged so as to be located in different directions from each other. That is, the corners of the insert member 2 are 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 portion (sharp corner) of the insert member 2 is a thin portion. The above test piece 10 is cooled at -40 ° C for 1.5 hours using a thermal shock tester (manufactured by ESPEC CORPORATION), and then heated at 180 ° C for 1.5 hours, repeating a cycle of 20 cycles. The weld part was observed every time. The number of cycles when a crack occurred in the weld portion was evaluated as an index of heat shock resistance, 200 cycles or more was evaluated as ⊚, 100 cycles or more was evaluated as ◯, and less than 100 cycles was evaluated as x. The results are shown in Table 1.

(5) Strand break The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (TEX-30 manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ, and the cylinder temperature. When melt-kneaded under the conditions of 260 ° C., screw rotation speed 120 rpm, and extrusion rate 15 kg / hr, extruded into strands from a die, and then cooled and cut to obtain pellets of the polybutylene terephthalate resin composition, the strands were broken. The occurrence status was confirmed, and those in which almost no strand breakage occurred were evaluated as ◯, and those in which frequent occurrences were evaluated as x. The results are shown in Table 1.

(6) Melt fluidity After the pellet obtained by the method (5) above was dried at 140 ° C. for 3 hours, the box-shaped molded product shown in FIG. 3 (thickness of walls and bottom on all sides was 0.7 mm). ) Is injection-molded 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. evaluated.

(7) Adhesion to the mold After 6000 shots of the strip-shaped test piece used for the evaluation of the above (3) were continuously formed, the surface of the mold cavity was evaluated by visual observation. Those in which no mold deposits were observed were evaluated as ◯, and those in which adhesion was observed were evaluated as x.

表中のＮ．Ｄ．は検出限界（０．１ｐｐｍ）以下であることを示す。
含有量の単位は、質量部である。

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

Claims (12)

(A) 100 parts by mass of polybutylene terephthalate resin and
(B) Halogenated benzyl acrylate flame retardant 3 to 50 parts by mass and
(C) 5 to 100 parts by mass of a resin for improving heat shock resistance,
(D) 10 to 200 parts by mass of a filler for improving heat shock resistance,
(E) Contains 0.1 to 30 parts by mass of an additive for improving heat shock resistance,
A flame-retardant polybutylene terephthalate resin composition having a content of a halogenated aromatic compound other than the flame retardant of less than 0.5 ppm, which is measured by a headspace gas chromatograph method (heating at 150 ° C. for 1 hour). The additive for improving heat shock resistance is characterized by containing one or more selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, an aromatic polyvalent carboxylic acid ester, and a combination thereof. Flame-retardant polybutylene terephthalate resin composition. (B) The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated benzyl acrylate-based flame retardant 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 X is a bromine atom, and m is a number of 10 to 2000.) (B) The flame-retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the halogenated benzyl acrylate-based 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 benzene halide. 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. Claim 1 contains a polybutylene terephthalate resin and a halogenated benzyl acrylate-based flame retardant having a protonic compound content of 10 to 1000 ppm, which is measured by a headspace gas chromatograph method (heating at 180 ° C. for 1 hour). The flame-retardant polybutylene terephthalate resin composition according to any one of 5 to 5. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 6, wherein the polybutylene terephthalate resin contains 50 to 1000 ppm of a linear low molecular weight substance. The flame-retardant polybutylene terephthalate resin composition according to claim 6, wherein the protonic compound is derived from a polymerization solvent of a halogenated benzyl acrylate-based flame retardant. The flame-retardant polybutylene terephthalate resin composition according to claim 6 or 8, wherein the protonic compound is an alkoxyalcohol. The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 9.
(B) A production method comprising a step of producing a halogenated benzyl acrylate-based flame retardant, wherein the content of the halogenated aromatic compound in the solvent used in the step is 1000 ppm or less. (B) The production method according to claim 10, wherein a halogenated aromatic compound is not used as a solvent in the production process of the halogenated benzyl acrylate flame retardant. (B) The method according to claim 10 or 11, wherein in the process for producing the 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 the solvent. Manufacturing method.

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