WO2019039464A1 - Flame-retardant polybutylene terephthalate resin composition - Google Patents
Flame-retardant polybutylene terephthalate resin composition Download PDFInfo
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- WO2019039464A1 WO2019039464A1 PCT/JP2018/030796 JP2018030796W WO2019039464A1 WO 2019039464 A1 WO2019039464 A1 WO 2019039464A1 JP 2018030796 W JP2018030796 W JP 2018030796W WO 2019039464 A1 WO2019039464 A1 WO 2019039464A1
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- terephthalate resin
- polybutylene terephthalate
- resin composition
- flame
- flame retardant
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- 0 CC(C)(C)CC(C(C)(C)C)C(*Cc1c(*)c(*)c(*)c(C)c1*)=O Chemical compound CC(C)(C)CC(C(C)(C)C)C(*Cc1c(*)c(*)c(*)c(C)c1*)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- 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 in various applications such as electric and electronic parts because it is excellent in various electric characteristics. In these applications, in order to prevent ignition due to tracking and the like, materials used are required to be flame retardant.
- the polybutylene terephthalate resin is used as a flame retardant resin composition to which a flame retardant is added because the flame retardancy is insufficient by itself.
- Patent Document 1 discloses polypentabromobenzyl acrylate (PBBPA) as a halogenated benzyl acrylate flame retardant which is a kind of flame retardant added to polybutylene terephthalate resin.
- PBBPA polypentabromobenzyl acrylate
- paragraph [0004] of Patent Document 1 is a method of polymerizing pentabromobenzyl acrylate as a monomer in ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether or in chlorobenzene The method is illustrated.
- a flame retardant polybutylene terephthalate resin composition to which such a flame retardant is added may be used as a component of a circuit breaker (relay).
- Patent Document 2 describes that, in a circuit breaker, the decomposition gas of a halogen-based flame retardant corrodes a metal to cause contact failure, and that a non-halogen-based nitrogen-based flame retardant is advantageous It is disclosed.
- the object of the present invention is to provide a flame retardant polybutylene terephthalate resin composition which can be used for parts such as arc-extinguishing members which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker. I assume.
- the inventor of the present invention is to provide a flame retardant polybutylene terephthalate resin composition which can be used for parts such as arc-extinguishing members which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker.
- a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research as an object the polybutylene terephthalate resin composition contains a certain amount or more of a halogenated aromatic compound such as chlorobenzene.
- a halogenated aromatic compound such as chlorobenzene
- the present invention relates to the following (1) to (9).
- the flame-retardant polybutylene terephthalate resin composition, wherein the content of the halogenated aromatic compound other than the flame retardant is from 0.5 ppm to 5 ppm.
- a flame retardant polybutylene terephthalate resin composition that can be used for parts such as arc-extinguishing members, which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker. Can.
- Polybutylene terephthalate resin is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as C 1-6 alkyl ester or acid halide), and an alkylene glycol having at least 4 carbon atoms Or 4-butanediol) or a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing an ester-forming derivative thereof (eg, an acetylated compound).
- PBT resin is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as C 1-6 alkyl ester or acid halide), and an alkylene glycol having at least 4 carbon atoms Or 4-butanediol) or a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing an ester-forming derivative thereof (eg, an acetylated compound).
- the polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of butylene terephthalate units, and contains 75 mol% or more and 95 mol% or less of butylene terephthalate units It may be a copolymer.
- the amount of terminal carboxyl groups of the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but 30 meq / kg or less is preferable, and 25 meq / kg or less is more preferable.
- the intrinsic viscosity of the 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 1.2 dL / g or less, preferably 0.65 dL / g or more and 0.9 dL / g. It is more preferable that it is g or less.
- the polybutylene terephthalate resin of the intrinsic viscosity of such a range the polybutylene-terephthalate resin composition obtained becomes what was especially excellent in the moldability.
- the intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities.
- a polybutylene terephthalate resin having an inherent viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an inherent viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an inherent viscosity of 0.7 dL / g. Can.
- the intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35.degree.
- 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
- isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'- C 8-14 aromatic dicarboxylic acids such as dicarboxy diphenyl ether
- C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid
- C 5-10 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid Acids: ester-forming derivatives of these dicarboxylic acid components (such as C 1-6 alkyl ester derivatives and acid halides) can be used.
- These dicarboxylic acid components can be used alone or in combination of two or more.
- 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.
- glycol component other than 1,4-butanediol is used as a comonomer component in the preparation of the polybutylene terephthalate resin
- polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol
- alicyclic diols such as cyclohexane dimethanol and hydrogenated bisphenol A
- bisphenol A aromatic diols such as 4,4'-dihydroxybiphenyl
- ethylene oxide 2-mole adduct of bisphenol A, propylene oxide of bisphenol A Such as 3 mole adduct, alkylene oxide adducts of C 2-4 of bisphenol A; or ester-forming derivatives of these glycols
- C 2-6 alkylene glycols such as ethylene glycol and trimethylene glycol
- polyoxyalkylene glycols such as diethylene glycol
- alicyclic diols such as cyclohexane dimethanol are more preferable.
- comonomer component which can be used in addition to the dicarboxylic acid component and the glycol component, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl etc.
- Aromatic hydroxycarboxylic acids include aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg ⁇ -caprolactone); esters of these comonomer components Examples include forming derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylated compounds and the like).
- the content of the polybutylene terephthalate resin is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 70% by mass of the total mass of the resin composition. .
- halogenated benzyl acrylate flame retardant examples include brominated acrylic polymers represented by the following general formula (I).
- X is bromine.
- the number of X is 1 to 5 in one constitutional unit, but is preferably 3 to 5 in view of the effect of flame retardancy.
- the average degree of polymerization m is from 10 to 2,000, preferably from 15 to 1,000. When the average degree of polymerization is low, the thermal stability is deteriorated, and when it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated.
- the brominated acrylic polymers may be used alone or in combination of two or more.
- the halogenated benzyl acrylate flame retardant used in the present invention is preferably 100 ppm to 1500 ppm, more preferably 120 ppm to 1000 ppm of a halogenated aromatic compound, in addition to the above-mentioned brominated acrylic polymer that is the flame retardant itself. It is preferable to polymerize in a state of 150 ppm or more and 800 ppm or less, more preferably 200 ppm or more and 500 ppm or less.
- the content of the halogenated aromatic compound other than the flame retardant can be determined, for example, by measuring the generated gas when the sample obtained by pulverizing the halogenated benzyl acrylate flame retardant is heat-treated in the head space by gas chromatograph. It can obtain
- the brominated acrylic polymer represented by the general formula (I) can be obtained by polymerizing bromine-containing benzyl acrylate 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. Among them, pentabromobenzyl acrylate is preferred.
- a benzyl methacrylate which is a component which can be copolymerized the methacrylate corresponding to the above-mentioned acrylate is mentioned.
- copolymerization with a vinyl monomer is also possible, and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as benzyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate And methacrylic acid esters such as styrene, unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid and maleic acid or anhydrides thereof, vinyl acetate, vinyl chloride and the like.
- crosslinkable vinyl monomers xylylene diacrylate, xylylene methacrylate, tetrabromo xylylene acrylate, tetrabromo xylylene methacrylate, butadiene, isoprene and divinyl benzene can also be used. These are used in an equimolar amount or less, preferably 0.5 times or less the molar amount with respect to benzyl acrylate and benzyl methacrylate.
- brominated acrylic polymer As an example of the method for producing the above-mentioned brominated acrylic polymer, there can be mentioned a method in which a monomer of brominated acrylic is reacted to a predetermined polymerization degree by solution polymerization or bulk polymerization. In the case of solution polymerization, it is preferable to use a halogenated benzene or a halogenated aromatic compound such as chlorobenzene as a solvent.
- the above-mentioned brominated acrylic polymer is preferably washed with an aqueous solution containing water and / or an alkali (earth) metal ion in order to remove reaction by-products such as sodium polyacrylate remaining.
- An aqueous solution containing an alkali (earth) metal ion can be easily obtained by introducing an alkali (earth) metal salt into water, but an alkali (earth) metal containing no chloride ion, phosphate ion, etc.
- Certain hydroxides eg calcium hydroxide
- calcium hydroxide for example, is used as the alkali (earth metal) metal salt, calcium hydroxide is generally soluble in water at 100 ° C.
- the concentration of the aqueous solution is not particularly limited as far as it is soluble.
- the method of washing with an aqueous solution containing water and / or alkali (earth) metal ions is not particularly limited, and the brominated acrylic polymer contains water and / or alkali (earth) metal ions for a suitable time. It may be a method of immersing in an aqueous solution.
- the content of the halogenated aromatic compound other than the above-mentioned flame retardant is 0.5 ppm or more and 5 ppm or less, preferably 0.8 ppm or more and 4 ppm or less, more preferably Is 1.0 ppm or more and 3 ppm or less.
- the flame retardant polybutylene terephthalate resin composition of the present invention is used for applications such as circuit breakers by containing a halogenated aromatic compound other than a flame retardant in the above range, contact defects due to arcing are suppressed Generation of arc-extinguishing gas.
- gases such as gases derived from the above-mentioned halogenated aromatic compounds and inert gases are known as gases acting as arc extinguishing gases, and decomposition gases derived from polybutylene terephthalate resin are also included therein. It is possible.
- the content of the halogenated aromatic compound other than such a flame retardant is, for example, measured by gas chromatograph the gas generated when the sample obtained by pulverizing the polybutylene terephthalate resin composition is heat-treated in the head space, It can obtain
- an antimony-based flame retardant auxiliary In the flame retardancy of the above-mentioned resin, it is preferable to use an antimony-based flame retardant auxiliary together.
- Typical examples of the flame retardant auxiliary include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate and the like.
- an anti-dripping agent such as polytetrafluoroethylene for the purpose of preventing fire spreading due to dripping of the burned resin.
- the range of addition of the above-mentioned brominated acrylic polymer and antimony-based flame retardant auxiliary to the resin is 3 to 30 parts by mass of the above-mentioned polymer with respect to 100 parts by mass of polybutylene terephthalate resin, and 1 to 20 antimony-based flame retardant auxiliary A range of parts by weight is preferred.
- the addition amount of the brominated acrylic polymer and the antimony-based flame retardant auxiliary is too small, sufficient flame retardancy can not be imparted, and when it is too large, physical properties as a molded article may be deteriorated.
- Fillers are optionally used in the compositions of the present invention. Such a filler is preferably blended to obtain properties excellent in performance such as mechanical strength, heat resistance, dimensional stability, electrical properties and the like, and is particularly effective for the purpose of enhancing rigidity. Depending on the purpose, fibrous, particulate or plate-like fillers may be used.
- fibrous fillers examples include glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and further stainless steel, aluminum, titanium, Examples thereof include fibrous materials of metals such as copper and brass. In addition, a high melting point organic fibrous material such as polyamide, fluorine resin and acrylic resin can also be used.
- Particulate fillers include carbon black, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, silicates such as diatomaceous earth, wollastonite, iron oxide, titanium oxide, alumina, etc.
- Metal oxides, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and others, silicon carbide, silicon nitride, boron nitride, various metal powders and the like can be mentioned.
- the type of filler is not particularly limited, and one or more fillers can be added.
- potassium titanate fiber, mica, talc and wollastonite are preferably used.
- the addition amount of the filler is not particularly limited, it is preferably 200 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin.
- the filler is added in excess, the formability deteriorates and the toughness decreases.
- thermoplastic resins and the like can be used in combination in order to impart desired properties other than flame retardancy.
- stabilizers such as antioxidants, ultraviolet light absorbers, light stabilizers, etc.
- antistatic agents such as antioxidants, ultraviolet light absorbers, light stabilizers, etc.
- lubricants such as talc, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, etc.
- mold release agents such as lubricants, etc.
- coloring agents such as dyes and pigments, plasticizers, etc.
- the addition of an antioxidant to improve the heat resistance is effective.
- the form of the flame-retardant polybutylene terephthalate resin composition of the present invention may be a powder-particle mixture, or may be a melt mixture (melt-kneaded product) such as pellets.
- the method for producing the polybutylene terephthalate resin composition of one embodiment of the present invention is not particularly limited, and can be produced using equipment and methods known in the art. For example, necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. A plurality of extruders or other melt kneading apparatuses may be used. Moreover, all the components may be simultaneously fed from the hopper, or some components may be fed from the side feed port.
- the flame retardant polybutylene terephthalate resin composition of the present invention is preferably produced by vacuum drying (vacuum evacuation).
- vacuum drying a commonly used evaporator, an oven or the like can be used.
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Abstract
[Problem] The problem addressed by the present invention is to provide a flame-retardant polybutylene terephthalate resin composition that can be used in components such as an arc extinguishing member and that is less likely to cause contact failure due to corrosion of a contact metal by an arc in a circuit breaker. [Solution] The problem is solved by using at least a certain amount of a halogenated aromatic compound such as chlorobenzene in the flame retardant production process in a polybutylene terephthalate resin composition that uses a halogenated benzyl acrylate flame retardant as a flame retardant.
Description
本発明は、難燃性ポリブチレンテレフタレート樹脂組成物、及びその製造方法に関する。
The present invention relates to a flame retardant polybutylene terephthalate resin composition and a method for producing the same.
ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、各種の電気的特性に優れるため、エンジニアリングプラスチックとして、電気・電子部品等の種々の用途に広く利用されている。これらの用途では、トラッキング等による発火を防ぐため、使用される材料には難燃性が要求されている。ポリブチレンテレフタレート樹脂は、それ自体では難燃性が不足するため、難燃剤を添加した難燃性樹脂組成物として使用されている。
Polybutylene terephthalate resin (PBT resin) is widely used as an engineering plastic in various applications such as electric and electronic parts because it is excellent in various electric characteristics. In these applications, in order to prevent ignition due to tracking and the like, materials used are required to be flame retardant. The polybutylene terephthalate resin is used as a flame retardant resin composition to which a flame retardant is added because the flame retardancy is insufficient by itself.
ポリブチレンテレフタレート樹脂に添加される難燃剤の一種であるハロゲン化ベンジルアクリレート系難燃剤として、特許文献１には、ポリペンタブロモベンジルアクリレート（ＰＢＢＰＡ）が紹介されている。この難燃剤を製造する方法として特許文献１の段落［0004］には、モノマーであるペンタブロモベンジルアクリレートを、エチレングリコールモノメチルエーテルや、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中で重合する方法やクロロベンゼン中で重合する方法が例示されている。
Patent Document 1 discloses polypentabromobenzyl acrylate (PBBPA) as a halogenated benzyl acrylate flame retardant which is a kind of flame retardant added to polybutylene terephthalate resin. As a method of producing this flame retardant, paragraph [0004] of Patent Document 1 is a method of polymerizing pentabromobenzyl acrylate as a monomer in ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether or in chlorobenzene The method is illustrated.
このような難燃剤を添加した難燃性ポリブチレンテレフタレート樹脂組成物を回路遮断器（リレー）の部品に用いる場合がある。一方、特許文献２では、回路遮断器において、ハロゲン系難燃剤の分解ガスが金属を腐蝕させ接点不良の原因となる旨が記載されており、ノンハロゲン系の窒素系難燃剤が有利であることが開示されている。
A flame retardant polybutylene terephthalate resin composition to which such a flame retardant is added may be used as a component of a circuit breaker (relay). On the other hand, Patent Document 2 describes that, in a circuit breaker, the decomposition gas of a halogen-based flame retardant corrodes a metal to cause contact failure, and that a non-halogen-based nitrogen-based flame retardant is advantageous It is disclosed.
本発明は、回路遮断器において、アークによる接点金属の腐蝕に起因する接点不良を起こしにくい、消弧部材などの部品に使用可能な、難燃性ポリブチレンテレフタレート樹脂組成物を提供することを課題とする。
The object of the present invention is to provide a flame retardant polybutylene terephthalate resin composition which can be used for parts such as arc-extinguishing members which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker. I assume.
本発明者は、回路遮断器において、アークによる接点金属の腐蝕に起因する接点不良を起こしにくい、消弧部材などの部品に使用可能な、難燃性ポリブチレンテレフタレート樹脂組成物を提供することを課題とする研究の過程で、難燃剤としてハロゲン化ベンジルアクリレート系難燃剤を用いるポリブチレンテレフタレート樹脂組成物において、当該ポリブチレンテレフタレート樹脂組成物が、クロロベンゼンなどのハロゲン化芳香族化合物を一定量以上含有する、特に当該難燃剤の製造工程に由来するハロゲン化芳香族化合物の量を調節することで、上記の課題を解決できることを見出し、本発明を完成させるに至った。
The inventor of the present invention is to provide a flame retardant polybutylene terephthalate resin composition which can be used for parts such as arc-extinguishing members which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker. In a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research as an object, the polybutylene terephthalate resin composition contains a certain amount or more of a halogenated aromatic compound such as chlorobenzene. In particular, by adjusting the amount of the halogenated aromatic compound derived from the production process of the flame retardant, it is found that the above-mentioned problems can be solved, and the present invention has been completed.
すなわち、本発明は以下の（１）～（９）に関する。
（１）ポリブチレンテレフタレート樹脂と、ハロゲン化ベンジルアクリレート系難燃剤とを含有する難燃性ポリブチレンテレフタレート樹脂組成物であって、ヘッドスペースガスクロマトグラフ法（１５０℃、１時間加熱）により測定される、前記難燃剤以外のハロゲン化芳香族化合物の含有量が０．５ｐｐｍ以上５ｐｐｍ以下であることを特徴とする、難燃性ポリブチレンテレフタレート樹脂組成物。
（２）ハロゲン化ベンジルアクリレート系難燃剤が、一般式（Ｉ）で表されるブロム化アクリル重合体である、（１）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。
（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は臭素であり、ｍは１０～２０００の数である。）
（３）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である、（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である、（１）から（３）のいずれか一項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、クロロベンゼンである、（１）から（４）のいずれか一項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）ハロゲン化ベンジルアクリレート系難燃剤の製造時に、溶媒としてハロゲン化芳香族化合物を用いることを特徴とする、（１）から（５）のいずれか一項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。
（７）ハロゲン化芳香族化合物が、ハロゲン化ベンゼンである、（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の製造方法。
（８）ハロゲン化芳香族化合物が、クロロベンゼンである、（６）または（７）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。
（９）真空乾燥を行う、（６）から（８）のいずれか一項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。 That is, the present invention relates to the following (1) to (9).
(1) A flame-retardant polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a halogenated benzyl acrylate flame retardant, which is measured by a head space gas chromatography method (150 ° C., heating for 1 hour) The flame-retardant polybutylene terephthalate resin composition, wherein the content of the halogenated aromatic compound other than the flame retardant is from 0.5 ppm to 5 ppm.
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate flame retardant is a brominated acrylic polymer represented by the general formula (I).
(Wherein, X is a hydrogen atom or a bromine atom, at least one or more of X is a bromine, 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 is 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 is a 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 is chlorobenzene.
(6) The flame-retardant polybutylene terephthalate according to any one of (1) to (5), characterized in that a halogenated aromatic compound is used as a solvent in the production of the halogenated benzyl acrylate flame retardant. Method for producing a resin composition.
(7) The manufacturing method of the flame-retardant polybutylene terephthalate resin composition as described in (6) whose halogenated aromatic compound is halogenated benzene.
(8) The method for producing a flame-retardant polybutylene terephthalate resin composition according to (6) or (7), wherein the halogenated aromatic compound is chlorobenzene.
(9) The method for producing a flame retardant polybutylene terephthalate resin composition according to any one of (6) to (8), wherein vacuum drying is performed.
（１）ポリブチレンテレフタレート樹脂と、ハロゲン化ベンジルアクリレート系難燃剤とを含有する難燃性ポリブチレンテレフタレート樹脂組成物であって、ヘッドスペースガスクロマトグラフ法（１５０℃、１時間加熱）により測定される、前記難燃剤以外のハロゲン化芳香族化合物の含有量が０．５ｐｐｍ以上５ｐｐｍ以下であることを特徴とする、難燃性ポリブチレンテレフタレート樹脂組成物。
（２）ハロゲン化ベンジルアクリレート系難燃剤が、一般式（Ｉ）で表されるブロム化アクリル重合体である、（１）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。
（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は臭素であり、ｍは１０～２０００の数である。）
（３）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である、（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である、（１）から（３）のいずれか一項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、クロロベンゼンである、（１）から（４）のいずれか一項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）ハロゲン化ベンジルアクリレート系難燃剤の製造時に、溶媒としてハロゲン化芳香族化合物を用いることを特徴とする、（１）から（５）のいずれか一項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。
（７）ハロゲン化芳香族化合物が、ハロゲン化ベンゼンである、（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の製造方法。
（８）ハロゲン化芳香族化合物が、クロロベンゼンである、（６）または（７）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。
（９）真空乾燥を行う、（６）から（８）のいずれか一項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。 That is, the present invention relates to the following (1) to (9).
(1) A flame-retardant polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a halogenated benzyl acrylate flame retardant, which is measured by a head space gas chromatography method (150 ° C., heating for 1 hour) The flame-retardant polybutylene terephthalate resin composition, wherein the content of the halogenated aromatic compound other than the flame retardant is from 0.5 ppm to 5 ppm.
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate flame retardant is a brominated acrylic polymer represented by the general formula (I).
(Wherein, X is a hydrogen atom or a bromine atom, at least one or more of X is a bromine, 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 is 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 is a 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 is chlorobenzene.
(6) The flame-retardant polybutylene terephthalate according to any one of (1) to (5), characterized in that a halogenated aromatic compound is used as a solvent in the production of the halogenated benzyl acrylate flame retardant. Method for producing a resin composition.
(7) The manufacturing method of the flame-retardant polybutylene terephthalate resin composition as described in (6) whose halogenated aromatic compound is halogenated benzene.
(8) The method for producing a flame-retardant polybutylene terephthalate resin composition according to (6) or (7), wherein the halogenated aromatic compound is chlorobenzene.
(9) The method for producing a flame retardant polybutylene terephthalate resin composition according to any one of (6) to (8), wherein vacuum drying is performed.
本発明によれば、回路遮断器において、アークによる接点金属の腐蝕に起因する接点不良を起こしにくい、消弧部材などの部品に使用可能な、難燃性ポリブチレンテレフタレート樹脂組成物を提供することができる。
According to the present invention, it is possible to provide a flame retardant polybutylene terephthalate resin composition that can be used for parts such as arc-extinguishing members, which are less likely to cause contact failure due to corrosion of contact metal due to arc in a circuit breaker. Can.
以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。
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 as long as the effects of the present invention are not impaired.
［難燃性ポリブチレンテレフタレート樹脂組成物］
以下、本実施形態の難燃性ポリブチレンテレフタレート樹脂組成物の各成分の詳細を例を挙げて説明する。 [Flame retardant polybutylene terephthalate resin composition]
Hereinafter, the details of each component of the flame retardant polybutylene terephthalate resin composition of the present embodiment will be described by way of examples.
以下、本実施形態の難燃性ポリブチレンテレフタレート樹脂組成物の各成分の詳細を例を挙げて説明する。 [Flame retardant polybutylene terephthalate resin composition]
Hereinafter, the details of each component of the flame retardant polybutylene terephthalate resin composition of the present embodiment will be described by way of examples.
（ポリブチレンテレフタレート樹脂）
ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１－６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート樹脂である。本実施形態において、ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を６０モル％以上含有する共重合体であればよく、ブチレンテレフタレート単位を７５モル％以上９５モル％以下含有する共重合体であってもよい。 (Polybutylene terephthalate resin)
Polybutylene terephthalate resin (PBT resin) is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as C 1-6 alkyl ester or acid halide), and an alkylene glycol having at least 4 carbon atoms Or 4-butanediol) or a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing an ester-forming derivative thereof (eg, an acetylated compound). In the present embodiment, the polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of butylene terephthalate units, and contains 75 mol% or more and 95 mol% or less of butylene terephthalate units It may be a copolymer.
ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１－６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート樹脂である。本実施形態において、ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を６０モル％以上含有する共重合体であればよく、ブチレンテレフタレート単位を７５モル％以上９５モル％以下含有する共重合体であってもよい。 (Polybutylene terephthalate resin)
Polybutylene terephthalate resin (PBT resin) is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as C 1-6 alkyl ester or acid halide), and an alkylene glycol having at least 4 carbon atoms Or 4-butanediol) or a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing an ester-forming derivative thereof (eg, an acetylated compound). In the present embodiment, the polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of butylene terephthalate units, and contains 75 mol% or more and 95 mol% or less of butylene terephthalate units It may be a copolymer.
ポリブチレンテレフタレート樹脂の末端カルボキシル基量は、本発明の目的を阻害しない限り特に限定されないが、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ／ｋｇ以下がより好ましい。
The amount of terminal carboxyl groups of the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but 30 meq / kg or less is preferable, and 25 meq / kg or less is more preferable.
ポリブチレンテレフタレート樹脂の固有粘度は本発明の目的を阻害しない範囲で特に制限されないが、０．６０ｄＬ／ｇ以上１．２ｄＬ／ｇ以下であるのが好ましく、０．６５ｄＬ／ｇ以上０．９ｄＬ／ｇ以下であるのがより好ましい。このような範囲の固有粘度のポリブチレンテレフタレート樹脂を用いる場合には、得られるポリブチレンテレフタレート樹脂組成物が特に成形性に優れたものとなる。また、異なる固有粘度を有するポリブチレンテレフタレート樹脂をブレンドして、固有粘度を調整することもできる。例えば、固有粘度１．０ｄＬ／ｇのポリブチレンテレフタレート樹脂と固有粘度０．７ｄＬ／ｇのポリブチレンテレフタレート樹脂とをブレンドすることにより、固有粘度０．９ｄＬ／ｇのポリブチレンテレフタレート樹脂を調製することができる。ポリブチレンテレフタレート樹脂の固有粘度は、例えば、ｏ－クロロフェノール中で温度３５℃の条件で測定することができる。
The intrinsic viscosity of the 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 1.2 dL / g or less, preferably 0.65 dL / g or more and 0.9 dL / g. It is more preferable that it is g or less. When using the polybutylene terephthalate resin of the intrinsic viscosity of such a range, the polybutylene-terephthalate resin composition obtained becomes what was especially excellent in the moldability. The intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an inherent viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an inherent viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an inherent viscosity of 0.7 dL / g. Can. The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35.degree.
ポリブチレンテレフタレート樹脂の調製において、コモノマー成分としてテレフタル酸以外の芳香族ジカルボン酸又はそのエステル形成性誘導体を用いる場合、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８－１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４－１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５－１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体や酸ハロゲン化物等）を用いることができる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。
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, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'- C 8-14 aromatic dicarboxylic acids such as dicarboxy diphenyl ether; C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid Acids: ester-forming derivatives of these dicarboxylic acid components (such as C 1-6 alkyl ester derivatives and acid halides) can be used. These dicarboxylic acid components can be used alone or in combination of two or more.
これらのジカルボン酸成分の中では、イソフタル酸等のＣ８－１２の芳香族ジカルボン酸、及び、アジピン酸、アゼライン酸、セバシン酸等のＣ６－１２のアルカンジカルボン酸がより好ましい。
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.
ポリブチレンテレフタレート樹脂の調製において、コモノマー成分として１，４－ブタンジオール以外のグリコール成分を用いる場合、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２－１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２－４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）を用いることができる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。
When a glycol component other than 1,4-butanediol is used as a comonomer component in the preparation of the polybutylene terephthalate resin, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl C 2-10 alkylene glycols such as glycol and 1,3-octanediol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; alicyclic diols such as cyclohexane dimethanol and hydrogenated bisphenol A; bisphenol A, aromatic diols such as 4,4'-dihydroxybiphenyl; ethylene oxide 2-mole adduct of bisphenol A, propylene oxide of bisphenol A Such as 3 mole adduct, alkylene oxide adducts of C 2-4 of bisphenol A; or ester-forming derivatives of these glycols (acetylated, etc.) can be used. These glycol components can be used alone or in combination of two or more.
これらのグリコール成分の中では、エチレングリコール、トリメチレングリコール等のＣ２－６のアルキレングリコール、ジエチレングリコール等のポリオキシアルキレングリコール、又は、シクロヘキサンジメタノール等の脂環式ジオール等がより好ましい。
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 cyclohexane dimethanol are more preferable.
ジカルボン酸成分及びグリコール成分の他に使用できるコモノマー成分としては、例えば、４－ヒドロキシ安息香酸、３－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４－カルボキシ－４’－ヒドロキシビフェニル等の芳香族ヒドロキシカルボン酸；グリコール酸、ヒドロキシカプロン酸等の脂肪族ヒドロキシカルボン酸；プロピオラクトン、ブチロラクトン、バレロラクトン、カプロラクトン（ε－カプロラクトン等）等のＣ３－１２ラクトン；これらのコモノマー成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体、酸ハロゲン化物、アセチル化物等）が挙げられる。
As a comonomer component which can be used in addition to the dicarboxylic acid component and the glycol component, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl etc. Aromatic hydroxycarboxylic acids; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg ε-caprolactone); esters of these comonomer components Examples include forming derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylated compounds and the like).
ポリブチレンテレフタレート樹脂の含有量は、樹脂組成物の全質量の３０～９０質量％であることが好ましく、４０～８０質量％であることがより好ましく、５０～７０質量％であることがさらに好ましい。
The content of the polybutylene terephthalate resin is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 70% by mass of the total mass of the resin composition. .
（ハロゲン化ベンジルアクリレート系難燃剤）
本発明に用いられるハロゲン化ベンジルアクリレート系難燃剤としては、下記一般式（Ｉ）で示されるブロム化アクリル重合体が挙げられる。
式中のＸは少なくとも１つ以上が臭素である。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。 (Halogenated benzyl acrylate flame retardant)
Examples of halogenated benzyl acrylate flame retardants used in the present invention include brominated acrylic polymers represented by the following general formula (I).
In the formula, at least one or more of X is bromine. The number of X is 1 to 5 in one constitutional unit, but is preferably 3 to 5 in view of the effect of flame retardancy. The average degree of polymerization m is from 10 to 2,000, preferably from 15 to 1,000. When the average degree of polymerization is low, the thermal stability is deteriorated, and when it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated. The brominated acrylic polymers may be used alone or in combination of two or more.
本発明に用いられるハロゲン化ベンジルアクリレート系難燃剤としては、下記一般式（Ｉ）で示されるブロム化アクリル重合体が挙げられる。
式中のＸは少なくとも１つ以上が臭素である。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。 (Halogenated benzyl acrylate flame retardant)
Examples of halogenated benzyl acrylate flame retardants used in the present invention include brominated acrylic polymers represented by the following general formula (I).
In the formula, at least one or more of X is bromine. The number of X is 1 to 5 in one constitutional unit, but is preferably 3 to 5 in view of the effect of flame retardancy. The average degree of polymerization m is from 10 to 2,000, preferably from 15 to 1,000. When the average degree of polymerization is low, the thermal stability is deteriorated, and when it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated. The brominated acrylic polymers may be used alone or in combination of two or more.
本発明に用いられるハロゲン化ベンジルアクリレート系難燃剤は、当該難燃剤自体である上記のブロム化アクリル重合体以外に、ハロゲン化芳香族化合物を、好ましくは１００ｐｐｍ以上１５００ｐｐｍ以下、より好ましくは１２０ｐｐｍ以上１０００ｐｐｍ以下、さらに好ましくは１５０ｐｐｍ以上８００ｐｐｍ以下、特に好ましくは２００ｐｐｍ以上５００ｐｐｍ以下の状態で重合することが好ましい。難燃剤以外のハロゲン化芳香族化合物の含有量は、例えば、ハロゲン化ベンジルアクリレート系難燃剤を粉砕した試料を、ヘッドスペース中で加熱処理した際の発生ガスを、ガスクロマトグラフにより測定し、ハロゲン化芳香族化合物に由来するガス発生量から求めることができる。
The halogenated benzyl acrylate flame retardant used in the present invention is preferably 100 ppm to 1500 ppm, more preferably 120 ppm to 1000 ppm of a halogenated aromatic compound, in addition to the above-mentioned brominated acrylic polymer that is the flame retardant itself. It is preferable to polymerize in a state of 150 ppm or more and 800 ppm or less, more preferably 200 ppm or more and 500 ppm or less. The content of the halogenated aromatic compound other than the flame retardant can be determined, for example, by measuring the generated gas when the sample obtained by pulverizing the halogenated benzyl acrylate flame retardant is heat-treated in the head space by gas chromatograph. It can obtain | require from the gas generation amount originating in an aromatic compound.
一般式（Ｉ）で表されるブロム化アクリル重合体は臭素を含有するベンジルアクリレートを単独で重合することによって得られるが、類似構造のベンジルメタクリレート等を共重合させてもよい。臭素含有ベンジルアクリレートとしては、ペンタブロモベンジルアクリレート、テトラブロモベンジルアクリレート、トリブロモベンジルアクリレート、又はその混合物が挙げられる。中でも、ペンタブロモベンジルアクリレートが好ましい。また、共重合可能な成分であるベンジルメタクリレートとしては、上記したアクリレートに対応するメタクリレートが挙げられる。さらにはビニル系モノマーとの共重合も可能であり、アクリル酸、メチルアクリレート、エチルアクリレート、ブチルアクリレート、ベンジルアクリレートのようなアクリル酸エステル類、メタクリル酸、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、ベンジルメタクリレートのようなメタクリル酸エステル類、スチレン、アクリロニトリル、フマル酸、マレイン酸のような不飽和カルボン酸又はその無水物、酢酸ビニル、塩化ビニルなどが挙げられる。また、架橋性のビニル系モノマー、キシリレンジアクリレート、キシリレンジメタクリレート、テトラブロムキシリレンジアクリレート、テトラブロムキシリレンジメタクリレート、ブタジエン、イソプレン、ジビニルベンゼンも使用できる。これらはベンジルアクリレートやベンジルメタクリレートに対し等モル量以下、好ましくは０．５倍モル量以下が使用される。
The brominated acrylic polymer represented by the general formula (I) can be obtained by polymerizing bromine-containing benzyl acrylate 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. Among them, pentabromobenzyl acrylate is preferred. Moreover, as a benzyl methacrylate which is a component which can be copolymerized, the methacrylate corresponding to the above-mentioned acrylate is mentioned. Furthermore, copolymerization with a vinyl monomer is also possible, and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as benzyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate And methacrylic acid esters such as styrene, unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid and maleic acid or anhydrides thereof, vinyl acetate, vinyl chloride and the like. Further, crosslinkable vinyl monomers, xylylene diacrylate, xylylene methacrylate, tetrabromo xylylene acrylate, tetrabromo xylylene methacrylate, butadiene, isoprene and divinyl benzene can also be used. These are used in an equimolar amount or less, preferably 0.5 times or less the molar amount with respect to benzyl acrylate and benzyl methacrylate.
上記のブロム化アクリル重合体の製造法の一例を示すと、ブロム化アクリルのモノマーを溶液重合あるいは、塊状重合にて所定の重合度に反応させる方法が挙げられる。溶液重合の場合、溶媒としてハロゲン化ベンゼンや、クロロベンゼンなどのハロゲン化芳香族化合物を用いることが好ましい。
As an example of the method for producing the above-mentioned brominated acrylic polymer, there can be mentioned a method in which a monomer of brominated acrylic is reacted to a predetermined polymerization degree by solution polymerization or bulk polymerization. In the case of solution polymerization, it is preferable to use a halogenated benzene or a halogenated aromatic compound such as chlorobenzene as a solvent.
上記のブロム化アクリル重合体は、残留ポリアクリル酸ナトリウム等の反応副生成物を除去するために、水及び／又はアルカリ（土類）金属イオンを含有する水溶液にて洗浄されることが好ましい。アルカリ（土類）金属イオンを含有する水溶液はアルカリ（土類）金属塩を水に投入することで容易に得られるが、塩化物イオン、リン酸イオン等を含まないアルカリ（土類）金属である水酸化物（例えば水酸化カルシウム）が最適である。アルカリ（土類）金属塩として、例えば水酸化カルシウムを用いる場合、水酸化カルシウムは一般に２０℃において１００ｇの水中に０．１２６ｇ程度可溶であり、水溶液濃度は溶解度までであれば特に規定はない。また、水及び／又はアルカリ（土類）金属イオンを含有する水溶液による洗浄の手法も特に限定されず、ブロム化アクリル重合体を適当な時間、水及び／又はアルカリ（土類）金属イオンを含有する水溶液に浸漬させる等の手法で良い。上記、水及び／又はアルカリ（土類）金属イオンを含有する水溶液による洗浄処理を終えたブロム化アクリル重合体は、一般的に温水抽出分中の乾固分が１００ｐｐｍ以下のものとなり、このようなブロム化アクリル重合体を用いる場合、その成形品表面に異物を発生させることが殆どなくなる。
The above-mentioned brominated acrylic polymer is preferably washed with an aqueous solution containing water and / or an alkali (earth) metal ion in order to remove reaction by-products such as sodium polyacrylate remaining. An aqueous solution containing an alkali (earth) metal ion can be easily obtained by introducing an alkali (earth) metal salt into water, but an alkali (earth) metal containing no chloride ion, phosphate ion, etc. Certain hydroxides (eg calcium hydroxide) are optimal. When calcium hydroxide, for example, is used as the alkali (earth metal) metal salt, calcium hydroxide is generally soluble in water at 100 ° C. at about 0.126 g, and the concentration of the aqueous solution is not particularly limited as far as it is soluble. . Also, the method of washing with an aqueous solution containing water and / or alkali (earth) metal ions is not particularly limited, and the brominated acrylic polymer contains water and / or alkali (earth) metal ions for a suitable time. It may be a method of immersing in an aqueous solution. The brominated acrylic polymer that has been washed with an aqueous solution containing water and / or an alkali (earth) metal ion, as described above, generally has a dry matter content of 100 ppm or less in a hot water extract, When a brominated acrylic polymer is used, the generation of foreign matter on the surface of the molded article is almost eliminated.
本発明の難燃性ポリブチレンテレフタレート樹脂組成物は、前述の難燃剤以外のハロゲン化芳香族化合物の含有量が、０．５ｐｐｍ以上５ｐｐｍ以下であり、好ましくは０．８ｐｐｍ以上４ｐｐｍ以下、より好ましくは１．０ｐｐｍ以上３ｐｐｍ以下である。難燃剤以外のハロゲン化芳香族化合物を上記範囲で含有することにより、本発明の難燃性ポリブチレンテレフタレート樹脂組成物を回路遮断器等の用途に用いた場合、アークによる接点不良を抑制するための消弧ガスの発生を促すことができる。なお、消弧ガスとして作用するガスとしては、上記のハロゲン化芳香族化合物に由来するガスや不活性ガスなど種々のものが知られており、ポリブチレンテレフタレート樹脂に由来する分解ガスもこれに含まれうる。このような難燃剤以外のハロゲン化芳香族化合物の含有量は、例えば、ポリブチレンテレフタレート樹脂組成物を粉砕した試料を、ヘッドスペース中で加熱処理した際の発生ガスを、ガスクロマトグラフにより測定し、ハロゲン化芳香族化合物に由来するガス発生量から求めることができる。
In the flame retardant polybutylene terephthalate resin composition of the present invention, the content of the halogenated aromatic compound other than the above-mentioned flame retardant is 0.5 ppm or more and 5 ppm or less, preferably 0.8 ppm or more and 4 ppm or less, more preferably Is 1.0 ppm or more and 3 ppm or less. When the flame retardant polybutylene terephthalate resin composition of the present invention is used for applications such as circuit breakers by containing a halogenated aromatic compound other than a flame retardant in the above range, contact defects due to arcing are suppressed Generation of arc-extinguishing gas. In addition, various gases such as gases derived from the above-mentioned halogenated aromatic compounds and inert gases are known as gases acting as arc extinguishing gases, and decomposition gases derived from polybutylene terephthalate resin are also included therein. It is possible. The content of the halogenated aromatic compound other than such a flame retardant is, for example, measured by gas chromatograph the gas generated when the sample obtained by pulverizing the polybutylene terephthalate resin composition is heat-treated in the head space, It can obtain | require from the gas generation amount originating in a halogenated aromatic compound.
上記樹脂の難燃化において、アンチモン系の難燃助剤をあわせて使用することが好ましい。難燃助剤の代表的なものとしては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、ピロアンチモン酸ナトリウム等が挙げられる。さらに、燃焼した樹脂が滴下することによる延焼を防ぐ目的で、ポリテトラフルオロエチレン等の滴下防止剤をあわせて使用することも好ましい。
In the flame retardancy of the above-mentioned resin, it is preferable to use an antimony-based flame retardant auxiliary together. Typical examples of the flame retardant auxiliary include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate and the like. Furthermore, it is also preferable to use together an anti-dripping agent such as polytetrafluoroethylene for the purpose of preventing fire spreading due to dripping of the burned resin.
上記のブロム化アクリル重合体及びアンチモン系難燃助剤の樹脂に対する添加の範囲は、ポリブチレンテレフタレート樹脂１００質量部に対して前記重合体３～３０質量部、アンチモン系難燃助剤１～２０質量部の範囲が好ましい。ブロム化アクリル重合体及びアンチモン系難燃助剤の添加量が過少であると十分な難燃性を付与することができず、過大であると成形品としての物性を悪化させることがある。
The range of addition of the above-mentioned brominated acrylic polymer and antimony-based flame retardant auxiliary to the resin is 3 to 30 parts by mass of the above-mentioned polymer with respect to 100 parts by mass of polybutylene terephthalate resin, and 1 to 20 antimony-based flame retardant auxiliary A range of parts by weight is preferred. When the addition amount of the brominated acrylic polymer and the antimony-based flame retardant auxiliary is too small, sufficient flame retardancy can not be imparted, and when it is too large, physical properties as a molded article may be deteriorated.
（充填剤）
本発明の組成物には必要に応じて充填剤が使用される。このような充填剤は、機械的強度、耐熱性、寸法安定性、電気的性質等の性能に優れた性質を得るためには配合することが好ましく、特に剛性を高める目的で有効である。これは目的に応じて繊維状、粉粒状又は板状の充填剤が用いられる。 (filler)
Fillers are optionally used in the compositions of the present invention. Such a filler is preferably blended to obtain properties excellent in performance such as mechanical strength, heat resistance, dimensional stability, electrical properties and the like, and is particularly effective for the purpose of enhancing rigidity. Depending on the purpose, fibrous, particulate or plate-like fillers may be used.
本発明の組成物には必要に応じて充填剤が使用される。このような充填剤は、機械的強度、耐熱性、寸法安定性、電気的性質等の性能に優れた性質を得るためには配合することが好ましく、特に剛性を高める目的で有効である。これは目的に応じて繊維状、粉粒状又は板状の充填剤が用いられる。 (filler)
Fillers are optionally used in the compositions of the present invention. Such a filler is preferably blended to obtain properties excellent in performance such as mechanical strength, heat resistance, dimensional stability, electrical properties and the like, and is particularly effective for the purpose of enhancing rigidity. Depending on the purpose, fibrous, particulate or plate-like fillers may be used.
繊維状充填剤としては、ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化珪素繊維、硼素繊維、チタン酸カリ繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物などが挙げられる。なお、ポリアミド、フッ素樹脂、アクリル樹脂などの高融点の有機質繊維状物質も使用することができる。
Examples of fibrous fillers include glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and further stainless steel, aluminum, titanium, Examples thereof include fibrous materials of metals such as copper and brass. In addition, a high melting point organic fibrous material such as polyamide, fluorine resin and acrylic resin can also be used.
粉粒状充填剤としては、カーボンブラック、石英粉末、ガラスビーズ、ガラス粉、珪酸カルシウム、珪酸アルミニウム、カオリン、タルク、クレー、珪藻土、ウォラストナイトなどの珪酸塩、酸化鉄、酸化チタン、アルミナなどの金属の酸化物、炭酸カルシウム、炭酸マグネシウムなどの金属の炭酸塩、硫酸カルシウム、硫酸バリウムなどの金属の硫酸塩、その他、炭化珪素、窒化珪素、窒化硼素、各種金属粉末等が挙げられる。
Particulate fillers include carbon black, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, silicates such as diatomaceous earth, wollastonite, iron oxide, titanium oxide, alumina, etc. Metal oxides, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and others, silicon carbide, silicon nitride, boron nitride, various metal powders and the like can be mentioned.
また、板状無機充填剤としては、マイカ、ガラスフレーク、各種金属箔等が挙げられる。
Moreover, as a plate-like inorganic filler, mica | cuttle-fish, glass flakes, various metal foil etc. are mentioned.
充填剤の種類は特に限定されず、１種又は複数種以上の充填剤を添加することができる。特に、チタン酸カリ繊維、マイカ、タルク、ウォラストナイトを使用することが好ましい。
The type of filler is not particularly limited, and one or more fillers can be added. In particular, potassium titanate fiber, mica, talc and wollastonite are preferably used.
充填剤の添加量は特に規定されるものではないが、ポリブチレンテレフタレート樹脂１００質量部に対して２００質量部以下が好ましい。充填剤を過剰に添加した場合は成形性に劣り靭性の低下が見られる。
Although the addition amount of the filler is not particularly limited, it is preferably 200 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin. When the filler is added in excess, the formability deteriorates and the toughness decreases.
（添加剤）
さらに本発明の組成物には、その目的に応じ、難燃性以外の所望の特性を付与するために、一般に熱可塑性樹脂等に添加される公知の物質を添加併用することができる。例えば酸化防止剤、紫外線吸収剤、光安定剤等の安定剤、帯電防止剤、滑剤、離型剤、染料や顔料等の着色剤、可塑剤等いずれも配合することが可能である。特に耐熱性を向上させるための酸化防止剤の添加は効果的である。 (Additive)
Furthermore, in accordance with the purpose of the composition of the present invention, known materials generally added to thermoplastic resins and the like can be used in combination in order to impart desired properties other than flame retardancy. For example, stabilizers such as antioxidants, ultraviolet light absorbers, light stabilizers, etc., antistatic agents, lubricants, mold release agents, coloring agents such as dyes and pigments, plasticizers, etc. can be blended. In particular, the addition of an antioxidant to improve the heat resistance is effective.
さらに本発明の組成物には、その目的に応じ、難燃性以外の所望の特性を付与するために、一般に熱可塑性樹脂等に添加される公知の物質を添加併用することができる。例えば酸化防止剤、紫外線吸収剤、光安定剤等の安定剤、帯電防止剤、滑剤、離型剤、染料や顔料等の着色剤、可塑剤等いずれも配合することが可能である。特に耐熱性を向上させるための酸化防止剤の添加は効果的である。 (Additive)
Furthermore, in accordance with the purpose of the composition of the present invention, known materials generally added to thermoplastic resins and the like can be used in combination in order to impart desired properties other than flame retardancy. For example, stabilizers such as antioxidants, ultraviolet light absorbers, light stabilizers, etc., antistatic agents, lubricants, mold release agents, coloring agents such as dyes and pigments, plasticizers, etc. can be blended. In particular, the addition of an antioxidant to improve the heat resistance is effective.
［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］
本発明の難燃性ポリブチレンテレフタレート樹脂組成物の形態は、粉粒体混合物であってもよいし、ペレット等の溶融混合物（溶融混練物）であってもよい。本発明の一実施形態のポリブチレンテレフタレート樹脂組成物の製造方法は特に限定されるものではなく、当該技術分野で知られている設備及び方法を用いて製造することができる。例えば、必要な成分を混合し、１軸又は２軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。押出機又はその他の溶融混練装置は複数使用してもよい。また、全ての成分をホッパから同時に投入してもよいし、一部の成分はサイドフィード口から投入してもよい。 [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 powder-particle mixture, or may be a melt mixture (melt-kneaded product) such as pellets. The method for producing the polybutylene terephthalate resin composition of one embodiment of the present invention is not particularly limited, and can be produced using equipment and methods known in the art. For example, necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. A plurality of extruders or other melt kneading apparatuses may be used. Moreover, all the components may be simultaneously fed from the hopper, or some components may be fed from the side feed port.
本発明の難燃性ポリブチレンテレフタレート樹脂組成物の形態は、粉粒体混合物であってもよいし、ペレット等の溶融混合物（溶融混練物）であってもよい。本発明の一実施形態のポリブチレンテレフタレート樹脂組成物の製造方法は特に限定されるものではなく、当該技術分野で知られている設備及び方法を用いて製造することができる。例えば、必要な成分を混合し、１軸又は２軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。押出機又はその他の溶融混練装置は複数使用してもよい。また、全ての成分をホッパから同時に投入してもよいし、一部の成分はサイドフィード口から投入してもよい。 [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 powder-particle mixture, or may be a melt mixture (melt-kneaded product) such as pellets. The method for producing the polybutylene terephthalate resin composition of one embodiment of the present invention is not particularly limited, and can be produced using equipment and methods known in the art. For example, necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. A plurality of extruders or other melt kneading apparatuses may be used. Moreover, all the components may be simultaneously fed from the hopper, or some components may be fed from the side feed port.
また、本発明の難燃性ポリブチレンテレフタレート樹脂組成物は、真空乾燥（真空引き）により製造することが好ましい。真空乾燥には、一般的に用いられているエバポレーターや、オーブンなどを用いることができる。
Further, the flame retardant polybutylene terephthalate resin composition of the present invention is preferably produced by vacuum drying (vacuum evacuation). For vacuum drying, a commonly used evaporator, an oven or the like can be used.
（実施例）
以下、実施例により本発明を具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、特性評価は以下の方法により行った。
（１）ハロゲン化芳香族化合物含有量、消弧ガス発生
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを粉砕したものを試料とした。試料を５ｇとり、２０ｍｌのヘッドスペース中に１５０℃で１時間放置した後、装置：横河ヒューレット・パッカード社製ＨＰ５８９０Ａ、カラム：ＨＲ－１７０１（０．３２ｍｍ径×３０ｍ）を用い、５０℃で１分間保持後、５℃／ｍｉｎで昇温させ、ガスクロマトグラフにより、ハロゲン化芳香族化合物に由来するガス発生量を測定し、ハロゲン化芳香族化合物の含有量をｐｐｍで示すとともに、消弧ガスの発生状態を評価した。消弧ガスの発生が確認されたものを○、そうでないものを×とした。結果を表１に示す。
（２）金属腐蝕性
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレット５０ｇを、１ｃｍ×１ｃｍの銀板とともに３００ｍｌのガラス製共栓ビンに入れ栓をして、１２０℃のギアオーブン中で２００時間静置した後、銀板の表面を目視にて確認し、腐蝕が発生していないものを◎、腐蝕がほとんど発生していないものを○、腐蝕がわずかに発生しているものを△、著しい腐蝕が発生していたものを×として評価した。結果を表１に示す。
（３）難燃性
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを、１４０℃で３時間乾燥させた後、シリンダー温度２５０℃、金型温度７０℃にて射出成形し、ＵＬ９４に準拠し、厚さ１／３２インチの試験片を作製して燃焼性を評価した。結果を表１に示す。 (Example)
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The characteristics were evaluated by the following method.
(1) Halogenated aromatic compound content, arc extinguishing gas generation A twin screw extruder having a screw of 30 mmφ (made by Nippon Steel Co., Ltd.) having a material obtained by dry blending the components and composition (parts by mass) shown in Table 1 ) And melt-kneaded at 260 ° C., and pellets of the obtained polybutylene terephthalate resin composition were crushed to obtain a sample. Take 5 g of the sample and leave it in a head space of 20 ml at 150 ° C. for 1 hour, then use the device: HP 5890A by Yokogawa Hewlett Packard, column: HR-1701 (0.32 mm diameter × 30 m) at 50 ° C. After holding for 1 minute, the temperature is raised at 5 ° C./min, and the gas generation amount derived from the halogenated aromatic compound is measured by the gas chromatograph to show the content of the halogenated aromatic compound in ppm and the arc extinguishing gas Of the occurrence of The thing in which generation | occurrence | production of arc-extinguishing gas was confirmed was made into O, and the thing which is not so was made into *. The results are shown in Table 1.
(2) Metal corrosion property The material dry blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin screw extruder (made by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. After kneading, 50 g of the pellet of the obtained polybutylene terephthalate resin composition was put into a 300 ml glass stopper bottle together with a 1 cm × 1 cm silver plate and stoppered and allowed to stand for 200 hours in a gear oven at 120 ° C. After that, the surface of the silver plate was visually checked, and those with no corrosion were ◎, those with little corrosion were ○, those with slight corrosion were Δ, significant corrosion occurred Those that had been evaluated were evaluated as x. 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 (made by Japan Steel Works Ltd.) having a screw of 30 mmφ and melted at 260 ° C. The pellets of the polybutylene terephthalate resin composition thus obtained are kneaded and 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. in accordance with UL94, thickness 1 Test pieces of / 32 inches were prepared to evaluate their flammability. The results are shown in Table 1.
以下、実施例により本発明を具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、特性評価は以下の方法により行った。
（１）ハロゲン化芳香族化合物含有量、消弧ガス発生
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを粉砕したものを試料とした。試料を５ｇとり、２０ｍｌのヘッドスペース中に１５０℃で１時間放置した後、装置：横河ヒューレット・パッカード社製ＨＰ５８９０Ａ、カラム：ＨＲ－１７０１（０．３２ｍｍ径×３０ｍ）を用い、５０℃で１分間保持後、５℃／ｍｉｎで昇温させ、ガスクロマトグラフにより、ハロゲン化芳香族化合物に由来するガス発生量を測定し、ハロゲン化芳香族化合物の含有量をｐｐｍで示すとともに、消弧ガスの発生状態を評価した。消弧ガスの発生が確認されたものを○、そうでないものを×とした。結果を表１に示す。
（２）金属腐蝕性
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレット５０ｇを、１ｃｍ×１ｃｍの銀板とともに３００ｍｌのガラス製共栓ビンに入れ栓をして、１２０℃のギアオーブン中で２００時間静置した後、銀板の表面を目視にて確認し、腐蝕が発生していないものを◎、腐蝕がほとんど発生していないものを○、腐蝕がわずかに発生しているものを△、著しい腐蝕が発生していたものを×として評価した。結果を表１に示す。
（３）難燃性
表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを、１４０℃で３時間乾燥させた後、シリンダー温度２５０℃、金型温度７０℃にて射出成形し、ＵＬ９４に準拠し、厚さ１／３２インチの試験片を作製して燃焼性を評価した。結果を表１に示す。 (Example)
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The characteristics were evaluated by the following method.
(1) Halogenated aromatic compound content, arc extinguishing gas generation A twin screw extruder having a screw of 30 mmφ (made by Nippon Steel Co., Ltd.) having a material obtained by dry blending the components and composition (parts by mass) shown in Table 1 ) And melt-kneaded at 260 ° C., and pellets of the obtained polybutylene terephthalate resin composition were crushed to obtain a sample. Take 5 g of the sample and leave it in a head space of 20 ml at 150 ° C. for 1 hour, then use the device: HP 5890A by Yokogawa Hewlett Packard, column: HR-1701 (0.32 mm diameter × 30 m) at 50 ° C. After holding for 1 minute, the temperature is raised at 5 ° C./min, and the gas generation amount derived from the halogenated aromatic compound is measured by the gas chromatograph to show the content of the halogenated aromatic compound in ppm and the arc extinguishing gas Of the occurrence of The thing in which generation | occurrence | production of arc-extinguishing gas was confirmed was made into O, and the thing which is not so was made into *. The results are shown in Table 1.
(2) Metal corrosion property The material dry blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin screw extruder (made by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. After kneading, 50 g of the pellet of the obtained polybutylene terephthalate resin composition was put into a 300 ml glass stopper bottle together with a 1 cm × 1 cm silver plate and stoppered and allowed to stand for 200 hours in a gear oven at 120 ° C. After that, the surface of the silver plate was visually checked, and those with no corrosion were ◎, those with little corrosion were ○, those with slight corrosion were Δ, significant corrosion occurred Those that had been evaluated were evaluated as x. 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 (made by Japan Steel Works Ltd.) having a screw of 30 mmφ and melted at 260 ° C. The pellets of the polybutylene terephthalate resin composition thus obtained are kneaded and 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. in accordance with UL94, thickness 1 Test pieces of / 32 inches were prepared to evaluate their flammability. The results are shown in Table 1.
表中のＮ．Ｄ．は検出限界（０．１ｐｐｍ）以下であることを示す。
N. in the table. D. Indicates that it is below the detection limit (0.1 ppm).
表１に記載の各成分の詳細は下記の通りである。
ＰＢＴ樹脂：ウィンテックポリマー株式会社製、末端カルボキシル基濃度１８ｍｅｑ／ｋｇ、固有粘度０．８８ｄＬ／ｇのポリブチレンテレフタレート樹脂
難燃剤１：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量１５０ｐｐｍ）
難燃剤２：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量２５０ｐｐｍ）
難燃剤３：溶媒にエチレングリコールモノメチルエーテルを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量８ｐｐｍ）
難燃剤４：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量１８００ｐｐｍ）
難燃助剤：三酸化アンチモン
滴下防止剤：ポリテトラフルオロエチレン
酸化防止剤：テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン株式会社製「イルガノックス１０１０」）
離型剤：低分子量ポリエチレン（三洋化成工業株式会社製「サンワックス１６１－Ｐ」） The details of each component described in Table 1 are as follows.
PBT resin: manufactured by Wintech Polymer Co., Ltd., polybutylene terephthalate resin flame retardant 1 having a terminal carboxyl group concentration of 18 meq / kg and an intrinsic viscosity of 0.88 dL / g 1: polypentabromobenzyl acrylate polymerized using chlorobenzene as a solvent Content of halogenated aromatic compounds other than flame retardant 150 ppm)
Flame Retardant 2: Polypentabromobenzyl acrylate polymerized with chlorobenzene as solvent (250 ppm content of halogenated aromatic compounds other than flame retardants)
Flame retardant 3: Polypentabromobenzyl acrylate polymerized using ethylene glycol monomethyl ether as a solvent (halogenated aromatic compound content other than flame retardant 8 ppm)
Flame Retardant 4: Polypentabromobenzyl acrylate polymerized using chlorobenzene as solvent (1800 ppm content of halogenated aromatic compounds other than flame retardants)
Flame retardant auxiliary agent: Antimony trioxide antidripping agent: polytetrafluoroethylene antioxidant: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan Ltd.) Made of "Irganox 1010")
Release agent: Low molecular weight polyethylene ("Sun wax 161-P" manufactured by Sanyo Chemical Industries, Ltd.)
ＰＢＴ樹脂：ウィンテックポリマー株式会社製、末端カルボキシル基濃度１８ｍｅｑ／ｋｇ、固有粘度０．８８ｄＬ／ｇのポリブチレンテレフタレート樹脂
難燃剤１：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量１５０ｐｐｍ）
難燃剤２：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量２５０ｐｐｍ）
難燃剤３：溶媒にエチレングリコールモノメチルエーテルを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量８ｐｐｍ）
難燃剤４：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量１８００ｐｐｍ）
難燃助剤：三酸化アンチモン
滴下防止剤：ポリテトラフルオロエチレン
酸化防止剤：テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン株式会社製「イルガノックス１０１０」）
離型剤：低分子量ポリエチレン（三洋化成工業株式会社製「サンワックス１６１－Ｐ」） The details of each component described in Table 1 are as follows.
PBT resin: manufactured by Wintech Polymer Co., Ltd., polybutylene terephthalate resin flame retardant 1 having a terminal carboxyl group concentration of 18 meq / kg and an intrinsic viscosity of 0.88 dL / g 1: polypentabromobenzyl acrylate polymerized using chlorobenzene as a solvent Content of halogenated aromatic compounds other than flame retardant 150 ppm)
Flame Retardant 2: Polypentabromobenzyl acrylate polymerized with chlorobenzene as solvent (250 ppm content of halogenated aromatic compounds other than flame retardants)
Flame retardant 3: Polypentabromobenzyl acrylate polymerized using ethylene glycol monomethyl ether as a solvent (halogenated aromatic compound content other than flame retardant 8 ppm)
Flame Retardant 4: Polypentabromobenzyl acrylate polymerized using chlorobenzene as solvent (1800 ppm content of halogenated aromatic compounds other than flame retardants)
Flame retardant auxiliary agent: Antimony trioxide antidripping agent: polytetrafluoroethylene antioxidant: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan Ltd.) Made of "Irganox 1010")
Release agent: Low molecular weight polyethylene ("Sun wax 161-P" manufactured by Sanyo Chemical Industries, Ltd.)
Claims (9)
- ポリブチレンテレフタレート樹脂と、
ハロゲン化ベンジルアクリレート系難燃剤とを含有する難燃性ポリブチレンテレフタレート樹脂組成物であって、
ヘッドスペースガスクロマトグラフ法（１５０℃、１時間加熱）により測定される、前記難燃剤以外のハロゲン化芳香族化合物の含有量が０．５ｐｐｍ以上５ｐｐｍ以下であることを特徴とする、難燃性ポリブチレンテレフタレート樹脂組成物。 Polybutylene terephthalate resin,
A flame retardant polybutylene terephthalate resin composition comprising a halogenated benzyl acrylate flame retardant,
The flame retardant poly is characterized in that the content of the halogenated aromatic compound other than the flame retardant is 0.5 ppm or more and 5 ppm or less, which is measured by head space gas chromatography (150 ° C., heating for 1 hour) Butylene terephthalate resin composition. - ハロゲン化ベンジルアクリレート系難燃剤が、一般式（Ｉ）で表されるブロム化アクリル重合体である、請求項１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。
（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は臭素であり、ｍは１０～２０００の数である。） The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated benzyl acrylate flame retardant is a brominated acrylic polymer represented by the general formula (I).
(Wherein, X is a hydrogen atom or a bromine atom, at least one or more of X is a bromine, and m is a number of 10 to 2000). - 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である、請求項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。 The flame-retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the halogenated benzyl acrylate flame retardant is polypentabromobenzyl acrylate.
- 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である、請求項１から３のいずれか一項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。 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 is a halogenated benzene.
- 前記難燃剤以外のハロゲン化芳香族化合物が、クロロベンゼンである、請求項１から４のいずれか一項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。 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 is chlorobenzene.
- ハロゲン化ベンジルアクリレート系難燃剤の製造時に、溶媒としてハロゲン化芳香族化合物を用いることを特徴とする、請求項１から５のいずれか一項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。 The process for producing a flame retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5, wherein a halogenated aromatic compound is used as a solvent at the time of producing the halogenated benzyl acrylate flame retardant. Method.
- ハロゲン化芳香族化合物が、ハロゲン化ベンゼンである、請求項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の製造方法。 The manufacturing method of the flame-retardant polybutylene-terephthalate-resin composition of Claim 6 whose halogenated aromatic compound is halogenated benzene.
- ハロゲン化芳香族化合物が、クロロベンゼンである、請求項６または７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。 The manufacturing method of the flame-retardant polybutylene terephthalate resin composition of Claim 6 or 7 whose halogenated aromatic compound is chlorobenzene.
- 真空乾燥を行う、請求項６から８のいずれか一項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。
The manufacturing method of the flame-retardant polybutylene terephthalate resin composition as described in any one of Claims 6-8 which vacuum-dry.
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| CN105669885B (en) * | 2016-01-26 | 2018-09-28 | 寿光市泰源化工有限公司 | A kind of high-purity high stability polypentabrombenzamide acrylate industrialized process for preparing |
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2017
- 2017-08-22 JP JP2017159370A patent/JP7079578B2/en active Active
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2018
- 2018-08-21 WO PCT/JP2018/030796 patent/WO2019039464A1/en active Application Filing
- 2018-08-21 CN CN201880053899.XA patent/CN111051431B/en active Active
- 2018-08-22 TW TW107129221A patent/TWI780210B/en active
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| US4514607A (en) * | 1981-04-13 | 1985-04-30 | The Electricity Council | Electrical circuit interrupting devices |
| WO2003044818A1 (en) * | 2001-11-20 | 2003-05-30 | Mitsubishi Denki Kabushiki Kaisha | Circuit breaker |
| WO2011148796A1 (en) * | 2010-05-27 | 2011-12-01 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition |
| JP2014125515A (en) * | 2012-12-26 | 2014-07-07 | Mitsubishi Engineering Plastics Corp | Polyester resin composition for circuit breaker |
| JP2015212381A (en) * | 2014-05-05 | 2015-11-26 | ランクセス・ドイチュランド・ゲーエムベーハー | Polyester compositions |
| WO2017043334A1 (en) * | 2015-09-11 | 2017-03-16 | 三菱エンジニアリングプラスチックス株式会社 | Polyester-based resin composition and production method for same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI780210B (en) | 2022-10-11 |
| TW201920410A (en) | 2019-06-01 |
| JP7079578B2 (en) | 2022-06-02 |
| CN111051431A (en) | 2020-04-21 |
| JP2019038865A (en) | 2019-03-14 |
| CN111051431B (en) | 2023-03-31 |
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