JP2006291076A - Thermoplastic resin composition as coil-sealing material - Google Patents
Thermoplastic resin composition as coil-sealing material Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 38
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 38
- 239000003566 sealing material Substances 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229920001955 polyphenylene ether Polymers 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000000945 filler Substances 0.000 claims description 21
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000412 polyarylene Polymers 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- -1 arylene sulfide Chemical compound 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 238000005259 measurement Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000010445 mica Substances 0.000 description 5
- 229910052618 mica group Inorganic materials 0.000 description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
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Abstract
Description
本発明は射出成形や押し出し成形に適したコイル封止材用熱可塑性樹脂組成物に関する。更に詳しくは、特に帯電防止性能と絶縁性能を兼ね備え、低反り性で、耐熱性に優れたコイル封止材用熱可塑性樹脂に関する。 The present invention relates to a thermoplastic resin composition for a coil sealing material suitable for injection molding and extrusion molding. More specifically, the present invention relates to a thermoplastic resin for a coil sealing material that has both antistatic performance and insulation performance, low warpage, and excellent heat resistance.
近年、電機・電子機器、自動車機器、化学機器などを構成する部品材料には機器の小型化や軽量化を目的として機械的強度、耐熱性、耐薬品性に優れ、更には難燃性に優れた熱可塑性樹脂の要求が高まっている。また、これらの熱可塑性樹脂が使用される部品には、作動部品あるいは、駆動用のコイル部品があるが、これらの部品が作動した時に熱可塑性樹脂組成物が帯電し、これらの機器に重大な影響を与えることが知られている。従って、熱可塑性樹脂組成物に帯電防止性能を付与する技術の開発が必要となっている。但し、熱可塑性樹脂組成物が帯電防止性能を超えて、導電性能を有する様になると、コイルに電流を流した場合に、通電してしまい、同様にこれらの機器に重大な影響を与える可能性がある。従って、コイル封止用熱可塑性樹脂組成物には、帯電防止性能と絶縁性能を兼ね備えることが要求されている。更には、これらの部品は作動又は駆動した時に高温となる為、部品を構成する熱可塑性樹脂は耐熱性に優れることも要求されている。 In recent years, component materials that make up electrical and electronic equipment, automotive equipment, chemical equipment, etc. have excellent mechanical strength, heat resistance, chemical resistance, and flame resistance for the purpose of downsizing and weight reduction of equipment. There is a growing demand for thermoplastic resins. In addition, the parts using these thermoplastic resins include working parts or coil parts for driving. When these parts are operated, the thermoplastic resin composition is charged, which is serious for these devices. It is known to have an impact. Therefore, it is necessary to develop a technique for imparting antistatic performance to the thermoplastic resin composition. However, if the thermoplastic resin composition exceeds the antistatic performance and has conductive performance, it will be energized when a current is passed through the coil, which may also have a significant impact on these devices. There is. Therefore, the thermoplastic resin composition for coil sealing is required to have both antistatic performance and insulation performance. Furthermore, since these parts become high temperature when actuated or driven, the thermoplastic resin constituting the parts is also required to have excellent heat resistance.
これらの熱可塑性樹脂の帯電性を改良する方法として、有機電解質を混合する方法（特許文献１参照）が開示されているが、コイル封止材やモーター封止材に使用できる程の十分な耐熱性は有していない。また、耐熱性に優れる熱可塑性樹脂組成物として、液晶性ポリエステルに黒鉛を混合する方法（例えば特許文献２参照）が開示されているが、線膨張係数の異方性が大きくなる為に成形品とした時に反り、表面抵抗値に異方性があることから、帯電防止性能の安定性が十分ではないという欠点があった。
本発明は、射出成形や押し出し成形が可能であり、帯電防止性能と絶縁性能を兼ね備え、低反り性で、耐熱性に優れたコイル封止材用熱可塑性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a thermoplastic resin composition for a coil sealing material that can be injection-molded or extruded, has both antistatic performance and insulating performance, has low warpage, and is excellent in heat resistance. To do.
本発明者らは、前記課題を解決する為、鋭意検討を重ねた結果、本発明をなすに至った。
即ち、本発明は、
［１］ 表面抵抗値が１×１０６〜１×１０１１Ωの範囲であり、表面抵抗値の異方性が１．０〜２．０の範囲であり、線膨張係数の異方性が１．０〜２．５であり、かつ荷重たわみ温度が１５０℃〜２８０℃の範囲であることを特徴とするコイル封止材用熱可塑性樹脂組成物、
［２］ 熱可塑性樹脂組成物がポリアリーレンサルファイド樹脂（Ａ）、ポリフェニレンエーテル樹脂（Ｂ）からなる樹脂組成物に、相溶化剤（Ｃ）、カーボン系充填剤（Ｄ）、及び無機質充填剤（Ｅ）を配合してなることを特徴とする［１］に記載のコイル封止材用熱可塑性樹脂組成物、
［３］ 熱可塑性樹脂組成物がポリアリーレンサルファイド樹脂（Ａ）３０〜９０質量％、ポリフェニレンエーテル樹脂（Ｂ）７０〜１０質量％からなる樹脂組成物１００質量部に対して、相溶化剤（Ｃ）１〜１００質量部、及びカーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量が５〜３００質量部を配合してなることを特徴とする［１］又は［２］に記載のコイル封止材用熱可塑性樹脂組成物、
［４］ カーボン系充填剤（Ｄ）がカーボンファイバー（Ｄ−１）、カーボングラファイト（Ｄ−２）、カーボンブラック（Ｄ−３）又はそれらの混合物であることを特徴とする［１］〜［３］のいずれかに記載のコイル封止材用熱可塑性樹脂組成物、
である。
In order to solve the above-mentioned problems, the present inventors have made extensive studies and have come to make the present invention.
That is, the present invention
[1] The surface resistance value is in the range of 1 × 10 6 to 1 × 10 11 Ω, the anisotropy of the surface resistance value is in the range of 1.0 to 2.0, and the anisotropy of the linear expansion coefficient is A thermoplastic resin composition for a coil sealing material, which is 1.0 to 2.5 and has a deflection temperature under load in a range of 150 ° C. to 280 ° C.,
[2] A resin composition comprising a thermoplastic resin composition comprising a polyarylene sulfide resin (A) and a polyphenylene ether resin (B), a compatibilizer (C), a carbon-based filler (D), and an inorganic filler ( E) is blended, and the thermoplastic resin composition for coil sealing materials according to [1],
[3] Compatibilizer (C) with respect to 100 parts by mass of the resin composition comprising 30 to 90% by mass of the polyarylene sulfide resin (A) and 70 to 10% by mass of the polyphenylene ether resin (B). 1) to 100 parts by mass, and the total amount of the carbon-based filler (D) and the inorganic filler (E) is 5 to 300 parts by mass. [1] or [2] A thermoplastic resin composition for a coil sealing material,
[4] The carbon-based filler (D) is carbon fiber (D-1), carbon graphite (D-2), carbon black (D-3) or a mixture thereof [1] to [1] 3] The thermoplastic resin composition for coil sealing materials according to any one of
It is.
本発明のコイル封止材用熱可塑性樹脂組成物は、射出成形品や押し出し成形品とした時に特に帯電防止性能と絶縁性能を兼ね備え、低反り性で、耐熱性に優れるといった効果を有する。 The thermoplastic resin composition for a coil sealing material of the present invention has an effect of having both anti-static performance and insulation performance, low warpage, and excellent heat resistance, particularly when an injection-molded product or an extruded product.
本発明について、以下具体的に説明する。
本発明におけるコイル封止材用熱可塑性樹脂組成物の表面抵抗値は１×１０６〜１×１０１１Ωの範囲であり、好ましくは１×１０６〜１×１０１０Ω、更に好ましくは、１×１０７〜１×１０９Ωである。表面抵抗値は成形品のショートを防ぐといった絶縁性能の観点から、１×１０６Ω以上が好ましく、成形品の帯電防止性能の観点から、１×１０１１Ω以下が好ましい。ここで、本発明における表面抵抗値は、樹脂温度３１０℃、金型温度６５℃の射出成形温度条件で得た成形品を用い、印加電圧１００Ｖ、印加時間５ｓｅｃ、測定距離１ｃｍにて測定でき、測定電極端子は１〜７ｍｍ幅、０．１〜３ｍｍ厚みのもので測定できる。表面抵抗値を測定する為の成形品は、７５ｍｍ四方、３ｍｍ厚以上のものが好ましい。また、測定電極端子を接触させる部分には導電性のペースト等は塗布しない。
The present invention will be specifically described below.
The surface resistance value of the thermoplastic resin composition for a coil sealing material in the present invention is in the range of 1 × 10 6 to 1 × 10 11 Ω, preferably 1 × 10 6 to 1 × 10 10 Ω, more preferably, 1 × 10 7 to 1 × 10 9 Ω. The surface resistance value is preferably 1 × 10 6 Ω or more from the viewpoint of insulation performance such as preventing short circuit of the molded product, and is preferably 1 × 10 11 Ω or less from the viewpoint of antistatic performance of the molded product. Here, the surface resistance value in the present invention can be measured at an applied voltage of 100 V, an application time of 5 sec, and a measurement distance of 1 cm using a molded product obtained under injection molding temperature conditions of a resin temperature of 310 ° C. and a mold temperature of 65 ° C. The measurement electrode terminal can be measured with a width of 1 to 7 mm and a thickness of 0.1 to 3 mm. The molded product for measuring the surface resistance is preferably 75 mm square, 3 mm thick or more. Moreover, a conductive paste or the like is not applied to the portion where the measurement electrode terminal is brought into contact.
本発明における表面抵抗値の異方性は、１．０〜２．０であり、好ましくは１．０〜１．９、更に好ましくは１．０〜１．８である。表面抵抗値の異方性は、成形品の帯電防止性能の安定性の観点から、１．０〜２．０である。ここで、本発明における表面抵抗値の異方性とは、本発明における熱可塑性樹脂を成形した時の樹脂の流動方向の表面抵抗値と樹脂の流動と垂直方向の表面抵抗値の内から、大きい値を小さい値で除した値である。従って、異方性が全くない樹脂組成物の場合、１．０となる。
本発明における線膨張係数の異方性は１．０〜２．５であり、好ましくは１．０〜２．２、更に好ましくは１．０〜２．０である。成形品の反りを低減するといった観点から、線膨張係数の異方性を１．０〜２．５にすることが必要である。本発明における線膨張係数異方性とは垂直方向線膨張係数を流動方向線膨張係数で除して算出したものであり、流動方向とは射出成形時にゲートから金型内に樹脂が射出され、流動する方向を示し、垂直方向とは樹脂が流動する方向に対して垂直な方向を示す。従って線膨張係数異方性の全く無い材料の値は１．０となる。本発明における線膨張係数の測定方法は、ＡＳＴＭ Ｅ−８３１に準拠され、例えばＴＭＡ法によって測定できる。本発明における線膨張係数の測定はＡＳＴＭ Ｄ−６３８に準じて樹脂温度３１０℃、金型温度９０℃にて成形したダンベルから図１（（１）はゲート位置）に示される様に一方の端から１０８ｍｍの位置より切り出した垂直方向（２）及び流動方向（３）のそれぞれ長さ１０ｍｍ（両端の平行度は±０．０２５ｍｍ）、１片が３〜５ｍｍである円柱の試験片（図２）をＴＭＡの本体に設置し、−３５℃から毎分５℃で６５℃まで昇温して長さの変位量を測定することにより算出した。
The anisotropy of the surface resistance value in the present invention is 1.0 to 2.0, preferably 1.0 to 1.9, and more preferably 1.0 to 1.8. The anisotropy of the surface resistance value is 1.0 to 2.0 from the viewpoint of the stability of the antistatic performance of the molded product. Here, the anisotropy of the surface resistance value in the present invention is from the surface resistance value in the flow direction of the resin and the surface resistance value in the vertical direction of the resin flow when the thermoplastic resin in the present invention is molded, The value obtained by dividing the large value by the small value. Therefore, in the case of a resin composition having no anisotropy, it is 1.0.
The anisotropy of the linear expansion coefficient in the present invention is 1.0 to 2.5, preferably 1.0 to 2.2, and more preferably 1.0 to 2.0. From the viewpoint of reducing warpage of the molded product, it is necessary to set the anisotropy of the linear expansion coefficient to 1.0 to 2.5. The linear expansion coefficient anisotropy in the present invention is calculated by dividing the linear expansion coefficient in the vertical direction by the linear expansion coefficient in the flow direction, and the flow direction is a resin injected from the gate into the mold during injection molding, The direction which flows is shown, and a perpendicular direction shows a direction perpendicular | vertical with respect to the direction where resin flows. Therefore, the value of a material having no linear expansion coefficient anisotropy is 1.0. The method for measuring the linear expansion coefficient in the present invention is based on ASTM E-831 and can be measured, for example, by the TMA method. The linear expansion coefficient in the present invention is measured at one end as shown in FIG. 1 ((1) is the gate position) from a dumbbell molded at a resin temperature of 310 ° C. and a mold temperature of 90 ° C. according to ASTM D-638. 10 mm in length in the vertical direction (2) and the flow direction (3) cut out from a position of 108 mm from each other (parallelism of both ends is ± 0.025 mm), and a cylindrical test piece having a length of 3 to 5 mm (FIG. 2) ) Was installed in the main body of TMA, and the temperature was increased from −35 ° C. to 65 ° C. at 5 ° C. per minute, and the length displacement was calculated.
本発明における荷重たわみ温度は１５０〜２８０℃の範囲であり、好ましくは１６０〜２７０℃、更に好ましくは１７０〜２６０℃である。コイルで発生する熱により変形しないという観点から、荷重たわみ温度を１５０℃以上にすることが必要であり、成形性の観点から２８０℃以下にすることが必要である。本発明における荷重たわみ温度は樹脂温度３１０℃、金型温度９０℃で成形した長さ１２０ｍｍ、幅６．４ｍｍ、高さ１２．７ｍｍの試験片を用い、測定方法はＡＳＴＭ Ｄ−６４８に準拠され、荷重１．８２ＭＰａ、支点間距離１００ｍｍ、加熱速度２℃／分にて、０．２５４ｍｍたわんだ時の温度を測定した。 The deflection temperature under load in the present invention is in the range of 150 to 280 ° C, preferably 160 to 270 ° C, more preferably 170 to 260 ° C. From the viewpoint of not being deformed by the heat generated in the coil, the deflection temperature under load is required to be 150 ° C. or higher, and from the viewpoint of formability, it is required to be 280 ° C. or lower. The deflection temperature under load in the present invention is a test piece having a length of 120 mm, a width of 6.4 mm, and a height of 12.7 mm molded at a resin temperature of 310 ° C. and a mold temperature of 90 ° C., and the measuring method conforms to ASTM D-648. At a load of 1.82 MPa, a distance between fulcrums of 100 mm, and a heating rate of 2 ° C./min, the temperature when bent by 0.254 mm was measured.
また、本発明における表面抵抗値、線膨張係数、荷重たわみ温度を測定する為の成形品を作成に用いるペレットには従来公知のブラベンダー、ニーダー、バンバリーミキサー、押出機等によって得られるものであれば、パウダーからペレット化したもの、一旦ペレット化したものを更に押出機等により再ペレット化したもの、成形された成形品を粉砕したもの、更には成形された成形品を粉砕したものを押出機等によりペレット化したもの等を用いることができる。
本発明におけるポリアリーレンサルファイド樹脂（Ａ）（以下「ＰＡＳ」と略記する。）は、下記一般式（１）で示されるアリーレンサルファイドの繰り返し単位を通常５０モル％以上、好ましくは７０モル％以上、更に好ましくは９０モル％以上を含む重合体である。
［−Ａｒ−Ｓ−］ （１）
（ここで、Ａｒはアリーレン基を示す。）
In addition, pellets used for producing a molded product for measuring the surface resistance value, linear expansion coefficient, and deflection temperature under load in the present invention may be obtained by a conventionally known Brabender, kneader, Banbury mixer, extruder, or the like. Extruders that have been pelletized from powder, those that have been pelletized once, further pelletized with an extruder, etc., those that have been pulverized, and those that have been pulverized What was pelletized by etc. can be used.
In the polyarylene sulfide resin (A) (hereinafter abbreviated as “PAS”) in the present invention, the repeating unit of arylene sulfide represented by the following general formula (1) is usually 50 mol% or more, preferably 70 mol% or more. More preferably, it is a polymer containing 90 mol% or more.
[-Ar-S-] (1)
(Here, Ar represents an arylene group.)
アリーレン基としては、例えばｐ−フェニレン基、ｍ−フェニレン基、置換フェニレン基（置換基とは炭素数１〜１０のアルキル基、フェニル基が好ましい。）、ｐ，ｐ′−ジフェニレンスルホン基、ｐ，ｐ′−ビフェニレン基、ｐ，ｐ′−ジフェニレンカルボニル基、ナフチレン基等を挙げることができる。ここでＰＡＳは構成単位であるアリーレン基が１種のホモポリマーを用いても良いが、加工性や耐熱性の観点から、２種以上のアリーレン基を混合したコポリマーを用いても良い。これらのＰＡＳの中でも、ｐ−フェニレンサルファイドの繰り返し単位を主構成要素とするポリフェニレンサルファイド樹脂が、加工性、耐熱性、寸法安定性に優れ、しかも工業的に入手が容易であることから、特に好ましい。 Examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms, and a phenyl group), a p, p′-diphenylene sulfone group, A p, p'-biphenylene group, a p, p'-diphenylenecarbonyl group, a naphthylene group, etc. can be mentioned. Here, PAS may use a homopolymer having a structural unit of arylene groups of one type, but from the viewpoint of processability and heat resistance, a copolymer in which two or more types of arylene groups are mixed may be used. Among these PASs, a polyphenylene sulfide resin having a repeating unit of p-phenylene sulfide as a main constituent element is particularly preferable because it is excellent in processability, heat resistance and dimensional stability, and is easily available industrially. .
また、本発明で用いるＰＡＳは、３２０℃における溶融粘度（せん断速度１０００／秒）が１００〜１００００ポイズの中から任意に選ぶ事ができ、更にＰＡＳの構造は、直鎖状のもの、分岐状のもの何れでも良く、またこれら構造の混合物であっても構わないが、好ましくは直鎖状の構造を持つＰＡＳである。更にこのＰＡＳは酸変性されたＰＡＳでも構わない。ここで酸変性したＰＡＳとは、上記ＰＡＳを酸化合物で変性する事によって得られるものであり、該酸化合物としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、無水マレイン酸等の不飽和カルボン酸又はその無水物や、飽和型の脂肪族カルボン酸や芳香族置換カルボン酸等も挙げることができる。更に酢酸、塩酸、硫酸、リン酸、ケイ酸、炭酸等の無機化合物系の酸化合物も該酸化合物として挙げることができる。
本発明におけるポリフェニレンエーテル樹脂（以下「ＰＰＥ」と略記する。）とは、下記一般式（２）、（３）で表される構造を有し、構成単位が一般式（２）及び（３）から選ばれる少なくとも１種からなる単独重合体、あるいは共重合体が使用できる。
The PAS used in the present invention can be arbitrarily selected from a melt viscosity (shear rate of 1000 / second) at 320 ° C. of 100 to 10000 poise, and the PAS structure is linear or branched. Any of these may be used, and a mixture of these structures may be used, but a PAS having a linear structure is preferred. Further, this PAS may be acid-modified PAS. Here, the acid-modified PAS is obtained by modifying the PAS with an acid compound, and the acid compound includes unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride. Examples thereof also include carboxylic acids or anhydrides thereof, saturated aliphatic carboxylic acids and aromatic substituted carboxylic acids. In addition, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid and carbonic acid can also be mentioned as the acid compound.
The polyphenylene ether resin (hereinafter abbreviated as “PPE”) in the present invention has a structure represented by the following general formulas (2) and (3), and the structural units are the general formulas (2) and (3). A homopolymer or copolymer comprising at least one selected from the group consisting of:
（式中、Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６は、炭素１〜４のアルキル基、アリール基、ハロゲン、水素等の一価の残基であり、Ｒ５，Ｒ６は同時に水素ではない。）
ＰＰＥの単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、およびポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、等のホモポリマーが挙げられる。
(In the formula, R1, R2, R3, R4, R5, and R6 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, and R5 and R6 are not hydrogen at the same time. )
Representative examples of PPE homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1) , 4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether Include homopolymers and the like.
ＰＰＥの共重合体は、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体、２，６−ジメチルフェノールとｏ−クレゾールとの共重合体、あるいは２，６−ジメチルフェノールと２，３，６−トリメチルフェノール及びｏ−クレゾールとの共重合体等、ポリフェニレンエーテル構造を主体としてなるポリフェニレンエーテル共重合体を包含する。また、このＰＰＥは、還元粘度（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）が、０．１５〜２．０の範囲である事が好ましく、上記したものの他に、マレイン酸，無水マレイン酸，フマル酸，イタコン酸，アクリル酸，アクリル酸エステル，メタクリル酸，メタクリル酸エステル等のα，β−不飽和カルボン酸又はその誘導体にて変性された変性ポリフェニレンエーテル樹脂でも良い。 The copolymer of PPE is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethyl. It includes polyphenylene ether copolymers mainly composed of a polyphenylene ether structure, such as a copolymer of phenol, 2,3,6-trimethylphenol and o-cresol. The PPE preferably has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 2.0. In addition to the above, maleic acid, maleic anhydride A modified polyphenylene ether resin modified with an α, β-unsaturated carboxylic acid such as acid, fumaric acid, itaconic acid, acrylic acid, acrylic ester, methacrylic acid or methacrylic ester or a derivative thereof may be used.
本発明において用いられる相溶化剤（Ｃ）は、エポキシ樹脂、グリシジル基含化合物、α，β−不飽和カルボン酸の誘導体で変性した水添ブロック共重合体、オキサゾニル基含有化合物等の、ＰＡＳとＰＰＥの相溶化剤として公知である物質を使用する事が出来る。中でもスチレン−グリシジルメタクリレート共重合体、ゴム補強スチレン−グリシジルメタクリレート共重合体、スチレン−アクリロニトリル−グリシジルメタクリレート共重合体等のグリシジル基含有スチレン系樹脂を用いる事が特に好ましい。
本発明におけるカーボン系充填剤（Ｄ）としては、カーボンファイバー（Ｄ−１）、カーボングラファイト（Ｄ−２）およびカーボンブラック（Ｄ−３）が挙げられ、これらは単独で又は併用して用いることができる。
The compatibilizer (C) used in the present invention is an epoxy resin, a glycidyl group-containing compound, a hydrogenated block copolymer modified with an α, β-unsaturated carboxylic acid derivative, an oxazonyl group-containing compound, and the like. Substances known as compatibilizers for PPE can be used. Among them, it is particularly preferable to use a glycidyl group-containing styrene resin such as a styrene-glycidyl methacrylate copolymer, a rubber-reinforced styrene-glycidyl methacrylate copolymer, and a styrene-acrylonitrile-glycidyl methacrylate copolymer.
Examples of the carbon-based filler (D) in the present invention include carbon fiber (D-1), carbon graphite (D-2), and carbon black (D-3). These may be used alone or in combination. Can do.
本発明におけるカーボンファイバー（Ｄ−１）は、ピッチ系、ＰＡＮ系いずれでも良く、平均径は１〜２０μｍ、好ましくは３〜１５μｍ、更に好ましくは５〜１３μｍであり、平均長は１〜２０ｍｍ、好ましくは２〜１５ｍｍ、更に好ましくは４〜１０ｍｍである。安定した帯電防止性能および耐熱性の観点から平均径が１μｍ以上、平均長が１ｍｍ以上であり、短絡を防止するといった観点から、平均径が２０μｍ以下、平均長が２０ｍｍ以下である。
本発明におけるカーボングラファイト（Ｄ−２）は平均粒径が０．２〜３００μｍであり、好ましくは１〜２００μｍ、更に好ましくは２〜１００μｍである。帯電防止性能の観点から０．２μｍ以上であり、絶縁性、成形品の低反り性の観点から３００μｍ以下である。
The carbon fiber (D-1) in the present invention may be either pitch type or PAN type, the average diameter is 1 to 20 μm, preferably 3 to 15 μm, more preferably 5 to 13 μm, and the average length is 1 to 20 mm. Preferably it is 2-15 mm, More preferably, it is 4-10 mm. From the viewpoint of stable antistatic performance and heat resistance, the average diameter is 1 μm or more, the average length is 1 mm or more, and from the viewpoint of preventing short circuit, the average diameter is 20 μm or less and the average length is 20 mm or less.
The carbon graphite (D-2) in the present invention has an average particle size of 0.2 to 300 μm, preferably 1 to 200 μm, more preferably 2 to 100 μm. From the viewpoint of antistatic performance, it is 0.2 μm or more, and from the viewpoint of insulation and low warpage of the molded product, it is 300 μm or less.
本発明におけるカーボンブラック（Ｄ−３）は平均粒系が、１ｎｍ〜５００ｎｍであり、好ましくは５ｎｍ〜１００ｎｍ、更に好ましくは１０ｎｍ〜１００ｎｍである。帯電防止性能の観点から、１ｎｍ以上であり、絶縁性の観点から１０μｍ以下である。
本発明における無機質充填剤（Ｅ）としては、ガラスファイバー、ガラスフレーク、マイカ、タルクおよび炭酸カルシウムが挙げられ、これらから選ばれる１種でまたは２種以上の混合物で用いることができる。無機質充填剤（Ｅ）は成形品の反り、優れた耐熱性、優れた機械的特性を得る為に重要である。また、特に本発明における表面抵抗値で１×１０６〜１×１０１１Ωを安定的に得る為には、カーボン系充填剤（Ｄ）と共に、この無機質充填剤（Ｅ）を含有することが非常に重要である。本発明において、カーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量における無機質充填剤（Ｅ）の含有率は５０〜９５％であり、好ましくは６０〜９５％、更に好ましくは７０〜９５％である。
Carbon black (D-3) in the present invention has an average particle size of 1 nm to 500 nm, preferably 5 nm to 100 nm, and more preferably 10 nm to 100 nm. From the viewpoint of antistatic performance, it is 1 nm or more, and from the viewpoint of insulation, it is 10 μm or less.
Examples of the inorganic filler (E) in the present invention include glass fibers, glass flakes, mica, talc and calcium carbonate, and these can be used alone or in a mixture of two or more. The inorganic filler (E) is important for obtaining warpage of the molded product, excellent heat resistance, and excellent mechanical properties. In particular, in order to stably obtain 1 × 10 6 to 1 × 10 11 Ω as the surface resistance value in the present invention, the inorganic filler (E) may be contained together with the carbon-based filler (D). Very important. In the present invention, the content of the inorganic filler (E) in the total amount of the carbon-based filler (D) and the inorganic filler (E) is 50 to 95%, preferably 60 to 95%, more preferably 70. ~ 95%.
本発明におけるガラスファイバーは平均繊維径が８〜２５μｍ、平均繊維長が２０〜５０００μｍであることが好ましく、従来公知のカップリング剤、収束剤で処理されている事が特に好ましい。平均繊維径及び平均繊維長は、強度の観点から、それぞれ８μｍ以上、２０μｍ以上であり、外観の観点から、それぞれ２５μｍ以下、５０００μｍ以下である。
ガラスフレークの形状としては、長径が１０００μｍ以下、好ましくは１〜８００μｍの範囲であり、且つアスペクト比（長径と厚みとの比）が５以上、好ましくは１０以上、更に好ましくは３０以上である。ガラスフレークの長径は、樹脂成分との均一混合の容易性や成形品の物性バラツキの観点から１０００μｍ以下が好ましい。一方、アスペクト比は成形品の耐熱性、剛性、耐衝撃性の点から５以上が好ましい。該ガラスフレークは、市販されているものをそのまま用いる事が出来るが、樹脂に配合する際に適宜粉砕して用いても良い。上記ガラスフレークは、樹脂との親和性を改良する目的で、例えばシラン系やチタネート系等の種々のカップリング剤で処理したガラスフレークを使用できる。
The glass fiber in the present invention preferably has an average fiber diameter of 8 to 25 μm and an average fiber length of 20 to 5000 μm, and is particularly preferably treated with a conventionally known coupling agent and sizing agent. The average fiber diameter and the average fiber length are respectively 8 μm or more and 20 μm or more from the viewpoint of strength, and are respectively 25 μm or less and 5000 μm or less from the viewpoint of appearance.
As the shape of the glass flakes, the major axis is 1000 μm or less, preferably 1 to 800 μm, and the aspect ratio (ratio of major axis to thickness) is 5 or more, preferably 10 or more, more preferably 30 or more. The major axis of the glass flakes is preferably 1000 μm or less from the viewpoint of easy uniform mixing with the resin component and variations in physical properties of the molded product. On the other hand, the aspect ratio is preferably 5 or more from the viewpoint of heat resistance, rigidity and impact resistance of the molded product. As the glass flakes, commercially available ones can be used as they are, but they may be appropriately pulverized when used in the resin. For the purpose of improving the affinity with the resin, the glass flakes treated with various coupling agents such as silane and titanate can be used.
タルクの粒径に関しては、特に制限はなく、従来より慣用されている粒径、例えば、平均粒径として０．１μｍ〜３０μｍ程度が適当である。
マイカについては、スゾライト・マイカ（商標）が好適に使用できる。長径が１０００μｍ以下、好ましくは５００μｍ以下、更に好ましくは２００μｍ以下のものが好適で、剛性賦与の観点から重量平均アスペクト比（マイカの平均直径／平均厚み）が１０以上、好ましくは３０以上、更に好ましくは１００以上である。前記マイカは樹脂との親和性を改良する為、カップリング剤で表面処理したマイカが特に良好に使用できる。
炭酸カルシウムの粒径に関しては、特に制限はなく、例えば平均粒径が０．０１〜１０μｍ程度が適当である。
The particle size of talc is not particularly limited, and a conventionally used particle size, for example, an average particle size of about 0.1 μm to 30 μm is appropriate.
As for mica, Suzolite Mica (trademark) can be preferably used. The major axis is preferably 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less, and the weight average aspect ratio (average mica diameter / average thickness) is 10 or more, preferably 30 or more, more preferably from the viewpoint of imparting rigidity. Is 100 or more. Since the mica improves the affinity with the resin, mica surface-treated with a coupling agent can be used particularly well.
The particle size of calcium carbonate is not particularly limited, and for example, an average particle size of about 0.01 to 10 μm is appropriate.
本発明において、熱可塑性樹脂はポリアリーレンサルファイド樹脂（Ａ）３０〜９０質量％、ポリフェニレンエーテル樹脂（Ｂ）７０〜１０質量％からなる樹脂組成物１００質量部に対して、相溶化剤（Ｃ）１〜１００質量部、及びカーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量が５〜３００質量部である。好ましくは、ポリアリーレンサルファイド樹脂（Ａ）４０〜８０質量％、ポリフェニレンエーテル樹脂（Ｂ）６０〜２０質量％からなる樹脂組成物１００質量部に対して、相溶化剤（Ｃ）２〜５０質量部、及びカーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量が１０〜２５０質量部であり、更に好ましくは、ポリアリーレンサルファイド樹脂（Ａ）５０〜７０質量％、ポリフェニレンエーテル樹脂（Ｂ）５０〜３０質量％からなる樹脂組成物１００質量部に対して、相溶化剤（Ｃ）３〜１０質量部、及びカーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量が２０〜２００質量部である。流動性の観点から、ポリアリーレンサルファイド樹脂（Ａ）３０質量％以上、ポリフェニレンエーテル樹脂（Ｂ）７０質量％以下であり、成形品の反り、成形時に成形品にバリが発生しない（低バリ性）といった成形性の観点から、ポリアリーレンサルファイド樹脂（Ａ）９０質量％以下、ポリフェニレンエーテル樹脂（Ｂ）１０質量％以上である。カーボン系充填剤（Ｄ）と無機質充填剤（Ｅ）の合計量は樹脂組成物１００質量部に対し、５〜３００質量部の範囲であることは、本発明における表面抵抗値の安定性、即ち帯電防止性能と絶縁性能を兼ね備えた熱可塑性樹脂組成物を得る為に非常に重要であり、更には、剛性、耐熱性の観点から５質量部以上であり、成形品の反り、成形時の流動性の観点から、３００質量部以下である。 In the present invention, the thermoplastic resin is used as a compatibilizer (C) with respect to 100 parts by mass of the resin composition comprising 30 to 90% by mass of the polyarylene sulfide resin (A) and 70 to 10% by mass of the polyphenylene ether resin (B). 1-100 mass parts and the total amount of a carbon type filler (D) and an inorganic filler (E) are 5-300 mass parts. Preferably, the compatibilizer (C) is 2 to 50 parts by mass with respect to 100 parts by mass of the resin composition composed of 40 to 80% by mass of the polyarylene sulfide resin (A) and 60 to 20% by mass of the polyphenylene ether resin (B). , And the total amount of the carbon-based filler (D) and the inorganic filler (E) is 10 to 250 parts by mass, more preferably 50 to 70% by mass of the polyarylene sulfide resin (A), the polyphenylene ether resin (B ) 3 to 10 parts by mass of the compatibilizer (C) and the total amount of the carbon filler (D) and the inorganic filler (E) is 20 with respect to 100 parts by mass of the resin composition consisting of 50 to 30% by mass. -200 parts by mass. From the viewpoint of fluidity, the polyarylene sulfide resin (A) is 30% by mass or more and the polyphenylene ether resin (B) is 70% by mass or less, and warpage of the molded product, and no burrs are generated in the molded product (low burrs). From the viewpoint of moldability, the polyarylene sulfide resin (A) is 90% by mass or less and the polyphenylene ether resin (B) is 10% by mass or more. The total amount of the carbon-based filler (D) and the inorganic filler (E) is in the range of 5 to 300 parts by mass with respect to 100 parts by mass of the resin composition. It is very important for obtaining a thermoplastic resin composition having both antistatic performance and insulation performance. Furthermore, it is 5 parts by mass or more from the viewpoint of rigidity and heat resistance, warping of molded products, flow during molding. From the viewpoint of property, it is 300 parts by mass or less.
また、本発明におけるコイル封止材用熱可塑性樹脂組成物には必要に応じて、ポリスチレン樹脂、ゴム補強のポリスチレン樹脂（ハイインパクト−ポリスチレン樹脂）、ＡＢＳ樹脂等のスチレン系樹脂、ポリカーボネート樹脂、ポリブチレンテレフタレート樹脂、液晶ポリエステル、ポリエチレンテレフタレート樹脂、ポリアミド樹脂、ポリプロピレン樹脂、ポリアセタール樹脂等が添加できる。
更に必要に応じて通常の熱可塑性樹脂に添加される添加剤、例えば熱安定剤、紫外線吸収剤、難燃剤、離型剤、滑剤、染料、顔料などを配合する事も特に制限されるものではない。
In addition, the thermoplastic resin composition for a coil sealing material in the present invention may include polystyrene resin, rubber-reinforced polystyrene resin (high impact polystyrene resin), styrene resin such as ABS resin, polycarbonate resin, Butylene terephthalate resin, liquid crystal polyester, polyethylene terephthalate resin, polyamide resin, polypropylene resin, polyacetal resin and the like can be added.
Furthermore, it is not particularly limited to add additives that are added to ordinary thermoplastic resins as necessary, for example, heat stabilizers, UV absorbers, flame retardants, mold release agents, lubricants, dyes, pigments and the like. Absent.
また、本発明のコイル封止材用熱可塑性樹脂組成物の調製は、ブラベンダー、ニーダー、バンバリーミキサー、押出機などの従来公知の技術によって達成されるが、特に好ましくは押出機である。また、各構成成分の配合の順番は特に限定されるものではなく、例えば、ＰＡＳ（Ａ）にＰＰＥ（Ｂ）を相溶化剤（Ｃ）と共に押し出し混合したペレットにカーボン系充填剤（Ｄ）及び無機質充填剤（Ｅ）を配合して押し出し混合する方法、ＰＡＳ（Ａ）、ＰＰＥ（Ｂ）、相溶化剤（Ｃ）、カーボン系充填剤（Ｄ）、無機質充填剤（Ｅ）を同時に押し出し混合する方法、ＰＡＳ（Ａ）又はＰＰＥ（Ｂ）と相溶化剤（Ｃ）、カーボン系充填剤（Ｄ）及び無機質充填剤（Ｅ）を予め押し出し混合したマスターバッチにＰＰＥ（Ｂ）又はＰＡＳ（Ａ）を混合して押し出し混合する方法、ＰＡＳ（Ａ）とカーボン系充填剤（Ｄ）及び／又は無機質充填剤（Ｅ）を予め押し出し混合したマスターバッチとＰＰＥ（Ｂ）とカーボン系充填剤（Ｄ）及び／又は無機質充填剤（Ｅ）を予め押し出し混合したマスターバッチを相溶化剤（Ｃ）と共に混合する方法、ＰＡＳ（Ａ）、ＰＰＥ（Ｂ）、カーボン系充填剤（Ｄ）、無機質充填剤（Ｅ）を相溶化剤（Ｃ）と共に予め押し出し混合したマスターバッチとＰＡＳ（Ａ）及び／又はＰＰＥ（Ｂ）を混合する方法等である。 Moreover, the preparation of the thermoplastic resin composition for a coil sealing material of the present invention is achieved by a conventionally known technique such as Brabender, kneader, Banbury mixer, and extruder, and an extruder is particularly preferable. In addition, the order of blending each component is not particularly limited. For example, the carbon-based filler (D) and the pellet obtained by extruding and mixing PPE (B) with the compatibilizer (C) in PAS (A) Extruded and mixed with inorganic filler (E), PAS (A), PPE (B), compatibilizer (C), carbon-based filler (D), and inorganic filler (E) simultaneously extruded and mixed Method, PAS (A) or PPE (B), compatibilizer (C), carbon-based filler (D) and inorganic filler (E) are pre-extruded and mixed into a master batch with PPE (B) or PAS (A ) And extruding and mixing, a master batch in which PAS (A) and carbon filler (D) and / or inorganic filler (E) are extruded and mixed in advance, PPE (B) and carbon filler (D And / or A method of mixing a master batch obtained by extruding and mixing an inorganic filler (E) with a compatibilizer (C), PAS (A), PPE (B), carbon-based filler (D), and inorganic filler (E). For example, a master batch that has been extruded and mixed together with the compatibilizer (C) and PAS (A) and / or PPE (B) are mixed.
本発明のコイル封止材用熱可塑性樹脂組成物は、一般的な射出成形、インジェクションプレス成形、又はガスインジェクション成形等の公知の成形方法にて成形を行う事が可能である。特に本発明で得られたコイル封止材用熱可塑性樹脂組成物を用いて、電機・電子機器、自動車機器、化学機器などを構成するコイル封止部品材、モーター封止部品材、トランジスタ封止部品材、バッテリー部品材に使用できる。 The thermoplastic resin composition for a coil sealing material of the present invention can be molded by a known molding method such as general injection molding, injection press molding, or gas injection molding. In particular, using the thermoplastic resin composition for a coil sealing material obtained in the present invention, a coil sealing component material, a motor sealing component material, a transistor sealing constituting an electric / electronic device, an automobile device, a chemical device, etc. Can be used for parts and battery parts.
本発明を実施例に基づいて説明する。実施例及び比較例における測定法及び用語は以下の通りである。
〈表面抵抗値及び異方性〉
超絶縁計（ＳＭ８２２０：東亜ディーケーケー製）を用いて、縦７５±５ｍｍ、横７５±５ｍｍ、厚さ３±５ｍｍの成形品表面に、３±１ｍｍ幅、０．８±０．４の面積で接触する測定電極端子を１０±２ｍｍの距離で接触させ、印加電圧１００Ｖ、印加時間５ｓｅｃ後の抵抗値を読み取った。抵抗値は射出成形時にゲートから金型内に樹脂が射出されて流動する方向、またその垂直方向、それぞれの方向で測定し、大きい値を小さい値で除した値を異方性とした。また、表面抵抗値は流動方向、垂直方向とも同一成形品内で５箇所を測定して平均値を取り、成形品は少なくとも３枚測定し、安定性を確認した。また、測定電極端子を接触させる部分には導電性のペースト等は塗布しなかった。
The present invention will be described based on examples. The measurement methods and terms in Examples and Comparative Examples are as follows.
<Surface resistance and anisotropy>
Using a superinsulator (SM8220: manufactured by Toa DKK), on the surface of a molded product with a length of 75 ± 5 mm, a width of 75 ± 5 mm, and a thickness of 3 ± 5 mm, an area of 3 ± 1 mm width and 0.8 ± 0.4 The contacting measurement electrode terminals were brought into contact with each other at a distance of 10 ± 2 mm, and the resistance value after an applied voltage of 100 V and an application time of 5 sec was read. The resistance value was measured in each of the directions in which the resin was injected from the gate into the mold during the injection molding and in the vertical direction, and the value obtained by dividing the large value by the small value was defined as anisotropy. In addition, the surface resistance value was measured at five locations in the same molded product in both the flow direction and the vertical direction to obtain an average value, and at least three molded products were measured to confirm the stability. Also, no conductive paste or the like was applied to the portion where the measurement electrode terminal was brought into contact.
〈線膨張係数及び異方性〉
ＡＳＴＭ Ｄ−６９６に準拠したＴＭＡ法による。ＡＳＴＭ Ｄ−６３８に準じて樹脂温度３１０℃、金型温度９０℃にて成形したダンベルから図１の様に切り出した各試験片３ｍｍ×３ｍｍ×１０ｍｍを、ＴＭＡを用いて−３５℃から毎分５℃で６５℃まで昇温して長さの変移量から線膨張係数を測定した。また、線膨張係数異方性は射出成形時にゲートから金型内に樹脂が射出されて流動する方向となる流動方向のサンプルを用いて測定した線膨張係数で樹脂が流動する方向に対して垂直な方向となる垂直方向のサンプルを用いて測定した線膨張係数を除して算出した。
<Linear expansion coefficient and anisotropy>
According to the TMA method based on ASTM D-696. Each
〈荷重たわみ温度〉
樹脂温度３１０℃、金型温度９０℃の射出成形樹脂温度条件で成形した長さ１２０ｍｍ、幅６．４ｍｍ、高さ１２．７ｍｍの試験片を用い、ＡＳＴＭ Ｄ−６４８に準拠した方法である、荷重１．８２ＭＰａ、支点間距離１００ｍｍ、加熱速度２℃／分にて、０．２５４ｍｍたわんだ時の温度を測定した。
〈絶縁性能〉
図３の様に、縦２０ｍｍ、横２０ｍｍ、厚さ１ｍｍの銅版２枚を１０ｍｍ×２０ｍｍの部分が成形品内部に入るように、かつ、２枚の銅版が対辺の中央に位置するように、金型に設置し、樹脂部の大きさが縦７５ｍｍ、横７５ｍｍ、厚さ３ｍｍの成形品となるようなインサート成形品を樹脂温度３１０℃、金型温度６５℃の射出成形温度条件で得た後、銅版２枚に２００Ｖの直流電圧を掛け、ショートの有無を確認した。成形品は５枚を評価し、１枚でもショート（通電）した場合を×、ショート（通電）しない場合を○で示した。
<Load deflection temperature>
A test piece having a length of 120 mm, a width of 6.4 mm, and a height of 12.7 mm molded under an injection molding resin temperature condition of a resin temperature of 310 ° C. and a mold temperature of 90 ° C. is a method based on ASTM D-648. The temperature when bent by 0.254 mm was measured at a load of 1.82 MPa, a distance between fulcrums of 100 mm, and a heating rate of 2 ° C./min.
<Insulation performance>
As shown in FIG. 3, two copper plates having a length of 20 mm, a width of 20 mm, and a thickness of 1 mm are placed so that a 10 mm × 20 mm portion enters the inside of the molded product, and the two copper plates are positioned at the center of the opposite side. An insert-molded product that was placed in a mold and had a resin part size of 75 mm in length, 75 mm in width, and 3 mm in thickness was obtained under injection molding temperature conditions of a resin temperature of 310 ° C. and a mold temperature of 65 ° C. Thereafter, a DC voltage of 200 V was applied to the two copper plates, and the presence or absence of a short circuit was confirmed. Five molded products were evaluated. The case where even one sheet was short-circuited (energized) was indicated by x, and the case where no short-circuit (energized) was performed was indicated by ○.
〈成形品反り〉
縦１５０ｍｍ、横１５０ｍｍ、厚さ２ｍｍの成形品を樹脂温度３１０℃、金型温度９０℃、ゲート径を１．５ｍｍ、ゲート位置を任意の角からＸ軸方向に７５ｍｍ、Ｙ軸方向に２０ｍｍの位置に設けて作成し、３次元測定機（ＡＥ１２２：ミツトヨ製）を用いて任意の規定１５点におけるＺ軸方向の位置を測定し、最低位置と最高位置の差を算出した後、１ｍｍ以下である場合を○、１ｍｍを超える場合を×で示した。
〈耐熱性〉
成形品反りを測定した成形品と同じ条件で測定し、１３０℃に温度調整したオーブンに２４時間放置した後に、３次元測定機（ＡＥ１２２：ミツトヨ製）を用いて任意の規定１５点におけるＺ軸方向の位置を測定し、最低位置と最高位置の差を算出した後、２ｍｍ以下である場合を○、２ｍｍを超える場合を×で示した。
〈機械的特性〉
樹脂温度３１０℃、金型温度９０℃の射出成形樹脂温度条件で成形した長さ１２０ｍｍ、幅６．４ｍｍ、高さ１２．７ｍｍの試験片を用い、ＡＳＴＭ Ｄ−７９０に準拠して、曲げ弾性率を測定し、その値が４０００ＭＰａ以上である場合を○、４０００ＭＰａ未満である場合を×で示した。
<Molded product warpage>
A molded product having a length of 150 mm, a width of 150 mm, and a thickness of 2 mm has a resin temperature of 310 ° C., a mold temperature of 90 ° C., a gate diameter of 1.5 mm, a gate position of 75 mm in the X-axis direction and 20 mm in the Y-axis direction from any angle. Prepared at the position, measured the position in the Z-axis direction at any specified 15 points using a three-dimensional measuring machine (AE122: manufactured by Mitutoyo), and after calculating the difference between the lowest position and the highest position, 1 mm or less Some cases were marked with ◯, and more than 1 mm with x.
<Heat-resistant>
Z-axis at any specified 15 points using a three-dimensional measuring machine (AE122: manufactured by Mitutoyo) after measuring the warpage of the molded product under the same conditions as the molded product and leaving it in an oven adjusted to 130 ° C. for 24 hours. After measuring the position in the direction and calculating the difference between the lowest position and the highest position, the case where it is 2 mm or less is indicated by ○, and the case where it exceeds 2 mm is indicated by ×.
<Mechanical properties>
Using a test piece with a length of 120 mm, a width of 6.4 mm, and a height of 12.7 mm molded under the injection molding resin temperature conditions of a resin temperature of 310 ° C. and a mold temperature of 90 ° C., bending elasticity according to ASTM D-790 The rate was measured, and the case where the value was 4000 MPa or more was indicated by ◯, and the case where it was less than 4000 MPa was indicated by x.
〈使用樹脂及び充填剤〉
１）ＰＡＳ（Ａ）
溶融粘度（フローテスターを用いて、３００℃、荷重１９６Ｎ、Ｌ／Ｄ＝１０／１で６分間保持した後測定した値。）が５００ポイズである直鎖状構造を有するポリフェニレンサルファイド。
２）ＰＰＥ（Ｂ）
極限粘度［η］が０．５２（３０℃、クロロホルム中）であるポリ２，６−ジメチル−１，４−フェニレンエーテル（密度１．０６ｇ／ｃｍ3）
３）相溶化剤（Ｃ）
グリシジルメタクリレートを５重量％含有するスチレン−グリシジルメタクリレート共重合体（重量平均分子量１１０，０００）
４）カーボン系充填剤（Ｄ）
カーボンファイバー（Ｄ−１）：パイロフィルチョップドファイバ−ＴＲ０６６Ａ（三菱レーヨン製）、カーボングラファイト（Ｄ−２）：鱗片状グラファイトＦ＃２（日本黒鉛工業製）、カーボンブラック（Ｄ−３）：ケッチェンブラックＥＣ６００ＪＤ（ケッチェンブラックインターナショナル製）
５）無機質充填剤（Ｅ）
ガラスファイバー（Ｅ−１）：ＲＥＳ０３−ＴＰＯ１５（日本板硝子社製）、ガラスフレーク（Ｅ−２）：ＲＥＦＧ−３０２（日本板硝子製）、タルク：ハイトロンＡ（竹原化学工業製）
<Used resin and filler>
1) PAS (A)
Polyphenylene sulfide having a linear structure having a melt viscosity of 500 poise (melting viscosity (measured using a flow tester at 300 ° C., load 196 N, L / D = 10/1 for 6 minutes)).
2) PPE (B)
3) Compatibilizer (C)
Styrene-glycidyl methacrylate copolymer containing 5% by weight of glycidyl methacrylate (weight average molecular weight 110,000)
4) Carbon filler (D)
Carbon fiber (D-1): Pyrofil chopped fiber-TR066A (manufactured by Mitsubishi Rayon), carbon graphite (D-2): scaly graphite F # 2 (manufactured by Nippon Graphite Industry), carbon black (D-3): Chain Black EC600JD (Ketjen Black International)
5) Inorganic filler (E)
Glass fiber (E-1): RES03-TPO15 (manufactured by Nippon Sheet Glass), glass flake (E-2): REFG-302 (manufactured by Nippon Sheet Glass), talc: Hytron A (manufactured by Takehara Chemical Industries)
［実施例１〜４］
表１に示すような各成分の配合組成にて、温度２９０〜３２０℃、スクリュー回転数５００ｒｐｍに設定した二軸押出機（ＺＳＫ−４０：ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥ社製）にて溶融混練りし、組成物ペレットを得た。このペレットを用いて成形品を作成し、各種試験を行った。評価結果を表１に示した。
実施例１〜５は成形品の表面抵抗値の安定性は良く、絶縁性に優れ、反りが小さく、耐熱性、成形性、機械的特性に優れていた。
[Examples 1 to 4]
The composition composition of each component as shown in Table 1 was melt-kneaded with a twin screw extruder (ZSK-40: manufactured by WERNER & PFLEIDERE) set at a temperature of 290 to 320 ° C. and a screw rotation speed of 500 rpm, and the composition pellets Got. Using this pellet, a molded product was prepared and subjected to various tests. The evaluation results are shown in Table 1.
In Examples 1 to 5, the stability of the surface resistance value of the molded product was good, the insulation was excellent, the warp was small, and the heat resistance, moldability, and mechanical properties were excellent.
［比較例１〜２］
表１に示すような各成分の配合組成にて、温度２９０〜３２０℃、スクリュー回転数５００ｒｐｍに設定した二軸押出機（ＺＳＫ−４０：ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥ社製）にて溶融混練りし、組成物ペレットを得た。このペレットを用いて成形品を作成し、各種試験を行った。評価結果を表１に示した。
比較例１は、ショートが発生し、成形品にバリが発生し、反りも大きくなった。比較例２は、ショートが発生する成形品と発生しない成形品があり、即ち安定した絶縁性能が得られず、かつ成形品の反りが大きくなった。
[Comparative Examples 1-2]
The composition composition of each component as shown in Table 1 was melt-kneaded with a twin screw extruder (ZSK-40: manufactured by WERNER & PFLEIDERE) set at a temperature of 290 to 320 ° C. and a screw rotation speed of 500 rpm, and the composition pellets Got. Using this pellet, a molded product was prepared and subjected to various tests. The evaluation results are shown in Table 1.
In Comparative Example 1, short-circuiting occurred, burrs were generated in the molded product, and warpage was increased. In Comparative Example 2, there are a molded product in which a short circuit occurs and a molded product in which a short circuit does not occur, that is, a stable insulation performance cannot be obtained, and warping of the molded product is increased.
本発明のコイル封止材用熱可塑性樹脂組成物は、電機・電子機器、自動車機器、化学機器などを構成する作動用あるいは、駆動用のコイル部品におけるコイル封止材の分野で好適に利用できる。 The thermoplastic resin composition for a coil sealing material of the present invention can be suitably used in the field of coil sealing material in a coil component for operation or drive constituting an electric / electronic device, an automobile device, a chemical device and the like. .
（１）線膨張係数測定用成形品ゲート位置
（２）線膨張係数垂直方向切り出し位置
（３）線膨張係数流動方向切り出し位置
（４）絶縁性能評価用樹脂成形品ゲート位置
（５）電極用銅板
（６）電極用銅板
(1) Linear expansion coefficient measurement molded product gate position (2) Linear expansion coefficient vertical cutout position (3) Linear expansion coefficient flow direction cutout position (4) Insulation performance evaluation resin molded product gate position (5) Electrode copper plate (6) Copper plate for electrodes
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005114989A JP2006291076A (en) | 2005-04-12 | 2005-04-12 | Thermoplastic resin composition as coil-sealing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005114989A JP2006291076A (en) | 2005-04-12 | 2005-04-12 | Thermoplastic resin composition as coil-sealing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006291076A true JP2006291076A (en) | 2006-10-26 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005114989A Pending JP2006291076A (en) | 2005-04-12 | 2005-04-12 | Thermoplastic resin composition as coil-sealing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006291076A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007114056A1 (en) | 2006-03-30 | 2007-10-11 | Asahi Kasei Chemicals Corporation | Resin composition and molded product thereof |
| JP2014517108A (en) * | 2011-05-18 | 2014-07-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Thermoplastic molding material composed of polyarylene ether and polyphenylene sulfide having improved processing stability |
| JP2017514970A (en) * | 2014-05-06 | 2017-06-08 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Articles comprising a poly (phenylene ether) -polysiloxane copolymer composition |
| US10189990B2 (en) | 2015-04-27 | 2019-01-29 | Sabic Global Technologies B.V. | Poly(phenylene ether) composition and article |
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| WO2007114056A1 (en) | 2006-03-30 | 2007-10-11 | Asahi Kasei Chemicals Corporation | Resin composition and molded product thereof |
| US8487035B2 (en) | 2006-03-30 | 2013-07-16 | Asahi Kasei Chemicals Corporation | Resin composition and molded product thereof |
| US8658731B2 (en) | 2006-03-30 | 2014-02-25 | Asahi Kasei Chemicals Corporation | Resin composition and molded product thereof |
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| JP2017514970A (en) * | 2014-05-06 | 2017-06-08 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Articles comprising a poly (phenylene ether) -polysiloxane copolymer composition |
| US10113055B2 (en) | 2014-05-06 | 2018-10-30 | Sabic Global Technologies B.V. | Article comprising poly(phenylene ether)-polysiloxane copolymer composition |
| US10189990B2 (en) | 2015-04-27 | 2019-01-29 | Sabic Global Technologies B.V. | Poly(phenylene ether) composition and article |
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