JP4459604B2 - Conductive resin composition for molded body for packaging of members for electric and electronic parts, and molded body for packaging of members for electrical and electronic parts - Google Patents
Conductive resin composition for molded body for packaging of members for electric and electronic parts, and molded body for packaging of members for electrical and electronic parts Download PDFInfo
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- JP4459604B2 JP4459604B2 JP2003416284A JP2003416284A JP4459604B2 JP 4459604 B2 JP4459604 B2 JP 4459604B2 JP 2003416284 A JP2003416284 A JP 2003416284A JP 2003416284 A JP2003416284 A JP 2003416284A JP 4459604 B2 JP4459604 B2 JP 4459604B2
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- 239000011342 resin composition Substances 0.000 title claims description 42
- 238000004806 packaging method and process Methods 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 239000006229 carbon black Substances 0.000 claims description 28
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 21
- 229920001281 polyalkylene Polymers 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000006078 metal deactivator Substances 0.000 claims description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001230 polyarylate Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 2
- SMEPRGMDOPTYGL-UHFFFAOYSA-N 6-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]-4-oxohexanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 SMEPRGMDOPTYGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- -1 alkylene glycol Chemical compound 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000004898 kneading Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JHYLOZKQMTWGPP-UHFFFAOYSA-N 2,9-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]decanedioic acid Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC(CCCCCCC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(O)=O)C(O)=O)=C1 JHYLOZKQMTWGPP-UHFFFAOYSA-N 0.000 description 1
- LSQVLWRLMQMLGV-UHFFFAOYSA-N 2-(hydrazinylmethyl)phenol Chemical compound NNCC1=CC=CC=C1O LSQVLWRLMQMLGV-UHFFFAOYSA-N 0.000 description 1
- FVEAIIZMVQXSQE-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=CC(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O FVEAIIZMVQXSQE-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SVDMMNRMRJMYAR-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)(COC(=O)CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)COC(=O)CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O SVDMMNRMRJMYAR-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- GTIBACHAUHDNPH-WHYMJUELSA-N n,n'-bis[(z)-benzylideneamino]oxamide Chemical compound C=1C=CC=CC=1\C=N/NC(=O)C(=O)N\N=C/C1=CC=CC=C1 GTIBACHAUHDNPH-WHYMJUELSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical class NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- DXGIRFAFSFKYCF-UHFFFAOYSA-N propanehydrazide Chemical compound CCC(=O)NN DXGIRFAFSFKYCF-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、成形時に発生する揮発成分の発生量が少なく、電気・電子部品用部材の包装用成形体として好適な電気・電子部品用部材の包装用成形体用導電性樹脂組成物、及び電気・電子部品用部材の包装用成形体に関する。 The present invention has less amount of generation of volatile components generated during molding, packaging molded body conductive resin composition suitable for electrical and electronic components members as a packaging article for electrical and electronic components for members, and electrical -It is related with the molded object for packaging of the component for electronic components .
一般に、プラスチックス等を含む樹脂組成物は、電気抵抗が大きく、絶縁材料として利用されるが、このような樹脂組成物に金属微粉やカーボンブラック等の導電材を含有させて、前記樹脂組成物に導電性を付与した導電性樹脂組成物が知られている。特に、前記導電材としては、カーボンブラックが、樹脂組成物中への分散性、及び樹脂組成物の機械的物性などが良好であることから好適に用いられている。 In general, a resin composition containing plastics or the like has a large electric resistance and is used as an insulating material. However, the resin composition contains a conductive material such as metal fine powder or carbon black in such a resin composition. There is known a conductive resin composition imparted with conductivity. In particular, as the conductive material, carbon black is preferably used because of its good dispersibility in the resin composition and good mechanical properties of the resin composition.
しかしながら、所望の導電性を発揮させるために、大量のカーボンブラックを含有した導電性樹脂組成物を用いて、特に、微細成形、高速成形、長時間成形等の過酷な条件の加工法により成形品の成形などを行う場合、含有するカーボンブラックによって導電性樹脂組成物の分解又は劣化が促進され、この結果、成形時に揮発成分が生成されて、該揮発成分が金型に付着し、金型汚染や成形不良が発生するという問題がある。 However, in order to exhibit the desired conductivity, a molded product is produced by using a conductive resin composition containing a large amount of carbon black, particularly by processing under severe conditions such as fine molding, high-speed molding, and long-time molding. When performing molding or the like, decomposition or deterioration of the conductive resin composition is promoted by the carbon black contained, and as a result, volatile components are generated during molding, and the volatile components adhere to the mold and mold contamination. There is a problem that molding defects occur.
これらの問題を解決するため、ポリカーボネート樹脂と導電性物質とを含有するポリカーボネート樹脂組成物を溶融混練する前にポリカーボネート樹脂の乾燥温度を高くする等により、揮発成分の発生量を少なくすることが提案されている（特許文献１参照）。また、ポリエステル樹脂と灰分が３０ｐｐｍ以下のカーボンブラックとを含み、混練時のカーボンブラックによる加水分解や劣化の促進を抑制した樹脂組成物が提案されている（特許文献２参照）。
しかし、これらの場合でも、依然として成型品の成形時に生成される揮発成分を十分に抑制することが困難であるという問題がある。
In order to solve these problems, it is proposed to reduce the amount of volatile components generated by increasing the drying temperature of the polycarbonate resin before melt-kneading the polycarbonate resin composition containing the polycarbonate resin and the conductive material. (See Patent Document 1). In addition, a resin composition containing a polyester resin and carbon black having an ash content of 30 ppm or less and suppressing the promotion of hydrolysis and deterioration by carbon black during kneading has been proposed (see Patent Document 2).
However, even in these cases, there is still a problem that it is difficult to sufficiently suppress volatile components generated during molding of the molded product.
本発明は、前記従来における諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、機械的物性及びカーボンブラックの高分散性を損なうことなく、成形時に発生する揮発成分の発生量が少ない導電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 solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a conductive resin composition with a small amount of volatile components generated during molding without impairing mechanical properties and high dispersibility of carbon black.
前記課題を解決するために、本発明者らが鋭意検討を行った結果、ポリアルキレンフタレート樹脂と、カーボンブラックと、ヒンダードフェノール系酸化防止剤と、金属不活性化剤とを含有してなる導電性樹脂組成物が、機械的物性及びカーボンブラックの高分散性を損なうことなく、該導電性樹脂組成物を用いた成形品の成形時に発生する揮発成分の発生量を少なくすることができることを知見した。 As a result of intensive studies by the present inventors to solve the above problems, the present invention contains a polyalkylene phthalate resin, carbon black, a hindered phenolic antioxidant, and a metal deactivator. The conductive resin composition can reduce the amount of volatile components generated during molding of a molded product using the conductive resin composition without impairing mechanical properties and high dispersibility of carbon black. I found out.
本発明は、本発明者らの前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ ２価フェノールとカーボネート前駆体との重縮合により製造されたポリカーボネート樹脂及び２価フェノールと芳香族ジカルボン酸との重縮合により製造されたポリアリレート樹脂から選択される少なくともいずれかと、ポリアルキレンフタレート樹脂とからなる熱可塑性樹脂と、
ｎ―ジブチルフタレート（ＤＢＰ）吸油量が１００〜４００ｍｌ／１００ｇであるカーボンブラックと、
ヒンダードフェノール系酸化防止剤と、
金属不活性化剤とを含有する導電性樹脂組成物であって、
前記カーボンブラックの含有量が前記導電性樹脂組成物の合計１００質量部に対し、５質量部〜２０質量部であって、
前記金属不活性化剤が、２’，３−ビス［３−［３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］プロピオノヒドラジド及び３−Ｎ’−サリチロイルアミノ−１，２，４−トリアゾールから選択される少なくともいずれかであることを特徴とする電気・電子部品用部材の包装用成形体用導電性樹脂組成物である。
＜２＞ 前記＜１＞に記載の電気・電子部品用部材の包装用成形体用導電性樹脂組成物からなることを特徴とする電気・電子部品用部材の包装用成形体である。
The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> at least one selected from a polycarbonate resin produced by polycondensation of a dihydric phenol and a carbonate precursor and a polyarylate resin produced by polycondensation of a dihydric phenol and an aromatic dicarboxylic acid, and a polyalkylene A thermoplastic resin comprising a phthalate resin;
carbon black having an n-dibutyl phthalate (DBP) oil absorption of 100 to 400 ml / 100 g;
A hindered phenolic antioxidant,
A conductive resin composition containing a metal deactivator,
The content of the carbon black is 5 parts by mass to 20 parts by mass with respect to a total of 100 parts by mass of the conductive resin composition,
The metal deactivators are 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide and 3-N′-salicyloylamino-1. It is at least any one selected from 2,4-triazole, and is a conductive resin composition for a molded article for packaging an electrical / electronic component member.
<2> A molded product for packaging of members for electric / electronic parts, comprising the conductive resin composition for molded products for packaging of members for electrical / electronic parts according to <1>.
本発明によると、従来における諸問題を解決でき、機械的物性及びカーボンブラックの高分散性を損なうことなく、成形時に発生する揮発成分の発生量が少ない導電性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 conductive resin composition that can solve various problems in the prior art and has a small amount of volatile components generated during molding without impairing mechanical properties and high dispersibility of carbon black. .
（導電性樹脂組成物）
本発明の導電性樹脂組成物は、ポリアルキレンフタレート樹脂と、カーボンブラックと、ヒンダードフェノール系酸化防止剤と、金属不活性化剤とを含有してなり、更に必要に応じて適宜選択した、他の熱可塑性樹脂及びその他の成分を含有してなる。
(Conductive resin composition)
The conductive resin composition of the present invention comprises a polyalkylene phthalate resin, carbon black, a hindered phenol antioxidant, and a metal deactivator, and further appropriately selected as necessary. It contains other thermoplastic resin and other components.
−ポリアルキレンフタレート樹脂−
前記ポリアルキレンフタレート樹脂としては、特に制限はなく、目的に応じて適宜選択することができるが、各種フタル酸又はそのエステル誘導体と、アルキレングリコールとを主成分として重縮合して生成されるものであり、主たる構成が、ポリアルキレンフタレートよりなる樹脂であって、他の成分を含有した共重合体であってもよい。ポリアルキレンフタレート樹脂の分子構造は、特に制限はなく、コポリマーの場合は、ランダム体、ブロック体、分子が線状、分岐、架橋等いずれの分子構造であってもよい。また、ポリアルキレンフタレート樹脂の重合度については、成形加工性を有するものであれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ο−クロロフェノール溶液、２５℃の測定条件における固有粘度が０．５〜１．５（１００ｍｌ／ｇ）であるものが望ましい。
-Polyalkylene phthalate resin-
The polyalkylene phthalate resin is not particularly limited and may be appropriately selected depending on the intended purpose. The polyalkylene phthalate resin is produced by polycondensation of various phthalic acids or ester derivatives thereof and alkylene glycol as main components. In addition, the main structure may be a resin made of polyalkylene phthalate and a copolymer containing other components. The molecular structure of the polyalkylene phthalate resin is not particularly limited, and in the case of a copolymer, any molecular structure such as a random body, a block body, and a linear, branched, or crosslinked molecule may be used. In addition, the degree of polymerization of the polyalkylene phthalate resin is not particularly limited as long as it has molding processability, and can be appropriately selected according to the purpose. For example, measurement of ο-chlorophenol solution at 25 ° C. Those having an intrinsic viscosity of 0.5 to 1.5 (100 ml / g) are desirable.
前記ポリアルキレンフタレート樹脂としては、例えば、ポリブチレンテレフタレート、ポリブチレンテレフタレートイソフタレート共重合体、ポリエチレンテレフタレート、ポリエチレンテレフタレートイソフタレート共重合体などが挙げられる。前記ポリアルキレンフタレート樹脂は、単独又は一種類以上の他の熱可塑性樹脂と任意の割合で混合して使用することができる。 Examples of the polyalkylene phthalate resin include polybutylene terephthalate, polybutylene terephthalate isophthalate copolymer, polyethylene terephthalate, polyethylene terephthalate isophthalate copolymer, and the like. The polyalkylene phthalate resin can be used alone or mixed with one or more other thermoplastic resins at an arbitrary ratio.
前記他の熱可塑性樹脂としては、特に制限はなく、目的に応じて適宜選択することができるが、特に、ポリアルキレンフタレート樹脂との相溶性の観点から、ポリカーボネート樹脂及びポリアリレート樹脂が好ましい。なお、前記他の熱可塑性樹脂の添加量は、特に制限はなく、目的に応じて適宜選択することができるが、前記ポリアルキレンフタレート樹脂１００質量部に対し５〜２，３００質量部が好ましい。 There is no restriction | limiting in particular as said other thermoplastic resin, Although it can select suitably according to the objective, From a compatible viewpoint with polyalkylene phthalate resin, especially polycarbonate resin and polyarylate resin are preferable. The amount of the other thermoplastic resin added is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 to 2,300 parts by mass with respect to 100 parts by mass of the polyalkylene phthalate resin.
−ポリカーボネート樹脂−
前記ポリカーボネート樹脂としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、２価フェノールとカーボネート前駆体との溶液法あるいは溶融法で製造されるものが挙げられる。前記２価フェノールとしては、例えば、ビス（４−ヒドロキシフェニル）アルカン系化合物、ビスフェノールＡが好ましく、ビスフェノールＡがより好ましい。
前記２価フェノールとしては、単独、あるいは２種以上混合して使用することができ、例えば、ビスフェノールＡ[２,２−ビス（４−ヒドロキシフェニル）プロパン]、ビス（４−ヒドロキシフェニル）メタン、１,１−ビス（４−ヒドロキシフェニル）エタン、２,２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、などが挙げられる。また、前記カーボネート前駆体としては、例えば、カルボニルハライド、カーボネート、２価フェノールのジハロホルメート、これらの混合物、などが挙げられる。更に、芳香族ポリカーボネートの製造に際し、適当な分子量調整剤、分岐剤、触媒、などが使用できる。
-Polycarbonate resin-
There is no restriction | limiting in particular as said polycarbonate resin, Although it can select suitably according to the objective, For example, what is manufactured with the solution method or melting method of bihydric phenol and a carbonate precursor is mentioned. Examples of the divalent phenol include bis (4-hydroxyphenyl) alkane compounds and bisphenol A, and bisphenol A is more preferable.
The dihydric phenol can be used alone or in combination of two or more. For example, bisphenol A [2,2-bis (4-hydroxyphenyl) propane], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and the like. Examples of the carbonate precursor include carbonyl halides, carbonates, dihaloformates of dihydric phenols, and mixtures thereof. Furthermore, in the production of the aromatic polycarbonate, an appropriate molecular weight regulator, branching agent, catalyst, etc. can be used.
−ポリアリレート樹脂−
前記ポリアリレート樹脂としては、特に制限はなく、目的に応じて適宜選択することができるが、２価フェノールと芳香族ジカルボン酸とを溶融重合法、溶液重合法、界面重合法、などで製造されるものが挙げられる。
前記２価フェノールとしては、ビス（４−ヒドロキシフェニル）アルカン系化合物が好ましく、ビスフェノールＡがより好ましい。前記２価フェノールは、単独、あるいは２種以上混合して使用することができる。例えば、ビスフェノールＡ[２,２−ビス（４−ヒドロキシフェニル）プロパン]、ビス（４−ヒドロキシフェニル）メタン、１,１−ビス（４−ヒドロキシフェニル）エタン、２,２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、などが挙げられる。また、前記芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、などが挙げられる。
-Polyarylate resin-
The polyarylate resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is produced by a melt polymerization method, a solution polymerization method, an interfacial polymerization method, or the like using a dihydric phenol and an aromatic dicarboxylic acid. Can be mentioned.
As the divalent phenol, a bis (4-hydroxyphenyl) alkane compound is preferable, and bisphenol A is more preferable. The dihydric phenols can be used alone or in admixture of two or more. For example, bisphenol A [2,2-bis (4-hydroxyphenyl) propane], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy) -3-methylphenyl) propane, and the like. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like.
−カーボンブラック−
前記カーボンブラックとしては、特に制限はなく、目的に応じて適宜選択することができるが、導電性、カーボン分散性、などの観点から、ｎ―ジブチルフタレート（ＤＢＰ）給油量が１００〜４００ｍｌ／１００ｇが好ましい。前記ＤＢＰ給油量が４００ｍｌ／１００ｇを超えると、カーボンの分散状態が悪化することがあり、ＤＢＰ給油量が１００ｍｌ／１００ｇ未満であると、導電性付与効果に劣ることがある。
-Carbon black-
The carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of conductivity, carbon dispersibility, and the like, n-dibutyl phthalate (DBP) oil supply amount is 100 to 400 ml / 100 g. Is preferred. When the DBP oil supply amount exceeds 400 ml / 100 g, the carbon dispersion state may deteriorate, and when the DBP oil supply amount is less than 100 ml / 100 g, the conductivity imparting effect may be inferior.
前記カーボンブラックとしては、市販品を使用してもよく、例えば、ケッチェンブラックＥＣ（ライオン社製）、バルカンＸＣ−７２（キャボット社製）、デンカブラック（電気化学工業製）、などが挙げられる。その他、ナフサなどの炭化水素を水素及び酸素の存在下で部分酸化して、水素及び一酸化炭素を含む合成ガスを製造する際に複製する上記特性のカーボンブラック、あるいはこれを酸化または還元処理したｎ―ジブチルフタレート（ＤＢＰ）給油量が１００〜４００ｍｌ／１００ｇである前記特性のカーボンブラックなどが挙げられる。 Commercially available products may be used as the carbon black, and examples thereof include Ketjen Black EC (manufactured by Lion), Vulcan XC-72 (manufactured by Cabot), Denka Black (manufactured by Denki Kagaku Kogyo), and the like. . In addition, carbon black having the above characteristics that is replicated when producing a synthesis gas containing hydrogen and carbon monoxide by partially oxidizing hydrocarbons such as naphtha in the presence of hydrogen and oxygen, or this is oxidized or reduced. Examples thereof include carbon black having the above characteristics in which the amount of n-dibutyl phthalate (DBP) is 100 to 400 ml / 100 g.
前記カーボンブラックの含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記導電性樹脂組成物の合計１００質量部に対し、５質量部〜２０質量部が好ましく、６質量部〜１５質量部がより好ましい。
前記含有量が５質量部未満であると、成形体に導電性を付与する効果が低下することがあり、２０質量部を超えると、凝集物の量が増加し、カーボンブラックを樹脂中に均一に分散させることが困難となることがある。
There is no restriction | limiting in particular as content of the said carbon black, Although it can select suitably according to the objective, 5 mass parts-20 mass parts are preferable with respect to a total of 100 mass parts of the said conductive resin composition, 6-15 mass parts is more preferable.
When the content is less than 5 parts by mass, the effect of imparting conductivity to the molded product may be reduced. When the content exceeds 20 parts by mass, the amount of aggregates increases and carbon black is uniformly contained in the resin. It may be difficult to disperse the resin in the water.
−ヒンダードフェノール系酸化防止剤−
前記ヒンダードフェノール系酸化防止剤としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、ペンタエリスリトールテトラキス[３−（３，５−ジ−ｔ−ブチル−ヒドロキシフェニル）プロピオネート]、チオジエチレン[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]、オクタデシル−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、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス[３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオンアミド]、ベンゼンプロパン酸,３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシ,Ｃ７−Ｃ９側鎖アルキルエステル、ジエチル[[３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル]メチル]ホスフォネート、３，３’，３”，５，５’，５”，−ヘキサ−ｔ−ブチル−ａ，ａ’，ａ”−（メシチレン−２，４，６−トリイル）トリーｐ−クレゾール、エチレンビス（オキシエチレン）ビス[３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート]、ヘキサメチレンビス[３−（３，５−ジ−ｔ−ブチルー４−ヒドロキシフェニル）プロピオネート]、等が挙げられる。
-Hindered phenolic antioxidants-
The hindered phenol antioxidant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-hydroxyphenyl) Propionate], thiodiethylene [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N , N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) ) -4-hydroxy, C7-C9 side chain alkyl ester, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] me L] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″,-hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol , Ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], and the like.
前記ヒンダードフェノール酸化防止剤の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記導電性樹脂組成物の合計１００質量部に対し、０．０５〜２質量部が好ましく、０．１〜１質量部がより好ましい。
前記含有量が、０．０５質量部未満であると、効果が少ないことがあり、２質量部を超えると、成形時にブリードアウトして金型汚染の原因となることがある。
There is no restriction | limiting in particular as content of the said hindered phenol antioxidant, Although it can select suitably according to the objective, 0.05-2 mass with respect to a total of 100 mass parts of the said conductive resin composition. Part is preferable, and 0.1 to 1 part by mass is more preferable.
When the content is less than 0.05 parts by mass, the effect may be small. When the content exceeds 2 parts by mass, bleeding may occur during molding and cause mold contamination.
−金属不活性化剤−
前記金属不活性化剤としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、サリチル酸誘導体、ヒドラジド誘導体、シュウ酸アミド誘導体、イオウ含有フォスファイト、などが挙げられる。これらの中でも、揮発成分を抑制する効果が高いという点で、ヒドラジド誘導体が好適である。
前記金属不活性化剤としては、具体的には、２’，３−ビス[[３−[３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル]プロピオニル]プロピオノヒドラジド、３−Ｎ’−サリチロイルアミノ−１，２，４−トリアゾール、サリチルヒドラジン、サリチルアルデヒド、オキサリル−ビス[ベンジリデンヒドラジド]、トリス[２−ｔ−ブチル−４’−チオ（２’−メチル−４’−ヒドロキシ−５−ｔ−ブチル）フェニル−５−メチル]フェニルフォスファイト、などが挙げられる。
-Metal deactivator-
There is no restriction | limiting in particular as said metal deactivator, Although it can select suitably according to the objective, For example, a salicylic acid derivative, a hydrazide derivative, an oxalic acid amide derivative, a sulfur containing phosphite, etc. are mentioned. Among these, hydrazide derivatives are preferable because they have a high effect of suppressing volatile components.
Specific examples of the metal deactivator include 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, 3-N ′. -Salicyloylamino-1,2,4-triazole, salicylhydrazine, salicylaldehyde, oxalyl-bis [benzylidenehydrazide], tris [2-tert-butyl-4'-thio (2'-methyl-4'-hydroxy) -5-t-butyl) phenyl-5-methyl] phenyl phosphite, and the like.
前記金属不活性化剤の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記導電性樹脂組成物の合計１００質量部に対し、０．０５〜２質量部が好ましく、０．１〜１質量部がより好ましい。
前記含有量が、０．０５質量部未満であると、揮発成分の発生を抑制する効果が少ないことがあり、２質量部を超えると、成形時にブリードアウトして金型汚染の原因になることがある。
There is no restriction | limiting in particular as content of the said metal deactivator, Although it can select suitably according to the objective, 0.05-2 mass parts with respect to a total of 100 mass parts of the said conductive resin composition. Is preferable, and 0.1-1 mass part is more preferable.
When the content is less than 0.05 parts by mass, the effect of suppressing the generation of volatile components may be small. When the content exceeds 2 parts by mass, bleeding out during molding may cause mold contamination. There is.
−その他の成分−
前記その他の成分としては、例えば、潤滑剤、滑剤、核剤、染・顔料、離型剤、種々の安定剤、他の熱可塑性樹脂、強化剤、充填剤、などが挙げられる。
-Other ingredients-
Examples of the other components include lubricants, lubricants, nucleating agents, dyes / pigments, mold release agents, various stabilizers, other thermoplastic resins, reinforcing agents, fillers, and the like.
（導電性樹脂組成物の製造方法）
前記導電性樹脂組成物は、前記ポリアルキレンフタレート樹脂と、前記カーボンブラックと、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性化剤とを、適宜選択した公知の方法により混合、混練することにより調製することができ、例えば、溶融混練してペレット状コンパウンドとすることができる。
前記ペレット状コンパウンドとする方法としては、特に制限はなく、通常の樹脂組成物の混合、混練に用いられる装置、設備を用いて容易に製造することができる。例えば、前記ポリアルキレンフタレート樹脂を含む前記熱可塑性樹脂と、前記カーボンブラックと、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性剤とが全て共存し、前記ポリアルキレンフタレート樹脂を含む前記熱可塑性樹脂と、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性剤とが加熱溶融された状態で、３０秒以上混練することができる。
この際、前記各成分の配合順序は、特に限定されないが、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性剤と、前記ポリアルキレンフタレート樹脂とを同時に配合するのが好ましい。具体的には、前記ポリアルキレンフタレート樹脂を含む熱可塑性樹脂と、前記カーボンブラックと、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性剤とを予めタンブラー、又はヘンシェルミキサーなどの混合機で均一に混合した後、該混合物を１軸又は２軸の押出機に供給して溶融混練する方法、または、前記ポリアルキレンフタレート樹脂を含む前記熱可塑性樹脂と、前記ヒンダードフェノール系酸化防止剤と、前記金属不活性剤とを予め混合し、該混合物を１軸又は、２軸押出機に供給して溶融混練した後、前記カーボンブラックをサイドフィーダから供給する方法（例えば、特開平７−５３７６７号公報に開示された方法）、などにより、ペレット化した後、成形に供してもよく、また、直接成形してもよい。
(Method for producing conductive resin composition)
In the conductive resin composition, the polyalkylene phthalate resin, the carbon black, the hindered phenol antioxidant, and the metal deactivator are mixed and kneaded by appropriately selected known methods. For example, it can be melt-kneaded to form a pellet compound.
There is no restriction | limiting in particular as the method of setting it as the said pellet-form compound, It can manufacture easily using the apparatus and equipment used for mixing and kneading | mixing of a normal resin composition. For example, the thermoplastic resin containing the polyalkylene phthalate resin, the carbon black, the hindered phenolic antioxidant, and the metal deactivator all coexist, and the heat containing the polyalkylene phthalate resin. The plastic resin, the hindered phenol-based antioxidant, and the metal deactivator can be kneaded for 30 seconds or longer in a state where the resin is heated and melted.
At this time, the blending order of the respective components is not particularly limited, but it is preferable to blend the hindered phenol antioxidant, the metal deactivator, and the polyalkylene phthalate resin simultaneously. Specifically, the thermoplastic resin containing the polyalkylene phthalate resin, the carbon black, the hindered phenol-based antioxidant, and the metal deactivator are previously mixed with a mixer such as a tumbler or a Henschel mixer. After uniformly mixing, the mixture is supplied to a single or twin screw extruder and melt kneaded, or the thermoplastic resin containing the polyalkylene phthalate resin, and the hindered phenol antioxidant A method of supplying the carbon black from a side feeder after premixing the metal deactivator, supplying the mixture to a single-screw or twin-screw extruder and melt-kneading the mixture (for example, JP-A-7-53767). Etc.), etc., and may be subjected to molding or may be directly molded.
前記溶融混練する際の処理温度は、前記熱可塑性樹脂成分が溶融する温度より５〜５０℃高い温度が好ましく、前記熱可塑性樹脂の融点より１０〜３０℃高い温度であることが好ましい。前記処理温度が高温すぎると、樹脂の分解や異常反応を誘発することがある。前記溶融混練する際の処理時間は、３０秒〜１０分が好ましく、１〜５分がより好ましい。 The processing temperature at the time of the melt kneading is preferably 5 to 50 ° C. higher than the temperature at which the thermoplastic resin component melts, and preferably 10 to 30 ° C. higher than the melting point of the thermoplastic resin. If the treatment temperature is too high, resin decomposition and abnormal reactions may be induced. The treatment time for the melt kneading is preferably 30 seconds to 10 minutes, more preferably 1 to 5 minutes.
前記導電性樹脂組成物は、前記上述の調整方法により容易に得ることができるものである。得られた導電性樹脂組成物は、直接あるいはペレットを経由した射出成形、押出成形、トランスファー成形、インフレーション成形、などの公知の成形方法によって、シート、テープ、フィルム、所定形状の成形体、などの各種導電体を製造することができる。また、これらの１次成形体から真空成形、圧空成形、プレス成形などの公知の成形方法によって、キャリアテープ、ソフトトレー等、電気・電子部品用部材などの２次成形体を製造することができる。 The conductive resin composition can be easily obtained by the adjustment method described above. The obtained conductive resin composition can be obtained by a known molding method such as injection molding, extrusion molding, transfer molding, inflation molding, directly or via pellets, etc. Various conductors can be manufactured. In addition, secondary molded bodies such as carrier tapes, soft trays, and other members for electric and electronic parts can be produced from these primary molded bodies by known molding methods such as vacuum molding, pressure molding, and press molding. .
以下、本発明の実施例について説明するが、本発明はこの実施例に何ら限定されるものではない。 Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.
（参考例１、実施例２〜４及び比較例１〜４）
下記表１に示す組成の参考例１、実施例２〜４及び比較例１〜４の導電性樹脂組成物を常法に従って調製した。なお、表１中における数値は、前記導電性樹脂組成物１００質量部に対する質量部を表す。
( Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 4)
The conductive resin compositions of Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 4 having the compositions shown in Table 1 below were prepared according to a conventional method. In addition, the numerical value in Table 1 represents the mass part with respect to 100 mass parts of said conductive resin compositions.
具体的には、各配合成分を２軸押出機ＮＲ−ＩＩ（ナカタニ機械社製、スクリュー口径＝５７ｍｍ）を用い、前記押出機の元のホッパーより、予めプレブレンドしたポリアルキレンフタレート樹脂と、酸化防止剤と、金属不活性剤とを含む熱可塑性樹脂の混合物を定量フィーダーにて供給し、該熱可塑性樹脂が完全に溶融したところでカーボンブラックを定量フィーダーにより、サイドフィーダを通して強制的に前記押出機に供給し、導電性樹脂組成物を混練してコンパウンドを得た。次いで、これを冷却後、ペレタイザーを用いて円柱状ペレット（直径２ｍｍ、長さ２〜４ｍｍ）とした。 Specifically, each compounding component was pre-blended with a polyalkylene phthalate resin and oxidized using a twin screw extruder NR-II (manufactured by Nakatani Machinery Co., Ltd., screw diameter = 57 mm) from the original hopper of the extruder. A mixture of a thermoplastic resin containing an inhibitor and a metal deactivator is supplied by a quantitative feeder, and when the thermoplastic resin is completely melted, carbon black is forced through the side feeder by the quantitative feeder and the extruder. And the conductive resin composition was kneaded to obtain a compound. Subsequently, after cooling this, it was set as the cylindrical pellet (diameter 2mm, length 2-4mm) using the pelletizer.
得られたペレット化した前記導電性樹脂組成物を用いて下記の方法により揮発成分の評価を行った。結果を表１に示す。 Using the obtained pelletized conductive resin composition, volatile components were evaluated by the following method. The results are shown in Table 1.
−揮発成分の測定方法−
得られた前記ペレット化した導電性樹脂組成物７０ｇを、ラボプラストミル（東洋精機製）混練部に投入し、１０．０ｃｍ×１０．０ｃｍの硬質ガラスで完全に蓋をした。その状態で、３００℃にて５分間混練したときに発生する揮発分をガラス板に付着させ、デジタル変角光度計（スガ試験機製）により、ヘイズ値を測定し、下記評価基準により評価した。なお、ヘイズ値が小さいほど、ガラス板の曇り度が小さく、揮発成分の発生量が少ないことを示す。
〔評価基準〕
◎・・・ヘイズ値が２未満
○・・・ヘイズ値が２以上６未満
△・・・ヘイズ値が６以上１０未満
×・・・ヘイズ値が１０以上
-Measurement method of volatile components-
70 g of the obtained conductive resin composition pelletized was put into a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) and completely covered with 10.0 cm × 10.0 cm hard glass. In this state, the volatile matter generated when kneaded at 300 ° C. for 5 minutes was adhered to the glass plate, the haze value was measured with a digital goniophotometer (manufactured by Suga Test Instruments), and evaluated according to the following evaluation criteria. In addition, it shows that the haze value is small, the haze of the glass plate is small, and the generation amount of volatile components is small.
〔Evaluation criteria〕
◎ ・ ・ ・ Haze value less than 2 ○ ・ ・ ・ Haze value 2 or more and less than 6 △ ・ ・ ・ Haze value 6 or more and less than 10 × ・ ・ ・ Haze value 10 or more
上記表１中の略号は、下記の通りである。
・ＰＢＴ（ポリブチレンテレフタレート樹脂）：ポリプラスチックス製「７００ＦＰ」[固有粘度０．９７（１００ｍｌ／ｇ）]
・ＰＥＴ（ポリエチレンテレフタレート樹脂）：三菱レイヨン（株）製「ＭＡ５２１Ｈ」[固有粘度０．７８（１００ｍｌ／ｇ）]
・ＰＣ（ポリカーボネート樹脂）：出光石油化学（株）製「Ａ２７００」（ＭＦＲ：５ｇ／１０分）７３質量％と出光石油化学（株）製「ＩＲ１７００Ｈ」２７質量％の混合物
・ＰＡＲ（ポリアリレート樹脂）：ユニチカ（株）製「Ｕ１００」
・ＣＢ（カーボンブラック）：ライオン（株）ケッチェンブラックＥＣ（ＤＢＰ吸油量：３６０ｍｌ／１００ｇ）
・酸防（ｉ）（ヒンダードフェノール系酸化防止剤）：チバスペシャリティケミカルズ（株）製「イルガノックス１０１０」
・酸防（ｉｉ）（ヒンダードフェノール系酸化防止剤）：旭電化工業（株）製「アデカスタブＡＯ―３３０」
・酸防（ｉｉｉ）（フォスファイト系酸化防止剤）：旭電化工業（株）製「アデカスタブＰＥＰ−３６」
・酸防（ｉｖ）（イオウ系酸化防止剤）：チバスペシャリティケミカルズ（株）製「イルガノックスＰＳ８００ＦＬ」
・不活（ｉ）（ヒドラジド系金属不活性化剤）：チバスペシャリティケミカルズ（株）製「イルガノックスＭＤ１０２４」
・不活（ｉｉ）（サリチル酸系金属不活性化剤）：旭電化工業（株）製「アデカスタブＣＤＡ−１」
The abbreviations in Table 1 are as follows.
PBT (polybutylene terephthalate resin): “700FP” made by polyplastics [Intrinsic viscosity 0.97 (100 ml / g)]
PET (polyethylene terephthalate resin): “MA521H” manufactured by Mitsubishi Rayon Co., Ltd. [intrinsic viscosity 0.78 (100 ml / g)]
PC (polycarbonate resin): A mixture of 73% by mass “A2700” (MFR: 5 g / 10 min) manufactured by Idemitsu Petrochemical Co., Ltd. and 27% by mass of “IR1700H” manufactured by Idemitsu Petrochemical Co., Ltd. PAR (polyarylate resin) ): “U100” manufactured by Unitika Ltd.
CB (carbon black): Lion Corporation Ketjen Black EC (DBP oil absorption: 360 ml / 100 g)
Acid (i) (hindered phenol antioxidant): “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.
Acid-proof (ii) (hindered phenol antioxidant): “Adeka Stub AO-330” manufactured by Asahi Denka Kogyo Co., Ltd.
-Acid protection (iii) (phosphite antioxidant): "Adeka Stub PEP-36" manufactured by Asahi Denka Kogyo Co., Ltd.
-Acid protection (iv) (sulfur-based antioxidant): "Irganox PS800FL" manufactured by Ciba Specialty Chemicals Co., Ltd.
Inactive (i) (hydrazide metal deactivator): “Irganox MD1024” manufactured by Ciba Specialty Chemicals Co., Ltd.
Inactivation (ii) (salicylic acid-based metal deactivator): “Adeka Stub CDA-1” manufactured by Asahi Denka Kogyo Co., Ltd.
表１の結果から、参考例１、及び実施例２〜４の導電性樹脂組成物は、いずれも成形時に発生する揮発成分の発生量が少なく、金型汚染や成形不良を防止できることが判った。特に、金属不活性化剤として、ヒドラジド系金属不活性化剤を用いた参考例１、並びに実施例２及び４の導電性樹脂組成物が、成形時に発生する揮発成分の発生量を更に少なくすることができることが判った。これに対し、比較例１〜４の導電性樹脂組成物は、成形品の成形時に発生する揮発成分の量を満足するレベルまで抑制できないことが判った。 From the results of Table 1, it was found that the conductive resin compositions of Reference Example 1 and Examples 2 to 4 all had a small amount of volatile components generated during molding and could prevent mold contamination and molding defects. . In particular, the conductive resin compositions of Reference Example 1 and Examples 2 and 4 using a hydrazide-based metal deactivator as the metal deactivator further reduce the amount of volatile components generated during molding. It turns out that you can. On the other hand, it turned out that the conductive resin composition of Comparative Examples 1-4 cannot be suppressed to the level which satisfies the quantity of the volatile component which generate | occur | produces at the time of shaping | molding of a molded article.
本発明の導電性樹脂組成物は、ＩＣ、ＬＥＤ等の電気・電子部品用部材の包装としての、キャリアテープ、マガジン、トレイ、バッグ等の成形品に好適に利用可能である。特に、キャリアテープに好適であるが、強度、導電性ともにキャリアテープとして使用するのに十分な値を示すものである。
The conductive resin composition of the present invention can be suitably used for molded articles such as carrier tapes, magazines, trays, bags and the like as packaging for members for electric and electronic parts such as ICs and LEDs. Although it is particularly suitable for a carrier tape, both strength and conductivity are sufficient for use as a carrier tape.
Claims (2)
ｎ―ジブチルフタレート（ＤＢＰ）吸油量が１００〜４００ｍｌ／１００ｇであるカーボンブラックと、
ヒンダードフェノール系酸化防止剤と、
金属不活性化剤とを含有する導電性樹脂組成物であって、
前記カーボンブラックの含有量が前記導電性樹脂組成物の合計１００質量部に対し、５質量部〜２０質量部であって、
前記金属不活性化剤が、２’，３−ビス［３−［３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］プロピオノヒドラジド及び３−Ｎ’−サリチロイルアミノ−１，２，４−トリアゾールから選択される少なくともいずれかであることを特徴とする電気・電子部品用部材の包装用成形体用導電性樹脂組成物。 At least one selected from a polycarbonate resin produced by polycondensation of a dihydric phenol and a carbonate precursor and a polyarylate resin produced by polycondensation of a dihydric phenol and an aromatic dicarboxylic acid, and a polyalkylene phthalate resin; A thermoplastic resin comprising:
carbon black having an n-dibutyl phthalate (DBP) oil absorption of 100 to 400 ml / 100 g;
A hindered phenolic antioxidant,
A conductive resin composition containing a metal deactivator,
The content of the carbon black is 5 parts by mass to 20 parts by mass with respect to a total of 100 parts by mass of the conductive resin composition,
The metal deactivators are 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide and 3-N′-salicyloylamino-1. , 2,4-triazole, at least one selected from the group consisting of electrical and electronic parts, and a conductive resin composition for a molded article for packaging an electrical / electronic component member.
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