JP6990571B2 - Resin composition, manufacturing method of resin composition, and molded product - Google Patents
Resin composition, manufacturing method of resin composition, and molded product Download PDFInfo
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- JP6990571B2 JP6990571B2 JP2017237990A JP2017237990A JP6990571B2 JP 6990571 B2 JP6990571 B2 JP 6990571B2 JP 2017237990 A JP2017237990 A JP 2017237990A JP 2017237990 A JP2017237990 A JP 2017237990A JP 6990571 B2 JP6990571 B2 JP 6990571B2
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- 239000011342 resin composition Substances 0.000 title claims description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229920001955 polyphenylene ether Polymers 0.000 claims description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 33
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 238000004898 kneading Methods 0.000 claims description 22
- 230000032683 aging Effects 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 description 35
- 150000001875 compounds Chemical class 0.000 description 31
- 238000000034 method Methods 0.000 description 27
- 239000007788 liquid Substances 0.000 description 15
- 238000001746 injection moulding Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 230000002265 prevention Effects 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 5
- 101100323621 Drosophila melanogaster Drip gene Proteins 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 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
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- SGXRTWRRYSEZLP-UHFFFAOYSA-N (2-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 SGXRTWRRYSEZLP-UHFFFAOYSA-N 0.000 description 1
- DAZHWGHCARQALS-UHFFFAOYSA-N (2-methylphenyl) (4-methylphenyl) phenyl phosphate Chemical compound C1=CC(C)=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1 DAZHWGHCARQALS-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- UQLMRZPLTWMCRM-UHFFFAOYSA-N 3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=CC=2OC1=CC=2C1=CC=CC=C1 UQLMRZPLTWMCRM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LPRHLAXCXZTKNI-UHFFFAOYSA-N dibutyl methyl phosphate Chemical compound CCCCOP(=O)(OC)OCCCC LPRHLAXCXZTKNI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 1
- ANPYQJSSFZGXFE-UHFFFAOYSA-N ethyl dipropyl phosphate Chemical compound CCCOP(=O)(OCC)OCCC ANPYQJSSFZGXFE-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- ICMWSAALRSINTC-UHFFFAOYSA-N penta-1,4-dien-3-ol Chemical compound C=CC(O)C=C ICMWSAALRSINTC-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Description
本発明は、樹脂組成物、樹脂組成物の製造方法、及び成形体に関する。 The present invention relates to a resin composition, a method for producing a resin composition, and a molded product.
従来、ポリフェニレンエーテル系樹脂は、優れた電気絶縁性に加え、耐熱性、耐加水分解性及び難燃性を有していることから、家電・ＯＡ機器、自動車部品等に広く使用されている。 Conventionally, polyphenylene ether-based resins are widely used in home appliances, OA equipment, automobile parts, etc. because they have heat resistance, hydrolysis resistance, and flame retardancy in addition to excellent electrical insulation.
これらの用途には、火災の問題等から高い難燃性が要求されており、ポリフェニレンエーテル系樹脂はハロゲン化合物を用いることなくリン系化合物を添加することによって容易に難燃性を得ることができる。また、より高い剛性、耐熱性、寸法性が要求されることから、無機充填材を配合した強化系樹脂組成物が多く用いられるようになった。 High flame retardancy is required for these applications due to fire problems and the like, and the polyphenylene ether-based resin can be easily flame-retardant by adding a phosphorus-based compound without using a halogen compound. .. Further, since higher rigidity, heat resistance, and dimensionality are required, reinforced resin compositions containing an inorganic filler have come to be widely used.
一般的に、無機充填材を配合すると難燃性、流動性、外観が悪化する。特に難燃性に関しては、近年、以前よりも更に厳しいレベルの難燃性が要求され始めている。また、部品の小型化や構造の複雑化が進み、これらの材料は薄肉で成形されることが多くなるため、射出成形時に良好な流動性（成形加工性）を有していることも要求されている。 In general, the addition of an inorganic filler deteriorates flame retardancy, fluidity, and appearance. Especially with regard to flame retardancy, in recent years, even stricter levels of flame retardancy have begun to be required. In addition, as parts become smaller and their structures become more complicated, these materials are often molded with a thin wall, so it is also required to have good fluidity (molding workability) during injection molding. ing.
上記の要求に応えるものとして、従来、スチレン－アクリロニトリル共重合体を配合し、流動性、機械的物性等のバランス、難燃性に優れたポリフェニレンエーテル系樹脂組成物が開示されている（例えば、特許文献１参照）。 In order to meet the above requirements, conventionally, a polyphenylene ether-based resin composition containing a styrene-acrylonitrile copolymer and having excellent balance of fluidity, mechanical properties, etc. and flame retardancy has been disclosed (for example,). See Patent Document 1).
しかしながら、特許文献１に開示されている樹脂材料においても、近年要求され始めた高いレベルの難燃性を達成する観点から、さらなる改善の余地を有していた。 However, even in the resin material disclosed in Patent Document 1, there is room for further improvement from the viewpoint of achieving a high level of flame retardancy that has begun to be required in recent years.
そこで本発明においては、流動性、外観に優れ、高いレベルの難燃性を有する樹脂組成物、樹脂組成物の製造方法、及び成形体の提供を目的とする。 Therefore, an object of the present invention is to provide a resin composition having excellent fluidity and appearance and having a high level of flame retardancy, a method for producing the resin composition, and a molded product.
上記課題を解決するため鋭意検討を行った結果、ポリフェニレンエーテル系樹脂、スチレン系樹脂、リン系化合物、無機充填材、ポリテトラフルオロエチレンを含む樹脂組成物に対し、無機充填材の含有量及び熱エージング後の熱収縮率をある特定の範囲内に制御することによって、流動性、外観に優れ、高いレベルの難燃性が得られることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the content and heat of the inorganic filler in the resin composition containing the polyphenylene ether-based resin, the styrene-based resin, the phosphorus-based compound, the inorganic filler, and the polytetrafluoroethylene. By controlling the heat shrinkage rate after aging within a specific range, it has been found that excellent fluidity and appearance and a high level of flame retardancy can be obtained, and the present invention has been completed.
すなわち、本発明は、以下の通りである。 That is, the present invention is as follows.
［１］
（ａ）ポリフェニレンエーテル系樹脂と、
（ｂ）スチレン系樹脂と、
（ｃ）リン系化合物と、
（ｄ）無機充填材と、
（ｅ）ポリテトラフルオロエチレンと、
を含む樹脂組成物であり、
前記（ａ）成分が、還元粘度が異なる２以上のポリフェニレンエーテルを含み、
前記（ｃ）成分が、縮合リン酸エステル化合物であり、
前記樹脂組成物中に、前記（ｄ）成分を３５～６０質量％含み、
前記（ａ）成分、前記（ｂ）成分、及び前記（ｃ）成分の合計１００質量部に対して、前記（ｅ）成分を０．０５～１．５質量部含み、
流れ方向の長さ１２５ｍｍ、垂直方向の長さ１３ｍｍ、厚み１．６ｍｍの寸法で作成した前記樹脂組成物の試験片を、温度１５０℃、２４時間の条件下でエージングしたときの、下記式で示す試験片の収縮率が６～２０％であることを特徴とする、樹脂組成物。
試験片収縮率［％］＝（（エージング前の流れ方向の試験片の長さ［ｍｍ］－エージング後の流れ方向の試験片の長さ［ｍｍ］）／（エージング前の流れ方向の試験片の長さ［ｍｍ］））×１００
［２］
前記（ａ）成分、前記（ｂ）成分、及び前記（ｃ）成分の合計１００質量部に対して、
前記（ａ）成分を５０～７０質量部、
前記（ｂ）成分を１０～３０質量部、
前記（ｃ）成分を１０～３０質量部、及び
前記（ｅ）成分を０．０５～１質量部含む、［１］に記載の樹脂組成物。
［３］
前記（ａ）成分が、
（ａ－１）還元粘度が０．４５～０．５５ｄＬ／ｇのポリフェニレンエーテル系樹脂と、
（ａ－２）還元粘度が０．３５～０．４５ｄＬ／ｇのポリフェニレンエーテル系樹脂と、
を含み、
（ａ－１）成分と（ａ－２）成分との合計１００質量部に対する（ａ－２）成分の含有量が、６０～９０質量部である、［１］又は［２］に記載の樹脂組成物。
［４］
前記（ｄ）成分が、ガラス繊維及びマイカから選ばれる１種以上である、［１］～［３］のいずれかに記載の樹脂組成物。
［５］
［１］～［４］のいずれかに記載の樹脂組成物を含むことを特徴とする、成形体。
［６］
［１］～［４］のいずれかに記載の樹脂組成物の製造方法であって、
押出機を用いて、前記（ａ）成分～（ｅ）成分を溶融混練する工程を含むことを特徴とする、樹脂組成物の製造方法。
［７］
前記（ｅ）成分の粉体ポリテトラフルオロエチレン及び／又は改質ポリテトラフルオロエチレンを前記（ａ）成分～（ｄ）成分の少なくとも１成分とドライブレンドして前記押出機へ供給する工程を含む、［６］に記載の樹脂組成物の製造方法。
［８］
前記供給する工程において、前記（ｅ）成分の粉体ポリテトラフルオロエチレン及び／又は改質ポリテトラフルオロエチレンを前記（ａ）成分の全量又は一部とドライブレンドして前記押出機へ供給することを含む、［７］に記載の樹脂組成物の製造方法。
[1]
(A) Polyphenylene ether-based resin and
(B) Styrene-based resin and
(C) Phosphorus compounds and
(D) Inorganic filler and
(E) Polytetrafluoroethylene and
Is a resin composition containing
The component (a) contains two or more polyphenylene ethers having different reducing viscosities.
The component (c) is a condensed phosphoric acid ester compound.
The resin composition contains 35 to 60% by mass of the component (d).
The component (e) is contained in an amount of 0.05 to 1.5 parts by mass with respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c).
The following formula was used when a test piece of the resin composition prepared with dimensions of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness was aged under the conditions of a temperature of 150 ° C. and 24 hours. A resin composition, wherein the indicated test piece has a shrinkage rate of 6 to 20%.
Specimen shrinkage rate [%] = ((Length of test piece in flow direction before aging [mm] -Length of test piece in flow direction after aging [mm]) / (Test piece in flow direction before aging Length [mm])) x 100
[2]
With respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c).
50 to 70 parts by mass of the component (a),
10 to 30 parts by mass of the component (b),
The resin composition according to [1], which comprises 10 to 30 parts by mass of the component (c) and 0.05 to 1 part by mass of the component (e).
[3]
The component (a) is
(A-1) A polyphenylene ether-based resin having a reduced viscosity of 0.45 to 0.55 dL / g,
(A-2) A polyphenylene ether-based resin having a reduced viscosity of 0.35 to 0.45 dL / g,
Including
The resin according to [1] or [2], wherein the content of the component (a-2) is 60 to 90 parts by mass with respect to a total of 100 parts by mass of the component (a-1) and the component (a-2). Composition.
[4]
The resin composition according to any one of [1] to [3], wherein the component (d) is at least one selected from glass fiber and mica.
[5 ]
A molded product comprising the resin composition according to any one of [ 1] to [ 4 ].
[ 6 ]
The method for producing a resin composition according to any one of [1] to [ 4 ].
A method for producing a resin composition, which comprises a step of melt-kneading the components (a) to (e) using an extruder.
[ 7 ]
The step includes a step of dry-blending the powdered polytetrafluoroethylene and / or the modified polytetrafluoroethylene of the component (e) with at least one of the components (a) to (d) and supplying the mixture to the extruder. , [ 6 ]. The method for producing the resin composition.
[ 8 ]
In the supply step, the powder polytetrafluoroethylene and / or the modified polytetrafluoroethylene of the component (e) is dry-blended with all or part of the component (a) and supplied to the extruder. The method for producing a resin composition according to [ 7 ], which comprises.
本発明によれば、流動性、外観に優れ、高いレベルの難燃性を有する樹脂組成物、樹脂組成物の製造方法、及び成形体を提供することができる。 According to the present invention, it is possible to provide a resin composition having excellent fluidity and appearance and having a high level of flame retardancy, a method for producing the resin composition, and a molded product.
以下、本発明を実施するための形態（以下、「本実施形態」と言う。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明は、以下の実施形態に限定されるものではない。また、本発明は、その要旨の範囲内で適宜変形して実施することができる。 Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. Further, the present invention can be appropriately modified and carried out within the scope of the gist thereof.
＜樹脂組成物＞
本発明の樹脂組成物は、（ａ）ポリフェニレンエーテル系樹脂と、（ｂ）スチレン系樹脂と、（ｃ）リン系化合物と、（ｄ）無機充填材と、（ｅ）ポリテトラフルオロエチレンと、を含む樹脂組成物であり、前記樹脂組成物中に、前記（ｄ）成分を３５～６０質量％含み、流れ方向の長さ１２５ｍｍ、垂直方向の長さ１３ｍｍ、厚み１．６ｍｍの寸法で作成した前記樹脂組成物の試験片を、温度１５０℃、２４時間の条件下でエージングしたときの試験片の収縮率が６～２０％であることを特徴とする。
当該収縮率は、より好ましくは７～１８％、更に好ましくは７～１５％である。
当該収縮率は、６％以上であることで燃焼時の滴下防止性、外観に優れ、２０％以下であることで流動性、難燃性に優れる。
<Resin composition>
The resin composition of the present invention comprises (a) a polyphenylene ether-based resin, (b) a styrene-based resin, (c) a phosphorus-based compound, (d) an inorganic filler, and (e) polytetrafluoroethylene. The resin composition contains 35 to 60% by mass of the component (d) in the resin composition, and is prepared with dimensions of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness. When the test piece of the above resin composition is aged under the conditions of a temperature of 150 ° C. for 24 hours, the shrinkage rate of the test piece is 6 to 20%.
The shrinkage rate is more preferably 7 to 18%, still more preferably 7 to 15%.
When the shrinkage rate is 6% or more, it is excellent in dripping prevention property and appearance at the time of combustion, and when it is 20% or less, it is excellent in fluidity and flame retardancy.
＜樹脂組成物の試験片収縮率＞
本開示において、「エージング」とは、高温状態に一定時間置くことをいい、温度は１５０℃、時間は２４時間とする。
樹脂組成物の試験片は、乾燥させた樹脂組成物ペレットから射出成形機を用いて作製することができ、流れ方向の長さ１２５ｍｍ、垂直方向の長さ１３ｍｍ、厚み１．６ｍｍの大きさとする。
なお、本開示で、「流れ方向」とは、樹脂組成物を射出成形する際に樹脂組成物が流れる方向（ＭＤ）をいい、「垂直方向」とは、「流れ方向」に垂直な幅方向（ＴＤ）をいう。
<Test piece shrinkage rate of resin composition>
In the present disclosure, "aging" means to leave the product in a high temperature state for a certain period of time, and the temperature is 150 ° C. and the time is 24 hours.
The test piece of the resin composition can be produced from dried resin composition pellets using an injection molding machine, and has a size of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness. ..
In the present disclosure, the "flow direction" refers to the direction (MD) in which the resin composition flows when the resin composition is injection-molded, and the "vertical direction" is the width direction perpendicular to the "flow direction". (TD).
試験片の収縮率（％）は、下記式から求めることができる。
試験片収縮率［％］＝（（エージング前の流れ方向の試験片の長さ［ｍｍ］－エージング後の流れ方向の試験片の長さ［ｍｍ］）／（エージング前の流れ方向の試験片の長さ［ｍｍ］））×１００
The shrinkage rate (%) of the test piece can be calculated from the following formula.
Specimen shrinkage rate [%] = ((Length of test piece in flow direction before aging [mm] -Length of test piece in flow direction after aging [mm]) / (Test piece in flow direction before aging Length [mm])) x 100
試験片の収縮率は、６～２０％であり、より好ましくは７～１８％、更に好ましくは７～１５％である。当該収縮率は、６％以上であることで燃焼時の滴下防止性、外観に優れ、２０％以下であることで流動性、難燃性に優れる。
なお、樹脂組成物の試験片の収縮率は、具体的には、後述の実施例に記載の方法で測定することができる。
The shrinkage rate of the test piece is 6 to 20%, more preferably 7 to 18%, still more preferably 7 to 15%. When the shrinkage rate is 6% or more, it is excellent in dripping prevention property and appearance at the time of combustion, and when it is 20% or less, it is excellent in fluidity and flame retardancy.
Specifically, the shrinkage rate of the test piece of the resin composition can be measured by the method described in Examples described later.
エージング後の試験片の収縮率を高くする方法としては、例えば、樹脂組成物中の（ｅ）成分の含有量を増やす、（ｅ）成分の分散性を上げる、（ｅ）成分のフィブリル構造を増やす等が挙げられる。
逆に当該収縮率を低くする方法としては、例えば、樹脂組成物中の（ｅ）成分の含有量を減らす、（ｅ）成分の分散性を下げる、（ｅ）成分のフィブリル構造を減らす等が挙げられる。
As a method for increasing the shrinkage rate of the test piece after aging, for example, the content of the component (e) in the resin composition is increased, the dispersibility of the component (e) is increased, and the fibril structure of the component (e) is used. For example, increase.
On the contrary, as a method of lowering the shrinkage rate, for example, the content of the component (e) in the resin composition is reduced, the dispersibility of the component (e) is lowered, the fibril structure of the component (e) is reduced, and the like. Can be mentioned.
また、押出機のスクリュー回転数が高くなると（ｅ）成分の分散性は上がるが、（ｅ）成分のフィブリル構造は壊れやすくなり、逆に低くなると（ｅ）成分の分散性は下がるが、（ｅ）成分のフィブリル構造は壊れにくくなることから、適宜スクリュー回転数の調整を行って、当該収縮率を調整する。
スクリュー構成に関しても、混練性が高い構成にすると（ｅ）成分の分散性は上がるが、（ｅ）成分のフィブリル構造は壊れやすくなり、逆に混練性が低い構成にすると（ｅ）成分の分散性は下がるが、（ｅ）成分のフィブリル構造は壊れにくくなるため、適宜スクリュー構成の調整を行って、当該収縮率を調整する。
Further, when the screw rotation speed of the extruder is increased, the dispersibility of the component (e) is increased, but the fibril structure of the component (e) is fragile, and conversely, when the screw rotation speed is decreased, the dispersibility of the component (e) is decreased. e) Since the fibril structure of the component is hard to break, the screw rotation speed is adjusted as appropriate to adjust the shrinkage rate.
Regarding the screw structure, if the structure has high kneadability, the dispersibility of the component (e) increases, but the fibril structure of the component (e) becomes fragile, and conversely, if the structure has low kneadability, the dispersibility of the component (e) increases. Although the property is reduced, the fibril structure of the component (e) is less likely to be broken, so the screw configuration is appropriately adjusted to adjust the shrinkage rate.
このように、当該収縮率は、樹脂組成物中の成分（ａ）～（ｅ）の含有量、原料のブレンド方法、押出機への原料の投入方法、スクリュー構成、混練段階での押出機のスクリューの回転数、混練温度等により調整することができる。 As described above, the shrinkage ratio is the content of the components (a) to (e) in the resin composition, the method of blending the raw materials, the method of charging the raw materials into the extruder, the screw configuration, and the extruder in the kneading stage. It can be adjusted by the number of rotations of the screw, the kneading temperature, and the like.
－（ａ）ポリフェニレンエーテル系樹脂－
（ａ）ポリフェニレンエーテル系樹脂（本明細書において、「ＰＰＥ」と称する場合や、単に「（ａ）成分」と称する場合がある。）は、フェニレンエーテルの単独重合体（ホモポリマー）でもよいし、フェニレンエーテルと他の単量体との共重合体（コポリマー）でもあってもよい。
上記（ａ）成分は、１種のみを単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
-(A) Polyphenylene ether-based resin-
(A) The polyphenylene ether-based resin (in the present specification, it may be referred to as "PPE" or simply referred to as "component (a)") may be a homopolymer of phenylene ether. , It may also be a copolymer (copolymer) of phenylene ether and another monomer.
As the component (a), only one kind may be used alone, or two or more kinds may be used in combination.
上記（ａ）成分として、例えば、下記式（１）で表される繰り返し単位構造（フェニレンエーテルに由来する単位構造）を有する単独重合体及び／又は共重合体が挙げられる。
上記（ａ）成分としては、例えば、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－メチル－６－フェニル－１，４－フェニレンエーテル）、ポリ（２，６－ジクロロ－１，４－フェニレンエーテル）等の単独重合体；２，６－ジメチルフェノールと他のフェノール類（例えば、２，３，６－トリメチルフェノールや２－メチル－６－ブチルフェノール）等との共重合体；等が挙げられる。中でも、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）、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が好ましく、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）がより好ましい。 Examples of the component (a) include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-). Homopolymers such as 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and other phenols (eg 2,3). , 6-trimethylphenol, 2-methyl-6-butylphenol) and the like; Of these, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is preferable. ) Is more preferable.
上記（ａ）成分の製造方法は、従来公知の方法を適用できる。上記（ａ）成分の製造方法としては、例えば、第一銅塩とアミンとのコンプレックスを触媒として用いて、２，６－キシレノール等を酸化重合することによって製造する方法、特開昭５０－１５０７９８号公報、特開昭５０－０５１１９７号公報、特開昭６３－１５２６２８号公報等に記載される方法等が挙げられる。 A conventionally known method can be applied to the method for producing the component (a). As a method for producing the component (a), for example, a method for producing by oxidative polymerization of 2,6-xylenol or the like using a complex of a cuprous salt and an amine as a catalyst, JP-A-50-15798. Examples thereof include the methods described in Japanese Patent Application Laid-Open No. 50-051197, Japanese Patent Application Laid-Open No. 63-152628, and the like.
上記（ａ）成分の還元粘度（０．５ｇ／ｄＬのクロロホルム溶液、３０℃測定、ウベローデ型粘度管で測定）は、流動性の観点から、０．７ｄＬ／ｇ以下であることが好ましく、０．６ｄＬ／ｇ以下であることがより好ましく、滴下防止性の観点から０．２ｄＬ／ｇ以上であることが好ましく、０．３ｄＬ／ｇ以上であることがより好ましい。 The reduced viscosity of the component (a) (0.5 g / dL chloroform solution, measured at 30 ° C., measured with an Ubbelohde viscous tube) is preferably 0.7 dL / g or less from the viewpoint of fluidity, and is 0. It is more preferably 0.6 dL / g or less, preferably 0.2 dL / g or more, and more preferably 0.3 dL / g or more from the viewpoint of dripping prevention.
上記（ａ）成分としては、還元粘度が異なる２以上のポリフェニレンエーテルを混合して用いてもよい。上記（ａ）成分としては、流動性と燃焼時の滴下防止性とのバランスの観点から、（ａ－１）還元粘度が０．４５～０．５５ｄＬ／ｇ、好適には０．４８～０．５３ｄＬ／ｇのポリフェニレンエーテル系樹脂と、（ａ－２）還元粘度が０．３５～０．４５ｄＬ／ｇ、好適には０．３８～０．４３ｄＬ／ｇのポリフェニレンエーテル系樹脂とを含み、（ａ－１）成分と（ａ－２）成分との合計１００質量部に対する（ａ－２）成分の含有量が、６０～９０質量部であるものが好ましく、より好ましくは６５～８０質量部である。 As the component (a), two or more polyphenylene ethers having different reducing viscosities may be mixed and used. The component (a) has a reduced viscosity of 0.45 to 0.55 dL / g, preferably 0.48 to 0, from the viewpoint of the balance between fluidity and dripping prevention property during combustion. It contains .53 dL / g of a polyphenylene ether-based resin and (a-2) a polyphenylene ether-based resin having a reduced viscosity of 0.35 to 0.45 dL / g, preferably 0.38 to 0.43 dL / g. The content of the component (a-2) is preferably 60 to 90 parts by mass, more preferably 65 to 80 parts by mass with respect to 100 parts by mass of the total of the component (a-1) and the component (a-2). Is.
上記（ａ）成分は、全部又は一部が変性された変性ポリフェニレンエーテルを含んでいてもよい。
ここでいう変性ポリフェニレンエーテルとは、分子構造内に少なくとも１個の炭素－炭素二重結合及び／又は三重結合を有するとともに、カルボン酸基、酸無水物基、アミノ基、水酸基及びグリシジル基からなる群より選ばれる少なくとも１個の基を有する変性化合物（以下、単に「変性化合物」と記載する場合がある。）で変性されたポリフェニレンエーテルをいう。変性化合物は１種のみを単独で用いてもよく、２種以上を併用してもよい。
The component (a) may contain a modified polyphenylene ether that has been completely or partially modified.
The modified polyphenylene ether referred to here has at least one carbon-carbon double bond and / or triple bond in the molecular structure, and is composed of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group and a glycidyl group. A polyphenylene ether modified with a modified compound having at least one group selected from the group (hereinafter, may be simply referred to as "modified compound"). Only one kind of modified compound may be used alone, or two or more kinds may be used in combination.
上記変性ポリフェニレンエーテルの製造方法としては、以下に限定されるものではないが、例えば、ラジカル開始剤の存在下又は非存在下で、（１）１００℃以上ポリフェニレンエーテルのガラス転移温度未満の範囲の温度で、ポリフェニレンエーテルを溶融させることなく、ポリフェニレンエーテルと変性化合物とを反応させる方法、（２）ポリフェニレンエーテルのガラス転移温度以上３６０℃以下の範囲の温度で、ポリフェニレンエーテルと変性化合物とを溶融混練し、反応させる方法、（３）ポリフェニレンエーテルのガラス転移温度未満の温度で、ポリフェニレンエーテルと変性化合物とを溶液中で反応させる方法等が挙げられ、これらいずれの方法でもよいが、生産性の観点から、（１）又は（２）の方法が好ましい。 The method for producing the modified polyphenylene ether is not limited to the following, but is, for example, in the presence or absence of a radical initiator in the range of (1) 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether. A method of reacting the polyphenylene ether with the modified compound at a temperature without melting the polyphenylene ether, (2) melt-kneading the polyphenylene ether and the modified compound at a temperature in the range of the glass transition temperature of the polyphenylene ether or more and 360 ° C. or less. Examples thereof include a method of reacting the polyphenylene ether and a modified compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether, and any of these methods may be used, but from the viewpoint of productivity. Therefore, the method (1) or (2) is preferable.
次に、変性ポリフェニレンエーテルを製造するために用いる、上記変性化合物について説明する。 Next, the above-mentioned modified compound used for producing the modified polyphenylene ether will be described.
炭素－炭素二重結合を有するとともに、カルボン酸基及び／又は酸無水物基を有する上記変性化合物としては、例えば、マレイン酸、フマル酸、クロロマレイン酸、シス－４－シクロヘキセン－１，２－ジカルボン酸、及びこれらの酸無水物等が挙げられる。
中でも、ポリフェニレンエーテル系樹脂との反応性の観点から、マレイン酸、フマル酸、無水マレイン酸が好ましく、フマル酸、無水マレイン酸がより好ましい。また、これら不飽和ジカルボン酸の２個のカルボキシル基のうちの１個又は２個がエステルになっている化合物も変性化合物として使用可能である。
Examples of the modified compound having a carbon-carbon double bond and a carboxylic acid group and / or an acid anhydride group include maleic acid, fumaric acid, chloromaleic acid, and cis-4-cyclohexene-1,2-. Examples thereof include dicarboxylic acids and their acid anhydrides.
Of these, maleic acid, fumaric acid, and maleic anhydride are preferable, and fumaric acid and maleic anhydride are more preferable, from the viewpoint of reactivity with the polyphenylene ether-based resin. Further, a compound in which one or two of the two carboxyl groups of these unsaturated dicarboxylic acids are esters can also be used as a modified compound.
炭素－炭素二重結合を有するとともに、水酸基を有する上記変性化合物としては、例えば、アリルアルコール、４－ペンテン－１－オール等の一般式ＣnＨ2n-1ＯＨ（ｎは正の整数）で表される不飽和アルコール、１，４－ペンタジエン－３－オール等の一般式ＣnＨ2n-3ＯＨ（ｎは２以上の正の整数）で表される不飽和アルコール、一般式ＣnＨ2n-5ＯＨ（ｎは３以上の正の整数）で表される不飽和アルコール、ＣnＨ2n-7ＯＨ（ｎは４以上の正の整数）で表される不飽和アルコール等が挙げられる。 Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group include the general formula C n H 2n-1 OH (n is a positive integer) such as allyl alcohol and 4-penten-1-ol. Unsaturated alcohol represented by the general formula C n H 2n-3 OH such as 1,4-pentadiene-3-ol (n is a positive integer of 2 or more) Unsaturated alcohol represented by the general formula C n H Examples thereof include unsaturated alcohols represented by 2n-5 OH (n is a positive integer of 3 or more), unsaturated alcohols represented by C n H 2n-7 OH (n is a positive integer of 4 or more), and the like. ..
炭素－炭素二重結合を有するとともに、グリシジル基を有する上記変性化合物としては、例えば、アリルグリシジルエーテル、グリシジルアクリレート、グリシジルメタアクリレート、エポキシ化天然油脂等が挙げられる。中でも、グリシジルアクリレート、グリシジルメタアクリレートが好ましい。 Examples of the modified compound having a carbon-carbon double bond and a glycidyl group include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils. Of these, glycidyl acrylate and glycidyl methacrylate are preferable.
変性ポリフェニレンエーテルを製造する際の変性化合物の添加量は、ポリフェニレンエーテル１００質量部に対して、０．１～１０質量部が好ましく、０．３～５質量部がより好ましく、０．５～３質量部が更に好ましい。０．１質量部以上であればポリフェニレンエーテルの変性による効果が発現しやすく、１０質量部以下であれば変性による副作用が発現しにくい。 The amount of the modified compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyphenylene ether. The mass portion is more preferable. If it is 0.1 part by mass or more, the effect of the modification of the polyphenylene ether is likely to be exhibited, and if it is 10 parts by mass or less, the side effect due to the modification is unlikely to occur.
ラジカル開始剤を用いて変性ポリフェニレンエーテルを製造する際の、ラジカル開始剤の添加量は、ポリフェニレンエーテル１００質量部に対して、０．００１～１質量部が好ましく、より好ましくは０．０１～０．５質量部、更に好ましくは０．０５～０．３質量部である。０．００１質量部以上であれば変性効率に優れる。また、１質量部以下であれば変性ポリフェニレンエーテルの低分子量化が起こりにくく、変性率と物性とのバランスに優れる。 When producing a modified polyphenylene ether using a radical initiator, the amount of the radical initiator added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0, based on 100 parts by mass of the polyphenylene ether. It is 5.5 parts by mass, more preferably 0.05 to 0.3 parts by mass. If it is 0.001 part by mass or more, the modification efficiency is excellent. Further, if it is 1 part by mass or less, the modified polyphenylene ether is less likely to have a low molecular weight, and the balance between the modification rate and the physical properties is excellent.
また、変性ポリフェニレンエーテルへの変性化合物の付加率は、変性ポリフェニレンエーテルを１００質量％に対して０．０１～５質量％が好ましく、より好ましくは０．０５～３質量％、更に好ましくは０．１～１質量％である。変性ポリフェニレンエーテル中の未反応の変性化合物及び／又は変性化合物の重合体の残存量としては、５質量％未満が好ましく、より好ましくは３質量％以下、更に好ましくは１質量％以下である。 The addition rate of the modified compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.% by mass with respect to 100% by mass of the modified polyphenylene ether. It is 1 to 1% by mass. The residual amount of the unreacted modified compound and / or the polymer of the modified compound in the modified polyphenylene ether is preferably less than 5% by mass, more preferably 3% by mass or less, still more preferably 1% by mass or less.
本実施形態の樹脂組成物における（ａ）成分の含有量は、流動性、難燃性バランスの観点から、（ａ）成分、（ｂ）成分、（ｃ）成分の合計１００質量部に対して、５０～７０質量部であることが好ましく、より好ましくは５５～７０質量部、更に好ましくは６０～７０質量部である。 The content of the component (a) in the resin composition of the present embodiment is 100 parts by mass in total of the component (a), the component (b), and the component (c) from the viewpoint of fluidity and flame retardancy balance. , 50 to 70 parts by mass, more preferably 55 to 70 parts by mass, still more preferably 60 to 70 parts by mass.
－（ｂ）スチレン系樹脂－
本実施形態の（ｂ）スチレン系樹脂（本明細書において、単に「（ｂ）成分」と称する場合がある。）とは、スチレン系化合物、又はスチレン系化合物とスチレン系化合物に共重合可能な化合物とを、ゴム質重合体存在下又は非存在下に重合して得られる重合体である。
（ｂ）スチレン系樹脂は、１種類のみを単独で用いてもよいし、２種類以上を混合して用いてもよい。
-(B) Styrene resin-
The (b) styrene-based resin of the present embodiment (may be simply referred to as “component (b)” in the present specification) can be copolymerized with a styrene-based compound or a styrene-based compound and a styrene-based compound. It is a polymer obtained by polymerizing a compound in the presence or absence of a rubbery polymer.
(B) Only one type of styrene resin may be used alone, or two or more types may be mixed and used.
スチレン系化合物とは、下記式（２）で表される化合物を意味する。
スチレン系化合物の具体例としては、スチレン、α－メチルスチレン、２，４－ジメチルスチレン、モノクロロスチレン、ｐ－メチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、エチルスチレン等が挙げられ、中でもスチレンが好ましい。 Specific examples of the styrene-based compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like, and styrene is preferable.
また、スチレン系化合物と共重合可能な化合物としては、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル化合物類；無水マレイン酸等の酸無水物等が挙げられ、スチレン系化合物と共に使用される。中でもアクリロニトリルが好ましい。
スチレン系化合物と共重合可能な化合物の使用量は、スチレン系化合物とスチレン系化合物と共重合可能な化合物との合計量に対して、２０質量％以下が好ましく、１５質量％以下がより好ましい。
Examples of the compound that can be copolymerized with the styrene compound include methacrylic esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacryl nitrile; and acid anhydrides such as maleic anhydride. And used with styrene compounds. Of these, acrylonitrile is preferable.
The amount of the compound copolymerizable with the styrene compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount of the styrene compound and the compound copolymerizable with the styrene compound.
また、ゴム質重合体としては、共役ジエン系ゴム、共役ジエンと芳香族ビニル化合物とのコポリマー、若しくはこれらの水添物、又はエチレン－プロピレン共重合体系ゴム等が挙げられる。中でも、部分的に水素添加された不飽和度８０～２０％のポリブタジエン、１，４－シス結合を９０％以上含有するポリブタジエンがより好ましい。 Examples of the rubbery polymer include conjugated diene-based rubbers, copolymers of conjugated diene and aromatic vinyl compounds, hydrogenated products thereof, ethylene-propylene copolymerized rubbers, and the like. Of these, polybutadiene having a degree of unsaturation of 80 to 20% partially hydrogenated and polybutadiene containing 90% or more of 1,4-cis bonds are more preferable.
（ｂ）スチレン系樹脂としては、ポリスチレン、ゴム補強ポリスチレン（ハイインパクトポリスチレン（ＨＩＰＳ））、スチレン－アクリロニトリル共重合体（ＡＳ樹脂）、ゴム補強スチレン－アクリロニトリル共重合体（ＡＢＳ樹脂）、その他のスチレン系共重合体等が挙げられる。特に、ポリスチレン及び１，４－シス結合を９０％以上含有するポリブタジエンを用いたゴム補強ポリスチレンの組合せが好ましい。また、ホモポリスチレンも好ましく、アタクチックポリスチレン、シンジオタクチックポリスチレンのいずれも使用できる。 (B) Styrene-based resins include polystyrene, rubber-reinforced polystyrene (high-impact polystyrene (HIPS)), styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), and other styrenes. Examples include system copolymers. In particular, a combination of polystyrene and rubber-reinforced polystyrene using polybutadiene containing 90% or more of 1,4-cis bonds is preferable. Homopolystyrene is also preferable, and either atactic polystyrene or syndiotactic polystyrene can be used.
本実施形態の樹脂組成物における（ｂ）成分の含有量は、難燃性、流動性バランスの観点から、（ａ）成分、（ｂ）成分、（ｃ）成分の合計１００質量部に対して、１０～３０質量部であることが好ましく、より好ましくは１０～２５質量部、更に好ましくは１０～２０質量部である。 The content of the component (b) in the resin composition of the present embodiment is 100 parts by mass in total of the component (a), the component (b), and the component (c) from the viewpoint of flame retardancy and fluidity balance. It is preferably 10 to 30 parts by mass, more preferably 10 to 25 parts by mass, and further preferably 10 to 20 parts by mass.
－（ｃ）リン系化合物－
本実施形態の樹脂組成物は、（ｃ）リン系化合物（本明細書において、単に「（ｃ）成分」と称する場合がある。）を含有する。
上記（ｃ）成分は、１種のみを単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
-(C) Phosphorus compound-
The resin composition of the present embodiment contains (c) a phosphorus-based compound (in the present specification, it may be simply referred to as "component (c)").
As the component (c), only one kind may be used alone, or two or more kinds may be used in combination.
上記（ｃ）成分としては、有機リン化合物、赤リン、及び無機系リン酸塩等の当業界で知られたリン含有難燃剤であればいずれも使用できる。その中でもリン酸エステル化合物が好ましい。
上記（ｃ）成分としては、以下に限定されるものではないが、例えば、トリメチルホスフェート、トリエチルホスフェート、トリプロピルホスフェート、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリシクロヘキシルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、ジクレジルフェニルホスフェート、ジメチルエチルホスフェート、メチルジブチルホスフェート、エチルジプロピルホスフェート、ヒドロキシフェニルジフェニルホスフェート等のリン酸エステル化合物；これらを各種置換基で変性した変性リン酸エステル化合物；各種の縮合タイプの縮合リン酸エステル系化合物等が挙げられる。これらの中でも、縮合リン酸エステル系化合物が好ましい。
As the component (c), any phosphorus-containing flame retardant known in the art such as an organic phosphorus compound, red phosphorus, and an inorganic phosphate can be used. Among them, the phosphoric acid ester compound is preferable.
The component (c) is not limited to the following, but is not limited to, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, and tri. Phosphoric acid ester compounds such as cresyl phosphate, trixilenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate; these are modified with various substituents. Modified phosphate ester compounds; various condensation types of condensed phosphate ester compounds and the like can be mentioned. Among these, condensed phosphate ester compounds are preferable.
上記縮合リン酸エステル系化合物としては、下記式（３）及び下記式（４）で表される縮合リン酸エステルからなる群より選ばれる少なくとも１種を主成分として含むものが好ましい。
ここでいう「主成分」とは、下記式（３）及び下記式（４）で表される芳香族縮合リン酸エステルからなる群より選ばれる少なくとも１種の含有量が、（ｃ）成分１００質量％に対して、９０質量％以上含まれることをいい、好ましくは９５質量％以上、より好ましくは１００質量％である。
The "main component" here means that the content of at least one selected from the group consisting of the aromatic condensed phosphoric acid esters represented by the following formulas (3) and (4) is the content of the component (c) 100. It is said that it is contained in an amount of 90% by mass or more with respect to the mass%, preferably 95% by mass or more, and more preferably 100% by mass.
なお、上記式（３）及び上記式（４）で表される縮合リン酸エステル化合物は、それぞれ複数種の分子を含んでよい。また、式（３）のｘ、及び式（４）のｙは、１～３の整数であることが好ましい。 The condensed phosphoric acid ester compound represented by the above formula (3) and the above formula (4) may each contain a plurality of types of molecules. Further, x in the formula (3) and y in the formula (4) are preferably integers of 1 to 3.
中でも、上記（ｃ）成分としては、式（３）におけるＲ43及びＲ44がメチル基を表し、ｐ1、ｐ2、ｐ3、ｐ4、ｑ1、及びｑ2が０である縮合リン酸エステル、式（３）におけるＱ41、Ｑ42、Ｑ43、Ｑ44、Ｒ43及びＲ44がメチル基を表し、ｑ1、及びｑ2が０であり、ｐ1、ｐ2、ｐ3、及びｐ4が１～３の整数であり、ｘが１～３の整数（特にｘが１）であるリン酸エステルを、（ｃ）成分１００質量％に対して、５０質量％以上含むものであることが好ましい。これらの縮合リン酸エステル系化合物を用いることで、樹脂組成物の成形加工時の揮発性が一層低減できる。 Among them, as the component (c) above, condensed phosphorus in which R 43 and R 44 in the formula (3) represent a methyl group and p 1 , p 2 , p 3 , p 4 , q 1 and q 2 are 0. Acid ester, Q 41 , Q 42 , Q 43 , Q 44 , R 43 and R 44 in formula (3) represent a methyl group, q 1 and q 2 are 0, and p 1 , p 2 , p 3 , And p 4 is an integer of 1 to 3, and x is an integer of 1 to 3 (particularly x is 1). The phosphate ester is contained in an amount of 50% by mass or more with respect to 100% by mass of the component (c). Is preferable. By using these condensed phosphoric acid ester compounds, the volatility of the resin composition during molding can be further reduced.
本実施形態の樹脂組成物における（ｃ）成分の含有量は、機械的物性及び耐熱性と流動性及び難燃性バランスの観点から、（ａ）成分、（ｂ）成分、（ｃ）成分の合計１００質量部に対して、１０～３０質量部であることが好ましく、より好ましくは１０～２５質量部、更に好ましくは１５～２５質量部である。 The content of the component (c) in the resin composition of the present embodiment is the content of the component (a), the component (b), and the component (c) from the viewpoint of mechanical properties, heat resistance, fluidity, and flame retardancy balance. It is preferably 10 to 30 parts by mass, more preferably 10 to 25 parts by mass, and further preferably 15 to 25 parts by mass with respect to 100 parts by mass in total.
－（ｄ）無機充填材－
本実施形態の樹脂組成物に含まれる（ｄ）無機充填材（本明細書において、単に「（ｄ）成分」と称する場合がある。）としては、ガラス繊維、ガラスフレーク、マイカ、ウォラストナイト、タルク、焼成クレー等が挙げられる。低寸法異方性が要求される場合にはガラスビーズやガラスフレークを、高剛性、高耐衝撃性が要求される場合にはガラス繊維やウィスカー類を、導電性付与の目的には金属繊維を、高比重が要求される場合には酸化鉄を、選択して用いることが好ましい。機械的物性、難燃性の観点から、ガラス繊維及びマイカから選ばれる１種以上であることが好ましく、ガラス繊維及びマイカであることがより好ましい。
上記（ｄ）成分は１種単独で用いてもよいし、２種以上を組み合わせて用いてもよく、また、本発明の目的を損なわない範囲で、所望に応じシラン系カップリング剤による表面処理や、集束剤による集束処理が施されたものも用いることができる。
-(D) Inorganic filler-
Examples of the (d) inorganic filler contained in the resin composition of the present embodiment (may be simply referred to as “(d) component” in the present specification) include glass fiber, glass flakes, mica, and talc talc. , Talc, fired clay and the like. Glass beads and glass flakes are used when low dimensional anisotropy is required, glass fibers and whiskers are used when high rigidity and high impact resistance are required, and metal fibers are used for the purpose of imparting conductivity. When high specific gravity is required, iron oxide is preferably selected and used. From the viewpoint of mechanical properties and flame retardancy, one or more selected from glass fiber and mica is preferable, and glass fiber and mica are more preferable.
The above component (d) may be used alone or in combination of two or more, and may be surface-treated with a silane coupling agent, if desired, as long as the object of the present invention is not impaired. Alternatively, those subjected to a focusing treatment with a sizing agent can also be used.
本実施形態の樹脂組成物における（ｄ）成分の樹脂組成物中の含有量は、流動性と機械的物性及び寸法特性バランスの観点から、３５～６０質量％であり、好ましくは３５～５５質量％であり、より好ましくは４０～５０質量％である。 The content of the component (d) in the resin composition of the present embodiment is 35 to 60% by mass, preferably 35 to 55% by mass, from the viewpoint of fluidity, mechanical properties and dimensional characteristic balance. %, More preferably 40 to 50% by mass.
－（ｅ）ポリテトラフルオロエチレン－
本実施形態の（ｅ）ポリテトラフルオロエチレン（本明細書において、単に「（ｅ）成分」と称する場合がある。）（ＰＴＦＥ）は、ポリフェニレンエーテル中でフィブリル構造を形成することにより、ドリップの抑制効果が高く、ドリップ防止剤として好適である。
-(E) Polytetrafluoroethylene-
The (e) polytetrafluoroethylene of the present embodiment (sometimes referred to simply as "component (e)" in the present specification) (PTFE) is a drip by forming a fibril structure in polyphenylene ether. It has a high inhibitory effect and is suitable as a drip inhibitor.
上記（ｅ）成分としては、テトラフルオロエチレンの単独重合体、テトラフルオロエチレンと、ジフルオロエチレン、トリフルオロエチレン、ヘキサフルオロプロピレン等との共重合体等が挙げられ、１種のみを単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
その中でも、ＰＴＦＥを１０～９０質量％、好ましくは１５～７０質量％含有し、他樹脂により取り扱い性が改善された改質ＰＴＦＥを用いることが好ましい。このような改質ＰＴＦＥは、例えば特開平０９－９５５８３号や特開平１１－２９６７９号等に記載されており、商品としてはメタブレン（三菱レイヨン（株））やＢＬＥＮＤＥＸ ４４９（ケムチュラ社）の商品名で販売されている。
Examples of the component (e) include a homopolymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene and a copolymer of difluoroethylene, trifluoroethylene, hexafluoropropylene and the like, and only one of them is used alone. Alternatively, two or more kinds may be used in combination.
Among them, it is preferable to use modified PTFE containing 10 to 90% by mass, preferably 15 to 70% by mass of PTFE and having improved handleability by another resin. Such modified PTFE is described in, for example, JP-A-09-95583, JP-A-11-29679, etc., and as commercial products, the trade names of Metabren (Mitsubishi Rayon Co., Ltd.) and BLENDEX 449 (Chemtura) are used. It is sold at.
ＰＴＦＥの樹脂組成物への添加形態としては、本実施形態のような樹脂組成物中のＰＴＦＥの形態を取りうることが可能であれば、粉体、ディスパージョンいずれのものも用いることができる。また、ＰＴＦＥを、（ａ）ポリフェニレンエーテル系樹脂や他の樹脂等でマスターバッチを作成した後に添加する方法も考えられる。
ＰＴＦＥマスターバッチの場合は、マスターバッチを作る際と樹脂組成物を作る際の２度熱がかかることになる。優れた燃焼時の滴下防止性、外観を得る観点から、１度の押出により樹脂組成物を得ることが好ましい。
更に好ましくは粉体ＰＴＦＥ及び／又は改質ＰＴＦＥを用い、当該ＰＴＦＥに事前に（ａ）成分～（ｄ）成分の少なくとも１成分をドライブレンドして押出機に供給することが好ましい。また特に、当該ＰＴＦＥに事前に（ａ）ポリフェニレンエーテル系樹脂の全量又は一部のみをドライブレンドして押出機に供給することが好ましい。
As the form of addition of PTFE to the resin composition, either powder or dispersion can be used as long as it is possible to take the form of PTFE in the resin composition as in the present embodiment. Further, a method of adding PTFE after preparing a masterbatch with (a) a polyphenylene ether-based resin, another resin, or the like is also conceivable.
In the case of a PTFE masterbatch, heat is applied twice, once when the masterbatch is made and when the resin composition is made. From the viewpoint of obtaining excellent drip prevention property at the time of combustion and appearance, it is preferable to obtain the resin composition by one extrusion.
More preferably, it is preferable to use powdered PTFE and / or modified PTFE, and dry-blend at least one of the components (a) to (d) into the PTFE in advance and supply it to the extruder. In particular, it is preferable to dry-blend the PTFE with all or part of the (a) polyphenylene ether-based resin in advance and supply it to the extruder.
本実施形態の樹脂組成物における（ｅ）成分の含有量は、流動性及び難燃性と燃焼時の滴下防止性バランスの観点から、（ａ）成分、（ｂ）成分、（ｃ）成分の合計１００質量部に対して、０．０５～１質量部であることが好ましく、より好ましくは０．１～０．８質量部、更に好ましくは０．２～０．５質量部である。改質ＰＴＦＥを用いた場合の（ｅ）成分の含有量は、改質ＰＴＦＥ中のＰＴＦＥの正味の量を指す。 The content of the component (e) in the resin composition of the present embodiment is the content of the component (a), the component (b), and the component (c) from the viewpoint of the balance between fluidity and flame retardancy and dripping prevention during combustion. It is preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.8 part by mass, and further preferably 0.2 to 0.5 part by mass with respect to 100 parts by mass in total. The content of the component (e) when the modified PTFE is used refers to the net amount of PTFE in the modified PTFE.
＜添加剤＞
本実施形態の樹脂組成物には、更に他の特性を付与するため、本発明の効果を損なわない範囲で、例えば、可塑剤、酸化防止剤、並びに紫外線吸収剤等の安定剤、帯電防止剤、離型剤、染顔料、上記以外のその他の樹脂等の添加剤を添加することができる。また、従来から知られた各種難燃剤、及び難燃助剤、例えば結晶水を含有する、水酸化マグネシウム等のアルカリ土類金属水酸化物、水酸化アルミニウム、アルカリ金属水酸化物、ホウ酸亜鉛化合物、スズ酸亜鉛化合物等を添加して更なる難燃性の向上も可能である。
添加剤の含有量は、樹脂組成物１００質量％に対して、５質量％以下としてよい。
<Additives>
In order to impart other properties to the resin composition of the present embodiment, for example, a plasticizer, an antioxidant, a stabilizer such as an ultraviolet absorber, and an antistatic agent are provided to the extent that the effects of the present invention are not impaired. , Mold release agents, dye pigments, and other resins other than the above can be added. In addition, various conventionally known flame-retardant agents and flame-retardant aids, for example, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, and zinc borate containing crystalline water. It is also possible to further improve the flame retardancy by adding a compound, a zinc phosphate compound or the like.
The content of the additive may be 5% by mass or less with respect to 100% by mass of the resin composition.
＜樹脂組成物の物性＞
－流動性－
本実施形態の樹脂組成物のメルトフローレートは、流動性に一層優れる観点から、５ｇ／１０分以上であることが好ましく、より好ましくは１０ｇ／１０分以上である。また、燃焼試験時の滴下性防止の観点から３０ｇ／１０分以下であることが好ましい。
なお、樹脂組成物のメルトフローレートは、ＩＳＯ１１３３に準拠して測定することができ、具体的には、後述の実施例に記載の方法で測定することができる。
<Physical characteristics of resin composition>
-Liquidity-
The melt flow rate of the resin composition of the present embodiment is preferably 5 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, from the viewpoint of further excellent fluidity. Further, from the viewpoint of preventing dripping during the combustion test, it is preferably 30 g / 10 minutes or less.
The melt flow rate of the resin composition can be measured in accordance with ISO1133, and specifically, it can be measured by the method described in Examples described later.
－難燃性－
本実施形態の樹脂組成物は、厚さ１．６ｍｍの射出試験片を用いた、ＵＬ９４－Ｖ試験に基づく難燃性の評価において、Ｖ－０、Ｖ－１の評価であることが好ましい。より好ましくはＶ－０の評価であることである。
また、本実施形態の樹脂組成物は、厚さ２．８ｍｍの射出試験片を用いた、ＵＬ９４－５Ｖ試験に基づく難燃性の評価において、５ＶＡの評価であることが好ましい。より好ましくは、厚さ２．４ｍｍの射出試験片を用いた、ＵＬ９４－５Ｖ試験に基づく難燃性の評価において、５ＶＡの評価であることである。
なお、樹脂組成物の難燃性は、後述の実施例に記載の方法で評価することができる。
-Flame retardance-
The resin composition of the present embodiment is preferably evaluated as V-0 or V-1 in the evaluation of flame retardancy based on the UL94-V test using an injection test piece having a thickness of 1.6 mm. More preferably, it is an evaluation of V-0.
Further, the resin composition of the present embodiment is preferably evaluated at 5VA in the evaluation of flame retardancy based on the UL94-5V test using an injection test piece having a thickness of 2.8 mm. More preferably, the evaluation of flame retardancy based on the UL94-5V test using an injection test piece having a thickness of 2.4 mm is 5VA.
The flame retardancy of the resin composition can be evaluated by the method described in Examples described later.
＜樹脂組成物の製造方法＞
本実施形態の樹脂組成物の製造方法は、例えば、二軸押出機を用いて、上述の各成分を溶融混練する方法が挙げられる。上記二軸押出機としては、例えば、コペリオン社製のＺＳＫシリーズ、東芝機械社製のＴＥＭシリーズ、日本製鋼所社製のＴＥＸシリーズ等が挙げられる。
<Manufacturing method of resin composition>
Examples of the method for producing the resin composition of the present embodiment include a method of melt-kneading each of the above-mentioned components using a twin-screw extruder. Examples of the twin-screw extruder include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Japan Steel Works.
押出機のＬ／Ｄ（バレル有効長／バレル内径）は、含有成分をより均一に混練でき、一層優れた難燃性が得られる観点から、２０以上７５以下であることが好ましく、より好ましくは３０以上６０以下である。 The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more and 75 or less, more preferably 20 or more, from the viewpoint that the contained components can be kneaded more uniformly and more excellent flame retardancy can be obtained. It is 30 or more and 60 or less.
押出機の構成については、特に限定されないが、例えば、原料の流れ方向に対し、上流側に第１原料供給口、該第１原料供給口より下流に第１真空ベント、該第１真空ベントの下流に第２原料供給口を設け、該第２原料供給口の下流に液添ポンプを設け、該液添ポンプの下流に第３原料供給口を設け、該第３原料供給口の下流に第２真空ベントを設けたものが好ましい。特に、第１真空ベントの上流にニーディングセクションを設け、第２原料供給口と液添ポンプの間にニーディングセクションを設け、第３原料供給口と第２真空ベントの間にニーディングセクションを設けたものがより好ましい。 The configuration of the extruder is not particularly limited, but for example, the first raw material supply port is on the upstream side, the first vacuum vent is downstream from the first raw material supply port, and the first vacuum vent is located on the upstream side in the flow direction of the raw material. A second raw material supply port is provided downstream, a liquid addition pump is provided downstream of the second raw material supply port, a third raw material supply port is provided downstream of the liquid addition pump, and a second raw material supply port is provided downstream of the third raw material supply port. 2 It is preferable to provide a vacuum vent. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the second raw material supply port and the liquid addition pump, and a kneading section is provided between the third raw material supply port and the second vacuum vent. The one provided is more preferable.
本実施形態の樹脂組成物の製造方法における、溶融混練温度、スクリュー回転数等は、特に限定されず、溶融混練温度２００～３７０℃、スクリュー回転数１００～１２００ｒｐｍの範囲から適宜好適な条件を選択することができる。
樹脂組成物に、優れた燃焼時の滴下防止性を発現させる観点から、溶融混練温度は２８０～３２０℃とすることが好ましく、スクリュー回転数は２５０～５５０ｒｐｍとすることが好ましい。
The melt-kneading temperature, screw rotation speed, and the like in the method for producing the resin composition of the present embodiment are not particularly limited, and suitable conditions are appropriately selected from the range of the melt-kneading temperature of 200 to 370 ° C. and the screw rotation speed of 100 to 1200 rpm. can do.
From the viewpoint of exhibiting excellent drip-preventing properties during combustion in the resin composition, the melt-kneading temperature is preferably 280 to 320 ° C., and the screw rotation speed is preferably 250 to 550 rpm.
バレルに設けられるスクリュー構成としては、特に限定されることなく、右巻き、左巻き、直交（Ｎ型）、逆送り（Ｌ型）ニーディングディスクエレメントを適宜設ける構成としてよく、特に、優れた燃焼時の滴下防止性を発現させる観点から、第１原料供給口と第２原料供給口との間に、直交（Ｎ型）ニーディングディスクエレメント、逆送り（Ｌ型）ニーディングディスクエレメント、２条フライトスクリュー逆送り（左巻き）を各々少なくとも１つ以上設ける構成が好ましい。また、無機充填材を均一に分散させる観点から、第３原料供給口と第２真空ベントとの間に少なくとも２つの直交（Ｎ型）ニーディングディスクエレメント、少なくとも１つの２条フライトスクリュー逆送り（左巻き）を含むセクションを設ける構成がより好ましい。 The screw configuration provided on the barrel is not particularly limited, and may be a configuration in which right-handed, left-handed, orthogonal (N-type), and reverse-feed (L-type) kneading disc elements are appropriately provided, and particularly at the time of excellent combustion. Orthogonal (N-type) kneading disc element, reverse feed (L-type) kneading disc element, and two-row flight between the first raw material supply port and the second raw material supply port from the viewpoint of exhibiting the drip prevention property. It is preferable to provide at least one screw reverse feed (left-handed). Further, from the viewpoint of uniformly dispersing the inorganic filler, at least two orthogonal (N-type) kneading disc elements and at least one double-row flight screw reverse feed (N-type) between the third raw material supply port and the second vacuum vent (reverse feed). It is more preferable to provide a section including (left-handed).
二軸押出機に原料を供給するための原料供給装置としては、特に限定されず、例えば、単独スクリューフィーダー、二軸スクリューフィーダー、テーブルフィーダー、ロータリーフィーダー等が挙げられる。これらの中でも、原料供給の変動誤差が少ないという観点から、ロスインウェイトフィーダーが好ましい。 The raw material supply device for supplying the raw material to the twin-screw extruder is not particularly limited, and examples thereof include a single screw feeder, a twin-screw feeder, a table feeder, and a rotary feeder. Among these, the loss-in weight feeder is preferable from the viewpoint that the fluctuation error of the raw material supply is small.
液状の原料を供給する際は、押出機シリンダー部分に、液添ポンプ等を用いて、直接液状の原料をシリンダー系中に送り込むことで混練りすることができる。液添ポンプとしては、特に限定されず、例えば、ギアポンプやフランジ式ポンプ等が挙げられる。これらの中でも、ギアポンプが好ましい。更に、液添ポンプに使用する液状原料を貯めておくタンク、そのタンクとポンプ間の配管、及びポンプと押出機シリンダー間の配管等液状原料の流路となる部分等を、ヒーター等で加温することがより好ましい。これにより液状原料の粘度を低減することができるため、液添ポンプにかかる負荷を低減することができ、操作性等の観点から好ましい。 When supplying the liquid raw material, the liquid raw material can be kneaded by directly feeding the liquid raw material into the cylinder system by using a liquid addition pump or the like to the cylinder portion of the extruder. The liquid addition pump is not particularly limited, and examples thereof include a gear pump and a flange type pump. Of these, gear pumps are preferred. Furthermore, the tank that stores the liquid raw material used for the liquid addition pump, the piping between the tank and the pump, and the piping between the pump and the extruder cylinder, etc., which are the flow paths of the liquid raw material, are heated by a heater or the like. It is more preferable to do so. As a result, the viscosity of the liquid raw material can be reduced, so that the load applied to the liquid addition pump can be reduced, which is preferable from the viewpoint of operability and the like.
本実施形態の樹脂組成物の製造方法において、特に限定されるものではないが、優れた難燃性の樹脂組成物が得られる観点から、第１原料供給口から（ａ）成分の全量、（ｂ）成分の全量又は一部、（ｅ）成分の全量（但し、第２原料供給口から（ｅ）成分を全量添加した場合を除く）、第２原料供給口から（ｂ）成分の残り（但し、第１原料供給口から（ｂ）成分を全量添加した場合を除く）、（ｅ）成分の全量（但し、第１原料供給口から（ｅ）成分を全量添加した場合を除く）、（ｄ）成分の全量又は一部、液添ポンプから（ｃ）成分の全量、第３原料供給口から（ｄ）成分の残り（但し、第２原料供給口から（ｄ）成分を全量添加した場合を除く）を添加することが好ましい。中でも、（ｅ）成分の添加位置に関して、優れた燃焼時の滴下防止性、外観を発現させる観点から、第１原料供給口から添加することが好ましい。
また、（ｅ）成分の押出機への供給方法として、粉体ＰＴＦＥ及び／又は改質ＰＴＦＥを用い、当該ＰＴＦＥに事前に（ａ）成分～（ｄ）成分の少なくとも１成分をドライブレンドして押出機に供給する工程を含むことが好ましい。特に、より優れた燃焼時の滴下防止性、外観を発現させる観点から、上記ＰＴＦＥに事前に（ａ）ポリフェニレンエーテル系樹脂の全量又は一部のみをドライブレンドして押出機に供給する工程を含むことが好ましい。
The method for producing the resin composition of the present embodiment is not particularly limited, but from the viewpoint of obtaining an excellent flame-retardant resin composition, the total amount of the component (a) from the first raw material supply port, ( b) All or part of the component, (e) Total amount of the component (except when all the (e) component is added from the second raw material supply port), the rest of the (b) component from the second raw material supply port (b) However, (excluding the case where the entire amount of the component (b) is added from the first raw material supply port), (e) the total amount of the component (however, excluding the case where the entire amount of the component (e) is added from the first raw material supply port), ( d) All or part of the component, the total amount of the component (c) from the liquid addition pump, the rest of the component (d) from the third raw material supply port (however, when the whole amount of the component (d) is added from the second raw material supply port) It is preferable to add (excluding). Above all, regarding the addition position of the component (e), it is preferable to add the component (e) from the first raw material supply port from the viewpoint of exhibiting excellent drip prevention property at the time of combustion and appearance.
Further, as a method of supplying the component (e) to the extruder, powder PTFE and / or modified PTFE is used, and at least one component (a) to (d) is dry-blended into the PTFE in advance. It is preferable to include a step of supplying to the extruder. In particular, from the viewpoint of exhibiting better dripping prevention during combustion and appearance, the above-mentioned PTFE includes a step of dry-blending (a) all or part of the polyphenylene ether-based resin in advance and supplying it to the extruder. Is preferable.
＜成形体＞
本実施形態の樹脂組成物は、これを成形することにより成形体とすることができる。成形方法としては、特に限定されるものではないが、例えば、射出成形、中空成形、押出成形、シート成形、フィルム成形等、公知の成形方法を用いることもできる。上述の樹脂組成物を成形して得られる成形体は、種々の成形体として用いることができ、特に、家電、ＯＡ機器等に好適に使用できる。すなわち、本実施形態の成形体は、上記した樹脂組成物を含む、成形体である。
<Molded body>
The resin composition of the present embodiment can be made into a molded product by molding the resin composition. The molding method is not particularly limited, but for example, known molding methods such as injection molding, hollow molding, extrusion molding, sheet molding, and film molding can also be used. The molded product obtained by molding the above-mentioned resin composition can be used as various molded products, and can be particularly preferably used for home appliances, OA equipment and the like. That is, the molded product of the present embodiment is a molded product containing the above-mentioned resin composition.
本実施形態の樹脂組成物の成形方法は、特に限定されず、例えば、射出成形機を用いて、成形する方法等が挙げられる。このような射出成型機としては、特に限定されず、例えば、ＴＯＳＨＩＢＡ社製、「ＩＳ１００ＧＮ」等が挙げられる。 The method for molding the resin composition of the present embodiment is not particularly limited, and examples thereof include a method for molding using an injection molding machine. Such an injection molding machine is not particularly limited, and examples thereof include "IS100GN" manufactured by TOSHIBA.
本実施形態の樹脂組成物の成形方法における、溶融温度、金型温度等は、溶融温度２００～３２０℃、金型温度３０～１００℃の範囲から適宜好適な条件を選択することができるが、特にこれらに限定されるものではない。 In the method for molding the resin composition of the present embodiment, the melting temperature, the mold temperature, etc. can be appropriately selected from the range of the melting temperature of 200 to 320 ° C. and the mold temperature of 30 to 100 ° C. It is not particularly limited to these.
以下、実施例及び比較例によって、本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、使用した原料は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The raw materials used are as follows.
（ａ）ポリフェニレンエーテル樹脂（ＰＰＥ）
（ａ－１）還元粘度（０．５ｇ／ｄＬのクロロホルム溶液、３０℃測定）０．５２ｄＬ／ｇのポリ（２，６－ジメチル－１，４－フェニレンエーテル）
（ａ－２）還元粘度（０．５ｇ／ｄＬのクロロホルム溶液、３０℃測定）０．４１ｄＬ／ｇのポリ（２，６－ジメチル－１，４－フェニレンエーテル）
(A) Polyphenylene ether resin (PPE)
(A-1) Reduction viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.52 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
(A-2) Reduction viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.41 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
（ｂ）スチレン系樹脂
（ｂ－１）ハイインパクトポリスチレン（ＨＩＰＳ）
ペトロケミカル社製「ＣＴ６０」
（ｂ－２）スチレン－アクリロニトリル共重合体（ＡＳ）
（ｂ－２）のＡＳ共重合体は、以下のようにして製造した。
アクリロニトリル４．７質量部、スチレン７３．３質量部、エチルベンゼン２２質量部、重合開始剤としてのｔ－ブチルパーオキシ－イソプロピルカーボネート０．０２質量部よりなる混合液を、２．５リットル／時間の流速で、容量５リットルの完全混合型反応機に連続的に供給し、１４２℃で重合を行って重合液を得た。
得られた重合液を連続してベント付き押出機に導き、２６０℃、４０Ｔｏｒｒの条件下で未反応モノマー及び溶剤を除去し、ポリマーを連続して冷却固化し、細断して粒子状のスチレン－アクリロニトリル共重合体（以下、「ＡＳ」ということもある）を得た。
このスチレン－アクリロニトリル共重合体について、赤外吸収スペクトル法により組成分析したところ、アクリロニトリル単位９質量％とスチレン単位９１質量％であった。また、このスチレン－アクリロニトリル共重合体のメルトフローレートは、７８ｇ／１０分（ＡＳＴＭ Ｄ １２３８準拠、２２０℃、１０ｋｇ荷重で測定）であった。
(B) Styrene-based resin (b-1) High-impact polystyrene (HIPS)
"CT60" manufactured by Petrochemical Co., Ltd.
(B-2) Styrene-acrylonitrile copolymer (AS)
The AS copolymer of (b-2) was produced as follows.
2.5 liters / hour of a mixed solution consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropylcarbonate as a polymerization initiator. It was continuously supplied to a fully mixed reactor having a capacity of 5 liters at a flow velocity, and polymerized at 142 ° C. to obtain a polymerization solution.
The obtained polymer solution is continuously guided to an extruder with a vent, unreacted monomers and solvent are removed under the conditions of 260 ° C. and 40 Torr, the polymer is continuously cooled and solidified, and shredded into particulate styrene. -Acrylonitrile copolymer (hereinafter, also referred to as "AS") was obtained.
The composition of this styrene-acrylonitrile copolymer was analyzed by infrared absorption spectroscopy and found to be 9% by mass of acrylonitrile unit and 91% by mass of styrene unit. The melt flow rate of this styrene-acrylonitrile copolymer was 78 g / 10 minutes (measured according to ASTM D 1238, 220 ° C., 10 kg load).
（ｃ）リン系化合物
縮合リン酸エステル系化合物、商品名「Ｅ８９０」、大八化学工業株式会社製
(C) Phosphorus compound Condensed phosphoric acid ester compound, trade name "E890", manufactured by Daihachi Chemical Industry Co., Ltd.
（ｄ）無機充填材
（ｄ－１）マイカ
商品名「スゾライトマイカ２００ＨＫ」、西日本貿易株式会社製
（ｄ－２）ガラス繊維（ＧＦ）
商品名「マイクログラスサーフェストランド ＲＥＶ８」、オーウェンスコーニングジャパン社製
(D) Inorganic filler (d-1) Mica Product name "Suzolite Mica 200HK", manufactured by Nishinihon Trading Co., Ltd. (d-2) Glass fiber (GF)
Product name "Micro Glass Surface Tland REV8", manufactured by Owens Corning Japan
（ｅ）ポリテトラフルオロエチレン
アクリル酸エステル－メタクリル酸エステル共重合物を５０質量％含有する改質ＰＴＦＥ（商品名「メタブレンＡ３８００」、三菱レイヨン株式会社製）
(E) Modified PTFE containing 50% by mass of a polytetrafluoroethylene acrylic acid ester-methacrylic acid ester copolymer (trade name "Metabrene A3800", manufactured by Mitsubishi Rayon Co., Ltd.)
実施例及び比較例で得られた樹脂組成物の評価は、以下の方法及び条件で行った。 The evaluation of the resin compositions obtained in Examples and Comparative Examples was carried out by the following methods and conditions.
＜エージング後の試験片の収縮率＞
実施例及び比較例で得られた樹脂組成物ペレットを９０℃で１時間乾燥した。乾燥後の樹脂組成物ペレットから、ＩＳ－１００ＧＮ型射出成形機（東芝機械株式会社製、シリンダー温度を２４０～２８０℃、金型温度を８０℃に設定）を用いて、流れ方向の長さ１２５ｍｍ、垂直方向の長さ１３ｍｍ、厚み１．６ｍｍの試験片を作製した。
この試験片を温度１５０℃で２４時間エージングした後の、試験片の収縮率を下記式から求めた。
試験片収縮率［％］＝（（エージング前の流れ方向の試験片の長さ［ｍｍ］－エージング後の流れ方向の試験片の長さ［ｍｍ］）／（エージング前の流れ方向の試験片の長さ［ｍｍ］））×１００
<Shrinkage rate of test piece after aging>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. From the dried resin composition pellets, using an IS-100GN type injection molding machine (manufactured by Toshiba Machine Co., Ltd., the cylinder temperature is set to 240 to 280 ° C and the mold temperature is set to 80 ° C), the length in the flow direction is 125 mm. , A test piece having a length of 13 mm and a thickness of 1.6 mm in the vertical direction was prepared.
After aging this test piece at a temperature of 150 ° C. for 24 hours, the shrinkage rate of the test piece was calculated from the following formula.
Specimen shrinkage rate [%] = ((Length of test piece in flow direction before aging [mm] -Length of test piece in flow direction after aging [mm]) / (Test piece in flow direction before aging Length [mm])) x 100
＜外観＞
実施例及び比較例で得られた樹脂組成物ペレットを９０℃で１時間乾燥した。乾燥後の樹脂組成物ペレットから、ＩＳ－１００ＧＮ型射出成形機（東芝機械株式会社製、シリンダー温度を２４０～２８０℃、金型温度を８０℃に設定）を用いて、流れ方向の長さ９０ｍｍ、垂直方向の長さ５０ｍｍ、厚さ２．５ｍｍの試験片を作製した。
この試験片の外観を目視確認し、以下の評価基準で判定した。
○（優れる）：充填材の浮き上がりが少ない。
△（可）：充填材の浮き上がりがやや多い。
×（不良）：充填材の浮き上がりが多い。
<Appearance>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. From the dried resin composition pellets, use an IS-100GN type injection molding machine (manufactured by Toshiba Machine Co., Ltd., cylinder temperature is set to 240 to 280 ° C, mold temperature is set to 80 ° C), and the length in the flow direction is 90 mm. , A test piece having a length of 50 mm and a thickness of 2.5 mm in the vertical direction was prepared.
The appearance of this test piece was visually confirmed and judged according to the following evaluation criteria.
○ (excellent): There is little floating of the filler.
△ (possible): The filler is slightly lifted.
× (defective): The filler is often lifted.
＜メルトフローレート（ＭＦＲ）＞
実施例及び比較例で得られた樹脂組成物ペレットを用い、ＩＳＯ－１１３３に準じて２５０℃、１０ｋｇ荷重の条件で、メルトフローレート（ｇ／１０分）を測定した。
評価基準としては、メルトフローレートが大きい値であるほど流動性に優れていると評価した。
<Melt flow rate (MFR)>
Using the resin composition pellets obtained in Examples and Comparative Examples, the melt flow rate (g / 10 minutes) was measured under the conditions of 250 ° C. and 10 kg load according to ISO-1133.
As an evaluation standard, it was evaluated that the larger the melt flow rate, the better the fluidity.
＜難燃性＞
－Ｖ試験－
ＵＬ９４－Ｖ試験に基づき、１．６ｍｍ厚さの射出成形試験片を用いて難燃性を評価した。
まず、実施例及び比較例で得た樹脂組成物ペレットを９０℃で１時間乾燥した。乾燥したペレットを２４０～２８０℃に設定したスクリューインライン型射出成形機（商品名「ＩＳ－１００ＧＮ」、東芝機械株式会社製）に供給し、金型温度８０℃の条件で射出成形することで、当該規格で規定された寸法（縦１２５ｍｍ×横１３ｍｍ×厚さ１．６ｍｍ）の試験片を作成した。
上記試験片にガスバーナーの炎を当てて、その燃焼の程度を評価した。
なお、難燃等級には、ＵＬ９４－Ｖ試験によって分類される難燃性のクラスを示した。全ての試験片で試験は５本行い判定した。分類方法の概要は以下の通りである。
Ｖ－０：５本の合計燃焼時間５０秒以下、最大燃焼時間１０秒以下、有炎滴下なし
Ｖ－１：５本の合計燃焼時間２５０秒以下、最大燃焼時間３０秒以下、有炎滴下なし
<Flame retardant>
-V test-
Based on the UL94-V test, flame retardancy was evaluated using an injection molded test piece having a thickness of 1.6 mm.
First, the resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. The dried pellets are supplied to a screw in-line injection molding machine (trade name "IS-100GN", manufactured by Toshiba Machine Co., Ltd.) set at 240 to 280 ° C, and injection molded under the condition of a mold temperature of 80 ° C. A test piece having the dimensions specified in the standard (length 125 mm × width 13 mm × thickness 1.6 mm) was prepared.
The flame of the gas burner was applied to the above test piece, and the degree of combustion was evaluated.
In addition, the flame-retardant class shown as the flame-retardant class classified by the UL94-V test. Five tests were performed on all the test pieces and the judgment was made. The outline of the classification method is as follows.
V-0: 5 pieces total burning time 50 seconds or less, maximum burning time 10 seconds or less, no flame dripping V-1: 5 pieces total burning time 250 seconds or less, maximum burning time 30 seconds or less, no flame dripping
－５Ｖ試験－
ＵＬ９４－５Ｖ試験に基づき、２．４ｍｍ厚さ及び２．８ｍｍ厚さの射出成形試験片を用いて難燃性を評価した。
まず、実施例及び比較例で得た樹脂組成物ペレットを９０℃で１時間乾燥した。
短冊サンプルにおいては、乾燥したペレットを用いて２２０～２４０℃に設定したスクリューインライン型射出成形機（商品名「ＳＨ１００Ｃ」、住友重機械工業株式会社製）に供給し、金型温度３０℃の条件で射出成形することで、当該規格で規定された寸法（縦１２５ｍｍ×横１３ｍｍ×厚さ２．４ｍｍ及び厚さ２．８ｍｍ）の試験片を作成した。
板サンプルにおいては、乾燥したペレットを用いて２９０～３１０℃に設定したスクリューインライン型射出成形機（商品名「ＳＨ１００Ｃ」、住友重機械工業株式会社製）に供給し、金型温度１００℃の条件で射出成形することで、当該規格で規定された寸法（縦１５０ｍｍ×横１５０ｍｍ×厚さ２．４ｍｍ及び厚さ２．８ｍｍ）の試験片を作成した。
上記試験片にガスバーナーの炎を当てて、その燃焼の程度を評価した。
なお、難燃等級には、ＵＬ９４－５Ｖ試験によって分類される難燃性のクラスを示した。短冊サンプル５本、板サンプル３枚試験を行い、判定した。分類方法の概要は以下の通りである。
５ＶＡ：短冊サンプルにおいて５回目の接炎後の燃焼時間及びグローイング時間の合計が６０秒以下で、板サンプルにおいて接炎後の穴開きがなかった。
不合格：５ＶＡの基準に満たなかったものを不合格とした。
-5V test-
Based on the UL94-5V test, flame retardancy was evaluated using injection molding test pieces having a thickness of 2.4 mm and a thickness of 2.8 mm.
First, the resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour.
The strip sample is supplied to a screw in-line injection molding machine (trade name "SH100C", manufactured by Sumitomo Heavy Industries, Ltd.) set at 220 to 240 ° C using dried pellets, and the mold temperature is 30 ° C. By injection molding with, a test piece having the dimensions specified in the standard (length 125 mm × width 13 mm × thickness 2.4 mm and thickness 2.8 mm) was prepared.
The plate sample is supplied to a screw in-line injection molding machine (trade name "SH100C", manufactured by Sumitomo Heavy Industries, Ltd.) set at 290 to 310 ° C using dried pellets, and the mold temperature is 100 ° C. By injection molding with, a test piece having the dimensions specified in the standard (length 150 mm × width 150 mm × thickness 2.4 mm and thickness 2.8 mm) was prepared.
The flame of the gas burner was applied to the above test piece, and the degree of combustion was evaluated.
In addition, the flame-retardant class shown as the flame-retardant class classified by the UL94-5V test. Five strip samples and three plate samples were tested and judged. The outline of the classification method is as follows.
5VA: In the strip sample, the total burning time and glowing time after the fifth flame contact was 60 seconds or less, and there was no hole in the plate sample after the flame contact.
Fail: Those that did not meet the 5VA standard were rejected.
以下、各実施例及び各比較例について詳述する
樹脂組成物の製造装置として、二軸押出機（商品名「ＴＥＭ５８ＳＳ」、東芝機械社製）を用いた。該二軸押出機においてバレル数は１３ブロックであり、原料の流れ方向について、上流から１バレル目（第１供給口）、６バレル目（第２供給口）、９バレル目（第３供給口）にそれぞれ１ヶ所の計３ヶ所の供給口を設け、８バレル目に液添ポンプを設け、５バレル目、１２バレル目の２ヶ所真空ベントを設けた。また、第２供給口、第３供給口への原料供給方法は、押出機サイド開放口から強制サイドフィーダーを用いて供給する方法とした。
製造方法１～４における、バレルに設けるスクリュー構成、バレルの設定温度は、図１に記載の通りである。なお、上記スクリュー構成の標記に用いたニーディングディスクの略号の意味は、以下のとおりである。
・Ｒ１：ニーディングディスクライト（Ｌ／Ｄ＝１．０３）
・Ｒ２：ニーディングディスクライト（Ｌ／Ｄ＝０．５１）
・Ｌ：ニーディングディスクレフト（Ｌ／Ｄ＝０．５１）
・Ｎ１：ニーディングディスクニュートラル（Ｌ／Ｄ＝１．０３）
・Ｎ２：ニーディングディスクニュートラル（Ｌ／Ｄ＝０．５１）
・逆：２条フライトスクリュー逆送り（Ｌ／Ｄ＝０．３９）
・Ｓ：ＳＭＥスクリュー（Ｌ／Ｄ＝０．７８）
Hereinafter, a twin-screw extruder (trade name “TEM58SS”, manufactured by Toshiba Machine Co., Ltd.) was used as a resin composition manufacturing apparatus for detailing each Example and each Comparative Example. In the twin-screw extruder, the number of barrels is 13 blocks, and the first barrel (first supply port), the sixth barrel (second supply port), and the ninth barrel (third supply port) from the upstream are the flow directions of the raw materials. ), A total of three supply ports were provided, a liquid addition pump was provided at the 8th barrel, and two vacuum vents at the 5th and 12th barrels were provided. Further, the raw material supply method to the second supply port and the third supply port is a method of supplying from the extruder side opening port by using a forced side feeder.
The screw configuration provided on the barrel and the set temperature of the barrel in the manufacturing methods 1 to 4 are as described in FIG. The meanings of the abbreviations of the kneading discs used in the notation of the screw configuration are as follows.
・ R1: Kneading disc light (L / D = 1.03)
・ R2: Kneading disc light (L / D = 0.51)
・ L: Kneading disc left (L / D = 0.51)
・ N1: Kneading disc neutral (L / D = 1.03)
・ N2: Kneading disc neutral (L / D = 0.51)
・ Reverse: Two-row flight screw reverse feed (L / D = 0.39)
・ S: SME screw (L / D = 0.78)
〔実施例１～１０、比較例１～６〕
上記のように設定した二軸押出機において、表１、３に示した組成、製造条件の下、吐出量４００ｋｇ／時間の条件にて溶融混練し、樹脂組成物のペレットを得た。
〔実施例１１〕
上記のように設定した二軸押出機において、表２に示した組成、製造条件の下、吐出量４００ｋｇ／時間の条件にて溶融混練した。まず、第一の樹脂組成物を製造した後、その第一の樹脂組成物を用いて第二の樹脂組成物を製造し、樹脂組成物のペレットを得た。
[Examples 1 to 10, Comparative Examples 1 to 6]
In the twin-screw extruder set as described above, the resin composition was melt-kneaded under the conditions of the composition and production conditions shown in Tables 1 and 3 under the condition of a discharge rate of 400 kg / hour to obtain pellets of the resin composition.
[Example 11]
In the twin-screw extruder set as described above, the mixture was melt-kneaded under the conditions of the composition and manufacturing conditions shown in Table 2 and the discharge rate of 400 kg / hour. First, after producing the first resin composition, a second resin composition was produced using the first resin composition, and pellets of the resin composition were obtained.
各実施例及び比較例について、上述の測定方法により樹脂組成物の評価を行った結果を表１～３に示す。 Tables 1 to 3 show the results of evaluation of the resin composition by the above-mentioned measuring method for each Example and Comparative Example.
表１、２、３に示すとおり、温度１５０℃、２４時間の条件下でエージングしたときの、試験片の収縮率が６～２０％である実施例１～１１は、いずれも流動性、難燃性、機械的物性に優れていることがわかった。 As shown in Tables 1, 2 and 3, Examples 1 to 11 in which the shrinkage rate of the test piece is 6 to 20% when aged under the conditions of a temperature of 150 ° C. and 24 hours are all fluid and difficult. It was found to be excellent in flammability and mechanical properties.
本発明によれば、外観、流動性、高いレベルでの難燃性に優れた樹脂組成物を提供することができ、家電・ＯＡ機器用途等の材料として産業上の利用可能性を有している。 According to the present invention, it is possible to provide a resin composition having excellent appearance, fluidity, and flame retardancy at a high level, and has industrial applicability as a material for home appliances, OA equipment applications, and the like. There is.
Claims (8)
（ｂ）スチレン系樹脂と、
（ｃ）リン系化合物と、
（ｄ）無機充填材と、
（ｅ）ポリテトラフルオロエチレンと、
を含む樹脂組成物であり、
前記（ａ）成分が、還元粘度が異なる２以上のポリフェニレンエーテルを含み、
前記（ｃ）成分が、縮合リン酸エステル化合物であり、
前記樹脂組成物中に、前記（ｄ）成分を３５～６０質量％含み、
前記（ａ）成分、前記（ｂ）成分、及び前記（ｃ）成分の合計１００質量部に対して、前記（ｅ）成分を０．０５～１．５質量部含み、
流れ方向の長さ１２５ｍｍ、垂直方向の長さ１３ｍｍ、厚み１．６ｍｍの寸法で作成した前記樹脂組成物の試験片を、温度１５０℃、２４時間の条件下でエージングしたときの、下記式で示す試験片の収縮率が６～２０％であることを特徴とする、樹脂組成物。
試験片収縮率［％］＝（（エージング前の流れ方向の試験片の長さ［ｍｍ］－エージング後の流れ方向の試験片の長さ［ｍｍ］）／（エージング前の流れ方向の試験片の長さ［ｍｍ］））×１００ (A) Polyphenylene ether-based resin and
(B) Styrene-based resin and
(C) Phosphorus compounds and
(D) Inorganic filler and
(E) Polytetrafluoroethylene and
Is a resin composition containing
The component (a) contains two or more polyphenylene ethers having different reducing viscosities.
The component (c) is a condensed phosphoric acid ester compound.
The resin composition contains 35 to 60% by mass of the component (d).
The component (e) is contained in an amount of 0.05 to 1.5 parts by mass with respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c).
The following formula was used when a test piece of the resin composition prepared with dimensions of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness was aged under the conditions of a temperature of 150 ° C. and 24 hours. A resin composition, wherein the indicated test piece has a shrinkage rate of 6 to 20%.
Specimen shrinkage rate [%] = ((Length of test piece in flow direction before aging [mm] -Length of test piece in flow direction after aging [mm]) / (Test piece in flow direction before aging Length [mm])) x 100
前記（ａ）成分を５０～７０質量部、
前記（ｂ）成分を１０～３０質量部、
前記（ｃ）成分を１０～３０質量部、及び
前記（ｅ）成分を０．０５～１質量部含む、請求項１に記載の樹脂組成物。 With respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c).
50 to 70 parts by mass of the component (a),
10 to 30 parts by mass of the component (b),
The resin composition according to claim 1, which comprises 10 to 30 parts by mass of the component (c) and 0.05 to 1 part by mass of the component (e).
（ａ－１）還元粘度が０．４５～０．５５ｄＬ／ｇのポリフェニレンエーテル系樹脂と、
（ａ－２）還元粘度が０．３５～０．４５ｄＬ／ｇのポリフェニレンエーテル系樹脂と、
を含み、
（ａ－１）成分と（ａ－２）成分との合計１００質量部に対する（ａ－２）成分の含有量が、６０～９０質量部である、請求項１又は２に記載の樹脂組成物。 The component (a) is
(A-1) A polyphenylene ether-based resin having a reduced viscosity of 0.45 to 0.55 dL / g,
(A-2) A polyphenylene ether-based resin having a reduced viscosity of 0.35 to 0.45 dL / g,
Including
The resin composition according to claim 1 or 2, wherein the content of the component (a-2) is 60 to 90 parts by mass with respect to a total of 100 parts by mass of the component (a-1) and the component (a-2). ..
押出機を用いて、前記（ａ）成分～（ｅ）成分を溶融混練する工程を含むことを特徴とする、樹脂組成物の製造方法。 The method for producing a resin composition according to any one of claims 1 to 4 .
A method for producing a resin composition, which comprises a step of melt-kneading the components (a) to (e) using an extruder.
In the supply step, the powder polytetrafluoroethylene and / or the modified polytetrafluoroethylene of the component (e) is dry-blended with all or part of the component (a) and supplied to the extruder. 7. The method for producing a resin composition according to claim 7 .
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