JP2004137491A - Material having low dielectric characteristic at high frequency - Google Patents
Material having low dielectric characteristic at high frequency Download PDFInfo
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- JP2004137491A JP2004137491A JP2003333982A JP2003333982A JP2004137491A JP 2004137491 A JP2004137491 A JP 2004137491A JP 2003333982 A JP2003333982 A JP 2003333982A JP 2003333982 A JP2003333982 A JP 2003333982A JP 2004137491 A JP2004137491 A JP 2004137491A
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- resin
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- polyphenylene ether
- styrene
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- 239000000463 material Substances 0.000 title description 12
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000011342 resin composition Substances 0.000 claims abstract description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- -1 phosphate ester Chemical class 0.000 claims description 25
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229960001755 resorcinol Drugs 0.000 claims description 5
- 229920002050 silicone resin Polymers 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 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 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 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 9
- 229920001577 copolymer Polymers 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 5
- 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 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- KIEQPXTUHQNADD-UHFFFAOYSA-N n-[bis(dimethylamino)-phenylimino-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)(N(C)C)=NC1=CC=CC=C1 KIEQPXTUHQNADD-UHFFFAOYSA-N 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 0 CC(C)(*C(C)(C)c(cc1N)cc(*=*)c1O)c(cc1O*)cc(*)c1O Chemical compound CC(C)(*C(C)(C)c(cc1N)cc(*=*)c1O)c(cc1O*)cc(*)c1O 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 238000009940 knitting Methods 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [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
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
Description
本発明は、高周波数領域で使用される部品に用いられる樹脂組成物に関する。 The present invention relates to a resin composition used for a component used in a high frequency range.
近年、大量の情報量通信の必要性や、情報処理速度向上の必要性から、１ＧＨｚ以上の高周波数領域が使用されるようになってきた。
一方、これまで、電子材料、例えば、プリント基板材料や、封止材料などには、エポキシ樹脂、紙フェノールなどが、使用されてきた。ところが、１ＧＨｚ以上の高周波数領域では、これら材料は、誘電損失、誘電率が大きく、伝送損失が大きくなって誤作動の原因になったり、伝送速度が十分に上げられないといった不具合が出てきて、これら問題がない材料が求められていた。
従来、エポキシ樹脂が電子材料用途に使用されている。（例えば、特許文献１、特許文献２参照）しかし、最近、要求がますます強くなってきている周波数１ＧＨｚ以上の高周波数領域においては、エポキシ樹脂は、誘電率、誘電正接が高く、伝送速度が遅い、伝送損失が大きいなどの問題があった。
On the other hand, epoxy resins, paper phenols, and the like have been used as electronic materials, for example, printed circuit board materials and sealing materials. However, in the high frequency region of 1 GHz or more, these materials have a large dielectric loss and a large dielectric constant, resulting in a large transmission loss, causing malfunction, and a problem that the transmission speed cannot be sufficiently increased. Materials that do not have these problems have been demanded.
Conventionally, epoxy resins have been used for electronic materials. (For example, see Patent Documents 1 and 2) However, recently, in a high frequency region of a frequency of 1 GHz or more, which is increasingly required, epoxy resin has a high dielectric constant and a high dielectric loss tangent, and has a high transmission speed. There are problems such as slow transmission and large transmission loss.
１ＧＨｚ以上の周波数領域で使用した場合、誘電正接、誘電率が低く、従って伝送損失を少なく、伝送速度を速くできる高耐熱・高寸法安定な材料を提供することが課題である。 It is an object to provide a highly heat-resistant and dimensionally stable material that has a low dielectric loss tangent and a low dielectric constant when used in a frequency region of 1 GHz or more, and thus can reduce transmission loss and increase transmission speed.
１ＧＨｚ以上の周波数領域で使用した場合、伝送損失を少なく、伝送速度を速くできる材料を得るべく鋭意検討した結果、ポリフェニレンエーテル樹脂又は、ポリフェニレンエーテル樹脂とポリスチレン樹脂またはエポキシ樹脂からなる樹脂組成物が、目的を達成できる材料であることを見いだし、本発明に到達した。
即ち、本発明は
１．ポリフェニレンエーテル樹脂からなることを特徴とする１ＧＨｚ以上の周波数領域で使用される部品用樹脂組成物、
２．ポリフェニレンエーテル樹脂とスチレン系樹脂からなることを特徴とする１ＧＨｚ以上の周波数領域で使用される部品用樹脂組成物、
３．エポキシ樹脂を含有することを特徴とする上記１又は２の樹脂組成物、
４．縮合燐酸エステルを含有することを特徴とする上記１〜３のいずれかに記載の樹脂組成物、
When used in a frequency range of 1 GHz or higher, the transmission loss is reduced, and as a result of intensive studies to obtain a material capable of increasing the transmission speed, a resin composition comprising polyphenylene ether resin or polyphenylene ether resin and polystyrene resin or epoxy resin, The inventors have found that the material can achieve the object, and have reached the present invention.
That is, the present invention provides: A resin composition for parts used in a frequency range of 1 GHz or more, comprising a polyphenylene ether resin,
2. A resin composition for components used in a frequency range of 1 GHz or more, comprising a polyphenylene ether resin and a styrene resin,
3. The resin composition according to the above 1 or 2, characterized by containing an epoxy resin,
4. The resin composition according to any one of the above 1 to 3, which contains a condensed phosphate,
５．縮合燐酸エステルが、レゾルシンと２，６−キシレノールから合成される縮合燐酸エステルである上記４に記載の樹脂組成物、
６．シリコン樹脂を含有することを特徴とする上記１〜３のいずれかに記載の樹脂組成物、
７．ホスファゼン化合物を含有することを特徴とする上記１または２記載の樹脂組成物、および
８．ポリフェニレンエーテル樹脂の数平均分子量が５００〜５０００であることを特徴とする上記１〜６のいずれかに記載の樹脂組成物
である。
5. The resin composition according to 4, wherein the condensed phosphate is a condensed phosphate synthesized from resorcinol and 2,6-xylenol,
6. The resin composition according to any one of the above 1 to 3, which comprises a silicone resin,
7. 7. The resin composition according to the above 1 or 2, further comprising a phosphazene compound; 7. The resin composition according to any one of the above items 1 to 6, wherein the number average molecular weight of the polyphenylene ether resin is from 500 to 5,000.
本発明は、ハロゲンを含まず、難燃性に優れた高周波数帯域で良好な誘電特性を示す難燃性樹脂組成物を提供する。 The present invention provides a flame-retardant resin composition containing no halogen and exhibiting good dielectric properties in a high-frequency band excellent in flame retardancy.
本発明で用いられるポリフェニレンエーテル樹脂は、一般式（１）及び／または（２）で表される繰り返し単位を有する単独重合体、あるいは共重合体であることが好ましい。 ポ リ The polyphenylene ether resin used in the present invention is preferably a homopolymer or a copolymer having a repeating unit represented by the general formula (1) and / or (2).
（ここで、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は独立に炭素数１〜４のアルキル基、アリール基、水素を表す。但し、Ｒ５、Ｒ６は同時に水素ではない。）
ポリフェニレンエーテル樹脂の単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテルポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、等のホモポリマーが挙げられる。
(Here, R1, R2, R3, R4, R5, and R6 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. However, R5 and R6 are not hydrogen at the same time.)
Representative examples of the homopolymer of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4-phenylene) ether, Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1) , 4-phenylene) ether and the like.
この中で、ポリ（２，６−ジメチル−１，４−フェニレン）エーテルが好ましく、特開昭６３−３０１２２２号公報等に記載されている、２−（ジアルキルアミノメチル）−６−メチルフェニレンエーテルユニットや２−（Ｎ−アルキル−Ｎ−フェニルアミノメチル）−６−メチルフェニレンエーテルユニット等を部分構造として含んでいるポリフェニレンエーテルは特に好ましい。
ここでポリフェニレンエーテル共重合体とは、フェニレンエーテル構造を主単量単位とする共重合体である。その例としては、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体、２，６−ジメチルフェノールとｏ−クレゾールとの共重合体あるいは２，６−ジメチルフェノールと２，３，６−トリメチルフェノール及びｏ−クレゾールとの共重合体、２，６−ジメチルフェノールと下記一般式（３）で示されるビスフェノールとの共重合体等がある。
Among them, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-63-301222 and the like is preferred. Polyphenylene ether containing a unit or a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit as a partial structure is particularly preferable.
Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main unit unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or a copolymer of 2,6-dimethylphenol and 2 And 3,6-trimethylphenol and o-cresol, and a copolymer of 2,6-dimethylphenol and a bisphenol represented by the following general formula (3).
（ここで、Ｒ７、Ｒ８、Ｒ９、Ｒ１０は独立に炭素数１〜４のアルキル基、アリール基、水素を表す。また、式中Ｘは、―Ｃ（ＣＨ３）２−、−ＳＯ２−、−Ｓ−、または−Ｏ−を、ｙは０又は１を表す） (Here, R7, R8, R9, and R10 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. In the formula, X represents —C (CH 3 ) 2 —, —SO 2 —. , -S-, or -O-, and y represents 0 or 1.)
本発明においては、ポリフェニレンエーテル樹脂の一部または全部に、カルボキシル基、エポキシ基、アミノ基、水酸基、無水ジカルボキル基などの反応性官能基を、グラフト反応や、共重合など何らかの方法で導入した編成ポリフェニレンエーテル樹脂も本発明の目的を損なわない範囲で、使用できる。
ポリフェニレンエーテル樹脂の一部又は全部を、不飽和カルボン酸又はその官能的誘導体で変性された変性ポリフェニレンエーテル樹脂は、特開平２−２７６８２３号公報、特開昭６３−１０８０５９号公報、特開昭５９−５９７２４号公報等に記載されており、例えばラジカル開始剤の存在下または非存在下において、ポリフェニレンエーテル樹脂に不飽和カルボン酸やその官能的誘導体を溶融混練し、反応させることによって製造される。あるいは、ポリフェニレンエーテルと不飽和カルボン酸やその官能的誘導体とをラジカル開始剤存在下または非存在下で有機溶剤に溶かし、溶液下で反応させることによって製造される。
In the present invention, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a reactive functional group such as an anhydrous dicarboxy group, to some or all of the polyphenylene ether resin, a grafting reaction, knitting introduced by any method such as copolymerization Polyphenylene ether resins can also be used as long as the object of the present invention is not impaired.
Modified polyphenylene ether resins in which part or all of the polyphenylene ether resin is modified with an unsaturated carboxylic acid or a functional derivative thereof are disclosed in JP-A-2-276823, JP-A-63-108059, and JP-A-59-1984. For example, it is produced by melt-kneading and reacting an unsaturated carboxylic acid or a functional derivative thereof with a polyphenylene ether resin in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving a polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator, and reacting the resultant in a solution.
不飽和カルボン酸又はその官能的誘導体としては、例えばマレイン酸、フマル酸、イタコン酸、ハロゲン化マレイン酸、シス−４−シクロヘキセン１，２−ジカルボン酸、エンド−シス−ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸などや、これらジカルボン酸の酸無水物、エステル、アミド、イミドなど、さらにはアクリル酸、メタクリル酸などや、これらモノカルボン酸のエステル、アミドなどが挙げられる。また、飽和カルボン酸であるが変性ポリフェニレンエーテルを製造する際の反応温度でそれ自身が熱分解し、本発明で用いる官能的誘導体となり得る化合物も用いることができ、具体的にはリンゴ酸、クエン酸などが挙げられる。これらは１種又は２種以上を組み合わせて用いても良い。 Examples of the unsaturated carboxylic acid or its functional derivative include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo (2,2,1 ) -5-heptene-2,3-dicarboxylic acid, etc .; acid anhydrides, esters, amides, imides and the like of these dicarboxylic acids; and acrylic acid and methacrylic acid; and esters and amides of these monocarboxylic acids. No. In addition, a compound which is a saturated carboxylic acid but can be thermally decomposed at the reaction temperature in producing the modified polyphenylene ether itself and become a functional derivative used in the present invention can also be used. Specifically, malic acid, citric acid Acids and the like. These may be used alone or in combination of two or more.
本発明で用いることのできるポリフェニレンエーテルの分子量は、本発明の効果を損なわない範囲であれば、何等制限されるものではない。具体的には、数平均分子量が５００〜３００００のものを好適に用いることができる。成型加工性に優れた組成物を得る必要がある場合には、ポリフェニレンエーテルの数平均分子量が５００以上、５０００以下のもの、好ましくは１２００以上、４０００以下のものを好適に用いることができる。
本発明で用いられるスチレン系樹脂とは、スチレン系化合物、スチレン系化合物と共重合可能な化合物をゴム質重合体存在または非存在下に重合して得られる重合体である。
The molecular weight of the polyphenylene ether that can be used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. Specifically, those having a number average molecular weight of 500 to 30,000 can be suitably used. When it is necessary to obtain a composition having excellent moldability, a polyphenylene ether having a number average molecular weight of 500 or more and 5000 or less, preferably 1200 or more and 4000 or less can be suitably used.
The styrene resin used in the present invention is a polymer obtained by polymerizing a styrene compound and a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.
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、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、最も好ましいのはスチレンである。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ともに使用される。共重合可能な化合物の使用量は、スチレン系化合物との合計量に対して２０重量％以下が好ましく、さらに好ましくは１５重量％以下である。 具体 Specific examples of the styrene-based compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like, and styrene is most preferred. Examples of the compound copolymerizable with the styrene compound include methacrylates such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used together with styrenic compounds. The amount of the copolymerizable compound to be used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.
また、ゴム質重合体としては共役ジエン系ゴムあるいは共役ジエンと芳香族ビニル化合物との共重合体あるいはエチレン−プロピレン共重合体系ゴム等が挙げられる。具体的には特に、ポリブタジェンおよびスチレン−ブタジェン共重合体が好ましい。また、不飽和ゴム質重合体を用いる場合に、部分的に水添したゴムを用いることは好ましい。該スチレン系樹脂の具体例としては、ポリスチレンおよびゴム補強ポリスチレン、スチレン−アクリロニトリル共重合体（ＡＳ樹脂）およびゴム補強スチレン−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。特に好ましいのは、ポリスチレンおよびゴム変性ポリスチレンである。 Further, examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer rubber. Specifically, polybutadiene and a styrene-butadiene copolymer are particularly preferred. When an unsaturated rubbery polymer is used, it is preferable to use a partially hydrogenated rubber. Specific examples of the styrene resin include polystyrene and rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin) and rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), and other styrene copolymers. Can be Particularly preferred are polystyrene and rubber-modified polystyrene.
スチレン系樹脂を用いる場合は、組成物の耐熱性、寸法安定性の観点から、ポリフェニレンエーテル樹脂とスチレン系樹脂の合計量を１００重量％とした場合に、ポリフェニレンエーテル樹脂が５％重量以上含有していることが好ましい。より好ましくは、１０重量％以上、さらに好ましくは２０重量％以上含有しているものが良い。また、より良い誘電特性を得る場合、ポリフェニレンエーテル樹脂の配合量は、９５重量％以下、より好ましくは９０重量％以下、さらに好ましくは８０重量％以下であることが望ましい。
本発明において用いることのできるエポキシ樹脂は、分子中に少なくとも２個のエポキシ基を有する化合物であればよく、特に制限されるものではない。一例として、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、多官能型エポキシ樹脂等が挙げることができ、これらのエポキシ樹脂は単独又は二種以上を混合して用いることができる。また、必要に応じて従来公知の硬化剤、硬化促進剤を用いることができる。
When a styrene resin is used, from the viewpoint of heat resistance and dimensional stability of the composition, when the total amount of the polyphenylene ether resin and the styrene resin is 100% by weight, the polyphenylene ether resin contains 5% by weight or more. Is preferred. More preferably, the content is 10% by weight or more, more preferably 20% by weight or more. In order to obtain better dielectric properties, the blending amount of the polyphenylene ether resin is desirably 95% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less.
The epoxy resin that can be used in the present invention may be a compound having at least two epoxy groups in a molecule, and is not particularly limited. As an example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, polyfunctional type epoxy resin and the like can be mentioned. Epoxy resins can be used alone or in combination of two or more. Further, conventionally known curing agents and curing accelerators can be used as necessary.
エポキシ樹脂を用いる場合は、組成物の耐熱性、寸法安定性及び誘電特性の観点から、ポリフェニレンエーテル樹脂とエポキシ樹脂の合計量を１００重量％とした場合に、ポリフェニレンエーテル樹脂が５％重量以上含有していることが好ましい。より好ましくは、１０重量％以上、さらに好ましくは２０重量％以上含有しているものが良い。また、加工成形性の観点から、ポリフェニレンエーテル樹脂の配合量は、９５重量％以下、より好ましくは９０重量％以下、さらに好ましくは８０重量％以下であることが望ましい。
本発明でいう縮合燐酸エステルとは、下記構造式（４）、（５）を有する燐酸化合物である。
When an epoxy resin is used, from the viewpoint of heat resistance, dimensional stability and dielectric properties of the composition, when the total amount of the polyphenylene ether resin and the epoxy resin is 100% by weight, the content of the polyphenylene ether resin is 5% by weight or more. Preferably. More preferably, the content is 10% by weight or more, more preferably 20% by weight or more. From the viewpoint of processability, the amount of the polyphenylene ether resin is desirably 95% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less.
The condensed phosphoric acid ester referred to in the present invention is a phosphoric acid compound having the following structural formulas (4) and (5).
（ここで、Ｑ１、Ｑ２、Ｑ３、Ｑ４、Ｑ９、Ｑ１０、Ｑ１１、Ｑ１２は、独立に炭素数１から６のアルキル基を表し、Ｑ５，Ｑ６、Ｑ７、Ｑ８、Ｑ１３は独立に水素、またはメチル基を表す。ｍ１、ｍ２、ｍ３、ｍ４、ｍ７、ｍ８、ｍ９、ｍ１０は、独立に０から３の整数を示し、ｍ５、ｍ６は独立に０から２の整数を表し、ｍ１１は独立に０から４の整数を表す。ｎは自然数） (Here, Q1, Q2, Q3, Q4, Q9, Q10, Q11, and Q12 independently represent an alkyl group having 1 to 6 carbon atoms, and Q5, Q6, Q7, Q8, and Q13 independently represent hydrogen or methyl. M1, m2, m3, m4, m7, m8, m9, and m10 each independently represent an integer of 0 to 3, m5 and m6 each independently represent an integer of 0 to 2, and m11 independently represents 0. To an integer of 4. n is a natural number)
縮合燐酸エステルの中で、ビスフェノールＡとフェノールを原料として合成される縮合燐酸エステル、ビスフェノールＡまたはレゾルシンと２，６−キシレノールを原料として得られる縮合燐酸エステルは好ましい。
本発明でいうホスファゼン化合物は、公知の化合物であり、例えばJames E. Mark, Harry R. Allcock, Robert West著、”Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140に記載されている。これらホスファゼン化合物を得るための参考文献および合成例は、特公平３−７３５９０号公報、特開平９−７１７０８号公報、特開平９−１８３８６４号公報および特開平１１−１８１４２９号公報等に開示されている。
一般に下記構造式を有する。
Among the condensed phosphoric esters, condensed phosphoric esters synthesized from bisphenol A and phenol as raw materials, and condensed phosphoric esters obtained from bisphenol A or resorcin and 2,6-xylenol as raw materials are preferable.
The phosphazene compound referred to in the present invention is a known compound, and is described, for example, in James E. Mark, Harry R. Allcock, Robert West, “Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140. I have. References and synthesis examples for obtaining these phosphazene compounds are disclosed in JP-B-3-73590, JP-A-9-71708, JP-A-9-183864 and JP-A-11-181429. I have.
Generally has the following structural formula:
（式中ｎは正の整数。Ｒは、酸素、硫黄を含有していても良いアルキルもしくはアリール炭化水素残基）
ホスファゼン化合物の例としては、フェノキシホスファゼン、アルコキシホスファゼン、フェノキシアルコキシホスファゼン、アルキル置換フェノキシホスファゼン、フェニルホスファゼン、アルキルホスファゼン、フェニルアルキルホスファゼン、アルキル置換フェニルホスファゼン及びこれら混合物などが例示できる。これらホスファゼン化合物は、環状であっても鎖状であっても良いが耐熱性の観点からは、環状が好ましい。
本発明でいうシリコン樹脂とは、下記化学式を有するオリゴマーもしくはポリマーである。
(Where n is a positive integer; R is an alkyl or aryl hydrocarbon residue which may contain oxygen or sulfur)
Examples of the phosphazene compound include phenoxyphosphazene, alkoxyphosphazene, phenoxyalkoxyphosphazene, alkyl-substituted phenoxyphosphazene, phenylphosphazene, alkylphosphazene, phenylalkylphosphazene, alkyl-substituted phenylphosphazene, and mixtures thereof. These phosphazene compounds may be cyclic or chain-like, but are preferably cyclic from the viewpoint of heat resistance.
The silicone resin in the present invention is an oligomer or a polymer having the following chemical formula.
（Ｒ：フェニル基、炭素数１〜５のアルキル置換基を有するフェニル基、炭素数１〜１０のアルキル基を表す）
重量平均分子量は６００〜１５０００のものが好ましい。
シリコン樹脂の難燃化効果を高めるため、助剤を添加することは好ましい。助剤の具体的な例としては、メラム、タルクなどがある。
縮合リン酸エステル、ホスファゼン化合物、シリコン樹脂などの難燃剤の配合量は、本発明の樹脂組成物を難燃化するにたる量で良い。ポリフェニレンエーテル樹脂とその他の樹脂成分の合計１００重量部に対して、１〜５０重量部、好ましくは５〜５０重量部、さらに好ましくは、１０〜４０重量部である。
(R represents a phenyl group, a phenyl group having an alkyl substituent having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms)
The weight average molecular weight is preferably from 600 to 15,000.
In order to enhance the flame retardant effect of the silicone resin, it is preferable to add an auxiliary agent. Specific examples of auxiliaries include melam, talc and the like.
The compounding amount of the flame retardant such as the condensed phosphate ester, the phosphazene compound, and the silicone resin may be an amount sufficient to make the resin composition of the present invention flame-retardant. The amount is 1 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total of the polyphenylene ether resin and other resin components.
本発明の樹脂組成物は、何らかの方法で架橋することもできる。例えば、ジビニルベンゼンを添加したり、予めＰＰＥを変性してアリル基含有ＰＰＥとしたりして、これを加熱して熱架橋反応によって架橋する方法、また、ＰＰＥを変性して、アミノ基、カルボキシル基、無水ジカルボキシル基、エポキシ基などを含有するＰＰＥとし、これにポリアミン、ポリカルボン酸、その他の架橋剤を添加して架橋する方法などがある。
上記した樹脂組成物の中でも、ポリフェニレンエーテル樹脂とスチレン系樹脂からなる樹脂組成物または、ポリフェニレンエーテル樹脂、エポキシ樹脂および縮合燐酸エステルからなる樹脂組成物が好ましい。ポリフェニレンエーテル樹脂、エポキシ樹脂および縮合燐酸エステルからなる樹脂組成物である場合は、ポリフェニレンエーテル樹脂の数平均分子量が５０００〜５０００であることが好ましい。
The resin composition of the present invention can be crosslinked by any method. For example, a method in which divinylbenzene is added or PPE is previously modified to form an allyl group-containing PPE, and this is heated and cross-linked by a thermal cross-linking reaction. And a method of cross-linking by adding a polyamine, a polycarboxylic acid, and other cross-linking agents to the PPE containing a dicarboxylic acid anhydride, an epoxy group or the like.
Among the above resin compositions, a resin composition comprising a polyphenylene ether resin and a styrene-based resin, or a resin composition comprising a polyphenylene ether resin, an epoxy resin and a condensed phosphate ester is preferred. In the case of a resin composition comprising a polyphenylene ether resin, an epoxy resin and a condensed phosphate, the number average molecular weight of the polyphenylene ether resin is preferably 5,000 to 5,000.
本発明の樹脂組成物には、本発明の目的を損なわない範囲で、一般に樹脂に添加される添加剤を添加することができる。例えば、ガラス繊維、ガラスフレーク、カオリンクレー、タルク、マイカ等の無機充填剤やその他の繊維状、非繊維状補強剤である。また、耐衝撃付与剤としてゴム状重合体、例えばスチレン−ブタジエンブロック共重合体、スチレン−イソプレンブロック共重合体およびそれらの水素添加物などの熱可塑性エラストマーである。更に他の特性を付与するため、または本発明の効果を損なわない範囲で他の添加剤、例えば可塑剤、酸化防止剤、及び紫外線吸収剤などの安定剤、帯電防止剤、離型剤、染顔料、あるいはその他の樹脂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および難燃助剤、例えば結晶水を含有する水酸化マグネシウムや水酸化アルミニウム等のアルカリ金属水酸化物またはアルカリ土類金属水酸化物、ホウ酸亜鉛化合物、スズ酸亜鉛化合物、さらにはシリカ、カオリンクレー、タルクなどの無機ケイ素化合物を添加して更なる難燃性の向上も可能である。 添加 The resin composition of the present invention may contain additives generally added to the resin within a range that does not impair the purpose of the present invention. For example, inorganic fillers such as glass fiber, glass flake, kaolin clay, talc, and mica, and other fibrous and non-fibrous reinforcing agents. Further, the impact modifier is a thermoplastic elastomer such as a rubbery polymer, for example, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof. In order not to impair the effects of the present invention or to impart other properties, other additives such as a stabilizer such as a plasticizer, an antioxidant, and an ultraviolet absorber, an antistatic agent, a release agent, and a dye Pigments or other resins can be added. In addition, conventionally known various flame retardants and flame retardant aids, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing water of crystallization, zinc borate compounds, Addition of a zinc stannate compound and further an inorganic silicon compound such as silica, kaolin clay, and talc can further improve flame retardancy.
本発明の樹脂組成物の製造方法は、特に限定するものではない。熱可塑性樹脂においては、２軸押出機、１軸押出機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて混練製造することができる。その中でも押出機による混合が、生産性の面で好ましい。混合温度は、ベース樹脂の好ましい加工温度に従えばよい。
本発明組成物は、１ＧＨｚ以上の周波数領域で使用される部品用材料であり、具体的には、プリント配線板、半導体用封止剤、アンテナ材、筐体、構造体、電線被覆などで、１ＧＨｚ以上の周波数の電気信号を扱う環境下に使う部品用材料である。１ＧＨｚ以上要求される用途分野は、情報通信関係では、携帯電話、ＥＴＣ、ナビゲーションシステム、家電・ＯＡ無線システムなど、情報処理関係では、高速演算するコンピュータなどがある。
The method for producing the resin composition of the present invention is not particularly limited. The thermoplastic resin can be manufactured by kneading using a kneader such as a twin-screw extruder, a single-screw extruder, a heating roll, a kneader, and a Banbury mixer. Among them, mixing by an extruder is preferable in terms of productivity. The mixing temperature may be in accordance with the preferred processing temperature of the base resin.
The composition of the present invention is a component material used in a frequency region of 1 GHz or more, specifically, a printed wiring board, a sealant for a semiconductor, an antenna material, a housing, a structure, an electric wire covering, and the like. It is a component material used in an environment that handles electric signals of a frequency of 1 GHz or more. Application fields requiring 1 GHz or more include mobile phones, ETCs, navigation systems, home electric appliances and OA wireless systems in the information communication field, and computers that perform high-speed calculations in the information processing field.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の例に限定されるものではない。実施例および比較例で用いた各成分は以下のものである。
ポリフェニレンエーテル
（ＰＰＥ−１）：３０℃のクロロホルム溶液で測定したηｓｐ／ｃが０．５４のポリ−２，６−ジメチル−１，４−フェニレンエーテル。
（ＰＰＥ−２）：ＧＰＣによって測定したポリスチレン換算数平均分子量が２６００のポリ−２，６−ジメチル−１，４−フェニレンエーテル。
（ＰＰＥ−３）：ＰＰＥ−２を５００ｇ、ＡＥＲ２５０を２００ｇ及び、トリ−ｎ−ブチルアミン（和光純薬工業（株）製）１５ｇをよく混合した後、オートクレーブに密閉し、１３０℃、１時間加熱して得た。
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. The components used in the examples and comparative examples are as follows.
Polyphenylene ether (PPE-1): poly-2,6-dimethyl-1,4-phenylene ether having an ηsp / c of 0.54 measured with a chloroform solution at 30 ° C.
(PPE-2): poly-2,6-dimethyl-1,4-phenylene ether having a number average molecular weight in terms of polystyrene of 2,600 as measured by GPC.
(PPE-3): After 500 g of PPE-2, 200 g of AER250 and 15 g of tri-n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed well, the mixture was sealed in an autoclave and heated at 130 ° C. for 1 hour. I got it.
（ＰＰＥ−４）：ＧＰＣによって測定したポリスチレン換算数平均分子量が３６００のポリ−２，６−ジメチル−１，４−フェニレンエーテル。
（ＰＰＥ−５）：ＧＰＣによって測定したポリスチレン換算数平均分子量が２１００のポリ−２，６−ジメチル−１，４−フェニレンエーテル。
ゴム補強ポリスチレン（ＨＩＰＳ）
ゴム含量９％、３０℃、トルエン溶液で測定したマトリックスポリスチレンのηｓｐ／ｃが０．６４、体積平均ゴム粒子径が１．５μｍのゴム補強ポリスチレン。
ポリスチレン（ＰＳ）
トルエン溶液で測定したηｓｐ／ｃが、０．８のポリスチレン
フェノキシホスファゼン（ＦＲ１）
下記化学式（８）においてｎ＝３が９３．６ｗｔ％、ｎ＝４が４．０ｗｔ％、ｎ≧５が２．４ｗｔ％であるようなフェノキシホスファゼン
(PPE-4): poly-2,6-dimethyl-1,4-phenylene ether having a number average molecular weight in terms of polystyrene of 3,600 as measured by GPC.
(PPE-5): poly-2,6-dimethyl-1,4-phenylene ether having a number average molecular weight in terms of polystyrene of 2100 as measured by GPC.
Rubber reinforced polystyrene (HIPS)
Rubber reinforced polystyrene having a rubber content of 9%, ηsp / c of matrix polystyrene measured in a toluene solution at 30 ° C. of 0.64, and a volume average rubber particle diameter of 1.5 μm.
Polystyrene (PS)
Polystyrene phenoxyphosphazene (FR1) having a ηsp / c of 0.8 measured in a toluene solution
In the following chemical formula (8), n = 3 is 93.6 wt%, n = 4 is 4.0 wt%, and n ≧ 5 is 2.4 wt%.
レゾルシンと２，６−キシレノールを原料として合成される縮合リン酸エステル（ＦＲ２）
ＰＸ−２００（大八化学工業（株）社製）
Condensed phosphate ester synthesized from resorcinol and 2,6-xylenol (FR2)
PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
ビスフェノールＡとフェノールを原料として合成される縮合リン酸エステル（ＦＲ３）
下記化学式において、ｎ＝１である化合物を８５．３ｗｔ％、ｎ＝２である化合物を１２．６ｗｔ％含有する縮合リン酸エステル
Condensed phosphate ester synthesized from bisphenol A and phenol (FR3)
In the following chemical formula, a condensed phosphoric acid ester containing 85.3 wt% of a compound where n = 1 and 12.6 wt% of a compound where n = 2
トリフェニルホスフェート（ＴＰＰ）（ＦＲ４） Triphenyl phosphate (TPP) (FR4)
シリコンオリゴマーとメレムの混合物（ＦＲ５）
側鎖が、フェニル基とプロピル基（２：１）からなっており、重量平均分子量が約１８００であるシリコンオリゴマーとメレムの１：１混合物
エポキシ樹脂
ＡＥＲ２５０（旭化成エポキシ（株）社製）；エポキシ当量１８４〜１８６
硬化剤
ｍ−キシレン−α,α’−ジアミン（ｍ−ＸＤＡ）（東京化成工業（株）社製）
実施例、比較例における評価は以下の通り行った。
Mixture of silicone oligomer and melem (FR5)
Epoxy resin AER250 (manufactured by Asahi Kasei Epoxy Co., Ltd.); epoxy resin having side chain consisting of phenyl group and propyl group (2: 1), and having a weight average molecular weight of about 1800, and a 1: 1 mixture of silicon oligomer and melem. Equivalent 184-186
Curing agent m-xylene-α, α'-diamine (m-XDA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Evaluation in Examples and Comparative Examples was performed as follows.
誘電特性
樹脂組成物ペレットを射出成形又はプレス成型して、厚み２ｍｍの成形片を成形し、誘電特性測定装置にて、誘電正接、誘電率を測定した。
耐熱性
ＡＳＴＭ Ｄ６４８に従い、熱変形温度（ＨＤＴ）を測定した。
機械的物性
ＡＳＴＭ Ｄ２５６に従って、ＩＺＯＤ衝撃強度を、ＡＳＴＭ Ｄ６３８に従って引張強度（ＴＳ）を測定した。
（４）難燃性
ＵＬ−９４ 垂直燃焼試験に基づき、１／１６インチ厚みの射出成形試験片を用いて測定し、１０回接炎時の平均燃焼時間と燃焼時の滴下物による脱脂綿着火の有無を評価した。
Dielectric properties The resin composition pellets were injection-molded or press-molded to form molded pieces having a thickness of 2 mm, and the dielectric loss tangent and the dielectric constant were measured by a dielectric property measuring device.
Heat resistance The heat distortion temperature (HDT) was measured according to ASTM D648.
Mechanical properties IZOD impact strength was measured according to ASTM D256 and tensile strength (TS) was measured according to ASTM D638.
(4) Flame retardancy Based on the UL-94 vertical burning test, measured using an injection molded test piece having a thickness of 1/16 inch, the average burning time after 10 times flame contact and the ignition of absorbent cotton by dripping material during burning The presence or absence was evaluated.
［実施例１〜７、比較例１］
各成分を表１、表２に示す割合で混合し、加熱シリンダーの最高温度を３００℃に設定したスクリュー直径２５ｍｍの二軸押出機に供給して、スクリュー回転数３００ｒｐｍで溶融混合し、ストランドを冷却裁断して樹脂組成物ペレットを得た。
次に、得られた樹脂組成物ペレットを、射出成形により２４０〜２９０℃にて物性試験片を成形し、上記試験法により物性試験を行い、表１、２の結果を得た。
表２の難燃性試験の結果、滴下による脱脂綿の着火はなかった。
[Examples 1 to 7, Comparative Example 1]
The respective components were mixed at the ratios shown in Tables 1 and 2, and supplied to a twin-screw extruder having a screw diameter of 25 mm in which the maximum temperature of the heating cylinder was set to 300 ° C., and melt-mixed at a screw rotation speed of 300 rpm. The mixture was cooled and cut to obtain resin composition pellets.
Next, physical properties test pieces were molded from the obtained resin composition pellets at 240 to 290 ° C. by injection molding, and physical properties tests were performed by the above-described test methods. The results shown in Tables 1 and 2 were obtained.
As a result of the flame retardancy test in Table 2, there was no ignition of the absorbent cotton by dripping.
［実施例８〜１４、比較例２］
表３、表４に示す量のＡＥＲ２５０、ＰＰＥを設定温度１４０℃のオイルバス中で攪拌して均一に溶解させた後、１２０〜１４０℃に加熱したオイルバス中で難燃剤を溶解させた。温度を保ったまま、硬化剤を添加した後、型に流し込んだ。
次いで、１５０℃、０ｋｇｆ／ｃｍ2で１分間、１５０℃／１０ｋｇｆ／ｃｍ2で１分間、１５０℃／４０ｋｇｆ／ｃｍ2で１０分、熱プレス機で硬化させることにより物性試験片を成型し、上記試験法により物性試験を行い、表３、４の結果を得た。
[Examples 8 to 14, Comparative Example 2]
The amounts of AER250 and PPE shown in Tables 3 and 4 were uniformly dissolved by stirring in an oil bath at a set temperature of 140 ° C, and then the flame retardant was dissolved in an oil bath heated to 120 to 140 ° C. After the curing agent was added while maintaining the temperature, the mixture was poured into a mold.
Then, 0.99 ° C., molding the 0 kgf / cm 2 in 1 minute, 150 ℃ / 10kgf / cm 2 for 1 minute, 10 minutes at 150 ℃ / 40kgf / cm 2, the physical properties test piece by curing in a hot press, A physical property test was performed by the above test method, and the results in Tables 3 and 4 were obtained.
［実施例１５］
ＡＥＲ２５０（５０．１ｗｔ％）、ＰＰＥ−１（１６．７ｗｔ％）、ＦＲ−２（２４．０ｗｔ％）及びメチルエチルケトンを配合し、設定温度１４０℃のオイルバス中で攪拌したが、ＰＰＥ−１は溶解しなかった。そこで、設定温度１５０℃の減圧乾燥機で１ｍｍＨｇ以下で乾燥させてメチルエチルケトンを除去した。設定温度１４０℃のオイルバス中で硬化剤９．２ｗｔ％を添加し、実施例７と同様の方法で試験片を作製したところ、目視でもＰＰＥの粒子が確認でき、外観の悪いものとなった。この試験片の難燃性試験を行ったところ、平均燃焼時間が３.５秒で、Ｖ−０であった。また、１ＧＨｚでの誘電率は３．０２であった。
[Example 15]
AER250 (50.1 wt%), PPE-1 (16.7 wt%), FR-2 (24.0 wt%) and methyl ethyl ketone were blended and stirred in an oil bath at a set temperature of 140 ° C. Did not dissolve. Therefore, the product was dried at 1 mmHg or less using a reduced-pressure drier at a set temperature of 150 ° C. to remove methyl ethyl ketone. A test piece was prepared in the same manner as in Example 7 by adding 9.2% by weight of a curing agent in an oil bath at a set temperature of 140 ° C. As a result, PPE particles could be visually confirmed, and the appearance was poor. . When a flame retardancy test was performed on this test piece, the average burning time was 3.5 seconds and V-0. The dielectric constant at 1 GHz was 3.02.
本発明が提供する材料を使用することにより、大量の情報量通信や、高速情報処理を必要とするプリント基板や封止剤、アンテナなど、高周波数帯域での使用時、従来材料では伝送速度が不十分であったり、誤作動を起こすなど問題があった領域で、これら問題なく部品設計ができるようになることが期待される。 By using the material provided by the present invention, when using in high frequency bands such as printed circuit boards, sealants, antennas, etc. It is expected that parts can be designed without these problems in areas where there are problems such as insufficient or malfunction.
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| JP2013119240A (en) * | 2011-12-08 | 2013-06-17 | Furukawa Electric Co Ltd:The | Copper clad laminate for high frequency substrate, and surface treated copper foil used for the same |
| JP2015108154A (en) * | 2015-02-13 | 2015-06-11 | パナソニックＩｐマネジメント株式会社 | Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board |
| EP3047841A1 (en) | 2015-01-22 | 2016-07-27 | Hoyu Co., Ltd. | Stability improver of aromatic compound and method for improving stability of aromatic compound |
| EP4293080A1 (en) | 2022-06-16 | 2023-12-20 | SHPP Global Technologies B.V. | Polyphenylene ether composition with excellent flammability and dielectric properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013119240A (en) * | 2011-12-08 | 2013-06-17 | Furukawa Electric Co Ltd:The | Copper clad laminate for high frequency substrate, and surface treated copper foil used for the same |
| EP3047841A1 (en) | 2015-01-22 | 2016-07-27 | Hoyu Co., Ltd. | Stability improver of aromatic compound and method for improving stability of aromatic compound |
| KR20160090756A (en) | 2015-01-22 | 2016-08-01 | 호유 가부시키가이샤 | Stability enhancer of aromatic compound and stability enhancing method of aromatic compound |
| JP2015108154A (en) * | 2015-02-13 | 2015-06-11 | パナソニックＩｐマネジメント株式会社 | Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board |
| EP4293080A1 (en) | 2022-06-16 | 2023-12-20 | SHPP Global Technologies B.V. | Polyphenylene ether composition with excellent flammability and dielectric properties |
| WO2023242779A1 (en) | 2022-06-16 | 2023-12-21 | Shpp Global Technologies B.V. | Polyphenylene ether composition with excellent flammability and dielectric properties |
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