JP3540926B2 - Resin composition for electricity - Google Patents
Resin composition for electricity Download PDFInfo
- Publication number
- JP3540926B2 JP3540926B2 JP01669698A JP1669698A JP3540926B2 JP 3540926 B2 JP3540926 B2 JP 3540926B2 JP 01669698 A JP01669698 A JP 01669698A JP 1669698 A JP1669698 A JP 1669698A JP 3540926 B2 JP3540926 B2 JP 3540926B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ring
- composition
- thiirane
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims description 16
- 230000005611 electricity Effects 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 99
- 125000001730 thiiranyl group Chemical group 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 125000000466 oxiranyl group Chemical group 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 13
- 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 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 43
- -1 for example Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 150000003553 thiiranes Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 2
- MOABYHZDQQELLG-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC MOABYHZDQQELLG-UHFFFAOYSA-N 0.000 description 2
- LZNWGSIDNAGRAJ-UHFFFAOYSA-N P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 LZNWGSIDNAGRAJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 229920003054 adipate polyester Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical class CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- XZZWOTQMUOIIFX-UHFFFAOYSA-N 1-(2-diphenoxyphosphanyloxypropoxy)propan-2-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC(C)COCC(C)OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 XZZWOTQMUOIIFX-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- GAMCKBORIMJJBE-UHFFFAOYSA-N 2-(dimethylamino)-4-methylphenol Chemical compound CN(C)C1=CC(C)=CC=C1O GAMCKBORIMJJBE-UHFFFAOYSA-N 0.000 description 1
- AUABZJZJXPSZCN-UHFFFAOYSA-N 2-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC=C1O AUABZJZJXPSZCN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- NKVZFNUCUPOCQJ-UHFFFAOYSA-N 2-anilinopropanehydrazide Chemical compound NNC(=O)C(C)NC1=CC=CC=C1 NKVZFNUCUPOCQJ-UHFFFAOYSA-N 0.000 description 1
- XKZGIJICHCVXFV-UHFFFAOYSA-N 2-ethylhexyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCC(CC)CCCC)OC1=CC=CC=C1 XKZGIJICHCVXFV-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 1
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- IHBSKUPQOWXMOX-UHFFFAOYSA-N 3-(2-methyl-1h-imidazol-5-yl)propanenitrile Chemical compound CC1=NC(CCC#N)=CN1 IHBSKUPQOWXMOX-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は電気用樹脂組成物に関し、詳しくは、短時間に絶縁性を発現し、難燃性を併せ持ち、硬化性、金属への接着性に優れ、プリント基板の封止、プリプレグ用含浸樹脂等に用いられる電気用樹脂組成物に関する。
【０００２】
【従来の技術】
エポキシ樹脂組成物は、金属、プラスチック、ガラス、セラミックス等の多種多様な被着体に接着性を示し、かつ強い接着力とともに、耐熱性、耐薬品性、電気絶縁性等に優れ、さらに硬化時にガス発生が少なく、低収縮性である等の特性を有するため、電気・電子分野での利用が盛んである。例えば、プリント基板を物理的、化学的に保護し、かつ固着するための封止材料や、プリプレグ用の含浸樹脂として使用されている。近年の使用用途の拡大に伴い、さらに高い絶縁性、難燃性と接着性が求められている。また、製造工程の短縮化のために短時間で硬化し、絶縁性が発現することが求められている。
【０００３】
【発明が解決しようとする課題】
ところで、このエポキシ樹脂組成物の接着力は、主として硬化反応により発生する水酸基によって発現するものと考えられている。しかし、この水酸基は反応性（酸性度）が低く、物理的な親和力によって接着力が発現していると考えられている。したがって、硬化時に水酸基よりも化学的な反応性の高い置換基を発生させることができる高反応性の官能基を分子内に導入すれば、従来のエポキシ樹脂組成物よりも高い接着力を有し、かつ速硬化性の封止剤を得ることができると期待される。
【０００４】
そこで、本発明の目的は、従来の電気用樹脂組成物よりも短時間に絶縁性を発現し、難燃性を併せ持ち、硬化性、金属への接着性に優れ、プリント基板の封止、プリプレグ用含浸樹脂等の用途に好適な電気用樹脂組成物を提供することにある。
【０００５】
【課題を解決するための手段】
そこで、本発明は、前記課題を解決するために、エポキシ化合物が有するオキシラン環の一部を下記式（１）：
【化２】
水酸基、メルカプト基、アミノ基、もしくは、カルボキシル基を含む化合物からなる群より選ばれる少なくとも一種の硬化剤と、
前記化合物（Ａ）、または、該化合物（Ａ）および前記化合物（Ｂ）の合計量１００重量部に対し、２〜３０重量部の難燃剤とを含み、
オキシラン環／チイラン環の含有割合が９０／１０〜５０／５０であり、
前記化合物（Ａ）および／または前記化合物（Ｂ）としてハロゲン化化合物を含有する、電気用樹脂組成物を提供する。
【０００６】
前記電気用樹脂組成物において、オキシラン環およびチイラン環の合計に占めるチイラン環のモル分率をＸ、オキシラン環およびチイラン環の合計に対する硬化剤の当量比をＹとした場合に、Ｘ、Ｙが以下に示す関係を有するのが接着性能上好ましい。
１０％≦Ｘ＜５０％の場合 Ｙ＝（１００−Ｘ）／１００±０．２
Ｘ＝５０％の場合 Ｙ＝０．１〜０．７
【０００７】
前記難燃剤がアンチモン系難燃剤であるのが好ましい。
【０００８】
【発明の実施の形態】
以下、本発明の電気用樹脂組成物（以下、本発明の組成物と記す）について詳細に説明する。
本発明の組成物の主成分である化合物（Ａ）は、エポキシ化合物が有するオキシラン環の一部をチイラン環に置換してなる化合物であり、分子内のオキシラン環の一部のみがチイラン環に置換され、チイラン環とオキシラン環とを併有する化合物である。
【０００９】
化合物（Ａ）を得るために用いられるエポキシ化合物は、例えば、下記式（ａ）、（ｂ）、（ｄ）、（ｅ）または（ｆ）において、置換基Ｙが下記式（２）：
【化３】
【００１０】
【化４】
【化５】
【化６】
で表される化合物であってもよい。ハロゲン原子としては、臭素、塩素、フッ素等が挙げられる。ハロゲン含有量は、これらのエポキシ化合物より合成される化合物（Ａ）、または、化合物（Ａ）と化合物（Ｂ）の総量のうち、１〜１０重量％となる量が好ましい。
化合物（Ａ）としては、上述の種々のエポキシ化合物を用いて合成され、その分子内の水素原子またはその他の基、例えば芳香族環に結合するメチル基が臭素原子で置換されたものが、難燃性付与の観点から好ましい。
【００１２】
本発明において、化合物（Ａ）は、前記式（ａ）、（ｂ）、（ｃ）、（ｄ） （ｅ）、（ｆ）、または（ｇ）において、２以上のＹの少なくとも１つが、前記式（１）で表されるチイラン環であり、少なくとも１つが、前記式（２）で表されるオキシラン環である化合物、またはＺの少なくとも１つがＳであり、少なくとも１つがＯである化合物である。
【００１３】
この化合物（Ａ）の具体例として、下記式で表されるものが挙げられる。下記のそれぞれの式において、２以上のＹの少なくとも１つが前記式（１）で表されるチイラン環であり、少なくとも１つが前記式（２）で表されるオキシラン環である化合物、またはＺの少なくとも１つがＳであり、少なくとも１つがＯである化合物である。また、ｎは、０または０以上の数である。また、好ましくは、分子内の水素原子またはその他の基の一部が臭素原子で置換されたものである。
【００１４】
【化７】
【化８】
【化９】
【化１０】
【化１１】
この化合物（Ａ）の製造は、前記エポキシ化合物と、エピスルフィド化剤とを、極性溶媒中で、強攪拌下に反応させる方法にしたがって行うことができる。
【００２０】
用いられるエピスルフィド化剤としては、例えば、チオシアン酸カリウム（ＫＳＣＮ）、チオ尿素等が挙げられる。
【００２１】
極性溶媒としては、例えば、メタノール、エタノール、アセトン、水、あるいはこれらの混合溶媒等を用いることができる。特に、エピスルフィド化剤としてＫＳＣＮを用いる場合、チイラン化率が５０％、すなわち、オキシラン環／チイラン環の含有割合が１／１の化合物（Ａ）を得るためには、水／エタノールの２／１混合溶媒を用いるのが好ましい。
【００２２】
反応は、通常、１０〜３５℃の温度範囲、例えば、室温下、１０〜４０時間程度、例えば、２０時間程度の反応時間で行うことができる。また、反応の雰囲気は、空気中でもよいし、窒素等の不活性雰囲気でもよい。
【００２３】
この化合物（Ａ）の製造の具体例として、ビスフェノールＡ型エポキシ樹脂を出発原料として、チイラン環を有する化合物（Ａ）を製造する方法を例にとると、下記反応式で表される方法にしたがって行うことができる。ここでＸはＳまたはＯである。
【化１２】
本発明の組成物に含有される分子内にオキシラン環を有し、チイラン環を含まない化合物（Ｂ）としては、前述の化合物（Ａ）を得るために用いられるエポキシ化合物として例示されるエポキシ化合物の全てが利用可能である。具体的には、化合物（Ａ）の具体例として挙げられている前記全ての式の置換基Ｙが前記式（２）で表されるオキシラン環である化合物、または、すべてのＺがＯである化合物が例示される。ｎは０または、０以上の数である。
これらの中でも、接着性の観点から、分子内にオキシラン環を２個持つ２官能エポキシ化合物が好ましく、分子内にオキシラン環を２個持つ芳香族系の２官能エポキシ化合物がより好ましい。
また、化合物（Ｂ）も、化合物（Ａ）と同様に、上述のエポキシ化合物の分子内の水素原子またはその他の基の一部が臭素原子で置換されたものが難燃性付与の観点からさらにより好ましい。
【００２５】
本発明の組成物は、チイラン環のみを有する化合物と、チイラン環とオキシラン環を併有する化合物（即ち、化合物（Ａ））との両者を含んでいてもよいし、化合物（Ａ）のみを含むものであってもよい。例えば、下記のいずれの成分の組合せからなるものであってもよい。
（ｉ）化合物（Ａ）のみを含む組成物
(ii) 化合物（Ａ）と、化合物（Ｂ）とを含む組成物
(iii)化合物（Ａ）と、チイラン環のみを有する化合物と、化合物（Ｂ）とを含む組成物
特に、本発明において、高密着力を発現する組成物が求められる場合には、前記の (ii) の組合せからなる組成物が好ましい。
【００２６】
本発明の組成物において、オキシラン環／チイラン環の含有割合は、硬化時に水酸基とメルカプト基の両方の基を発生させることができ、高接着力を示す組成物が得られる点で、５０／５０〜９０／１０の範囲である。
【００２７】
本発明の組成物は、さらに水酸基、メルカプト基、アミノ基、もしくは、カルボキシル基を含む化合物からなる群より選ばれる少なくとも一種の硬化剤を含む。この硬化剤としては、アミン系硬化剤、カルボン酸系硬化剤、塩基性活性水素化合物、イミダゾール類、ポリメルカプタン系硬化剤、フェノール樹脂、ユリア樹脂、メラミン樹脂、潜在性硬化剤等が挙げられる。
【００２８】
本発明の組成物は、前記化合物（Ａ）、または化合物（Ａ）および化合物（Ｂ）と、硬化剤とを、それぞれ別体としておき、封止剤等の電気用樹脂組成物としての使用時に、両者を所定の割合で混合して、組成物の調合を行う二液型組成物とすることができる。また、本発明の組成物は、前記化合物（Ａ）、または化合物（Ａ）と化合物（Ｂ）を、加熱または加圧により硬化作用を発揮する潜在性硬化剤と混合して、一液型組成物とすることもできる。
【００２９】
アミン系硬化剤の具体例として、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンジアミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、１，３，６−トリスアミノメチルヘキサン等のポリアミン；トリメチルヘキサメチレンジアミン、ポリエーテルジアミン、ジエチルアミノプロピルアミン等のポリメチレンジアミン；メンセンジアミン、イソフォロンジアミン、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、Ｎ−アミノエチルピペラジン、ジアミノジシクロヘキシルメタン、ビスアミノメチルシクロヘキサン、３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラオキサスピロ（５．５）ウンデカン等の脂環式ポリアミン；メタキシリレンジアミン等の芳香環を含む脂肪族ポリアミン、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジアミノジエチルジフェニルメタン等の芳香族ポリアミン、また、３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラスピロ〔５．５〕ウンデカン等が挙げられる。また、アミンアダクト（ポリアミンエポキシ樹脂アダクト）、ポリアミン−エチレンオキシドアダクト、ポリアミン−プロピレンオキシドアダクト、シアノエチル化ポリアミン、脂肪族ポリアミンとケトンとの反応物であるケチミン；直鎖状ジアミン、テトラメチルグアニジン、トリエタノールアミン、ピペリジン、ピリジン、ベンジルジメチルアミン、ピコリン、２−（ジメチルアミノメチル）フェノール、ジメチルシクロヘキシルアミン、ジメチルベンジルアミン、ジメチルヘキシルアミン、ジメチルアミノフェノール、ジメチルアミノｐ−クレゾール、Ｎ，Ｎ’−ジメチルピペラジン、ピペリジン、１，４−ジアザジシクロ（２，２，２）オクタン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１．８−ジアザビシクロ（５．４．０）ウンデセン−１等の第二アミン類または第三アミン類など、あるいはダイマー酸とジエチレントリアミン、トリエチレンテトラミン等のポリアミンとを反応させてなる液体ポリアミドなどが挙げられる。
【００３０】
カルボン酸系硬化剤の具体例として、アジピン酸、アゼライン酸、デカンジカルボン酸等のポリカルボン酸などが挙げられる。
【００３１】
塩基性活性水素化合物の具体例としては、ジシアンジアミド、有機酸ジヒドラジドなどが挙げられる。
【００３２】
イミダゾール類の具体例としては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、２−メチルイミダゾリウム・イソシアヌレート、２，４−ジアミノ−６−〔２−メチルイミダゾリン−（１）〕−エチル−Ｓ−トリアジン、２，４−ジアミノ−６−〔２−エチル−４−メチルイミダゾリン−（１）〕−エチル−Ｓ−トリアジン等が挙げられる。
【００３３】
ポリメルカプタン系硬化剤の具体例としては、２，２’−ビスメルカプトエチルエーテルの部分エポキシ付加物、ペンタエリスリトールテトラチオグリコレート、ジペンタエリスリトールヘキサチオグリコレート、トリメチロールプロパントリチオグリコレート等のチオグリコール酸のエステル、末端にメルカプト基を有するポリスルフィドゴム等のメルカプト基を含む化合物などが挙げられる。
【００３４】
また、一液型硬化剤の調製に用いられる潜在性硬化剤としては、ｎ−ヘキシルアミン、モノエチルアミン、ベンジルアミン、ジエチルアミン、ピペリジン、トリエチルアミン、アニリン等のアミンと、三フッ化ホウ素との化合物である三フッ化ホウ素−アミン錯体；ジシアンジアミド、またはｏ−トリルビグアニド、α−２，５−ジメチルビグアニド、α，ω−ジフェニルビグアニド、５−ヒドロキシナフチル−１−ビグアニド等のジシアンジアミドの誘導体；コハク酸ヒドラジド、アジピン酸ヒドラジド、イソフタル酸ヒドラジド、ｐ−オキシ安息香酸ヒドラジド、サリチル酸ヒドラジド、フェニルアミノプロピオン酸ヒドラジド等の酸ヒドラジド；ジアミノマレオニトリルまたはその誘導体；ジアリルメラミン等のメラミンの誘導体；カルボン酸エステルとジメチルヒドラジンとエポキシ化合物により合成されるアミンイミド類；エチレンジアミン、ヘキサメチレンジアミン、ピペリジン等のジアミンとセバチン酸等の脂肪族ジカルボン酸との塩、２，４，４−トリメチル−２，４，７−トリヒドロキシフラバン等のポリアミンと、Ｎ，Ｎ’−ジメチル１，３−プロパンジアミン等のポリヒドロキシフェノールとの塩、ポリアミンのフェニルホスホン酸塩、ポリアミンのフェニルリン酸塩；などが挙げられる。
【００３５】
本発明の組成物におけるオキシラン環およびチイラン環の合計に占めるチイラン環のモル分率（以下、チイラン含有率と記す）をＸ、オキシラン環およびチイラン環の合計に対する硬化剤の当量比をＹとした場合に、Ｘ、Ｙが以下に示す関係を有するのが好ましい。
１０％≦Ｘ＜５０％の場合 Ｙ＝（１００−Ｘ）／１００±０．２
Ｘ＝５０％の場合 Ｙ＝０．１〜０．７
この範囲よりも硬化剤の当量比が大きいと、従来硬化剤は高価であるため、原料コストが高くなり好ましくない。この範囲よりも硬化剤の当量比が小さいと、硬化反応が十分に進まず組成物が硬化せず、接着性に劣る。
本発明の組成物においては、含有されるチイラン環は、化学的に反応性が高く、チイラン環の開環により生成する−ＳＨが硬化反応に寄与するため、オキシラン環のみを含有する化合物を用いる場合に比べ、硬化剤の使用量は、チイラン環の寄与分だけ少なくても硬化性は良好に保たれる。
ただし、Ｘが５０％では、硬化剤の反応性が飽和して、用いる硬化剤の当量比は、Ｘの値に無関係に、Ｙ＝０．１〜０．７の範囲であれば、硬化反応は良好に進む。Ｘが５０％未満の場合は、ＸとＹが上記の範囲であれば硬化性に優れ、より好ましくは、Ｙは、Ｙ＝（１００−Ｘ）／１００−０．１で与えられる。
【００３６】
また、本発明の組成物は、さらに難燃剤を含有する。難燃剤としては、リン系、アンチモン系、ハロゲン系、アルミニウム系、マグネシウム系が挙げられ、具体的には、水酸化ジルコニウム、メタホウ酸バリウム、水酸化アルミニウム、水酸化マグネシウム、トリクレジルホスフェート、ジフェニルクレジルホスフェート、ジフェニルオクチルホスフェート、トリスクロロエチルホスフェート、トリブチルホスフェート、トリス（ジブロモプロピル）ホスフェート、クロロアルキルホスフェート、アンモニウムポリホスフェート、クロロホスホネート、ブロモホスホネート、ジメチル・メチルホスホネート、四臭化エタン、塩素化パラフィン、塩素化ポリフェニル、三酸化アンチモン、五酸化アンチモン、ネオペンチルブロマイド−ポリエーテル、臭素化ポリエーテル等が挙げられる。これらは１種単独でも２種以上を組み合わせても用いられる。
上記化合物（Ａ）、化合物（Ｂ）と難燃剤の組合わせとしては、前記化合物（Ａ）、または化合物（Ｂ）としてハロゲン化エポキシ化合物と、アンチモン系難燃剤との併用が、難燃性についての高い効果が期待でき好ましい。
【００３７】
本発明の組成物中の、難燃剤の含有量は、難燃性付与の観点から、前記化合物（Ａ）、または該化合物（Ａ）および前記化合物（Ｂ）１００重量部に対し、２〜３０重量部が好ましく、５〜２０重量部がより好ましい。
【００３８】
また、本発明の組成物は、前記硬化剤以外に、硬化促進剤を配合してもよい。硬化促進剤としては、例えば、亜リン酸エステル類、フェノール類、三級アミン類等が挙げられる。これらの中で、亜リン酸エステルを含有する本発明の組成物は、貯蔵中に増粘その他の問題を生じない点で、好ましい。
【００３９】
用いられる亜リン酸エステル類としては、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリエチルホスファイト、トリブチルホスファイト、トリス（２−エチルヘキシル）ホスファイト、トリデシルホスファイト、トリス（トリデシル）ホスファイト、ジフェニルモノ（２−エチルヘキシル）ホスファイト、ジフェニルモノデシルホスファイト、ジフェニルモノ（トリデシル）ホスファイト、テトラフェニルジプロピレングリコールジホスファイト、テトラフェニルテトラ（トリデシル）ペンタエリスリトールテトラホスファイト、トリラウリルトリチオホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、トリステアリルホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリス（２、４−ジ−t −ブチルフェニル）ホスファイト、水添ビスフェノールＡ・ペンタエリスリトールホスファイトポリマー等のトリエステル体が挙げられる。また、これらのトリエステル体を部分的に加水分解したジ−、あるいはモノエステル体も用いることができる。これらは１種単独でも２種以上を組み合わせて配合してもよい。これらの中でも、テトラフェニルテトラ（トリデシル）ペンタエリスリトールテトラホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、水添ビスフェノールＡ・ペンタエリスリトールホスファイトポリマー等は、特に硬化の促進効果が高く、好適に用いられる。
【００４０】
三級アミンとしては、ベンジルメチルアミン、トリエチルアミン、ジメチルアミノメチルフェノール、トリスジメチルアミノメチルフェノール、１，８−ジアザビシクロ〔５．４．０〕ウンデセン−１、１，４−ジアザビシクロ〔２．２．２〕オクタン等が挙げられる。
【００４１】
本発明の組成物には、前記化合物（Ａ）、または化合物（Ｂ）もしくは硬化剤、難燃剤以外に、必要に応じて、各種の添加剤を配合することができる。例えば、充填剤、可塑剤、チクソトロピー性付与剤、老化防止剤、酸化防止剤、帯電防止剤、接着性付与剤、着色剤、分散剤、溶剤等を配合することができる。
【００４２】
充填剤としては、各種形状のものを使用することができ、例えば、ヒュームドシリカ、焼成シリカ、沈降シリカ、粉砕シリカ、溶融シリカ；けいそう土；酸化鉄、酸化亜鉛、酸化チタン、酸化バリウム、酸化マグレシウム；炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛；ろう石クレー、カオリンクレー、焼成クレー；カーボンブラックなどの有機または無機充填剤が挙げられ、またこれらの脂肪酸、樹脂酸、脂肪酸エステル処理物等が挙げられる。これらは１種単独でも２種以上を組み合わせても用いられる。
【００４３】
可塑剤としては、ジオクチルフタレート(DOP) 、ジブチルフタレート(DBP) ；アジピン酸ジオクチル、コハク酸イソデシル；ジエチレングリコールジベンゾエート、ペンタエリスリトールエステル；オレイン酸ブチル、アセチルリシノール酸メチル；リン酸トリクレジル、リン酸トリオクチル；アジピン酸プロピレングリコールポリエステル、アジピン酸ブチレングリコールポリエステル等が挙げられる。これらの可塑剤は、１種単独でも、２種以上を混合して使用してもよい。
【００４４】
チクソトロピー性付与剤としては、例えば、エアロジル（日本エアロジル（株）製）、ディスパロン（楠本化成（株）製）、炭酸カルシウム、テフロン等を、また帯電防止剤としては、一般的に、第４級アンモニウム塩、あるいはポリグリコールやエチレンオキサイド誘導体などの親水性化合物を挙げることができる。
【００４５】
老化防止剤としては、例えば、ヒンダードフェノール系等の化合物が挙げられる。
酸化防止剤としては、例えば、ブチルヒドロキシトルエン(BHT) 、ブチルヒドロキシアニソール(BHA) 等が挙げられる。
【００４６】
顔料としては、二酸化チタン、酸化亜鉛、群青、ベンガラ、リトポン、鉛、カドミウム、鉄、コバルト、アルミニウム、塩酸塩、硫酸塩等の無機顔料、アゾ顔料、銅フタロシアニン顔料等の有機顔料などが挙げられる。
【００４７】
接着性付与剤としては、例えば、テルペン樹脂、フェノール樹脂、テルペンーフェノール樹脂、ロジン樹脂、キシレン樹脂等が挙げられる。
【００４８】
本発明の組成物は、主成分である化合物（Ａ）が分子内にチイラン環を少なくとも１個含み、硬化時にチイラン環が開環して水酸基よりも高い酸性度を有するチオール基を生じるため、従来のプリント基板用封止剤やプリプレグ用含浸樹脂等の電気用樹脂組成物よりも高い接着力を示し、チイラン環がオキシラン環よりも高反応性であるために速硬化性を示すことができるものである。エポキシ樹脂の硬化物は従来より優れた絶縁性を示すものであるが、本発明の組成物は、その速硬化性により短時間で高い絶縁性を発現することができる。また、本発明の組成物は、臭いも少ない。
従って、本発明の組成物を用いてプリント基板やプリプレグ等を製造すれば、速硬化性により工程時間の短縮ができ、また、低臭であるので作業環境を良好に維持できる。
また、本発明の組成物は、前記化合物（Ａ）および／または前記化合物（Ｂ）としてハロゲン化化合物を含有し、かつ、難燃剤を含有するので、従来のプリント基板用封止剤やプリプレグ用含浸樹脂よりも高い難燃性を示し、安全性が高い。
【００４９】
【実施例】
以下、実施例および比較例によって本発明をより具体的に説明するが、本発明はこれらに限られるものではない。
【００５０】
チイラン環を含む化合物の合成例１
チオシアン酸カリウム１２１ｇを、エタノール７５ｍｌと水１００ｍｌの混合溶媒に溶解し、さらに、ビスフェノールＡジグリシジルエーテル８５ｇを加えて４時間放置した。その後、さらにビスフェノールＡジグリシジルエーテル８５ｇを加え、室温で４０時間激しく攪拌した。次に、クロロホルムで抽出し、水洗後、硫酸マグネシウムを用いて、反応混合物を乾燥し、クロロホルムを減圧留去した後、減圧乾燥して、反応生成物を得た。
得られた反応生成物のオキシラン環／チイラン環の含有割合を、ＮＭＲによって測定したところ、５５／４５であった。
【００５１】
この合成例にしたがって、ビスフェノールＡ型エポキシ樹脂（１）（住友化学（株）製、商品名：ＥＬＡ−１２８）を用い、このビスフェノールＡ型エポキシ樹脂（１）中のオキシラン環の全部または一部をチイラン環に置換して、オキシラン環／チイラン環の含有割合が５０／５０の化合物（以下、（１）のチイラン５０％変性品という）を製造した。
【００５２】
（実施例１〜５、比較例１〜３）
各例において、表１に示す配合処方で組成物を調製し、硬化性（タックフリータイム）、絶縁性（体積抵抗）、接着性（引張り剪断強度）、難燃性の測定に供した。結果を表１に示す。
【００５３】
硬化性
組成物を調製後、２０℃に放置し、タックがなくなるまでの時間（タックフリータイム）を計測した。
絶縁性
ＪＩＳ Ｋ６９１１に記載の方法に準拠して、５０Ｖ、１分間印加法で測定した。サンプルは室温で３日間放置後に測定に用いた。体積抵抗率を求め絶縁性として評価した。
接着性
１００ｍｍ×２５ｍｍ×２ｍｍの寸法の銅板（ＪＩＳ Ｃ１０２０）を２枚用意し、ＪＩＳ Ｋ６８５０に準拠して、それぞれの鋼板片の端部から１２．５×２５ｍｍの面積に実施例、比較例で得られた組成物を塗布し、２枚の鋼板片の組成物を塗布した箇所を重ね合わせて接合して試験片を作成する。この試験片について、５０ｍｍ／ｍｉｎの速度で引張りせん断試験を行い、剥離強度を測定した。また、アルミニウム板（ＪＩＳ Ａ２０２４Ｐ）についても同様の引張りせん断試験を行った。
難燃性
実施例、比較例で得られた組成物を含浸させた６インチ×０．５インチ（厚み１ｍｍ）の銅張積層体を試験片とし、ＵＬ規格の垂直法に準じて、試験片の長軸を垂直にし、１０秒間炎に下端をあて４回繰り返し、消炎するまでの時間を測定した。
結果を表１に示す。
【００５４】
【表１】
【発明の効果】
本発明の電気用樹脂組成物は、主成分である化合物（Ａ）が、分子内にチイラン環を少なくとも１個含み、硬化時にチイラン環が開環して水酸基よりも高い酸性度を有するチオール基を生じるため、従来の封止剤やプリプレグ用含浸樹脂等の電気用樹脂組成物よりも高い接着性を示し、チイラン環がオキシラン環よりも高反応性であるため速硬化性を示すものである。同時に短時間で高い絶縁性を発現するものである。また、本発明の組成物は低臭である。従って、本発明の組成物を電気用樹脂として用いれば製造工程時間が短縮でき、作業環境も良好に維持できる。
また、本発明の組成物は、難燃性に優れ、本発明の組成物を用いた電気・電子製品の安全性、信頼性の向上に大いに寄与するものである。
従って、本発明の電気用樹脂組成物は、プリント基板用封止剤、プリプレグ用含浸樹脂、コイル等の注型用樹脂、プリント基板用レジストインク、プリント基板用銅張積層材用樹脂等として好適に用いられる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin composition for electric use, and more specifically, it exhibits insulation properties in a short time, has flame retardancy, has excellent curability, excellent adhesion to metal, seals printed circuit boards, impregnated resin for prepreg, and the like. The present invention relates to a resin composition for electricity used in the invention.
[0002]
[Prior art]
Epoxy resin compositions exhibit adhesiveness to a wide variety of adherends, such as metals, plastics, glass, and ceramics, and have excellent adhesiveness, heat resistance, chemical resistance, electrical insulation, etc. Since it has characteristics such as low gas generation and low shrinkage, it is widely used in the electric and electronic fields. For example, it is used as a sealing material for physically and chemically protecting and fixing a printed circuit board, and as an impregnating resin for prepreg. With the recent expansion of applications, higher insulation, flame retardancy and adhesiveness are required. In addition, it is required that the composition be cured in a short time to exhibit an insulating property in order to shorten a manufacturing process.
[0003]
[Problems to be solved by the invention]
By the way, it is considered that the adhesive strength of the epoxy resin composition is mainly exhibited by a hydroxyl group generated by a curing reaction. However, this hydroxyl group has low reactivity (acidity), and it is considered that the adhesive force is developed by physical affinity. Therefore, when a highly reactive functional group capable of generating a substituent having a higher chemical reactivity than a hydroxyl group upon curing is introduced into a molecule, it has a higher adhesive strength than a conventional epoxy resin composition. It is expected that a fast-curing sealant can be obtained.
[0004]
Therefore, an object of the present invention is to provide an insulating property in a shorter time than conventional resin compositions for electric use, to have both flame retardancy, excellent curability, excellent adhesion to metal, sealing of printed circuit boards, prepreg, and the like. An object of the present invention is to provide a resin composition for electricity suitable for applications such as a resin impregnating resin.
[0005]
[Means for Solving the Problems]
Therefore, the present invention has been made in order to solve the above-mentioned problems.partTo the following equation (1):
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At least one curing agent selected from the group consisting of compounds containing a hydroxyl group, a mercapto group, an amino group, or a carboxyl groupWhen,
The compound (A) or a flame retardant of 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B),
An oxirane ring / thiirane ring content ratio of 90/10 to 50/50,
Containing a halogenated compound as the compound (A) and / or the compound (B),An electric resin composition is provided.
[0006]
In the electric resin composition, when the molar ratio of the thiirane ring to the total of the oxirane ring and the thiirane ring is X, and the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, X and Y are It is preferable to have the following relationship in terms of adhesive performance.
When 10% ≦ X <50% Y = (100−X) /100±0.2
X = 50%In the case of Y = 0.1 to 0.7
[0007]
Preferably, the flame retardant is an antimony-based flame retardant.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the electrical resin composition of the present invention (hereinafter, referred to as the composition of the present invention) will be described in detail.
Compound (A), which is the main component of the composition of the present invention, has an oxirane ring of the epoxy compound.partIs a compound obtained by substituting with a thiirane ring., MinutesCompounds in which only a part of the oxirane ring in the child is substituted with a thiirane ring and has both a thiirane ring and an oxirane ringIs.
[0009]
The epoxy compound used to obtain the compound (A) is, for example, a compound represented by the following formula (a), (b), (d), (e) or (f), wherein the substituent Y is represented by the following formula (2):
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[0010]
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The compound represented by Examples of the halogen atom include bromine, chlorine, and fluorine. The halogen content is preferably such that the compound (A) synthesized from these epoxy compounds or the total amount of the compound (A) and the compound (B) is 1 to 10% by weight.
As the compound (A), a compound synthesized using the above-described various epoxy compounds and having a hydrogen atom or another group in the molecule, for example, a methyl group bonded to an aromatic ring substituted with a bromine atom is difficult. It is preferable from the viewpoint of imparting flammability.
[0012]
In the present invention, compound (A) is a compound represented by the formula (a), (b), (c), (d), (e), (f) or (g), wherein at least one of two or more Y is A thiirane ring represented by the formula (1),At least one isA compound that is an oxirane ring represented by the formula (2), or at least one of Z is S;At least oneO is a compound.
[0013]
Specific examples of the compound (A) include those represented by the following formula. In each of the following formulas, at least one of two or more Y is a thiirane ring represented by the formula (1),At least oneA compound that is an oxirane ring represented by the formula (2), or at least one of Z is S;At least oneO is a compound. N is 0 or a number equal to or greater than 0. Preferably, a hydrogen atom or another group in the molecule is partially substituted with a bromine atom.
[0014]
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The production of the compound (A) can be carried out according to a method of reacting the epoxy compound and an episulfide agent in a polar solvent with vigorous stirring.
[0020]
Examples of the episulfide agent used include potassium thiocyanate (KSCN), thiourea and the like.
[0021]
As the polar solvent, for example, methanol, ethanol, acetone, water, a mixed solvent thereof or the like can be used. In particular, when KSCN is used as an episulfide agent, in order to obtain a compound (A) having a thiirination ratio of 50%, that is, a content ratio of oxirane ring / thiirane ring of 1/1, water / ethanol of 2/1 It is preferable to use a mixed solventNo.
[0022]
The reaction can be usually performed in a temperature range of 10 to 35 ° C., for example, at room temperature, for a reaction time of about 10 to 40 hours, for example, about 20 hours. The reaction atmosphere may be air or an inert atmosphere such as nitrogen.
[0023]
As a specific example of the production of the compound (A), taking a method of producing a compound (A) having a thiirane ring using a bisphenol A type epoxy resin as a starting material, according to a method represented by the following reaction formula: It can be carried out. Here, X is S or O.
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As the compound (B) having an oxirane ring in the molecule contained therein and not containing a thiirane ring, an epoxy compound exemplified as the epoxy compound used for obtaining the above-mentioned compound (A) is contained in the composition of the present invention. Are all available. Specifically, compounds in which the substituents Y in all the above formulas listed as specific examples of the compound (A) are oxirane rings represented by the above formula (2), or all Z are O Compounds are exemplified. n is 0 or a number greater than or equal to 0.
Among these, from the viewpoint of adhesiveness, a bifunctional epoxy compound having two oxirane rings in the molecule is preferable, and an aromatic bifunctional epoxy compound having two oxirane rings in the molecule is more preferable.
Similarly to the compound (A), the compound (B) may be a compound in which a hydrogen atom or another group in the molecule of the above-mentioned epoxy compound is partially substituted with a bromine atom from the viewpoint of imparting flame retardancy. More preferred.
[0025]
The composition of the present invention comprises a compound having only a thiirane ring.Things, A compound having both a thiirane ring and an oxirane ring(That is, compound (A))And both may be included,Compound (A)It may include only one. For example, it may be a combination of any of the following components.
(I)Compound(A)Composition containing only
(ii)Compound(A)And a composition comprising the compound (B)
(iii)Compound(A)Comprising: a compound having only a thiirane ring; and a compound (B)
In particular, in the present invention, when a composition expressing high adhesion is required,(ii)Are preferred.
[0026]
In the composition of the present invention, the content ratio of the oxirane ring / thiirane ring is, HardIn that both hydroxyl and mercapto groups can be generated at the time of polymerization, and a composition exhibiting high adhesion is obtained., 5In the range of 0/50 to 90/10.
[0027]
The composition of the present invention further contains at least one curing agent selected from the group consisting of compounds containing a hydroxyl group, a mercapto group, an amino group, or a carboxyl group. Examples of the curing agent include amine-based curing agents, carboxylic acid-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents, phenol resins, urea resins, melamine resins, and latent curing agents.
[0028]
In the composition of the present invention, the compound (A), or the compound (A) and the compound (B), and the curing agent are separately provided, and when used as an electric resin composition such as a sealing agent. Alternatively, the two components can be mixed at a predetermined ratio to prepare a two-part composition for preparing the composition. Further, the composition of the present invention is obtained by mixing the compound (A), or the compound (A) and the compound (B), with a latent curing agent that exerts a curing action by heating or pressurizing, to form a one-pack type composition. It can also be a thing.
[0029]
Specific examples of the amine-based curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, and 1,3,6-trisaminomethylhexane. Polyamine; polymethylenediamine such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, diaminodicyclohexylmethane Alicyclic polyamines such as, bisaminomethylcyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane; Aliphatic polyamines containing an aromatic ring such as taxylylenediamine, aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diaminodiethyldiphenylmethane, and 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraspiro [5.5] undecane and the like. Also, amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, cyanoethylated polyamines, ketimines which are reactants of aliphatic polyamines and ketones; linear diamines, tetramethylguanidine, triethanol Amine, piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino p-cresol, N, N'-dimethylpiperazine , Piperidine, 1,4-diazadicyclo (2,2,2) octane, 2,4,6-tris (dimethylaminomethyl) phenol, 1.8-diazabicyclo 5.4.0) undecene secondary amines such as -1 or tertiary amines, or dimer acid and diethylenetriamine and liquid polyamides obtained by reacting a polyamine such as triethylene tetramine.
[0030]
Specific examples of the carboxylic acid-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid.
[0031]
Specific examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.
[0032]
Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl- S-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine and the like.
[0033]
Specific examples of the polymercaptan-based curing agent include partial epoxy adducts of 2,2′-bismercaptoethyl ether, pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, and trimethylolpropane trithioglycolate. Compounds containing a mercapto group such as esters of thioglycolic acid and polysulfide rubbers having a mercapto group at the terminal are exemplified.
[0034]
Examples of the latent curing agent used for preparing the one-part curing agent include compounds such as n-hexylamine, monoethylamine, benzylamine, diethylamine, piperidine, triethylamine, and aniline, and boron trifluoride. Certain boron trifluoride-amine complexes; dicyandiamide, or derivatives of dicyandiamide such as o-tolylbiguanide, α-2,5-dimethylbiguanide, α, ω-diphenylbiguanide, 5-hydroxynaphthyl-1-biguanide; succinic hydrazide Acid hydrazides such as adipic hydrazide, isophthalic hydrazide, p-oxybenzoic hydrazide, salicylic hydrazide, phenylaminopropionic hydrazide; diaminomaleonitrile or derivatives thereof; melamine derivatives such as diallylmelamine; Amine imides synthesized from acid esters, dimethylhydrazine and epoxy compounds; salts of diamines such as ethylenediamine, hexamethylenediamine and piperidine with aliphatic dicarboxylic acids such as sebacic acid, and 2,4,4-trimethyl-2,4 And polyhydroxyphenols such as N, N'-dimethyl-1,3-propanediamine, phenylphosphonates of polyamines, phenylphosphates of polyamines, and the like. .
[0035]
In the composition of the present invention, the molar fraction of thiirane rings in the total of oxirane rings and thiirane rings (hereinafter referred to as thiirane content) was X, and the equivalent ratio of the curing agent to the total of oxirane rings and thiirane rings was Y. In this case, it is preferable that X and Y have the following relationship.
When 10% ≦ X <50% Y = (100−X) /100±0.2
X = 50%In the case of Y = 0.1 to 0.7
If the equivalent ratio of the curing agent is larger than this range, the conventional curing agent is expensive, so that the raw material cost increases, which is not preferable. If the equivalent ratio of the curing agent is smaller than this range, the curing reaction does not proceed sufficiently and the composition is not cured, resulting in poor adhesion.
In the composition of the present invention, the thiirane ring contained is chemically highly reactive, and -SH generated by ring-opening of the thiirane ring contributes to the curing reaction. Therefore, a compound containing only the oxirane ring is used. Compared with the case, the curability can be favorably maintained even if the amount of the curing agent used is smaller than that of the thiirane ring.
Where X is 50%soIs that the reactivity of the curing agent is saturated, and the curing reaction proceeds well if the equivalent ratio of the curing agent used is in the range of Y = 0.1 to 0.7 regardless of the value of X. When X is less than 50%, the curability is excellent if X and Y are in the above ranges. More preferably, Y is given by Y = (100−X) /100−0.1.
[0036]
Further, the composition of the present invention further contains a flame retardant.You.Examples of the flame retardant include phosphorus, antimony, halogen, aluminum, and magnesium. Specifically, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, tricresyl phosphate, diphenyl Cresyl phosphate, diphenyloctyl phosphate, trischloroethyl phosphate, tributyl phosphate, tris (dibromopropyl) phosphate, chloroalkyl phosphate, ammonium polyphosphate, chlorophosphonate, bromophosphonate, dimethyl methylphosphonate, ethane tetrabromide, chlorinated paraffin Chlorinated polyphenyl, antimony trioxide, antimony pentoxide, neopentyl bromide-polyether, brominated polyether and the like. These may be used alone or in combination of two or more.
As the combination of the compound (A), the compound (B) and the flame retardant, a combination of the compound (A) or the compound (B) with a halogenated epoxy compound and an antimony-based flame retardant may be used. It is preferable because high effect can be expected.
[0037]
The content of the flame retardant in the composition of the present invention is from 2 to 30 based on 100 parts by weight of the compound (A) or the compound (A) and the compound (B) from the viewpoint of imparting flame retardancy. It is preferably 5 parts by weight, more preferably 5 to 20 parts by weight.
[0038]
The composition of the present invention may contain a curing accelerator in addition to the curing agent. Examples of the curing accelerator include phosphites, phenols, tertiary amines, and the like. Among these, the composition of the present invention containing a phosphite is preferred because it does not cause thickening or other problems during storage.
[0039]
Examples of phosphites used include triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, and tris (tridecyl) phosphite. Phyte, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra phosphite, trilauryl trithi Ophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tristearylphos Aito, distearyl pentaerythritol diphosphite, tris (2,4-di -t - butyl phenyl) phosphite, hydrogenated bisphenol A · pentaerythritol phosphite triester such polymers. Further, di- or monoesters obtained by partially hydrolyzing these triesters can also be used. These may be used alone or in combination of two or more. Among these, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, hydrogenated bisphenol A. Pentaerythritol phosphite polymer and the like have a particularly high effect of accelerating curing and are preferably used.
[0040]
Examples of the tertiary amine include benzylmethylamine, triethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol, 1,8-diazabicyclo [5.4.0] undecene-1,1,4-diazabicyclo [2.2.2]. Octane and the like.
[0041]
In addition to the compound (A) or compound (B), the curing agent, and the flame retardant, various additives can be added to the composition of the present invention, if necessary. For example, a filler, a plasticizer, a thixotropy-imparting agent, an antioxidant, an antioxidant, an antistatic agent, an adhesion-imparting agent, a coloring agent, a dispersant, a solvent and the like can be blended.
[0042]
As the filler, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, Magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; limestone clay, kaolin clay, calcined clay; organic or inorganic fillers such as carbon black; and fatty acid, resin acid, and fatty acid ester-treated products thereof. Can be These may be used alone or in combination of two or more.
[0043]
Plasticizers include dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; Examples include propylene glycol adipate polyester and butylene glycol adipate polyester. These plasticizers may be used alone or in combination of two or more.
[0044]
Examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparone (manufactured by Kusumoto Kasei Co., Ltd.), calcium carbonate, Teflon, and the like. Examples thereof include ammonium salts and hydrophilic compounds such as polyglycol and ethylene oxide derivatives.
[0045]
Antioxidants include, for example, hindered phenol compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
[0046]
Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, azo pigments, and organic pigments such as copper phthalocyanine pigment. .
[0047]
Examples of the adhesion-imparting agent include a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, a xylene resin, and the like.
[0048]
In the composition of the present invention, the compound (A) as a main component contains at least one thiirane ring in the molecule, and the thiirane ring opens upon curing to generate a thiol group having a higher acidity than a hydroxyl group. Shows higher adhesive strength than conventional resin compositions for electrical applications such as conventional printed circuit board sealants and prepreg impregnated resins, and can exhibit fast curing properties because thiirane rings are more reactive than oxirane rings. Things. Although a cured product of an epoxy resin shows better insulation than before, the composition of the present invention can exhibit high insulation in a short time due to its fast curing property. Further, the composition of the present invention has a low odor.
Therefore, when a printed circuit board, a prepreg, or the like is manufactured using the composition of the present invention, the process time can be reduced due to the quick curing property, and the working environment can be favorably maintained because of low odor.
Also,The composition of the present invention contains a halogenated compound as the compound (A) and / or the compound (B), andContains flame retardantBecauseIt shows higher flame retardancy than conventional sealants for printed circuit boards and impregnated resins for prepregs, and is highly safe.
[0049]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
[0050]
Synthesis Example 1 of Compound Containing Thiirane Ring
121 g of potassium thiocyanate was dissolved in a mixed solvent of 75 ml of ethanol and 100 ml of water, and 85 g of bisphenol A diglycidyl ether was further added and left for 4 hours. Thereafter, 85 g of bisphenol A diglycidyl ether was further added, and the mixture was stirred vigorously at room temperature for 40 hours. Next, the reaction mixture was extracted with chloroform, washed with water, and dried over magnesium sulfate using magnesium sulfate. The chloroform was distilled off under reduced pressure and then dried under reduced pressure to obtain a reaction product.
The content ratio of oxirane ring / thiirane ring in the obtained reaction product was measured by NMR and found to be 55/45.
[0051]
According to this synthesis example, bisphenol A type epoxy resin (1) (manufactured by Sumitomo Chemical Co., Ltd., trade name: ELA-128) was used, and all or a part of the oxirane ring in the bisphenol A type epoxy resin (1) was used. Was substituted with a thiirane ring to produce a compound having a 50/50 oxirane ring / thiirane ring content (hereinafter referred to as a 50% modified thiirane of (1)).
[0052]
(Examples 1 to5, Comparative Examples 1 to3)
In each example, a composition was prepared according to the formulation shown in Table 1 and subjected to measurement of curability (tack-free time), insulation (volume resistance), adhesion (tensile shear strength), and flame retardancy. Table 1 shows the results.
[0053]
Curability
After the composition was prepared, it was left at 20 ° C. and the time until tack disappeared (tack free time) was measured.
Insulation
According to the method described in JIS K6911, measurement was performed by applying a voltage of 50 V for 1 minute. The sample was used for measurement after standing at room temperature for 3 days. The volume resistivity was determined and evaluated as insulation.
Adhesiveness
Two copper plates (JIS C1020) having dimensions of 100 mm × 25 mm × 2 mm are prepared, and are obtained in Examples and Comparative Examples in an area of 12.5 × 25 mm from the end of each steel sheet according to JIS K6850. A test piece is prepared by applying the composition thus prepared, and superposing and joining the portions where the composition of the two steel plate pieces has been applied. This test piece was subjected to a tensile shear test at a speed of 50 mm / min, and the peel strength was measured. Further, the same tensile shear test was performed on an aluminum plate (JIS A2024P).
Flame retardance
A 6-inch × 0.5-inch (1 mm-thick) copper-clad laminate impregnated with the compositions obtained in Examples and Comparative Examples was used as a test piece, and the major axis of the test piece was used in accordance with the UL standard vertical method. Was repeated vertically four times with the lower end on the flame for 10 seconds, and the time until the flame was extinguished was measured.
Table 1 shows the results.
[0054]
[Table 1]
【The invention's effect】
The resin composition for electric use according to the present invention is characterized in that the compound (A) as a main component contains at least one thiirane ring in the molecule, and the thiirane ring is opened at the time of curing to have a thiol group having a higher acidity than a hydroxyl group. To exhibit higher adhesiveness than conventional resin compositions for electrical use, such as sealing agents and prepreg impregnating resins, and exhibit fast curing properties because the thiirane ring is more reactive than the oxirane ring. . At the same time, a high insulating property is developed in a short time. Further, the composition of the present invention has low odor. Therefore, if the composition of the present invention is used as an electric resin, the production process time can be shortened, and the working environment can be favorably maintained.
Also,BookThe composition of the present invention is excellent in flame retardancy and greatly contributes to improvement of safety and reliability of electric and electronic products using the composition of the present invention.
Therefore, the electrical resin composition of the present invention is suitable as a sealing agent for printed circuit boards, an impregnating resin for prepreg, a casting resin such as a coil, a resist ink for printed circuit boards, a resin for printed circuit board copper-clad laminates, and the like. Used for
Claims (3)
水酸基、メルカプト基、アミノ基、もしくは、カルボキシル基を含む化合物からなる群より選ばれる少なくとも一種の硬化剤と、
前記化合物（Ａ）、または、該化合物（Ａ）および前記化合物（Ｂ）の合計量１００重量部に対し、２〜３０重量部の難燃剤とを含み、
オキシラン環／チイラン環の含有割合が９０／１０〜５０／５０であり、
前記化合物（Ａ）および／または前記化合物（Ｂ）としてハロゲン化化合物を含有する、電気用樹脂組成物。 Part of the oxirane ring of the epoxy compound is represented by the following formula (1):
Hydroxyl group, mercapto group, amino group, or at least one curing agent selected from the group consisting of compounds containing a carboxyl group ,
The compound (A) or a flame retardant of 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B),
An oxirane ring / thiirane ring content ratio of 90/10 to 50/50,
An electric resin composition containing a halogenated compound as the compound (A) and / or the compound (B) .
１０％≦Ｘ＜５０％の場合 Ｙ＝（１００−Ｘ）／１００±０．２
Ｘ＝５０％の場合 Ｙ＝０．１〜０．７When the molar ratio of the thiirane ring to the total of the oxirane ring and the thiirane ring is X, and when the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, X and Y have the following relationship. 2. The resin composition for electricity according to 1.
When 10% ≦ X <50% Y = (100−X) /100±0.2
When X = 50% Y = 0.1 to 0.7
Priority Applications (1)
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| JP01669698A JP3540926B2 (en) | 1998-01-29 | 1998-01-29 | Resin composition for electricity |
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| JP01669698A JP3540926B2 (en) | 1998-01-29 | 1998-01-29 | Resin composition for electricity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004142133A (en) * | 2002-10-22 | 2004-05-20 | Japan Epoxy Resin Kk | Laminates for electric laminates |
| JP4826728B2 (en) * | 2005-09-28 | 2011-11-30 | 株式会社スリーボンド | Thermosetting resin composition |
| JP7325207B2 (en) * | 2019-03-29 | 2023-08-14 | 株式会社Adeka | resin composition |
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