WO2023008183A1 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- WO2023008183A1 WO2023008183A1 PCT/JP2022/027449 JP2022027449W WO2023008183A1 WO 2023008183 A1 WO2023008183 A1 WO 2023008183A1 JP 2022027449 W JP2022027449 W JP 2022027449W WO 2023008183 A1 WO2023008183 A1 WO 2023008183A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- adhesive composition
- styrene
- acid
- composition according
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 229920001971 elastomer Polymers 0.000 claims abstract description 27
- 239000000806 elastomer Substances 0.000 claims abstract description 27
- -1 tertiary amine salt Chemical class 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 16
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 229920006132 styrene block copolymer Polymers 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 239000002313 adhesive film Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 3
- 125000000101 thioether group Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 150000003440 styrenes Chemical class 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000012790 adhesive layer Substances 0.000 description 11
- 239000007822 coupling agent Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012787 coverlay film Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 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 5
- 238000000034 method Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VXYDHPDQMSVQCU-UHFFFAOYSA-N 2-[4-cyano-4-(3-cyclopentyloxy-4-methoxyphenyl)piperidin-1-yl]-n-hydroxyacetamide Chemical compound COC1=CC=C(C2(CCN(CC(=O)NO)CC2)C#N)C=C1OC1CCCC1 VXYDHPDQMSVQCU-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-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
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- HVMHLMJYHBAOPL-UHFFFAOYSA-N 4-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propan-2-yl]-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1C(C)(C)C1CC2OC2CC1 HVMHLMJYHBAOPL-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
Definitions
- the present invention relates to an adhesive composition that has excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) and adhesiveness, and is suitable for manufacturing electronic components, particularly members related to flexible printed wiring boards (hereinafter referred to as FPC).
- FPC flexible printed wiring boards
- coverlay film a laminate with an adhesive layer called “coverlay film” is used in order to protect the wiring part when manufacturing the FPC. And it is also required to have strong adhesiveness to the base film.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive composition that has low dielectric properties and excellent adhesiveness between resin and metal.
- the present inventors have made intensive studies to solve the above problems, and found that (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized and (C) free of tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators.
- the present invention includes the following inventions.
- An adhesive composition containing the following (A) and (B) and not containing the following (C).
- (A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides;
- [4] (B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of [1] to [3] The adhesive composition described.
- X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .
- the adhesive composition of the present invention has low dielectric properties and excellent adhesion between resin and metal. Therefore, the adhesive composition of the present invention is suitably used for applications such as laminates with an adhesive layer (coverlay films, bonding sheets), resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like. be able to.
- the adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized.
- A an acid-modified styrene-based elastomer
- B an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized.
- the adhesive composition of the present invention uses, as a main component, a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer).
- a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer).
- methods for modifying a styrene-based elastomer include a method of grafting a styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
- styrene elastomers include styrene-butadiene block copolymers, styrene-ethylene propylene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS ), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and the like.
- SBS styrene-butadiene block copolymers
- SIS styrene-isoprene-styrene block copolymers
- SEBS styrene-ethylenebutylene-styrene block copolymer
- SEPS styrene-ethylenepropylene-styrene block copolymer
- styrene-based elastomers styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) are preferable from the viewpoint of adhesiveness and low dielectric properties.
- SEBS styrene-ethylenebutylene-styrene block copolymer
- SEPS styrene-ethylenepropylene-styrene block copolymer
- Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid.
- Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and fumaric anhydride. Among these unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, maleic acid, fumaric acid and maleic anhydride are preferred, and maleic anhydride is more preferred.
- the amount of modification with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides is usually about 0.1 to 10% by mass of the total acid-modified styrene elastomer.
- at least part of all the acid groups in the acid-modified elastomer are preferably acid anhydrides.
- the acid value of the acid-modified styrene-based elastomer is not particularly limited, but for example, the lower limit is 0.1 mg CH 3 ONa/g or more, preferably 0.5 mg CH 3 ONa/g or more, more preferably 1.0 mg CH 3 ONa/g or more. and the upper limit is 20 mg CH 3 ONa/g or less, preferably 18 mg CH 3 ONa/g or less, more preferably 15 mg CH 3 ONa/g or less.
- the molecular weight of the acid-modified styrene-based elastomer is, for example, a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably. is less than 200,000.
- the weight average molecular weight in the present invention is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).
- Examples of commercially available acid-modified styrene-based elastomers include the Tuftec M series manufactured by Asahi Kasei Corporation and the Kraton FG series manufactured by Kraton Polymer Japan.
- the above acid-modified styrene-based elastomers may be used alone, or two or more of them may be used in combination.
- Alicyclic epoxy resins are epoxy resins containing an alicyclic structure.
- the structure in which the unsaturated bond of the cyclic olefin structure is epoxidized includes a cycloalkane structure corresponding to the cyclic olefin structure and an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the cycloalkane structure. ,including.
- Cyclic olefin structures may be monocyclic or polycyclic.
- the cyclic olefin structure may have a substituent such as an alkyl group.
- Examples of the alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized include compounds represented by the following formulas (1) to (4).
- X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .
- Examples of the compound represented by the above formula (1) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), 2 , 2-bis(3,4-epoxycyclohexyl)propane, the following formula (1-1):
- alicyclic epoxy resins containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized include Celoxide 2021P, Celoxide 8010P, Celoxide 2081 from Daicel, Epolead GT401, and THI- from ENEOS. DE, DE-102, DE-103, Shin-Etsu Silicone Co., Ltd. X-40-2669, KR-470 and the like.
- the alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized may be used alone or in combination of two or more.
- the amount of (B) contained in the adhesive composition of the present invention is generally 0.1-50 parts by weight, preferably 0.4-30 parts by weight, more preferably 0.4-30 parts by weight, per 100 parts by weight of (A). 4 to 20 parts by weight, more preferably 0.4 to 4 parts by weight.
- the adhesive composition of the present invention contains (A) a thermoplastic resin other than the acid-modified styrene elastomer, a tackifier, a flame retardant, a coupling agent, and an antioxidant. , a filler and (D) an organic solvent.
- thermoplastic resins examples include styrene-based elastomers containing no acid anhydride groups, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene-based resins, and polypropylene-based resins. Examples thereof include resins and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
- tackifiers examples include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
- Examples of the flame retardant include organic flame retardants and inorganic flame retardants.
- Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate.
- inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, oxide Metal oxides such as zinc, molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants may be used alone or in combination of two or more.
- the coupling agent examples include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane-based coupling agents such as imidazole silane; titanate-based coupling agents; aluminate-based coupling agents; and zirconium-based coupling agents. These coupling agents may be used alone or in combination of two or more.
- antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate , tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, tri Phenolic antioxidants such as ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3' - sulfur-based antioxidants such as dithiopropionate; may be used alone or in combination of two or more.
- filler examples include polyacrylate powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as multi-layered core shells using silicone, acrylic, styrene-butadiene rubber, butadiene rubber, etc.
- Polymer filler silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate , sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Inorganic fillers such as nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate. These fillers may be used alone or in combination of two or more. As for the shape, for example, spherical, powdery, fibrous, needle-like, scale-like, etc. can be used.
- Examples of the organic solvent (D) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cyclohexane, methylcyclohexane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tetrahydrofuran.
- N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, dioxane, cyclopentyl methyl ether, methylene chloride, chloroform, 1 , 2-dichloroethane, ⁇ -butyrolactone, cellosolve, butyl cellosolve, carbitol, butyl carbitol and the like.
- These organic solvents may be used alone or in combination of two or more.
- the adhesive composition of the present invention includes, for example, light stabilizers, weather stabilizers, stabilizers such as heat stabilizers, leveling agents, anionic and cationic stabilizers such as antifoaming agents. , nonionic surfactants, dyes, pigments, plasticizers and the like can also be contained to such an extent that the functions of the adhesive composition are not affected.
- the adhesive composition of the present invention is usually used for the purpose of promoting the reaction between the elastomer and the epoxy resin, as is clear from the comparison with the examples and comparative examples of Patent Document 1.
- (C) Does not contain tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators (so-called curing accelerators). By not containing these, excellent adhesiveness is exhibited as shown in the section of Examples described later.
- tertiary amines examples include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N-dimethyl piperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like.
- tertiary amine salts include the formate, ethylhexanoate, octylate, p-toluenesulfonate, o-phthalate of 1,8-diazabicyclo[5.4.0]undecene.
- phenol salts or phenol novolac resin salts and 1,5-diazabicyclo[4.3.0]nonene formates, ethylhexanoates, octylates, p-toluenesulfonates, o-phthalates. , phenol salts, phenol novolac resin salts, and the like.
- imidazoles examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4- Diamino-6-[2-undecylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]ethyl-s-triazine, 2 , 4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine isocyanurate,
- the adhesive composition of the present invention comprises (A) an acid-modified styrene elastomer, (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized, and other components as necessary. It can be manufactured by mixing. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution (hereinafter referred to as a liquid adhesive composition), the (D) organic solvent is also usually used. By using a liquid adhesive composition, when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
- a liquid adhesive composition when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
- the solid content concentration is, for example, 3 to 80% by weight, preferably 10 to 50% by weight, more preferably 20 to 20% by weight, from the viewpoint of workability including formation of an adhesive layer. 35% by weight.
- the adhesive composition of the present invention has low dielectric properties and excellent adhesiveness between resin and metal, it can be suitably used as an adhesive (e.g., adhesive film, etc.) for manufacturing FPC-related members.
- an adhesive e.g., adhesive film, etc.
- FPC-related members in the present invention include coverlay films, bonding sheets, resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like.
- the adhesive layer being in a B-stage state refers to a semi-cured state in which a part of the adhesive composition has begun to cure, and curing of the adhesive composition further progresses by heating or the like. is in a state to
- Examples 1 to 7, Comparative Examples 1 to 6 Each component was added to a 1000 ml flask equipped with a stirrer in the proportions (parts by weight) shown in Table 1 or Table 2, and dispersed by stirring at room temperature for 6 hours to prepare an adhesive composition. Using the obtained adhesive composition, each physical property was measured by the following methods. The obtained results are shown in Table 1 or Table 2.
- Dielectric Constant, Dielectric Loss Tangent A release-treated glass plate was prepared, and the adhesive composition prepared as described above was applied so that the thickness after drying was 100 ⁇ m. Next, the coated glass plate is placed in an oven and dried at 100° C. for 10 minutes to form a B-stage adhesive layer (thickness: 100 ⁇ m). It was left to stand inside and subjected to heat curing treatment at 160° C. for 60 minutes to prepare a test piece. The dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece at a measurement temperature of 25° C. and a measurement frequency of 10 GHz were obtained by the cavity resonator method using a dielectric constant measuring device manufactured by AET Corporation.
- Dk dielectric constant
- Df dielectric loss tangent
- a flexible copper-clad laminate was obtained by thermocompression bonding under these conditions for 60 minutes. Cut this flexible copper-clad laminate into a width of 10 mm x length of 100 mm, and use an Autograph AGS-500 manufactured by Shimadzu Corporation to measure the peel adhesion strength in the 90 ° direction (direction perpendicular to the plane direction of the laminate) as follows. was measured under the measurement conditions of The measurement conditions were a test speed of 50 mm/min.
- each component in Table 1 and Table 2 is as follows.
- B-1 Celoxide 2021P (3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
- B-2) Celoxide 8010P (4,4′-bis(1,2-epoxycyclohexane), manufactured by Daicel Corporation)
- B-3 DE-103 (compound represented by the above formula (4), manufactured by Eneos)
- C-1 U-CAT SA102 (manufactured by San-Apro, tertiary amine salts, 2-ethylhexanoate of DBU)
- C-2 San-Aid 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic sulfonium salt)
- C-3 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)
- D Toluene
- E HP-7200L (glycidyl ether type epoxy resin, manufactured by DIC Corporation)
- F Tuftec H1041 (acid-unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Provided is an adhesive composition that: includes (A) an acid-modified styrene elastomer and (B) an alicyclic epoxy resin that includes a structure formed by epoxidation of the unsaturated bond of a cyclic olefin structure; but does not include (C) a tertiary amine, a tertiary amine salt, an imidazole, or a cationic polymerization initiator.
Description
本発明は、低誘電特性(低誘電率、低誘電正接)及び接着性に優れ、電子部品、特にフレキシブルプリント配線板(以下、FPC)の関連部材の製造に適した接着剤組成物に関する。
The present invention relates to an adhesive composition that has excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) and adhesiveness, and is suitable for manufacturing electronic components, particularly members related to flexible printed wiring boards (hereinafter referred to as FPC).
近年、スマートフォンやモバイルパソコンなど無線通信技術の進展に伴って大容量の情報を高速で処理することが要求され、伝送信号の高周波化が進展している。高周波化に伴い、無線通信デバイスの構成要素の1つであるFPC及びその関連部材にも高周波帯域での低誘電特性(低誘電率、低誘電正接)が求められている(例えば、国際公開第2016/017473号(特許文献1))。
In recent years, with the progress of wireless communication technology such as smartphones and mobile personal computers, there is a demand for high-speed processing of large amounts of information, and transmission signals are becoming higher frequency. With the increase in frequency, low dielectric properties (low dielectric constant, low dielectric loss tangent) in high frequency bands are required for FPC and its related members, which are one of the components of wireless communication devices (for example, International Publication No. 2016/017473 (Patent Document 1)).
また、上記関連部材として、例えば、FPCを製造する際に配線部分を保護するために、「カバーレイフィルム」と呼ばれる接着剤層付き積層体が用いられるが、該接着剤層には、配線部分及び基材フィルムに対して強固な接着性を有することも求められている。
Further, as the related member, for example, a laminate with an adhesive layer called "coverlay film" is used in order to protect the wiring part when manufacturing the FPC. And it is also required to have strong adhesiveness to the base film.
本発明は、このような事情に鑑み為されたものであって、低誘電特性及び樹脂と金属との接着性に優れる接着剤組成物を提供することを目的とする。
The present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive composition that has low dielectric properties and excellent adhesiveness between resin and metal.
本発明者らは、上記課題を解決するために鋭意検討した結果、(A)酸変性スチレン系エラストマー及び(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂を含み、且つ(C)第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤を含まない接着剤組成物によれば、上記課題が解決可能であることを見出した。具体的には、本発明は以下の発明を含む。
The present inventors have made intensive studies to solve the above problems, and found that (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized and (C) free of tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators. Specifically, the present invention includes the following inventions.
〔1〕
下記(A)及び(B)を含み、且つ下記(C)を含まない、接着剤組成物。
(A)酸変性スチレン系エラストマー
(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂
(C)第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤 [1]
An adhesive composition containing the following (A) and (B) and not containing the following (C).
(A) Acid-modified styrene elastomer (B) Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized (C) Tertiary amines, tertiary amine salts, imidazoles and cations polymerization initiator
下記(A)及び(B)を含み、且つ下記(C)を含まない、接着剤組成物。
(A)酸変性スチレン系エラストマー
(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂
(C)第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤 [1]
An adhesive composition containing the following (A) and (B) and not containing the following (C).
(A) Acid-modified styrene elastomer (B) Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized (C) Tertiary amines, tertiary amine salts, imidazoles and cations polymerization initiator
〔2〕
(A)100重量部に対し、(B)を0.1~50重量部含有する、〔1〕に記載の接着剤組成物。 [2]
The adhesive composition according to [1], which contains 0.1 to 50 parts by weight of (B) per 100 parts by weight of (A).
(A)100重量部に対し、(B)を0.1~50重量部含有する、〔1〕に記載の接着剤組成物。 [2]
The adhesive composition according to [1], which contains 0.1 to 50 parts by weight of (B) per 100 parts by weight of (A).
〔3〕
(A)が、スチレン-エチレンブチレン-スチレンブロック共重合体及びスチレン-エチレンプロピレンブロック共重合体からなる群より選択される少なくとも1種のスチレン系エラストマーを不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種によりで変性したものである、〔1〕又は〔2〕に記載の接着剤組成物。 [3]
(A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; The adhesive composition according to [1] or [2], which is modified with at least one selected from the group consisting of:
(A)が、スチレン-エチレンブチレン-スチレンブロック共重合体及びスチレン-エチレンプロピレンブロック共重合体からなる群より選択される少なくとも1種のスチレン系エラストマーを不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種によりで変性したものである、〔1〕又は〔2〕に記載の接着剤組成物。 [3]
(A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; The adhesive composition according to [1] or [2], which is modified with at least one selected from the group consisting of:
〔4〕
(B)が、下記式(1)~(4)で表される化合物からなる群から選ばれる少なくとも1種の脂環式エポキシ樹脂である、〔1〕~〔3〕のいずれか一項に記載の接着剤組成物。 [4]
(B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of [1] to [3] The adhesive composition described.
(B)が、下記式(1)~(4)で表される化合物からなる群から選ばれる少なくとも1種の脂環式エポキシ樹脂である、〔1〕~〔3〕のいずれか一項に記載の接着剤組成物。 [4]
(B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of [1] to [3] The adhesive composition described.
(上記式(1)におけるXは、単結合、又は2価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。)
(X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
〔5〕
更に、(D)有機溶媒を含む、〔1〕~〔4〕のいずれか一項に記載の接着剤組成物。 [5]
The adhesive composition according to any one of [1] to [4], further comprising (D) an organic solvent.
更に、(D)有機溶媒を含む、〔1〕~〔4〕のいずれか一項に記載の接着剤組成物。 [5]
The adhesive composition according to any one of [1] to [4], further comprising (D) an organic solvent.
〔6〕
〔1〕~〔5〕のいずれか一項に記載の接着剤組成物を用いてなる接着フィルム。 [6]
An adhesive film using the adhesive composition according to any one of [1] to [5].
〔1〕~〔5〕のいずれか一項に記載の接着剤組成物を用いてなる接着フィルム。 [6]
An adhesive film using the adhesive composition according to any one of [1] to [5].
本発明の接着剤組成物は、低誘電特性及び樹脂と金属との接着性に優れる。そのため、本発明の接着剤組成物は、例えば、接着剤層付き積層体(カバーレイフィルム、ボンディングシート)、樹脂付き銅箔、フレキシブル銅張積層板、及びフレキシブルフラットケーブル等の用途に好適に用いることができる。
The adhesive composition of the present invention has low dielectric properties and excellent adhesion between resin and metal. Therefore, the adhesive composition of the present invention is suitably used for applications such as laminates with an adhesive layer (coverlay films, bonding sheets), resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like. be able to.
以下、本発明について詳細に記載する。なお、本発明は以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。
The present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
<本発明の接着剤組成物>
本発明の接着剤組成物は、(A)酸変性スチレン系エラストマー及び(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂を含む。以下、上記(A)及び(B)について、具体的に説明する。 <Adhesive composition of the present invention>
The adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized. The above (A) and (B) will be specifically described below.
本発明の接着剤組成物は、(A)酸変性スチレン系エラストマー及び(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂を含む。以下、上記(A)及び(B)について、具体的に説明する。 <Adhesive composition of the present invention>
The adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized. The above (A) and (B) will be specifically described below.
[(A)酸変性スチレン系エラストマー]
本発明の接着剤組成物は、主成分として、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種により変性したスチレン系エラストマー(酸変性スチレン系エラストマー)を用いる。スチレン系エラストマーを変性する方法としては、例えば、スチレン系エラストマーと不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種とをグラフト化反応させる方法等が挙げられる。 [(A) Acid-modified styrene-based elastomer]
The adhesive composition of the present invention uses, as a main component, a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer). Examples of methods for modifying a styrene-based elastomer include a method of grafting a styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
本発明の接着剤組成物は、主成分として、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種により変性したスチレン系エラストマー(酸変性スチレン系エラストマー)を用いる。スチレン系エラストマーを変性する方法としては、例えば、スチレン系エラストマーと不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種とをグラフト化反応させる方法等が挙げられる。 [(A) Acid-modified styrene-based elastomer]
The adhesive composition of the present invention uses, as a main component, a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer). Examples of methods for modifying a styrene-based elastomer include a method of grafting a styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
スチレン系エラストマーの具体例としては、スチレン-ブタジエンブロック共重合体、スチレン-エチレンプロピレンブロック共重合体、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-イソプレン-スチレンブロック共重合体(SIS)、スチレン-エチレンブチレン-スチレンブロック共重合体(SEBS)、スチレン-エチレンプロピレン-スチレンブロック共重合体(SEPS)等が挙げられる。これらスチレン系エラストマーの中でも、接着性と低誘電特性の観点から、スチレン-エチレンブチレン-スチレンブロック共重合体(SEBS)、スチレン-エチレンプロピレン-スチレンブロック共重合体(SEPS)が好ましい。
Specific examples of styrene elastomers include styrene-butadiene block copolymers, styrene-ethylene propylene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS ), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and the like. Among these styrene-based elastomers, styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) are preferable from the viewpoint of adhesiveness and low dielectric properties.
不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸等が挙げられる。不飽和カルボン酸無水物としては、例えば、無水マレイン酸、無水イタコン酸、無水フマル酸等が挙げられる。これら不飽和カルボン酸及び不飽和カルボン酸無水物の中でも、マレイン酸、フマル酸、無水マレイン酸が好ましく、無水マレイン酸がより好ましい。不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種による変性量は、通常、酸変性スチレン系エラストマー全体の0.1~10質量%程度である。また、酸変性スチレン系エラストマーは、該酸変性エラストマー中の全酸性基の少なくとも一部が酸無水物であることが好ましい。
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and fumaric anhydride. Among these unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, maleic acid, fumaric acid and maleic anhydride are preferred, and maleic anhydride is more preferred. The amount of modification with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides is usually about 0.1 to 10% by mass of the total acid-modified styrene elastomer. Moreover, in the acid-modified styrene-based elastomer, at least part of all the acid groups in the acid-modified elastomer are preferably acid anhydrides.
酸変性スチレン系エラストマーの酸価は特に限定されないが、例えば、下限が0.1mgCH3ONa/g以上、好ましくは0.5mgCH3ONa/g以上、より好ましくは1.0mgCH3ONa/g以上であり、上限が20mgCH3ONa/g以下、好ましくは18mgCH3ONa/g以下、より好ましくは15mgCH3ONa/g以下である。
The acid value of the acid-modified styrene-based elastomer is not particularly limited, but for example, the lower limit is 0.1 mg CH 3 ONa/g or more, preferably 0.5 mg CH 3 ONa/g or more, more preferably 1.0 mg CH 3 ONa/g or more. and the upper limit is 20 mg CH 3 ONa/g or less, preferably 18 mg CH 3 ONa/g or less, more preferably 15 mg CH 3 ONa/g or less.
酸変性スチレン系エラストマーの分子量は、例えば、重量平均分子量で1万以上、好ましくは3万以上、より好ましくは5万以上であり、また、例えば、50万以下、好ましくは30万以下、より好ましくは20万以下である。なお、本発明における重量平均分子量とは、ゲル・パーミエーションクロマトグラフィー(GPC)により測定したポリスチレン換算の分子量である。
The molecular weight of the acid-modified styrene-based elastomer is, for example, a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably. is less than 200,000. In addition, the weight average molecular weight in the present invention is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).
酸変性スチレン系エラストマーの市販品としては、例えば、旭化成社製のタフテックMシリーズや、クレイトンポリマージャパン社製のクレイトンFGシリーズ等が挙げられる。
Examples of commercially available acid-modified styrene-based elastomers include the Tuftec M series manufactured by Asahi Kasei Corporation and the Kraton FG series manufactured by Kraton Polymer Japan.
本発明において、上記した酸変性スチレン系エラストマーは、単独で用いてもよく、2種以上を併用してもよい。
In the present invention, the above acid-modified styrene-based elastomers may be used alone, or two or more of them may be used in combination.
[(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂]
脂環式エポキシ樹脂は、脂環構造を含むエポキシ樹脂である。環状オレフィン構造の不飽和結合がエポキシ化された構造は、環状オレフィン構造に対応するシクロアルカン構造と、前記シクロアルカン構造を構成する隣接する2つの炭素原子と酸素原子とで構成されたエポキシ基と、を含む。環状オレフィン構造は単環式でも多環式でもよい。環状オレフィン構造は、アルキル基等の置換基を有していてもよい。環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂としては、例えば、下記式(1)~(4)で表される化合物等が挙げられる。 [(B) Alicyclic Epoxy Resin Containing Structure in which Unsaturated Bond of Cyclic Olefin Structure is Epoxidized]
Alicyclic epoxy resins are epoxy resins containing an alicyclic structure. The structure in which the unsaturated bond of the cyclic olefin structure is epoxidized includes a cycloalkane structure corresponding to the cyclic olefin structure and an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the cycloalkane structure. ,including. Cyclic olefin structures may be monocyclic or polycyclic. The cyclic olefin structure may have a substituent such as an alkyl group. Examples of the alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized include compounds represented by the following formulas (1) to (4).
脂環式エポキシ樹脂は、脂環構造を含むエポキシ樹脂である。環状オレフィン構造の不飽和結合がエポキシ化された構造は、環状オレフィン構造に対応するシクロアルカン構造と、前記シクロアルカン構造を構成する隣接する2つの炭素原子と酸素原子とで構成されたエポキシ基と、を含む。環状オレフィン構造は単環式でも多環式でもよい。環状オレフィン構造は、アルキル基等の置換基を有していてもよい。環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂としては、例えば、下記式(1)~(4)で表される化合物等が挙げられる。 [(B) Alicyclic Epoxy Resin Containing Structure in which Unsaturated Bond of Cyclic Olefin Structure is Epoxidized]
Alicyclic epoxy resins are epoxy resins containing an alicyclic structure. The structure in which the unsaturated bond of the cyclic olefin structure is epoxidized includes a cycloalkane structure corresponding to the cyclic olefin structure and an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the cycloalkane structure. ,including. Cyclic olefin structures may be monocyclic or polycyclic. The cyclic olefin structure may have a substituent such as an alkyl group. Examples of the alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized include compounds represented by the following formulas (1) to (4).
(上記式(1)におけるXは、単結合、又は2価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。)
(X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
上記式(1)で表される化合物としては、例えば、3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、4,4’-ビス(1,2-エポキシシクロヘキサン)、2,2-ビス(3,4-エポキシシクロヘキシル)プロパン、以下式(1-1):
Examples of the compound represented by the above formula (1) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), 2 , 2-bis(3,4-epoxycyclohexyl)propane, the following formula (1-1):
これら環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂の中でも、3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、4,4’-ビス(1,2-エポキシシクロヘキサン)、上記式(1-1)で表される化合物、上記式(2)で表される化合物、上記式(3)で表される化合物、上記式(4)で表される化合物が好ましい。
Among these alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4′-bis( 1,2-epoxycyclohexane), a compound represented by the above formula (1-1), a compound represented by the above formula (2), a compound represented by the above formula (3), a compound represented by the above formula (4) are preferred.
また、環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂の市販品としては、例えば、ダイセル社のセロキサイド2021P、セロキサイド8010P、セロキサイド2081、エポリードGT401、ENEOS社のTHI-DE、DE-102、DE-103、信越シリコーン社のX-40-2669、KR-470等が挙げられる。
Commercially available alicyclic epoxy resins containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized include Celoxide 2021P, Celoxide 8010P, Celoxide 2081 from Daicel, Epolead GT401, and THI- from ENEOS. DE, DE-102, DE-103, Shin-Etsu Silicone Co., Ltd. X-40-2669, KR-470 and the like.
本発明において、上記した環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂は、単独で用いても、2種以上を併用してもよい。
In the present invention, the alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized may be used alone or in combination of two or more.
本発明の接着剤組成物に含まれる(B)の量は、(A)100重量部に対し、通常0.1~50重量部、好ましくは0.4~30重量部、より好ましくは0.4~20重量部、更に好ましくは0.4~4重量部である。
The amount of (B) contained in the adhesive composition of the present invention is generally 0.1-50 parts by weight, preferably 0.4-30 parts by weight, more preferably 0.4-30 parts by weight, per 100 parts by weight of (A). 4 to 20 parts by weight, more preferably 0.4 to 4 parts by weight.
[その他の成分]
本発明の接着剤組成物は、上記(A)及び(B)の他、(A)酸変性スチレン系エラストマー以外の他の熱可塑性樹脂、粘着付与剤、難燃剤、カップリング剤、酸化防止剤、フィラー及び(D)有機溶媒等を含有することができる。 [Other ingredients]
In addition to the above (A) and (B), the adhesive composition of the present invention contains (A) a thermoplastic resin other than the acid-modified styrene elastomer, a tackifier, a flame retardant, a coupling agent, and an antioxidant. , a filler and (D) an organic solvent.
本発明の接着剤組成物は、上記(A)及び(B)の他、(A)酸変性スチレン系エラストマー以外の他の熱可塑性樹脂、粘着付与剤、難燃剤、カップリング剤、酸化防止剤、フィラー及び(D)有機溶媒等を含有することができる。 [Other ingredients]
In addition to the above (A) and (B), the adhesive composition of the present invention contains (A) a thermoplastic resin other than the acid-modified styrene elastomer, a tackifier, a flame retardant, a coupling agent, and an antioxidant. , a filler and (D) an organic solvent.
上記他の熱可塑性樹脂としては、例えば、酸無水物基を含有しないスチレン系エラストマー、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキシド樹脂、ポリウレタン樹脂、ポリアセタール樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂及びポリビニル系樹脂等が挙げられる。これらの熱可塑性樹脂は、単独で用いてもよく、2種以上を併用してもよい。
Examples of the other thermoplastic resins include styrene-based elastomers containing no acid anhydride groups, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene-based resins, and polypropylene-based resins. Examples thereof include resins and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
上記粘着付与剤としては、例えば、クマロン-インデン樹脂、テルペン樹脂、テルペン-フェノール樹脂、ロジン樹脂、p-t-ブチルフェノール-アセチレン樹脂、フェノール-ホルムアルデヒド樹脂、キシレン-ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、テレピン系樹脂等が挙げられる。これらの粘着付与剤は、単独で用いてもよいし、2種以上を併用してもよい。
Examples of the tackifier include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
上記難燃剤としては、例えば、有機系難燃剤、無機系難燃剤等が挙げられる。有機系難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート、トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタン等のリン系難燃剤;メラミン、メラム、メラミンシアヌレート等のトリアジン系化合物や、シアヌル酸化合物、イソシアヌル酸化合物、トリアゾール系化合物、テトラゾール化合物、ジアゾ化合物、尿素等の窒素系難燃剤;シリコーン化合物、シラン化合物等のケイ素系難燃剤等が挙げられる。また、無機系難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム等の金属水酸化物;酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化ニッケル等の金属酸化物;炭酸亜鉛、炭酸マグネシウム、炭酸バリウム、ホウ酸亜鉛、水和ガラス等が挙げられる。これらの難燃剤は、単独で用いてもよく、2種以上を併用してもよい。
Examples of the flame retardant include organic flame retardants and inorganic flame retardants. Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. , aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , Titanyl bismethylethylphosphinate, Titanium tetrakismethylethylphosphinate, Titanyl bisdiphenylphosphinate, Titanium tetrakisdiphenylphosphinate, etc.; , isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea, and other nitrogen-based flame retardants; silicone compounds, silane compounds, and other silicon-based flame retardants. Examples of inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, oxide Metal oxides such as zinc, molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants may be used alone or in combination of two or more.
上記カップリング剤としては、例えば、ビニルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトシキシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリエトキシシラン、イミダゾールシラン等のシラン系カップリング剤;チタネート系カップリング剤;アルミネート系カップリング剤;ジルコニウム系カップリング剤等が挙げられる。これらカップリング剤は、単独で用いてもよく、2種以上を併用してもよい。
Examples of the coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane-based coupling agents such as imidazole silane; titanate-based coupling agents; aluminate-based coupling agents; and zirconium-based coupling agents. These coupling agents may be used alone or in combination of two or more.
上記酸化防止剤としては、例えば、2,6-ジ-tert-ブチル-4-メチルフェノール、n-オクタデシル-3-(3’,5’-ジ-tert-ブチル-4’-ヒドロキシフェニル)プロピオネート、テトラキス〔メチレン-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート〕メタン、ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェノール、トリエチレングリコール-ビス〔3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート等のフェノール系酸化防止剤;ジラウリル-3,3’-チオジプロピオネート、ジミリスチル-3,3’-ジチオプロピオネート等のイオウ系酸化防止剤;トリスノニルフェニルホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト等のリン系酸化防止剤等が挙げられる。これら酸化防止剤は、単独で用いてもよく、2種以上を併用してもよい。
Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate , tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, tri Phenolic antioxidants such as ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3' - sulfur-based antioxidants such as dithiopropionate; may be used alone or in combination of two or more.
上記フィラーとしては、例えば、ポリアクリル酸エステル粉末、エポキシ樹脂粉末、ポリアミド粉末、ポリウレタン粉末、ポリシロキサン粉末等の他、シリコーン、アクリル、スチレンブタジエンゴム、ブタジエンゴム等を用いた多層構造のコアシェル等の高分子フィラー;シリカ、マイカ、タルク、カオリン、クレー、ハイドロタルサイト、ウォラストナイト、ゾノトライト、窒化ケイ素、窒化ホウ素、窒化アルミニウム、リン酸水素カルシウム、リン酸カルシウム、ガラスフレーク、水和ガラス、チタン酸カルシウム、セピオライト、硫酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム、酸化チタン、酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化アンチモン、酸化ニッケル、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、ホウ酸亜鉛、ホウ酸アルミニウム等の無機フィラー等が挙げられる。これらフィラーは、単独で用いてもよく、2種以上を併用してもよい。また、形状としては、例えば、球状、粉状、繊維状、針状、鱗片状等を用いることができる。
Examples of the filler include polyacrylate powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as multi-layered core shells using silicone, acrylic, styrene-butadiene rubber, butadiene rubber, etc. Polymer filler; silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate , sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Inorganic fillers such as nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate. These fillers may be used alone or in combination of two or more. As for the shape, for example, spherical, powdery, fibrous, needle-like, scale-like, etc. can be used.
上記(D)有機溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、シクロヘキサン、メチルシクロヘキサン、トルエン、キシレン、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、テトラヒドロフラン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、ジメチルスルホキサイド、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールジメチルエーテル、ジオキサン、シクロペンチルメチルエーテル、塩化メチレン、クロロホルム、1,2-ジクロロエタン、γ-ブチロラクトン、セロソルブ、ブチルセロソルブ、カルビトール、ブチルカルビトール等が挙げられる。これらの有機溶媒は、単独で用いてもよく、2種以上を併用してもよい。
Examples of the organic solvent (D) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cyclohexane, methylcyclohexane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tetrahydrofuran. , N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, dioxane, cyclopentyl methyl ether, methylene chloride, chloroform, 1 , 2-dichloroethane, γ-butyrolactone, cellosolve, butyl cellosolve, carbitol, butyl carbitol and the like. These organic solvents may be used alone or in combination of two or more.
また、本発明の接着剤組成物は、上記したその他の成分の他、例えば、耐光安定剤、耐候安定剤、熱安定剤等の安定剤、レベリング剤、消泡剤等のアニオン系、カチオン系、ノニオン系の界面活性剤、染料、顔料、可塑剤等も、接着剤組成物の機能に影響を与えない程度に含有することができる。
In addition to the above-described other components, the adhesive composition of the present invention includes, for example, light stabilizers, weather stabilizers, stabilizers such as heat stabilizers, leveling agents, anionic and cationic stabilizers such as antifoaming agents. , nonionic surfactants, dyes, pigments, plasticizers and the like can also be contained to such an extent that the functions of the adhesive composition are not affected.
なお、本発明の接着剤組成物は、例えば、特許文献1の各実施例及び比較例との対比からも明らかな通り、通常、エラストマーとエポキシ樹脂との反応を促進させる目的で使用される、(C)第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤(所謂、硬化促進剤)を含まない。これらを含まないことにより、後述する実施例の項にて示す通り、優れた接着性を示す。
The adhesive composition of the present invention is usually used for the purpose of promoting the reaction between the elastomer and the epoxy resin, as is clear from the comparison with the examples and comparative examples of Patent Document 1. (C) Does not contain tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators (so-called curing accelerators). By not containing these, excellent adhesiveness is exhibited as shown in the section of Examples described later.
第三級アミン類の例としては、ベンジルジメチルアミン、2-(ジメチルアミノメチル)フェノール、2,4,6-トリス(ジメチルアミノメチル)フェノール、テトラメチルグアニジン、トリエタノールアミン、N,N-ジメチルピペラジン、トリエチレンジアミン、1,8-ジアザビシクロ[5.4.0]ウンデセン等が挙げられる。第三級アミン塩類の例としては、1,8-ジアザビシクロ[5.4.0]ウンデセンの、ギ酸塩、エチルへキサン酸塩、オクチル酸塩、p-トルエンスルホン酸塩、o-フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩や、1,5-ジアザビシクロ[4.3.0]ノネンの、ギ酸塩、エチルへキサン酸塩、オクチル酸塩、p-トルエンスルホン酸塩、o-フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩等が挙げられる。イミダゾール類の例としては、2-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、1,2-ジメチルイミダゾール、2-メチル-4-エチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、2,4-ジアミノ-6-[2-メチルイミダゾリル-(1)]エチル-s-トリアジン、2,4-ジアミノ-6-[2-ウンデシルイミダゾリル-(1)]エチル-s-トリアジン、2,4-ジアミノ-6-[2-エチル-4-メチルイミダゾリル-(1)]エチル-s-トリアジン、2,4-ジアミノ-6-[2-メチルイミダゾリル-(1)]エチル-s-トリアジンイソシアヌル酸付加物、2-フェニルイミダゾールイソシアヌル酸付加物、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等が挙げられる。カチオン重合開始剤の例としては、芳香族ヨードニウム塩、芳香族スルホニウム塩等が挙げられる。
Examples of tertiary amines include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N-dimethyl piperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like. Examples of tertiary amine salts include the formate, ethylhexanoate, octylate, p-toluenesulfonate, o-phthalate of 1,8-diazabicyclo[5.4.0]undecene. , phenol salts or phenol novolac resin salts, and 1,5-diazabicyclo[4.3.0]nonene formates, ethylhexanoates, octylates, p-toluenesulfonates, o-phthalates. , phenol salts, phenol novolac resin salts, and the like. Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4- Diamino-6-[2-undecylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]ethyl-s-triazine, 2 , 4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- phenyl-4-methyl-5-hydroxymethylimidazole and the like. Examples of cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts and the like.
本発明の接着剤組成物は、(A)酸変性スチレン系エラストマー、(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂、及び必要に応じてその他成分を混合することにより製造することができる。混合方法は特に限定されず、接着剤組成物が均一になればよい。接着剤組成物は、溶液の状態(以下、液状の接着剤組成物と称する。)で好ましく用いられることから、通常は、上記(D)有機溶媒も使用される。液状の接着剤組成物とすることにより、FPC関連部材を製造する際に、基材フィルムへの塗工及び接着剤層の形成を円滑に行うことができ、所望の厚さの接着剤層をより容易に得ることができる。
The adhesive composition of the present invention comprises (A) an acid-modified styrene elastomer, (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized, and other components as necessary. It can be manufactured by mixing. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution (hereinafter referred to as a liquid adhesive composition), the (D) organic solvent is also usually used. By using a liquid adhesive composition, when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
液状の接着剤組成物とする場合、接着剤層の形成を含む作業性等の観点から、固形分濃度は、例えば、3~80重量%、好ましくは10~50重量%、より好ましくは20~35重量%である。
When a liquid adhesive composition is used, the solid content concentration is, for example, 3 to 80% by weight, preferably 10 to 50% by weight, more preferably 20 to 20% by weight, from the viewpoint of workability including formation of an adhesive layer. 35% by weight.
<用途>
本発明における接着剤組成物は、低誘電特性及び樹脂と金属との接着性に優れることから、FPCの関連部材を製造するための接着剤(例えば、接着フィルム等)として好適に用いることができる。本発明におけるFPCの関連部材としては、例えば、カバーレイフィルム、ボンディングシート、樹脂付き銅箔、フレキシブル銅張積層板、フレキシブルフラットケーブル等が挙げられる。 <Application>
Since the adhesive composition of the present invention has low dielectric properties and excellent adhesiveness between resin and metal, it can be suitably used as an adhesive (e.g., adhesive film, etc.) for manufacturing FPC-related members. . Examples of FPC-related members in the present invention include coverlay films, bonding sheets, resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like.
本発明における接着剤組成物は、低誘電特性及び樹脂と金属との接着性に優れることから、FPCの関連部材を製造するための接着剤(例えば、接着フィルム等)として好適に用いることができる。本発明におけるFPCの関連部材としては、例えば、カバーレイフィルム、ボンディングシート、樹脂付き銅箔、フレキシブル銅張積層板、フレキシブルフラットケーブル等が挙げられる。 <Application>
Since the adhesive composition of the present invention has low dielectric properties and excellent adhesiveness between resin and metal, it can be suitably used as an adhesive (e.g., adhesive film, etc.) for manufacturing FPC-related members. . Examples of FPC-related members in the present invention include coverlay films, bonding sheets, resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like.
以下、実施例等を挙げて本発明をより詳細に説明するが、本発明はこれらに何ら限定されるものではない。なお、以下実施例等において、接着剤層がBステージ状であるとは、接着剤組成物の一部が硬化し始めた半硬化状態をいい、加熱等により接着剤組成物の硬化が更に進行する状態である。
The present invention will be described in more detail below with reference to Examples, etc., but the present invention is not limited to these. In the following examples, etc., the adhesive layer being in a B-stage state refers to a semi-cured state in which a part of the adhesive composition has begun to cure, and curing of the adhesive composition further progresses by heating or the like. is in a state to
(実施例1~7、比較例1~6)
撹拌装置付き1000mlフラスコに、各成分を表1又は表2に示す割合(重量部)で添加し、室温下で6時間撹拌して分散させることにより接着剤組成物を調製した。得られた接着剤組成物を用いて、以下の方法で各物性の測定を行った。得られた結果を表1又は表2に示す。 (Examples 1 to 7, Comparative Examples 1 to 6)
Each component was added to a 1000 ml flask equipped with a stirrer in the proportions (parts by weight) shown in Table 1 or Table 2, and dispersed by stirring at room temperature for 6 hours to prepare an adhesive composition. Using the obtained adhesive composition, each physical property was measured by the following methods. The obtained results are shown in Table 1 or Table 2.
撹拌装置付き1000mlフラスコに、各成分を表1又は表2に示す割合(重量部)で添加し、室温下で6時間撹拌して分散させることにより接着剤組成物を調製した。得られた接着剤組成物を用いて、以下の方法で各物性の測定を行った。得られた結果を表1又は表2に示す。 (Examples 1 to 7, Comparative Examples 1 to 6)
Each component was added to a 1000 ml flask equipped with a stirrer in the proportions (parts by weight) shown in Table 1 or Table 2, and dispersed by stirring at room temperature for 6 hours to prepare an adhesive composition. Using the obtained adhesive composition, each physical property was measured by the following methods. The obtained results are shown in Table 1 or Table 2.
(1)誘電率、誘電正接
離型処理をしたガラス板を用意し、上記の通り調製した接着剤組成物を、乾燥後の厚さが100μmとなるように塗布した。次いで、この塗膜付きガラス板をオーブン内に静置して、100℃で10分間乾燥させてBステージ状の接着剤層(厚さ100μm)を形成し、次に、この接着剤層をオーブン内に静置して、160℃で60分間加熱硬化処理をして、試験片を作製した。この試験片について、エー・イー・ティー社製の誘電率測定装置を用い、空洞共振器法により、測定温度25℃、測定周波数10GHzにおける誘電率(Dk)及び誘電正接(Df)を求めた。 (1) Dielectric Constant, Dielectric Loss Tangent A release-treated glass plate was prepared, and the adhesive composition prepared as described above was applied so that the thickness after drying was 100 μm. Next, the coated glass plate is placed in an oven and dried at 100° C. for 10 minutes to form a B-stage adhesive layer (thickness: 100 μm). It was left to stand inside and subjected to heat curing treatment at 160° C. for 60 minutes to prepare a test piece. The dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece at a measurement temperature of 25° C. and a measurement frequency of 10 GHz were obtained by the cavity resonator method using a dielectric constant measuring device manufactured by AET Corporation.
離型処理をしたガラス板を用意し、上記の通り調製した接着剤組成物を、乾燥後の厚さが100μmとなるように塗布した。次いで、この塗膜付きガラス板をオーブン内に静置して、100℃で10分間乾燥させてBステージ状の接着剤層(厚さ100μm)を形成し、次に、この接着剤層をオーブン内に静置して、160℃で60分間加熱硬化処理をして、試験片を作製した。この試験片について、エー・イー・ティー社製の誘電率測定装置を用い、空洞共振器法により、測定温度25℃、測定周波数10GHzにおける誘電率(Dk)及び誘電正接(Df)を求めた。 (1) Dielectric Constant, Dielectric Loss Tangent A release-treated glass plate was prepared, and the adhesive composition prepared as described above was applied so that the thickness after drying was 100 μm. Next, the coated glass plate is placed in an oven and dried at 100° C. for 10 minutes to form a B-stage adhesive layer (thickness: 100 μm). It was left to stand inside and subjected to heat curing treatment at 160° C. for 60 minutes to prepare a test piece. The dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece at a measurement temperature of 25° C. and a measurement frequency of 10 GHz were obtained by the cavity resonator method using a dielectric constant measuring device manufactured by AET Corporation.
(2)剥離接着強度
厚さ25μmのポリイミドフィルム[東レ・デュポン社製「カプトン100EN」]を用意し、その一方の表面に、上記の通り調製した接着剤組成物を塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、100℃で5分間乾燥させてBステージ状の接着剤層(厚さ約15μm)を形成し、カバーレイフィルム(接着剤層付き積層体)を得た。その後、厚さ20μmの圧延銅箔を、カバーレイフィルムの接着剤層の表面に面接触するように重ね合わせ(ポリイミドフィルム/接着剤層/銅箔)、温度160℃、及び圧力4.5MPaの条件で60分間加熱圧着し、フレキシブル銅張積層板を得た。このフレキシブル銅張積層板を幅10mm×長さ100mmにカットし、島津製作所社製オートグラフAGS-500を用いて、90°方向(積層板の面方向に直交する方向)における剥離接着強度を以下の測定条件にて測定した。測定条件は、テストスピードを50mm/minとした。 (2) Peel Adhesive Strength A polyimide film [“Kapton 100EN” manufactured by DuPont Toray] having a thickness of 25 μm was prepared, and the adhesive composition prepared as described above was applied to one surface of the film. Next, the coated film is left in an oven and dried at 100° C. for 5 minutes to form a B-stage adhesive layer (thickness of about 15 μm), coverlay film (laminate with adhesive layer) body). After that, a rolled copper foil having a thickness of 20 μm was superimposed so as to be in surface contact with the surface of the adhesive layer of the coverlay film (polyimide film/adhesive layer/copper foil), and the temperature was 160 ° C. and the pressure was 4.5 MPa. A flexible copper-clad laminate was obtained by thermocompression bonding under these conditions for 60 minutes. Cut this flexible copper-clad laminate into a width of 10 mm x length of 100 mm, and use an Autograph AGS-500 manufactured by Shimadzu Corporation to measure the peel adhesion strength in the 90 ° direction (direction perpendicular to the plane direction of the laminate) as follows. was measured under the measurement conditions of The measurement conditions were a test speed of 50 mm/min.
厚さ25μmのポリイミドフィルム[東レ・デュポン社製「カプトン100EN」]を用意し、その一方の表面に、上記の通り調製した接着剤組成物を塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、100℃で5分間乾燥させてBステージ状の接着剤層(厚さ約15μm)を形成し、カバーレイフィルム(接着剤層付き積層体)を得た。その後、厚さ20μmの圧延銅箔を、カバーレイフィルムの接着剤層の表面に面接触するように重ね合わせ(ポリイミドフィルム/接着剤層/銅箔)、温度160℃、及び圧力4.5MPaの条件で60分間加熱圧着し、フレキシブル銅張積層板を得た。このフレキシブル銅張積層板を幅10mm×長さ100mmにカットし、島津製作所社製オートグラフAGS-500を用いて、90°方向(積層板の面方向に直交する方向)における剥離接着強度を以下の測定条件にて測定した。測定条件は、テストスピードを50mm/minとした。 (2) Peel Adhesive Strength A polyimide film [“Kapton 100EN” manufactured by DuPont Toray] having a thickness of 25 μm was prepared, and the adhesive composition prepared as described above was applied to one surface of the film. Next, the coated film is left in an oven and dried at 100° C. for 5 minutes to form a B-stage adhesive layer (thickness of about 15 μm), coverlay film (laminate with adhesive layer) body). After that, a rolled copper foil having a thickness of 20 μm was superimposed so as to be in surface contact with the surface of the adhesive layer of the coverlay film (polyimide film/adhesive layer/copper foil), and the temperature was 160 ° C. and the pressure was 4.5 MPa. A flexible copper-clad laminate was obtained by thermocompression bonding under these conditions for 60 minutes. Cut this flexible copper-clad laminate into a width of 10 mm x length of 100 mm, and use an Autograph AGS-500 manufactured by Shimadzu Corporation to measure the peel adhesion strength in the 90 ° direction (direction perpendicular to the plane direction of the laminate) as follows. was measured under the measurement conditions of The measurement conditions were a test speed of 50 mm/min.
なお、表1及び表2中の各成分は以下の通りである。
[(A):酸変性スチレン系エラストマー]
(A-1):タフテックM1911(無水マレイン酸変性スチレン-エチレンブチレン-スチレンブロック共重合体、酸価:2mgCH3ONa/g、重量平均分子量:15万、旭化成ケミカルズ社製) In addition, each component in Table 1 and Table 2 is as follows.
[(A): acid-modified styrene-based elastomer]
(A-1): Tuftec M1911 (maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer, acid value: 2 mg CH 3 ONa/g, weight average molecular weight: 150,000, manufactured by Asahi Kasei Chemicals)
[(A):酸変性スチレン系エラストマー]
(A-1):タフテックM1911(無水マレイン酸変性スチレン-エチレンブチレン-スチレンブロック共重合体、酸価:2mgCH3ONa/g、重量平均分子量:15万、旭化成ケミカルズ社製) In addition, each component in Table 1 and Table 2 is as follows.
[(A): acid-modified styrene-based elastomer]
(A-1): Tuftec M1911 (maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer, acid value: 2 mg CH 3 ONa/g, weight average molecular weight: 150,000, manufactured by Asahi Kasei Chemicals)
[(B):環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂]
(B-1):セロキサイド2021P(3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、ダイセル社製)
(B-2):セロキサイド8010P(4,4’-ビス(1,2-エポキシシクロヘキサン)、ダイセル社製)
(B-3):DE-103(上記式(4)で表される化合物、エネオス社製)
(B-4):X-40-2669(上記式(1-1)で表される化合物、信越シリコーン社製) [(B): Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized]
(B-1): Celoxide 2021P (3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
(B-2): Celoxide 8010P (4,4′-bis(1,2-epoxycyclohexane), manufactured by Daicel Corporation)
(B-3): DE-103 (compound represented by the above formula (4), manufactured by Eneos)
(B-4): X-40-2669 (compound represented by the above formula (1-1), manufactured by Shin-Etsu Silicone Co., Ltd.)
(B-1):セロキサイド2021P(3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、ダイセル社製)
(B-2):セロキサイド8010P(4,4’-ビス(1,2-エポキシシクロヘキサン)、ダイセル社製)
(B-3):DE-103(上記式(4)で表される化合物、エネオス社製)
(B-4):X-40-2669(上記式(1-1)で表される化合物、信越シリコーン社製) [(B): Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized]
(B-1): Celoxide 2021P (3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
(B-2): Celoxide 8010P (4,4′-bis(1,2-epoxycyclohexane), manufactured by Daicel Corporation)
(B-3): DE-103 (compound represented by the above formula (4), manufactured by Eneos)
(B-4): X-40-2669 (compound represented by the above formula (1-1), manufactured by Shin-Etsu Silicone Co., Ltd.)
[その他]
(C-1):U-CAT SA102(サンアプロ社製、第3級アミン塩類、DBUの2-エチルヘキサン酸塩)
(C-2):サンエイド100L(三新化学社製、カチオン重合開始剤、芳香族スルホニウム塩)
(C-3):2E4MZ(2-エチル-4-メチルイミダゾール、和光純薬工業社製)
(D):トルエン
(E):HP-7200L(グリシジルエーテル型エポキシ樹脂、DIC社製)
(F):タフテックH1041(酸未変性スチレン系エラストマー、旭化成ケミカルズ社製) [others]
(C-1): U-CAT SA102 (manufactured by San-Apro, tertiary amine salts, 2-ethylhexanoate of DBU)
(C-2): San-Aid 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic sulfonium salt)
(C-3): 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)
(D): Toluene (E): HP-7200L (glycidyl ether type epoxy resin, manufactured by DIC Corporation)
(F): Tuftec H1041 (acid-unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals)
(C-1):U-CAT SA102(サンアプロ社製、第3級アミン塩類、DBUの2-エチルヘキサン酸塩)
(C-2):サンエイド100L(三新化学社製、カチオン重合開始剤、芳香族スルホニウム塩)
(C-3):2E4MZ(2-エチル-4-メチルイミダゾール、和光純薬工業社製)
(D):トルエン
(E):HP-7200L(グリシジルエーテル型エポキシ樹脂、DIC社製)
(F):タフテックH1041(酸未変性スチレン系エラストマー、旭化成ケミカルズ社製) [others]
(C-1): U-CAT SA102 (manufactured by San-Apro, tertiary amine salts, 2-ethylhexanoate of DBU)
(C-2): San-Aid 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic sulfonium salt)
(C-3): 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)
(D): Toluene (E): HP-7200L (glycidyl ether type epoxy resin, manufactured by DIC Corporation)
(F): Tuftec H1041 (acid-unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals)
Claims (6)
- 下記(A)及び(B)を含み、且つ下記(C)を含まない、接着剤組成物。
(A)酸変性スチレン系エラストマー
(B)環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂
(C)第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤 An adhesive composition containing the following (A) and (B) and not containing the following (C).
(A) Acid-modified styrene elastomer (B) Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized (C) Tertiary amines, tertiary amine salts, imidazoles and cations polymerization initiator - (A)100重量部に対し、(B)を0.1~50重量部含有する、請求項1に記載の接着剤組成物。 The adhesive composition according to claim 1, which contains 0.1 to 50 parts by weight of (B) per 100 parts by weight of (A).
- (A)が、スチレン-エチレンブチレン-スチレンブロック共重合体及びスチレン-エチレンプロピレンブロック共重合体からなる群より選択される少なくとも1種のスチレン系エラストマーを不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種により変性したものである、請求項1又は2に記載の接着剤組成物 (A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; The adhesive composition according to claim 1 or 2, which is modified with at least one selected from the group consisting of
- (B)が、下記式(1)~(4)で表される化合物からなる群から選ばれる少なくとも1種の脂環式エポキシ樹脂である、請求項1~3のいずれか一項に記載の接着剤組成物。
(上記式(1)におけるXは、単結合、又は2価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。)
(X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
- 更に、(D)有機溶媒を含む、請求項1~4のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, further comprising (D) an organic solvent.
- 請求項1~5のいずれか一項に記載の接着剤組成物を用いてなる接着フィルム。 An adhesive film using the adhesive composition according to any one of claims 1 to 5.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH01261478A (en) * | 1988-04-13 | 1989-10-18 | Hitachi Chem Co Ltd | Adhesive composition for circuit connection |
WO2020048799A1 (en) * | 2018-09-05 | 2020-03-12 | Tesa Se | Adhesive mass for a flexible display |
WO2021145240A1 (en) * | 2020-01-16 | 2021-07-22 | 住友精化株式会社 | Laminated body having copper foil and epoxy resin composition layer |
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- 2022-07-07 JP JP2022109431A patent/JP2023020939A/en active Pending
- 2022-07-12 TW TW111126153A patent/TW202413584A/en unknown
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01261478A (en) * | 1988-04-13 | 1989-10-18 | Hitachi Chem Co Ltd | Adhesive composition for circuit connection |
WO2020048799A1 (en) * | 2018-09-05 | 2020-03-12 | Tesa Se | Adhesive mass for a flexible display |
WO2021145240A1 (en) * | 2020-01-16 | 2021-07-22 | 住友精化株式会社 | Laminated body having copper foil and epoxy resin composition layer |
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