JP2019173034A - Thermosetting adhesive sheet and manufacturing method therefor - Google Patents
Thermosetting adhesive sheet and manufacturing method therefor Download PDFInfo
- Publication number
- JP2019173034A JP2019173034A JP2019128250A JP2019128250A JP2019173034A JP 2019173034 A JP2019173034 A JP 2019173034A JP 2019128250 A JP2019128250 A JP 2019128250A JP 2019128250 A JP2019128250 A JP 2019128250A JP 2019173034 A JP2019173034 A JP 2019173034A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- thermosetting
- adhesive sheet
- thermosetting adhesive
- thermoplastic
- 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.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 191
- 239000000853 adhesive Substances 0.000 title claims abstract description 151
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 150
- 239000011347 resin Substances 0.000 claims abstract description 150
- 239000002245 particle Substances 0.000 claims abstract description 89
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims description 26
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 22
- 229920001971 elastomer Polymers 0.000 claims description 22
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 229920003244 diene elastomer Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 239000009719 polyimide resin Substances 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 239000002783 friction material Substances 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 100
- 238000002844 melting Methods 0.000 description 33
- 230000008018 melting Effects 0.000 description 33
- 230000005484 gravity Effects 0.000 description 31
- 238000000576 coating method Methods 0.000 description 21
- 229920002799 BoPET Polymers 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- -1 polyethylene Polymers 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 229920003987 resole Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 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 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KIDLQRSWTHZIAF-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylhexane Chemical compound CC(C)CC(C)(C)CC(OOC(C)(C)C)OOC(C)(C)C KIDLQRSWTHZIAF-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- WUAFLNUJIPFKHQ-UHFFFAOYSA-N 1,3-bis[2-(2-methyl-1h-imidazol-5-yl)ethyl]urea Chemical compound N1C(C)=NC=C1CCNC(=O)NCCC1=CN=C(C)N1 WUAFLNUJIPFKHQ-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- VOJAMWORWOLUKL-UHFFFAOYSA-N 1-benzyl-2-ethyl-5-methylimidazole Chemical compound CCC1=NC=C(C)N1CC1=CC=CC=C1 VOJAMWORWOLUKL-UHFFFAOYSA-N 0.000 description 1
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-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
- PBODPHKDNYVCEJ-UHFFFAOYSA-M 1-benzyl-3-dodecyl-2-methylimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCN1C=C[N+](CC=2C=CC=CC=2)=C1C PBODPHKDNYVCEJ-UHFFFAOYSA-M 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 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 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- BOANVMYDGKUJAC-UHFFFAOYSA-N 2-(2-ethylimidazol-1-yl)ethanamine Chemical compound CCC1=NC=CN1CCN BOANVMYDGKUJAC-UHFFFAOYSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical compound CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- MLPBASQNOQYIGL-UHFFFAOYSA-N 2-(2-propan-2-yl-1h-imidazol-5-yl)propanenitrile Chemical compound CC(C)C1=NC=C(C(C)C#N)N1 MLPBASQNOQYIGL-UHFFFAOYSA-N 0.000 description 1
- SFPKYQLUNZBNQA-UHFFFAOYSA-N 2-[4,5-bis(2-cyanoethoxymethyl)-2-phenylimidazol-1-yl]propanenitrile Chemical compound N#CC(C)N1C(COCCC#N)=C(COCCC#N)N=C1C1=CC=CC=C1 SFPKYQLUNZBNQA-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-N 2-ethyl-1-methylimidazole Chemical compound CCC1=NC=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QFZKVFCEJRXRBD-UHFFFAOYSA-N 2-ethyl-4-[(2-ethyl-5-methyl-1h-imidazol-4-yl)methyl]-5-methyl-1h-imidazole Chemical compound N1C(CC)=NC(CC2=C(NC(CC)=N2)C)=C1C QFZKVFCEJRXRBD-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
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- QXSNXUCNBZLVFM-UHFFFAOYSA-N 2-methyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound CC1=NC=CN1.O=C1NC(=O)NC(=O)N1 QXSNXUCNBZLVFM-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- NXAFRGRYHSKXJB-UHFFFAOYSA-N 2-tert-butylperoxy-3,5,5-trimethylhexanoic acid Chemical compound CC(C)(C)CC(C)C(C(O)=O)OOC(C)(C)C NXAFRGRYHSKXJB-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-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
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、熱硬化性接着シートおよびその製造方法に関する。 The present invention relates to a thermosetting adhesive sheet and a method for producing the same.
従来、自動車等の分野において、ブレーキライニングのような摩擦材と金属部材とを接着するために、液状の接着剤が使用されている。しかし、液状の接着剤は、作業性が悪く、塗布量の制御が難しく、また、溶剤の除去が必要になるため、作業性が悪い問題がある。
そこで、熱硬化性固体フィルム接着剤を用いることが提案されている。熱硬化性固体フィルム接着剤として、例えば以下のものが提案されている。
（１）（Ａ）熱硬化性フェノール−アルデヒドレゾール樹脂、（Ｂ）分子当り平均１個より多い重合性アクリル基を持つ特定の光重合性樹脂、（Ｃ）成分（Ｂ）のための光重合開始剤、および（Ｄ）ポリビニルアセタールからなる液体組成物の層を化学線に暴露することにより得られる固体フィルム接着剤（特許文献１）。
上記（１）の固体フィルム接着剤は、例えば、剥離シート上に形成され、使用時に剥離シートが取り除かれ、適当な大きさに切断される。この固体フィルム接着剤を、結合すべき表面間に挟んで熱硬化させることでそれらの表面が結合される。
Conventionally, in the field of automobiles and the like, a liquid adhesive is used to bond a friction material such as a brake lining and a metal member. However, the liquid adhesive has poor workability, it is difficult to control the coating amount, and it is necessary to remove the solvent.
Therefore, it has been proposed to use a thermosetting solid film adhesive. As thermosetting solid film adhesives, for example, the following are proposed.
(1) (A) thermosetting phenol-aldehyde resol resin, (B) a specific photopolymerizable resin having an average of more than 1 polymerizable acrylic group per molecule, (C) photopolymerization for component (B) A solid film adhesive obtained by exposing an initiator and a layer of a liquid composition comprising (D) polyvinyl acetal to actinic radiation (Patent Document 1).
The solid film adhesive (1) is formed on, for example, a release sheet, and the release sheet is removed at the time of use and cut into an appropriate size. The solid film adhesive is bonded between the surfaces to be bonded and thermally cured to bond the surfaces.
しかし、上記（１）の固体フィルム接着剤は、ブレーキライニングのような粗面（多孔面）を有する摩擦材と滑面を有する金属部材との接着では、十分な接着強度を得ることができにくかった。また、接合されたとしても接着剤が被着体の接着部からはみ出すという問題を有していた。 However, the solid film adhesive of the above (1) is difficult to obtain a sufficient adhesive strength when bonding a friction material having a rough surface (porous surface) such as a brake lining and a metal member having a smooth surface. It was. Moreover, even if it joined, there existed a problem that an adhesive agent protruded from the adhesion part of a to-be-adhered body.
本発明は、上記の事情を鑑みてなされたものであり、粗面（多孔面）を有する摩擦材と滑面を有する金属部材のような平面度の悪い被着体同士や、平行度の悪い被着体同士を強固に接着でき、被着体から接着剤のはみ出しを抑えることができる熱硬化性接着シートおよびその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and adherends having poor flatness, such as a friction material having a rough surface (porous surface) and a metal member having a smooth surface, and poor parallelism. It is an object of the present invention to provide a thermosetting adhesive sheet capable of firmly bonding adherends to each other and suppressing protrusion of an adhesive from the adherends and a method for producing the same.
本発明は、以下の［１］〜［６］の構成を有する、熱硬化性接着シートおよびその製造方法を提供する。
［１］熱硬化性樹脂（Ａ）と下記から選ばれた１種または２種以上の熱可塑性樹脂（Ｂ）とが溶剤により溶解された組成物から得られた熱硬化性接着シートであって、前記組成物に未硬化の熱硬化性樹脂粒子（Ｃ）が含有され、前記未硬化の熱硬化性樹脂粒子（Ｃ）が下記から選ばれた少なくとも１種であることを特徴とする熱硬化性接着シート。
＜熱可塑性樹脂（Ｂ）＞
ポリオレフィン樹脂及びその変性物、ポリエステル樹脂、（メタ）アクリル樹脂、スチレン樹脂、ポリアミド樹脂、熱可塑性エラストマー、熱可塑性ポリイミド樹脂、ジエン系ゴム及びその水添物、オレフィン系ゴム
＜未硬化の熱硬化性樹脂粒子（Ｃ）＞
エポキシ樹脂、ビスマレイミド樹脂
［２］前記熱硬化性樹脂（Ａ）が、エポキシ樹脂、フェノール樹脂、ビスマレイミド樹脂の少なくとも１種類以上であることを特徴とする前記［１］に記載の熱硬化性接着シート。
［３］前記熱可塑性樹脂（Ｂ）が、ニトリルゴム、アクリルゴムの少なくとも１種類以上であることを特徴とする前記［１］に記載の熱硬化性接着シート。
The present invention provides a thermosetting adhesive sheet having the following configurations [1] to [6] and a method for producing the same.
[1] A thermosetting adhesive sheet obtained from a composition in which a thermosetting resin (A) and one or more thermoplastic resins (B) selected from the following are dissolved in a solvent, The composition comprises uncured thermosetting resin particles (C), and the uncured thermosetting resin particles (C) are at least one selected from the following: Adhesive sheet.
<Thermoplastic resin (B)>
Polyolefin resin and modified products thereof, polyester resin, (meth) acrylic resin, styrene resin, polyamide resin, thermoplastic elastomer, thermoplastic polyimide resin, diene rubber and hydrogenated product thereof, olefin rubber <uncured thermosetting Resin particles (C)>
Epoxy resin, bismaleimide resin [2] The thermosetting resin according to [1], wherein the thermosetting resin (A) is at least one of an epoxy resin, a phenol resin, and a bismaleimide resin. Adhesive sheet.
[3] The thermosetting adhesive sheet according to [1], wherein the thermoplastic resin (B) is at least one of nitrile rubber and acrylic rubber.
［４］硬化剤又は硬化促進剤を１種類以上含有することを特徴とする前記［１］乃至［３］のいずれか１項に記載の熱硬化性接着シート。
［５］熱硬化性接着シートの製造方法であって、熱硬化性樹脂（Ａ）、下記から選ばれた１種または２種以上の熱可塑性樹脂（Ｂ）、下記から選ばれた少なくとも１種の未硬化の熱硬化性樹脂粒子（Ｃ）及び前記熱硬化性樹脂（Ａ）と熱可塑性樹脂（Ｂ）を溶解し且つ未硬化の熱硬化性樹脂粒子（Ｃ）を溶解しない溶剤を含む液状の熱硬化性接着剤組成物を調製し、前記液状の熱硬化性接着剤組成物を基材上に塗布後、乾燥させて熱硬化性接着シートを得ることを特徴とする熱硬化性接着シートの製造方法。
＜熱可塑性樹脂（Ｂ）＞
ポリオレフィン樹脂及びその変性物、ポリエステル樹脂、（メタ）アクリル樹脂、スチレン樹脂、ポリアミド樹脂、熱可塑性エラストマー、熱可塑性ポリイミド樹脂、ジエン系ゴム及びその水添物、オレフィン系ゴム
＜未硬化の熱硬化性樹脂粒子（Ｃ）＞
エポキシ樹脂、ビスマレイミド樹脂
［６］前記液状の熱硬化性接着剤組成物に硬化剤又は硬化促進剤を１種類以上含有することを特徴とする前記［５］に記載の熱硬化性接着シートの製造方法。
[4] The thermosetting adhesive sheet according to any one of [1] to [3], wherein the thermosetting adhesive sheet contains at least one type of curing agent or curing accelerator.
[5] A method for producing a thermosetting adhesive sheet, comprising a thermosetting resin (A), one or more thermoplastic resins (B) selected from the following, and at least one selected from the following: Liquid containing a solvent that dissolves the uncured thermosetting resin particles (C) and the thermosetting resin (A) and the thermoplastic resin (B) and does not dissolve the uncured thermosetting resin particles (C). A thermosetting adhesive sheet, characterized in that a thermosetting adhesive sheet is prepared, and the liquid thermosetting adhesive composition is applied onto a substrate and then dried to obtain a thermosetting adhesive sheet. Manufacturing method.
<Thermoplastic resin (B)>
Polyolefin resin and modified products thereof, polyester resin, (meth) acrylic resin, styrene resin, polyamide resin, thermoplastic elastomer, thermoplastic polyimide resin, diene rubber and hydrogenated product thereof, olefin rubber <uncured thermosetting Resin particles (C)>
Epoxy resin, bismaleimide resin [6] The thermosetting adhesive sheet according to [5], wherein the liquid thermosetting adhesive composition contains one or more curing agents or curing accelerators. Production method.
本発明によれば粗面（多孔面）を有する摩擦材と滑面を有する金属部材のような平面度の悪い被着体同士や、平行度の悪い被着体同士を強固に接着でき、被着体から接着剤のはみ出しを抑えることができる熱硬化性接着シートおよびその製造方法を提供できる。 According to the present invention, adherends with poor flatness such as a friction material having a rough surface (porous surface) and a metal member having a smooth surface, and adherends with poor parallelism can be firmly bonded to each other. It is possible to provide a thermosetting adhesive sheet capable of suppressing the protrusion of the adhesive from the adherend and a method for producing the same.
以下、本発明の熱硬化性接着シートを説明する。
本発明の熱硬化性接着シートは、熱硬化性樹脂（Ａ）、熱可塑性樹脂（Ｂ）及び未硬化の熱硬化性樹脂粒子（Ｃ）を含有する。
＜熱硬化性樹脂（Ａ）＞
熱硬化性樹脂（Ａ）としては、例えば、尿素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、アセトグアナミン樹脂、フェノール樹脂、レゾルシノール樹脂、キシレン樹脂、フラン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、イソシアナート樹脂、エポキシ樹脂、マレイミド樹脂、ナジイミド樹脂等が挙げられる。これらの熱硬化性樹脂は、１種単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。この中でも特にエポキシ樹脂、フェノール樹脂、ビスマレイミド樹脂から選ばれた少なくとも１種類以上であることが熱硬化性接着シートの溶融粘度を容易に制御することができるため、平行度の悪い被着体同士を強固に接着でき、被着体から接着剤のはみ出しを抑えることができる。
また、熱硬化性接着シートには、酸無水物、ポリアミン、イソシアネート、イミダゾール類等の硬化剤を併用したり、有機過酸化物等の硬化応促進剤を添加してもよい。
Hereinafter, the thermosetting adhesive sheet of the present invention will be described.
The thermosetting adhesive sheet of the present invention contains a thermosetting resin (A), a thermoplastic resin (B), and uncured thermosetting resin particles (C).
<Thermosetting resin (A)>
Examples of the thermosetting resin (A) include urea resin, melamine resin, benzoguanamine resin, acetoguanamine resin, phenol resin, resorcinol resin, xylene resin, furan resin, unsaturated polyester resin, diallyl phthalate resin, isocyanate resin, Examples thereof include an epoxy resin, a maleimide resin, and a nadiimide resin. These thermosetting resins may be used alone or in a combination of two or more. Among these, since at least one selected from epoxy resin, phenol resin, and bismaleimide resin can easily control the melt viscosity of the thermosetting adhesive sheet, adherends with poor parallelism Can be firmly bonded, and the adhesive can be prevented from protruding from the adherend.
Moreover, you may use together hardening agents, such as an acid anhydride, a polyamine, isocyanate, and imidazoles, and hardening accelerators, such as an organic peroxide, to a thermosetting adhesive sheet.
＜熱可塑性樹脂（Ｂ）＞
熱可塑性樹脂（Ｂ）としては、例えば、ポリエチレンやポリプロピレンなどのポリオレフィン樹脂及びその変性物、ポリエチレンテレフタレートやポリブチレンテレフタレートなどのポリエステル樹脂、ポリメチルメタクリレートやポリエチルメタクリレートなどの（メタ）アクリル樹脂、ポリスチレン、アクリロニトリル−ブタジエン−スチレン樹脂、アクリロニトリル−アクリルゴム−スチレン樹脂、アクリロニトリル−エチレンゴム−スチレン樹脂、（メタ）アクリル酸エステル−スチレン樹脂、スチレン−ブタジエン−スチレン樹脂などのスチレン樹脂、アイオノマー樹脂、ポリアクリルニトリル、６-ナイロン、６，６-ナイロン、６Ｔ−ＰＡ、９Ｔ−ＰＡ、ＭＸＤ６−ナイロンなどのポリアミド樹脂、エチレン−酢酸ビニル樹脂、エチレン−アクリル酸樹脂、エチレン−エチルアクリレート樹脂、エチレン−ビニルアルコール樹脂、ポリ塩化ビニルやポリ塩化ビニリデンなどの塩素樹脂、ポリフッ化ビニルやポリフッ化ビニリデンなどのフッ素樹脂、ポリカーボネート樹脂、変性ポリフェニレンエーテル樹脂、メチルペンテン樹脂、セルロース樹脂等、ならびにオレフィン系エラストマー、グリシジル変性オレフィン系エラストマー、マレイン酸変性オレフィン系エラストマー、塩化ビニル系エラストマー、スチレン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー等の熱可塑性エラストマー、ポリフェニレンサルファイド樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、熱可塑性ポリイミド樹脂などが挙げられる。
<Thermoplastic resin (B)>
Examples of the thermoplastic resin (B) include polyolefin resins such as polyethylene and polypropylene and modified products thereof, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, (meth) acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, and polystyrene. Styrene resins such as acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylate ester-styrene resin, styrene-butadiene-styrene resin, ionomer resin, polyacryl Polyamide resins such as nitrile, 6-nylon, 6,6-nylon, 6T-PA, 9T-PA, MXD6-nylon, ethylene-vinyl acetate resin, Tylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, chlorine resin such as polyvinyl chloride and polyvinylidene chloride, fluorine resin such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resin, modified polyphenylene ether resin, Thermoplastics such as methylpentene resin, cellulose resin, etc., and olefin elastomers, glycidyl modified olefin elastomers, maleic acid modified olefin elastomers, vinyl chloride elastomers, styrene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, etc. Such as elastomer, polyphenylene sulfide resin, polyetherimide resin, polyetheretherketone resin, thermoplastic polyimide resin And so on.
また、本発明で使用できる熱可塑性樹脂（Ｂ）としては、ジエン系ゴム及びその水添物〔例えば、天然ゴム、イソプレンゴム、エポキシ化天然ゴム、スチレンブタジエンゴム、ブタジエンゴム、ニトリルゴム、水素化ＮＢＲ、水素化ＳＢＲ〕、オレフィン系ゴム〔例えば、エチレンプロピレンゴム、マレイン酸変性エチレンプロピレンゴム、ブチルゴム、イソブチレンと芳香族ビニル又はジエン系モノマー共重合体、アクリルゴム、アイオノマー〕、含ハロゲンゴム〔例えば、Ｂｒ−ＩＩＲ、ＣＩ−ＩＩＲ、臭素化イソブチレン−ｐ−メチルスチレン共重合体、クロロプレンゴム、ヒドリンゴム、クロロスルホン化ポリエチレンゴム、塩素化ポリエチレンゴム、マレイン酸変性塩素化ポリエチレンゴム〕、シリコーンゴム〔例えば、メチルビニルシリコーンゴム、ジメチルシリコーンゴム、メチルフェニルビニルシリコーンゴム〕、含イオウゴム〔例えば、ポリスルフィドゴム〕、フッ素ゴム〔例えば、ビニリデンフルオライド系ゴム、含フッ素ビニルエーテル系ゴム、テトラフルオロエチレン−プロピレン系ゴム、含フッ素シリコーン系ゴム、含フッ素ホスファゼン系ゴム〕等を挙げることができる。
これらの熱可塑性樹脂は１種または２種以上を併用して用いることができる。
この中でも特にニトリルゴム、アクリルゴムの少なくとも１種類以上であることが熱硬化性接着シートの溶融粘度を容易に制御することができるため、平面度の悪い被着体同士や、平行度の悪い被着体同士を強固に接着でき、被着体から接着剤のはみ出しを抑えることができる。
The thermoplastic resin (B) that can be used in the present invention includes diene rubbers and hydrogenated products thereof [for example, natural rubber, isoprene rubber, epoxidized natural rubber, styrene butadiene rubber, butadiene rubber, nitrile rubber, hydrogenated NBR, hydrogenated SBR], olefin rubber (for example, ethylene propylene rubber, maleic acid-modified ethylene propylene rubber, butyl rubber, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber, ionomer), halogen-containing rubber [for example Br-IIR, CI-IIR, brominated isobutylene-p-methylstyrene copolymer, chloroprene rubber, hydrin rubber, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, maleic acid-modified chlorinated polyethylene rubber], silicone rubber [eg , Methylbi Silicone rubber, dimethyl silicone rubber, methylphenyl vinyl silicone rubber), sulfur-containing rubber (for example, polysulfide rubber), fluorine rubber (for example, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, Fluorosilicone rubber, fluorinated phosphazene rubber] and the like.
These thermoplastic resins can be used alone or in combination of two or more.
Among them, in particular, at least one of nitrile rubber and acrylic rubber can easily control the melt viscosity of the thermosetting adhesive sheet. The adherends can be firmly bonded to each other, and the adhesive can be prevented from protruding from the adherend.
熱可塑性樹脂（Ｂ）の質量平均分子量（Ｍｗ）は、１０００〜３００万が好ましく、１万〜１５０万が特に好ましい。Ｍｗが前記範囲の下限値以上であれば、熱硬化性接着シートを被接着体に接着させた際に容易に接着可能であり、上限値以下であれば、熱硬化性接着シートでの強度に優れ、接着シートの取り扱い性が良好になる。熱可塑性樹脂（Ｂ）のＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレン換算で測定される。
熱可塑性樹脂（Ｂ）のガラス転移温度は、熱硬化性接着シートを被接着体に接着させた際に容易に接着可能とするため、−１００℃〜５０℃が好ましく、−５０℃〜４０℃が特に好ましい。
1000-3 million are preferable and, as for the mass average molecular weight (Mw) of a thermoplastic resin (B), 10,000-1 million are especially preferable. If Mw is not less than the lower limit of the above range, it can be easily bonded when the thermosetting adhesive sheet is adhered to the adherend, and if it is not more than the upper limit, the strength of the thermosetting adhesive sheet can be increased. Excellent and easy handling of the adhesive sheet. Mw of the thermoplastic resin (B) is measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
The glass transition temperature of the thermoplastic resin (B) is preferably −100 ° C. to 50 ° C., preferably −50 ° C. to 40 ° C., in order to enable easy adhesion when the thermosetting adhesive sheet is adhered to the adherend. Is particularly preferred.
熱可塑性樹脂（Ｂ）には、必要に応じて、例えば、粘着付与樹脂、充填剤、難燃剤、老化防止剤、帯電防止剤、軟化剤、紫外線吸収剤、酸化防止剤、可塑剤、界面活性剤等の公知の添加剤等が含まれていてもよい。 For the thermoplastic resin (B), for example, a tackifying resin, a filler, a flame retardant, an anti-aging agent, an antistatic agent, a softening agent, an ultraviolet absorber, an antioxidant, a plasticizer, and a surface active agent are optionally used. Known additives such as an agent may be included.
熱硬化性接着シートにおける熱硬化性樹脂（Ａ）と熱可塑性樹脂（Ｂ）との割合は、熱硬化性樹脂（Ａ）１００質量部に対して熱可塑性樹脂（Ｂ）が１００〜５００質量部が好ましく、更に１００〜２００質量部が好ましい。熱可塑性樹脂（Ｂ）が１００質量部未満の場合では、接着剤のシート化が困難となる（成膜性が悪くなる）。熱可塑性樹脂（Ｂ）が５００質量部より多い場合では、熱硬化性接着シートのＢステージが制御しにくくなる。したがって、接着剤の溶融粘度が低くなりすぎて被着体から接着剤のはみ出しを抑えにくくなったり、接着剤の溶融粘度が高くなりすぎて被着体への密着性が低下し、熱硬化した後の接合体にて、被着体界面での破壊が起こりやすくなる。 The ratio of the thermosetting resin (A) and the thermoplastic resin (B) in the thermosetting adhesive sheet is such that the thermoplastic resin (B) is 100 to 500 parts by mass with respect to 100 parts by mass of the thermosetting resin (A). Is preferable, and 100-200 mass parts is more preferable. When the thermoplastic resin (B) is less than 100 parts by mass, it is difficult to form an adhesive sheet (the film formability is deteriorated). When the thermoplastic resin (B) is more than 500 parts by mass, it becomes difficult to control the B stage of the thermosetting adhesive sheet. Accordingly, the melt viscosity of the adhesive is too low to make it difficult to prevent the adhesive from protruding from the adherend, or the adhesive has an excessively high melt viscosity and the adhesiveness to the adherend is reduced, resulting in heat curing. In the subsequent bonded body, breakage at the adherend interface is likely to occur.
＜未硬化の熱硬化性樹脂の粒子＞
「未硬化の熱硬化性樹脂」とは、いわゆるＢステージ以前の状態の熱硬化性樹脂をさす。具体的には、加熱により流動状態を経由して硬化にいたることのできる状態の熱硬化性樹脂をいう。つまり未硬化の熱硬化性樹脂は、融点を有しており、融点以上の温度に加熱すると溶融物となり、さらに加熱することで硬化物となる。
したがって、熱硬化性接着シートは、未硬化の熱硬化性樹脂粒子（Ｃ）の融点以上の温度に加熱すると、未硬化の熱硬化性樹脂粒子（Ｃ）が溶融して流動状態となる。流動状態となった未硬化の熱硬化性樹脂粒子（Ｃ）と熱可塑性樹脂（Ｂ）とが混和し、熱硬化性接着シートが通常の熱硬化性接着剤と同様の性状を示すようになる。その後、さらに加熱を行うことで、熱硬化性接着シートが硬化する。
<Uncured thermosetting resin particles>
"Uncured thermosetting resin" refers to a thermosetting resin in a state before the so-called B stage. Specifically, it refers to a thermosetting resin that can be cured by heating through a fluid state. That is, the uncured thermosetting resin has a melting point, becomes a melt when heated to a temperature equal to or higher than the melting point, and becomes a cured product when further heated.
Therefore, when the thermosetting adhesive sheet is heated to a temperature equal to or higher than the melting point of the uncured thermosetting resin particles (C), the uncured thermosetting resin particles (C) are melted and become a fluid state. The uncured thermosetting resin particles (C) and the thermoplastic resin (B) in a fluidized state are mixed, and the thermosetting adhesive sheet has the same properties as a normal thermosetting adhesive. . Thereafter, the thermosetting adhesive sheet is cured by further heating.
未硬化の熱硬化性樹脂粒子（Ｃ）における熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、イミド樹脂、ジアリルフタレート樹脂、ポリフェニレンエーテル樹脂等が挙げられる。これらは単独で用いる他、適宜混合したり、酸無水物、ポリアミン、イソシアネート、イミダゾール類等の硬化剤を併用したり、有機過酸化物等の反応促進剤を添加してもよい。
エポキシ樹脂は、フェノールノボラック型、クレゾールノボラック型、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型、ナフタレン型、ビフェニル型、ジシクロペンタジエン型のものが特に好ましい。
フェノール樹脂としては、具体的にはアルキルフェノール型、ｐ−フェニルフェノール型、ビスフェノールＡ型等のノボラックフェノール樹脂およびレゾールフェノール樹脂が好ましい。
イミド樹脂としては、アミドイミド樹脂、マレイミド樹脂、ナジイミド樹脂が好ましい。
Examples of the thermosetting resin in the uncured thermosetting resin particles (C) include an epoxy resin, a phenol resin, an imide resin, a diallyl phthalate resin, and a polyphenylene ether resin. These may be used alone, or may be mixed as appropriate, a curing agent such as an acid anhydride, polyamine, isocyanate, or imidazole may be used in combination, or a reaction accelerator such as an organic peroxide may be added.
The epoxy resin is particularly preferably a phenol novolak type, a cresol novolak type, a bisphenol A type, a bisphenol F type, a bisphenol S type, a naphthalene type, a biphenyl type, or a dicyclopentadiene type.
As the phenol resin, specifically, a novolak phenol resin such as an alkylphenol type, a p-phenylphenol type, or a bisphenol A type and a resole phenol resin are preferable.
As the imide resin, an amideimide resin, a maleimide resin, and a nadiimide resin are preferable.
熱硬化性樹脂粒子（Ｃ）としては、その熱硬化性樹脂粒子（Ｃ）の融点以上の温度に加熱して溶融させたときに、熱可塑性樹脂（Ｂ）と相溶するものが好ましい。これにより、熱硬化性接着シートを熱硬化性樹脂粒子（Ｃ）の融点以上の温度に加熱したときに、熱硬化性樹脂粒子（Ｃ）が溶融する。溶融した熱硬化性樹脂粒子（Ｃ）と熱可塑性樹脂（Ｂ）とが相溶して均一な組成物となり、硬化させたときに優れた接着強度が得られやすい。 The thermosetting resin particles (C) are preferably those that are compatible with the thermoplastic resin (B) when heated and melted at a temperature equal to or higher than the melting point of the thermosetting resin particles (C). Thereby, when a thermosetting adhesive sheet is heated to the temperature more than melting | fusing point of a thermosetting resin particle (C), a thermosetting resin particle (C) fuse | melts. The melted thermosetting resin particles (C) and the thermoplastic resin (B) are compatible to form a uniform composition, and excellent adhesive strength is easily obtained when cured.
熱硬化性樹脂粒子（Ｃ）の形状は特に限定されず、例えば球状、真球状、無定形、針状、繊維状、板状などでもよい。これらは２種類以上組み合わせて使用してもよい。熱硬化性樹脂粒子（Ｃ）の平均粒子径に関しても特に制限はないが、０．０１μｍ〜２００μｍのものが、接着剤塗料の塗工性、熱硬化性接着シートの溶融特性を制御しやすく好適である。 The shape of the thermosetting resin particles (C) is not particularly limited, and may be, for example, spherical, true spherical, amorphous, needle-like, fibrous, or plate-like. Two or more of these may be used in combination. The average particle size of the thermosetting resin particles (C) is not particularly limited, but 0.01 μm to 200 μm is preferable because it is easy to control the coating property of the adhesive paint and the melting property of the thermosetting adhesive sheet. It is.
熱硬化性接着シート中、熱硬化性樹脂（Ａ）及び熱可塑性樹脂（Ｂ）の合計１００質量部に対する熱硬化性樹脂粒子（Ｃ）の割合は、５０〜４００質量部が好ましく、１００〜３００質量部がより好ましい。熱硬化性樹脂粒子（Ｃ）の割合が５０質量部未満の場合は、熱硬化した後の、接着剤の耐熱性が不十分となり、熱時のせん断強度が低下し、熱時に熱硬化性接着シートを用いて接着した被着体の間（例えば金属部品と摩擦材との間）で破壊されやすくなる。つまり、接着剤の凝集破壊、または、被着体界面での破壊が起こりやすくなる。熱硬化性樹脂粒子（Ｃ）の割合が４００質量部より多いと、シート化が困難になる。
熱硬化性接着シート全体に対する熱硬化性樹脂粒子（Ｃ）の割合は、２０〜９５体積％であることが好ましく、２５〜８０体積％がより好ましい。熱硬化性樹脂粒子（Ｃ）の割合が２０体積％未満の場合は、熱硬化した後の、接着剤の耐熱性が不十分となり、熱時のせん断強度が低下し、熱時に熱硬化性接着シートを用いて接着した被着体の間（例えば金属部品と摩擦材との間）で破壊されやすくなる。つまり、熱時に、接着剤の凝集破壊、または、被着体界面での破壊が起こりやすくなる。一方、熱硬化性樹脂粒子（Ｃ）の割合が９５体積％より多いと、シート化が困難になる。
熱硬化性接着シートの厚さは、特に限定されず、用途等に応じて適宜設定できる。例えば１〜２０００μｍ程度とすることができる。
In the thermosetting adhesive sheet, the ratio of the thermosetting resin particles (C) to the total of 100 parts by mass of the thermosetting resin (A) and the thermoplastic resin (B) is preferably 50 to 400 parts by mass, and 100 to 300. Part by mass is more preferable. When the ratio of the thermosetting resin particles (C) is less than 50 parts by mass, the heat resistance of the adhesive after thermosetting becomes insufficient, the shear strength at the time of heating is lowered, and the thermosetting adhesion at the time of heating. It becomes easy to break between adherends bonded using a sheet (for example, between a metal part and a friction material). That is, the cohesive failure of the adhesive or the breakage at the adherend interface is likely to occur. When the ratio of the thermosetting resin particles (C) is more than 400 parts by mass, it becomes difficult to form a sheet.
The ratio of the thermosetting resin particles (C) to the entire thermosetting adhesive sheet is preferably 20 to 95% by volume, and more preferably 25 to 80% by volume. When the ratio of the thermosetting resin particles (C) is less than 20% by volume, the heat resistance of the adhesive after thermosetting becomes insufficient, the shear strength at the time of heating is lowered, and the thermosetting adhesion at the time of heating. It becomes easy to break between adherends bonded using a sheet (for example, between a metal part and a friction material). That is, during heating, the adhesive tends to cohesively break or break at the adherend interface. On the other hand, when the ratio of the thermosetting resin particles (C) is more than 95% by volume, it becomes difficult to form a sheet.
The thickness of a thermosetting adhesive sheet is not specifically limited, It can set suitably according to a use etc. For example, it can be set to about 1 to 2000 μm.
必要に応じて、上記の熱硬化性樹脂（Ａ）、熱可塑性樹脂（Ｂ）、熱硬化性樹脂粒子（Ｃ）、及び、これらの樹脂の混合物の硬化反応を促進させるため、または、熱硬化性樹脂（Ａ）、及び熱可塑性樹脂（Ｂ）を乾燥加熱時にある程度硬化させて、接着シートの溶融粘度を高めるために、硬化剤または硬化促進剤を導入することとも可能である。
例として、ジアザビシクロオクタン、又はメチルエチルケトンパーオキサイド、シクロヘキサンパーオキサイド、３,３,５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、アセチルアセトンパーオキサイド、１,１−ビス（ｔ−ブチルパーオキシ）−３,３,５トリメチルヘキサン、１,１−ビス（ｔ−ブチルパーオキシ）−シクロヘキサン、２,２−ビス（ｔ−ブチルパーオキシ）オクタン、ｎ−ブチル−４,４−ビス（ｔ−ブチルパーオキシ）バレート、２,２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジ−イソプロピルベンゼンハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、２,５−ジメチルヘキサン−２,５−ジハイドロパーオキサイド、１,１,３,３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−クミルパーオキサイド、α,α’−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、２,５−ジメチル−２,５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２,５−ジメチル−２,５−ジ（ｔ−ブチルパーオキシ）ヘキシン、アセチルパーオキサイド、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、３,５,５−トリメチルヘキサノイルパーオキサイド、スクシニックアシッドパーオキサイド、２,４−ジクロロベンゾイルパーオキサイド、ｍ−トルオイルパーオキサイド、ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ビス−（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ジ−ミリスティルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシジカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシジカーボネート、ジ−アリルパーオキシジカーボネート、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシネオデカネート、クミルパーオキシネオデカネート、ｔ−ブチルパーオキシ−２−エチルヘキサネート、ｔ−ブチルパーオキシ−３,５,５−トリメチルヘキサネート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレート、２,５−ジメチル−２,５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシマレイン酸、ｔ−ブチルパーオキシイソプロピルカーボネート、クミルパーオキシオクテート、ｔ−ヘキシルパーオキシネオデカネート、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチルパーオキシネオヘキサネート、アセチルシクロヘキシルスルフォニルパーオキサイド、ｔ−ブチルパーオキシアリルカーボネート等の有機過酸化物、１,２−ジメチルイミダゾール、１−メチル−２−エチルイミダゾール、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−ベンジル−２−フェニルイミダゾール、１−ベンジル−２−フェニルイミダゾール・トリメリット酸塩、１−ベンジル−２−エチルイミダゾール、１−ベンジル−２−エチル−５−メチルイミダゾール、２−エチルイミダゾール、２−イソプロピルイミダゾール、２−フェニル−４−ベンジルイミダゾール、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、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−イソプロピルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−メチルイミダゾリウムトリメリテート、１−シアノエチル−２−フェニルイミダゾリウムトリメリテート、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’−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’−ウンデシルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２−メチルイミダゾリウムイソシアヌール酸付加物、２−フェニルイミダゾリウムイソシアヌール酸付加物、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−イソシアヌール酸付加物、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−ベンジル−５−ヒドロキシメチルイミダゾール、４,４’−メチレン−ビス−（２−エチル−５−メチルイミダゾール）、１−アミノエチル−２−メチルイミダゾール、１−シアノエチル−２−フェニル−４,５−ジ（シアノエトキシメチル）イミダゾール、１−ドデシル−２−メチル−３−ベンジルイミダゾリウムクロライド、２−メチルイミダゾール・ベンゾトリアゾール付加物、１−アミノエチル−２−エチルイミダゾール、１−（シアノエチルアミノエチル）−２−メチルイミダゾール、Ｎ,Ｎ’−［２−メチルイミダゾリル−（１）−エチル］−アジポイルジアミド、Ｎ,Ｎ’−ビス−（２−メチルイミダゾリル−１−エチル）尿素、Ｎ−（２−メチルイミダゾリル−１−エチル）尿素、Ｎ,Ｎ’−［２−メチルイミダゾリル−（１）−エチル］ドデカンジオイルジアミド、Ｎ,Ｎ’−［２−メチルイミダゾリル−（１）−エチル］エイコサンジオイルジアミド、１−ベンジル−２−フェニルイミダゾール・塩化水素酸塩等のイミダゾール類、トリフェニルフォスフィン等の反応促進剤を添加することができる。
If necessary, to accelerate the curing reaction of the thermosetting resin (A), thermoplastic resin (B), thermosetting resin particles (C), and a mixture of these resins, or thermosetting In order to cure the adhesive resin (A) and the thermoplastic resin (B) to some extent during drying and heating to increase the melt viscosity of the adhesive sheet, it is possible to introduce a curing agent or a curing accelerator.
Examples include diazabicyclooctane or methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t -Butylperoxy) -3,3,5 trimethylhexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4 -Bis (t-butylperoxy) valate, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroper Oxai 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-kumi Ruperoxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexyne, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, Succinic acid peroxide, 2,4-dichlorobenzoyl peroxide, m Toluoyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, di- Myristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allyl peroxydicarbonate , T-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexa Nate, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2 , 5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate, t-hexylperoxyneodecanate, t-hexylperoxypivalate, organic peroxides such as t-butylperoxyneohexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallyl carbonate, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimi Sol, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 1-cyanoethyl-2-methylimidazole 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-ethyl-4-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]- Ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl -S-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimid Dodazole, 4,4′-methylene-bis- (2-ethyl-5-methylimidazole), 1-aminoethyl-2-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) Imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole / benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N ′-[2-methylimidazolyl- (1) -ethyl] -adipoyldiamide, N, N′-bis- (2-methylimidazolyl-1-ethyl) urea, N- (2-methylimidazolyl- 1-ethyl) urea, N, N ′-[2-methylimidazolyl- (1) -ethyl] dodecanedioyl diamide, N, N ′ [2-Methylimidazolyl- (1) -ethyl] eicosanedioyl diamide, imidazoles such as 1-benzyl-2-phenylimidazole / hydrochloride, reaction accelerators such as triphenylphosphine can be added. .
＜熱硬化性接着シートの製造方法＞
熱硬化性接着シートの製造方法としては、例えば、以下の工程を有する製造方法が挙げられる。
基材上に、熱硬化性樹脂（Ａ）、熱可塑性樹脂（Ｂ）、未硬化の熱硬化性樹脂粒子（Ｃ）及び前記熱硬化性樹脂（Ａ）と熱可塑性樹脂（Ｂ）を溶解し且つ未硬化の熱硬化性樹脂粒子（Ｃ）を溶解しない溶剤を含む液状の熱硬化性接着剤組成物を調製し、前記液状の熱硬化性接着剤組成物を基材上に塗布後、乾燥させて熱硬化性接着シートを形成する工程。
<Method for producing thermosetting adhesive sheet>
As a manufacturing method of a thermosetting adhesive sheet, the manufacturing method which has the following processes is mentioned, for example.
On the substrate, the thermosetting resin (A), the thermoplastic resin (B), the uncured thermosetting resin particles (C), and the thermosetting resin (A) and the thermoplastic resin (B) are dissolved. A liquid thermosetting adhesive composition containing a solvent that does not dissolve the uncured thermosetting resin particles (C) is prepared, and the liquid thermosetting adhesive composition is applied onto a substrate and then dried. And a step of forming a thermosetting adhesive sheet.
［熱硬化性接着剤組成物］
熱硬化性接着剤組成物における溶剤は、熱硬化性樹脂（Ａ）と熱可塑性樹脂（Ｂ）を溶解し且つ未硬化の熱硬化性樹脂粒子（Ｃ）を溶解しないものであれば特に限定されず、熱硬化性樹脂（Ａ）、熱可塑性樹脂（Ｂ）、未硬化の熱硬化性樹脂粒子（Ｃ）それぞれの材質に応じて公知の溶剤のなかから適宜選択できる。
前記の工程を有する製造方法により熱硬化性接着シートを製造する場合、熱硬化性樹脂粒子（Ｃ）を構成する未硬化の熱硬化性樹脂としては、乾燥（溶剤を除去）する際の温度では溶融しないものが用いられる。具体的には、融点が溶剤の沸点よりも高い熱硬化性樹脂が用いられる。
また、融点が溶剤の沸点よりも高い未硬化の熱硬化性樹脂粒子（Ｃ）を用い、（Ｃ）の融点以下の温度で乾燥することで、（Ｃ）を溶融、反応させずに、熱硬化性樹脂（Ａ）同士、熱可塑性樹脂（Ｂ）同士、または、（Ａ）と（Ｂ）同士を反応させて、接着剤の溶融粘度、Ｂステージの状態を調整することが可能となる。前記の有機化酸化物、イミダゾール類、トリフェニルホスフィン等の反応促進剤を添加することも、接着剤の溶融粘度、Ｂステージの制御に有効である。
[Thermosetting adhesive composition]
The solvent in the thermosetting adhesive composition is not particularly limited as long as it dissolves the thermosetting resin (A) and the thermoplastic resin (B) and does not dissolve the uncured thermosetting resin particles (C). It can select suitably from well-known solvents according to each material of a thermosetting resin (A), a thermoplastic resin (B), and an uncured thermosetting resin particle (C).
When a thermosetting adhesive sheet is produced by the production method having the above-described steps, the uncured thermosetting resin constituting the thermosetting resin particles (C) is a temperature at which drying (removing the solvent) is performed. Those that do not melt are used. Specifically, a thermosetting resin having a melting point higher than that of the solvent is used.
In addition, by using uncured thermosetting resin particles (C) whose melting point is higher than the boiling point of the solvent, and drying at a temperature not higher than the melting point of (C), without melting (C) and reacting, It is possible to adjust the melt viscosity of the adhesive and the state of the B stage by reacting the curable resins (A), the thermoplastic resins (B), or (A) and (B). It is also effective to control the melt viscosity and the B stage of the adhesive by adding a reaction accelerator such as the organic oxide, imidazoles, triphenylphosphine.
［基材］
基材としては、例えば剥離フィルム、剥離紙、その他の紙、不織布等が挙げられる。剥離フィルム、剥離紙としては、接着シートの特性を損なうものでなく、容易に剥離できるものであれば、いずれのものも使用できる。
剥離フィルムとしては、例えば樹脂フィルム、樹脂フィルムにシリコーン等の離型剤で剥離処理を施したもの等が挙げられ、剥離処理を施したものが好ましい。具体的には、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、シリコーン等で離型処理されたポリエチレンテレフタレートフィルム等が挙げられる。
剥離紙としては、例えば樹脂コート紙、紙にシリコーン等の離型剤で剥離処理を施したもの等が挙げられる。剥離紙として具体的には、ポリエチレンコート紙、ポリプロピレンコート紙、シリコーン離型紙等が挙げられる。
基材の厚さは、樹脂フィルムを母材に用いた剥離フィルムの場合は、１０〜１００μｍが好ましく、紙を母材に用いた剥離紙の場合は、５０〜２００μｍが好ましい。
[Base material]
Examples of the base material include release films, release papers, other papers, and non-woven fabrics. Any release film or release paper can be used as long as it does not impair the properties of the adhesive sheet and can be easily peeled off.
Examples of the release film include a resin film, a resin film that has been subjected to a release treatment with a release agent such as silicone, and the like. Specific examples include a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyethylene terephthalate film that has been subjected to a release treatment with silicone or the like.
Examples of release paper include resin-coated paper, and paper that has been subjected to release treatment with a release agent such as silicone. Specific examples of the release paper include polyethylene-coated paper, polypropylene-coated paper, and silicone release paper.
The thickness of the substrate is preferably 10 to 100 μm in the case of a release film using a resin film as a base material, and preferably 50 to 200 μm in the case of a release paper using paper as a base material.
［塗布・乾燥］
塗布、乾燥はそれぞれ公知の方法により行うことができる。
例えば塗布方法としては、通常の塗工方式や印刷方式が挙げられる。具体的には、エアドクターコーティング、バーコーティング、ブレードコーティング、ナイフコーティング、リバースコーティング、トランスファロールコーティング、グラビアロールコーティング、キスコーティング、キャストコーティング、スプレーコーティング、スロットオリフィスコーティング、カレンダーコーティング、ダムコーティング、ディップコーティング、ダイコーティング等のコーティングや、グラビア印刷等の凹版印刷、スクリーン印刷等の孔版印刷等の印刷等が使用できる。
乾燥方法としては、加熱方式、蒸気圧方式等が挙げられる。加熱方式としては、熱方式、赤外線方式、ランプ方式等が挙げられる。蒸気圧方式としては、真空方式、凍結乾燥方式、超臨海方式等が挙げられる。加熱方式によって、溶剤を加熱乾燥する際の乾燥条件は特に制限はないが、６０〜１５０℃の範囲で、使用する溶剤によって適宜調整することが望ましい。６０℃よりも低温であると熱硬化性接着シート中に溶剤が残り易く、また溶剤の揮発に伴って塗布した熱硬化性接着剤組成物の温度が低下して結露が起こり、樹脂成分が相分離、あるいは析出する場合があるため好ましくない。１５０℃よりも高温であると、未硬化の熱硬化性樹脂粒子（Ｃ）の溶融および硬化が進行したり、急な温度上昇によって塗膜が荒れるため好ましくない。乾燥時間についても特に制限は無いが、実用性を考慮すると１〜１０分の処理が好ましい。
[Coating / Drying]
Application | coating and drying can each be performed by a well-known method.
For example, as a coating method, a normal coating method or printing method can be used. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating Coating such as die coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.
Examples of the drying method include a heating method and a vapor pressure method. Examples of the heating method include a heat method, an infrared method, a lamp method, and the like. Examples of the vapor pressure method include a vacuum method, a freeze drying method, and a super coastal method. There are no particular restrictions on the drying conditions for heating and drying the solvent depending on the heating method, but it is desirable that the drying conditions be appropriately adjusted within the range of 60 to 150 ° C. If the temperature is lower than 60 ° C., the solvent tends to remain in the thermosetting adhesive sheet, and the temperature of the thermosetting adhesive composition applied as the solvent evaporates decreases, causing condensation, and the resin component is Since it may separate or precipitate, it is not preferable. A temperature higher than 150 ° C. is not preferable because melting and curing of the uncured thermosetting resin particles (C) proceed or the coating film becomes rough due to a sudden temperature rise. Although there is no restriction | limiting in particular also about drying time, when practicality is considered, the process for 1 to 10 minutes is preferable.
上記のようにして、熱硬化性接着シートに基材が積層した積層体が得られる。
得られた積層体は、ロール状に巻き取ってもよい。必要に応じて、前記積層体から基材を取り除く工程、前記積層体または熱硬化性接着シートを切断する工程等を行ってもよい。
乾燥後の熱硬化性接着シートには、基材側とは反対側に、セパレータ（保護層）として剥離フィルムまたは剥離紙を積層、ロール状に巻き取ることも可能である。剥離フィルムまたは剥離紙としては、前述に示した基材として使用できるものが好ましい。セパレータを有する基材付き熱硬化性接着シートを使用する際には、セパレータのみを剥離した後、熱硬化性接着シートを基材から剥離して使用する。
As described above, a laminate in which a base material is laminated on a thermosetting adhesive sheet is obtained.
The obtained laminate may be wound into a roll. You may perform the process of removing a base material from the said laminated body, the process of cut | disconnecting the said laminated body or a thermosetting adhesive sheet, etc. as needed.
The dried thermosetting adhesive sheet can be laminated with a release film or release paper as a separator (protective layer) on the side opposite to the substrate side and wound into a roll. As the release film or release paper, those that can be used as the substrate described above are preferable. When using a thermosetting adhesive sheet with a base material having a separator, the thermosetting adhesive sheet is peeled off from the base material after the separator alone is peeled off.
＜作用効果＞
熱硬化性接着シートにおいては、未硬化の熱硬化性樹脂粒子（Ｃ）を含有しているため、熱硬化性接着シートを、未硬化の熱硬化性樹脂粒子（Ｃ）の融点以上に加熱すれば、未硬化の熱硬化性樹脂粒子（Ｃ）が溶融し、熱硬化性接着シートが通常の熱硬化性接着剤と同様の性状を示し、他の部材との接着が可能となる。特に、溶融した未硬化の熱硬化性樹脂粒子（Ｃ）と熱可塑性樹脂（Ｂ）とが相溶する場合、未硬化の熱硬化性樹脂粒子（Ｃ）の融点以上に加熱したときに未硬化の熱硬化性樹脂粒子（Ｃ）と熱可塑性樹脂（Ｂ）とが均一な組成物となり、これを硬化させたときに優れた接着強度が得られやすい。
<Effect>
Since the thermosetting adhesive sheet contains uncured thermosetting resin particles (C), the thermosetting adhesive sheet is heated to a temperature equal to or higher than the melting point of the uncured thermosetting resin particles (C). For example, the uncured thermosetting resin particles (C) are melted, the thermosetting adhesive sheet exhibits the same properties as a normal thermosetting adhesive, and can be bonded to other members. In particular, when the melted uncured thermosetting resin particles (C) and the thermoplastic resin (B) are compatible, uncured when heated above the melting point of the uncured thermosetting resin particles (C). The thermosetting resin particles (C) and the thermoplastic resin (B) have a uniform composition, and when this is cured, excellent adhesive strength is easily obtained.
また、前記製造方法にあっては、熱硬化性接着剤組成物中の未硬化の熱硬化性樹脂粒子（Ｃ）が固形フィラーとして機能する。これにより熱硬化性接着剤組成物（塗料）に適度な粘性が付与され、厚い塗膜を形成することが可能となる。
未硬化の熱硬化性樹脂粒子（Ｃ）以外の固形フィラーを用いた場合、厚い塗膜を形成することはできるが、熱硬化性接着シートの接着力が低くなる問題がある。固形フィラーを含有させない場合、溶剤を多く入れると厚く塗れない問題があり、溶剤を少なくすると均一に塗れないか、又は全く塗れなくなる問題がある。
本発明では熱硬化性接着シートを厚く構成できるため、基材から熱硬化性接着シートを剥離しやすくなり、被接着体に接着させる場合に貼り付け器具又は人の手による取り扱いが容易となる。また、熱硬化性接着シートを厚く構成できるため、粗面（多孔面）を有する摩擦材と滑面を有する金属部材のような平面度の悪い被着体同士や、平行度の悪い被着体同士を強固に接着できる。
また、融点が溶剤の沸点よりも高い未硬化の熱硬化性樹脂粒子（Ｃ）を用い、（Ｃ）の融点以下の温度で乾燥することで、（Ｃ）を溶融、反応させずに、熱硬化性樹脂（Ａ）同士、熱可塑性樹脂（Ｂ）同士、または、（Ａ）と（Ｂ）同士を反応させて、接着剤の溶融粘度、Ｂステージの状態を調整することが可能となるため、被着体から接着剤のはみ出しを抑えることができる。
Moreover, in the said manufacturing method, the uncured thermosetting resin particle (C) in a thermosetting adhesive composition functions as a solid filler. Thereby, moderate viscosity is provided to the thermosetting adhesive composition (paint), and a thick coating film can be formed.
When a solid filler other than uncured thermosetting resin particles (C) is used, a thick coating film can be formed, but there is a problem that the adhesive strength of the thermosetting adhesive sheet is lowered. When the solid filler is not contained, there is a problem that it cannot be applied thickly when a large amount of solvent is added, and there is a problem that it cannot be applied uniformly or cannot be applied at all when the solvent is decreased.
In the present invention, since the thermosetting adhesive sheet can be made thick, the thermosetting adhesive sheet is easily peeled off from the base material, and when it is adhered to an adherend, it is easy to handle by a sticking instrument or a human hand. In addition, since the thermosetting adhesive sheet can be made thick, adherends with poor flatness, such as a friction material having a rough surface (porous surface) and a metal member having a smooth surface, and adherends with poor parallelism. Can be firmly bonded together.
In addition, by using uncured thermosetting resin particles (C) whose melting point is higher than the boiling point of the solvent, and drying at a temperature not higher than the melting point of (C), without melting (C) and reacting, Because it is possible to adjust the melt viscosity of the adhesive and the state of the B stage by reacting the curable resins (A), the thermoplastic resins (B), or (A) and (B). Further, it is possible to prevent the adhesive from protruding from the adherend.
＜用途＞
熱硬化性接着シートの用途は、特に限定されず、従来、熱硬化性接着シート（シート状の熱硬化性接着剤）が使用されている各種の用途に使用できる。具体例としては、自動車のドラムブレーキにおける金属部品と摩擦材との接着剤、建材用途などが挙げられる。
<Application>
The application of the thermosetting adhesive sheet is not particularly limited, and can be used for various applications in which a thermosetting adhesive sheet (sheet-like thermosetting adhesive) has been conventionally used. Specific examples include adhesives between metal parts and friction materials in automobile drum brakes, and building materials.
以上、本発明の接着シートについて、実施形態を示して説明したが、本発明は上記実施形態に限定されない。上記実施形態における各構成及びそれらの組み合わせ等は一例であり、本発明の趣旨を逸脱しない範囲内で、構成の付加、省略、置換、およびその他の変更が可能である。 The adhesive sheet of the present invention has been described with reference to the embodiment, but the present invention is not limited to the above embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other changes of the configuration can be made without departing from the spirit of the present invention.
以下、実施例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によって限定されるものではない。
（実施例１）
フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）５０質量部とニトリルゴム（アクリロニトリルブタジエン共重合体、ガラス転移温度＝−３０℃、質量平均分子量＝５０×１０４、トルエンに溶解）５０質量部とイミダゾール化合物１０質量部とをトルエン（沸点＝１１０．６℃）３００質量部に溶解した溶液へ、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）５０質量部を混合して液状の熱硬化性接着剤組成物を得た。この熱硬化性接着剤組成物は、ニトリルゴム溶液中に粒状のビスマレイミド樹脂粒子が分散した状態であった。
次に、厚さ３８μｍのポリエチレンテレフタレートフィルム（ＰＥＴフィルム）の片面に、上記熱硬化性接着剤組成物を、乾燥後の厚さが１００μｍになるように塗布し、熱風循環型乾燥機中にて脱溶剤して熱硬化性接着シートを形成した。これにより、ＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.
Example 1
50 parts by mass of phenol resin (resol phenol resin, specific gravity = 1.2, dissolved in toluene) and nitrile rubber (acrylonitrile butadiene copolymer, glass transition temperature = −30 ° C., mass average molecular weight = 50 × 10 4 , dissolved in toluene Bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm) into a solution in which 50 parts by mass and 10 parts by mass of imidazole compound were dissolved in 300 parts by mass of toluene (boiling point = 110.6 ° C.). Insoluble in toluene) 50 parts by mass was mixed to obtain a liquid thermosetting adhesive composition. This thermosetting adhesive composition was in a state where granular bismaleimide resin particles were dispersed in a nitrile rubber solution.
Next, the thermosetting adhesive composition was applied to one side of a 38 μm thick polyethylene terephthalate film (PET film) so that the thickness after drying was 100 μm, and then in a hot air circulating dryer. The solvent was removed to form a thermosetting adhesive sheet. This obtained the thermosetting adhesive sheet of this invention with a PET film.
（実施例２）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を４００質量部とした以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 2)
In the same manner as in Example 1 except that the content of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was 400 parts by mass, the present invention with PET film A thermosetting adhesive sheet was obtained.
（実施例３）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を２００質量部とし、更に有機過酸化物１０質量部を追加した以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 3)
In Example 1, the content of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was 200 parts by mass, and 10 parts by mass of organic peroxide was further added. A thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that.
（実施例４）
実施例１において、フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）５０質量部をフェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）２５質量部及びエポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、比重＝１．１、トルエンに溶解）２５質量部に代えて、更にビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を２００質量部とした以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 4)
In Example 1, phenol resin (resole phenol resin, specific gravity = 1.2, dissolved in toluene) 50 parts by mass phenol resin (resol phenol resin, specific gravity = 1.2, dissolved in toluene) 25 parts by mass and epoxy resin ( Bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) instead of 25 parts by mass, bisphenol A type epoxy resin, specific gravity = 1.1, dissolved in toluene) The thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that the content of was 200 parts by mass.
（実施例５）
実施例１において、フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）５０質量部をフェノール樹脂（レゾールフェノール樹脂、比重＝１．２、融点＝１３５℃、トルエンに溶解）２５質量部及びビスマレイミド樹脂２５質量部（比重１．２、トルエンに溶解）に代えて、更にビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を２００質量部とした以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 5)
In Example 1, phenol resin (resole phenol resin, specific gravity = 1.2, dissolved in toluene) 50 parts by mass phenol resin (resol phenol resin, specific gravity = 1.2, melting point = 135 ° C., dissolved in toluene) 25 mass In addition to 25 parts by mass of bismaleimide resin (specific gravity 1.2, dissolved in toluene), bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) A thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that the content was 200 parts by mass.
（実施例６）
実施例１において、フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）５０質量部をエポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、比重＝１．１、トルエンに溶解）２５質量部及びビスマレイミド樹脂（比重１．２、トルエンに溶解）２５質量部に代えて、更にビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を２００質量部とした以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 6)
In Example 1, phenol resin (resole phenol resin, specific gravity = 1.2, dissolved in toluene) 50 parts by mass epoxy resin (bisphenol A type epoxy resin, specific gravity = 1.1, dissolved in toluene) 25 parts by mass and bis Instead of 25 parts by mass of maleimide resin (specific gravity 1.2, dissolved in toluene), the content of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) A thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that the amount was 200 parts by mass.
（実施例７）
実施例１において、ニトリルゴム（アクリロニトリルブタジエン共重合体、ガラス転移温度＝−３０℃、質量平均分子量＝５０×１０４、トルエンに溶解）５０質量部をアクリルゴム（アクリル酸エステル共重合体、ガラス転移温度＝１５℃、質量平均分子量＝７０×１０４、トルエンに溶解）に代えて、更にビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を２００質量部に代えた以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 7)
In Example 1, 50 parts by mass of nitrile rubber (acrylonitrile butadiene copolymer, glass transition temperature = −30 ° C., mass average molecular weight = 50 × 10 4 , dissolved in toluene) was added to acrylic rubber (acrylic ester copolymer, glass). Instead of transition temperature = 15 ° C., mass average molecular weight = 70 × 10 4 , dissolved in toluene), bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle size 6 μm, undissolved in toluene) The thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that the content of was changed to 200 parts by mass.
（実施例８）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を１００質量部とし、更にレゾールフェノール樹脂粒子（比重＝１．２、融点＝１３５℃、平均粒子径６μｍ、トルエンに未溶解）１００質量部を追加した以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 8)
In Example 1, the content of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was 100 parts by mass, and resol phenol resin particles (specific gravity = 1. (2) Melting point = 135 ° C., average particle diameter 6 μm, undissolved in toluene) A thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that 100 parts by mass was added.
（実施例９）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）の含有量を１００質量部とし、更にエポキシ樹脂粒子（ビフェニル型エポキシ樹脂、比重＝１．２、平均粒子径６μｍ、トルエンに未溶解）１００質量部を追加した以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
Example 9
In Example 1, the content of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was 100 parts by mass, and epoxy resin particles (biphenyl type epoxy resin, A thermosetting adhesive sheet of the present invention with a PET film was obtained in the same manner except that 100 parts by mass (specific gravity = 1.2, average particle size 6 μm, undissolved in toluene) was added.
（実施例１０）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）５０質量部をレゾールフェノール樹脂粒子（比重＝１．２、融点＝１３５℃、平均粒子径６μｍ、トルエンに未溶解）１００質量部及びエポキシ樹脂粒子（ビフェニル型エポキシ樹脂、比重＝１．２、平均粒子径６μｍ、トルエンに未溶解）１００質量部に代えた以外は同様にしてＰＥＴフィルム付き本発明の熱硬化性接着シートを得た。
(Example 10)
In Example 1, 50 parts by mass of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) were added to resole phenol resin particles (specific gravity = 1.2, melting point = 135 ° C.). , Average particle diameter 6 μm, not dissolved in toluene) 100 parts by mass and epoxy resin particles (biphenyl type epoxy resin, specific gravity = 1.2, average particle diameter 6 μm, not dissolved in toluene) 100 parts by mass Thus, a thermosetting adhesive sheet of the present invention with a PET film was obtained.
（比較例１）
実施例１において、フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）の含有量を２５０質量部とし、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）を含有しない以外は同様にしてＰＥＴフィルム付き比較用の熱硬化性接着シートを得た。
(Comparative Example 1)
In Example 1, the content of phenol resin (resole phenol resin, specific gravity = 1.2, dissolved in toluene) was 250 parts by mass, and bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle size) A comparative thermosetting adhesive sheet with a PET film was obtained in the same manner except that it did not contain (6 μm, not dissolved in toluene).
（比較例２）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）５０質量部を２００重量部とし、溶剤をＮ，Ｎ−ジメチルホルムアミド（沸点＝１５３℃）３００質量部とし、マレイミド樹脂粒子を溶解させた以外は同様にしてＰＥＴフィルム付き比較用の熱硬化性接着シートを得た。
(Comparative Example 2)
In Example 1, 50 parts by mass of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was 200 parts by weight, and the solvent was N, N-dimethylformamide (boiling point). = 153 ° C) A thermosetting adhesive sheet for comparison with a PET film was obtained in the same manner except that 300 parts by mass and the maleimide resin particles were dissolved.
（比較例３）
実施例１において、フェノール樹脂（レゾールフェノール樹脂、比重＝１．２、トルエンに溶解）５０質量部をエポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、比重＝１．１、トルエンに溶解）２５０質量部に代えて、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）を含有しない以外は同様にしてＰＥＴフィルム付き比較用の熱硬化性接着シートを得た。
(Comparative Example 3)
In Example 1, 50 parts by mass of phenol resin (resole phenol resin, specific gravity = 1.2, dissolved in toluene) was replaced with 250 parts by mass of epoxy resin (bisphenol A type epoxy resin, specific gravity = 1.1, dissolved in toluene). Thus, a comparative thermosetting adhesive sheet with a PET film was obtained in the same manner except that it did not contain bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene). .
（比較例４）
実施例１において、ビスマレイミド樹脂粒子（比重＝１．４、融点＝１６０℃、平均粒子径６μｍ、トルエンに未溶解）５０質量部をシリカ微粒子（平均粒子径６μｍ）２００質量部に代えた以外は同様にしてＰＥＴフィルム付き比較用の熱硬化性接着シートを得た。
前記実施例１〜１０及び比較例１〜４における熱硬化性接着シートの配合組成をまとめて表１に示した。なお、表中の数値は質量部を意味する。
(Comparative Example 4)
In Example 1, except that 50 parts by mass of bismaleimide resin particles (specific gravity = 1.4, melting point = 160 ° C., average particle diameter 6 μm, undissolved in toluene) was replaced with 200 parts by mass of silica fine particles (average particle diameter 6 μm). In the same manner, a comparative thermosetting adhesive sheet with a PET film was obtained.
Table 1 summarizes the composition of the thermosetting adhesive sheets in Examples 1 to 10 and Comparative Examples 1 to 4. In addition, the numerical value in a table | surface means a mass part.
次に前記実施例１〜１０及び比較例１〜４の熱硬化性接着シートについて、次の評価を行い、その結果を表２に示した。
（厚塗り性）
乾燥後の、ＰＥＴフィルム付き熱硬化性接着シートにおいて、１００μｍ厚の接着シートが作製できたものを○、接着シートが作製できなかったもの（厚塗りできなかったもの、シート化できなかったもの、シートとしてＰＥＴフィルムから取り出せなかったもの）を×とした。
Next, the thermosetting adhesive sheets of Examples 1 to 10 and Comparative Examples 1 to 4 were evaluated as follows, and the results are shown in Table 2.
(Thick coatability)
In the thermosetting adhesive sheet with a PET film after drying, the one that the 100 μm-thick adhesive sheet was able to be produced was ○, the one that the adhesive sheet could not be produced (those that could not be thickly coated, the one that could not be made into a sheet, A sheet that could not be taken out from the PET film as a sheet) was evaluated as x.
（常温せん断強度）
ＰＥＴフィルム付き熱硬化性接着シートについて、ＰＥＴフィルムから熱硬化性接着シートを剥離し、接着面積が２０ｍｍ幅×５ｍｍ長となるように、平板に貼り付けた後、接着剤のもう一方の面に同素材の平板を配置し、０．５ＭＰａで圧締しながら、２００℃で３０分間熱処理をし、積層体を作製した。平板としては、冷間圧延鋼板（ＦＰＣＣ板、２０ｍｍ幅×３０ｍｍ長と９０ｍｍ長、厚さ１．６ｍｍ）を用いた。
得られた積層体について、接着強度の測定を次の通り行った。
２５℃環境下で、得られた積層体の熱硬化性接着シートを平板に対してせん断方向に引張った時の強度（常温せん断強度）を測定した。測定時の被着体−引張試験機のチャック間距離は約８０ｍｍ、引張速度は５０ｍｍ／分とした。測定には（株）今田製作所製の剪断力試験機ＳＬ５０００を使用した。常温せん断強度が３．５ＭＰａ以上のものを○とした。
(Normal temperature shear strength)
About the thermosetting adhesive sheet with PET film, after peeling the thermosetting adhesive sheet from the PET film and pasting it on a flat plate so that the adhesive area is 20 mm wide x 5 mm long, on the other side of the adhesive A flat plate of the same material was placed and heat treated at 200 ° C. for 30 minutes while pressing at 0.5 MPa to produce a laminate. As the flat plate, a cold-rolled steel plate (FPCC plate, 20 mm width × 30 mm length and 90 mm length, thickness 1.6 mm) was used.
About the obtained laminated body, the measurement of adhesive strength was performed as follows.
Under a 25 ° C. environment, the strength (room temperature shear strength) when the thermosetting adhesive sheet of the obtained laminate was pulled in the shear direction with respect to the flat plate was measured. The distance between the adherend and the tensile tester at the time of measurement was about 80 mm, and the tensile speed was 50 mm / min. For the measurement, a shear force tester SL5000 manufactured by Imada Manufacturing Co., Ltd. was used. The one having a normal-temperature shear strength of 3.5 MPa or more was rated as ◯.
（耐熱せん断強度）
上記常温せん断強度と同様の接着強度の測定を、平板を２００℃に加熱させて行った。加熱時間は３分間とした。せん断強度が、１．５ＭＰａ以上を示したものを○、１．５ＭＰａ未満のものを×とした。
(Heat resistant shear strength)
The measurement of the adhesive strength similar to the room temperature shear strength was performed by heating the flat plate to 200 ° C. The heating time was 3 minutes. A sample having a shear strength of 1.5 MPa or more was marked with ◯, and a sample with less than 1.5 MPa was marked with ×.
（溶融粘度）
熱硬化性接着シートを２ｍｍ厚に積層し、レオメーターにて、硬化前の接着シートの常温から３００℃までのせん断粘度を測定した。昇温条件は１０℃／ｍｉｎとした。また、使用機器は、ＨＡＡＫＥ社製ＭＡＲＳレオメーターを使用した。
測定温度域内で、せん断粘度が、５００Ｐａ・ｓ以上示していれば○、５００Ｐａ・ｓ未満であれば×とした。
(Melt viscosity)
A thermosetting adhesive sheet was laminated to a thickness of 2 mm, and the shear viscosity from room temperature to 300 ° C. of the adhesive sheet before curing was measured with a rheometer. The temperature raising condition was 10 ° C./min. The equipment used was a HARS MARS rheometer.
If the shear viscosity is 500 Pa · s or more in the measurement temperature range, it is rated as “good”, and if it is less than 500 Pa · s, it is marked as “poor”.
表２から明らかなように、実施例１〜１０の熱硬化性接着シートは、厚塗り性が良好であり、常温せん断強度も３．５ＭＰａ以上有するため、粗面（多孔面）を有する摩擦材と滑面を有する金属部材のような平面度の悪い被着体同士や、平行度の悪い被着体同士を強固に接着できる。また、実施例１〜１０の熱硬化性接着シートは、耐熱せん断強度が１．５ＭＰａ以上であり、溶融粘度（せん断粘度）が５００Ｐａ・ｓ以上であるため、被着体から接着剤のはみ出しを抑えることができる。
一方、比較例１〜４の熱硬化性接着シートは、厚塗り性、耐熱せん断強度、溶融粘度のいずれかが基準を満たさないため、平面度及び平行度の悪い被着体同士を強固に接着できなかったり、被着体から接着剤のはみ出しを抑えることができなかったりする。
As is apparent from Table 2, the thermosetting adhesive sheets of Examples 1 to 10 have a good thickness coating property and a room temperature shear strength of 3.5 MPa or more, so that the friction material has a rough surface (porous surface). And adherends with poor flatness, such as metal members having a smooth surface, and adherends with poor parallelism can be firmly bonded. In addition, since the thermosetting adhesive sheets of Examples 1 to 10 have a heat-resistant shear strength of 1.5 MPa or more and a melt viscosity (shear viscosity) of 500 Pa · s or more, the adhesive protrudes from the adherend. Can be suppressed.
On the other hand, the thermosetting adhesive sheets of Comparative Examples 1 to 4 firmly adhere to adherends having poor flatness and parallelism because any one of thick coatability, heat-resistant shear strength, and melt viscosity does not satisfy the standard. In some cases, the adhesive cannot stick out from the adherend.
Claims (6)
＜熱可塑性樹脂（Ｂ）＞
ポリオレフィン樹脂及びその変性物、ポリエステル樹脂、（メタ）アクリル樹脂、スチレン樹脂、ポリアミド樹脂、熱可塑性エラストマー、熱可塑性ポリイミド樹脂、ジエン系ゴム及びその水添物、オレフィン系ゴム
＜未硬化の熱硬化性樹脂粒子（Ｃ）＞
エポキシ樹脂、ビスマレイミド樹脂 A thermosetting adhesive sheet obtained from a composition in which a thermosetting resin (A) and one or more thermoplastic resins (B) selected from the following are dissolved in a solvent, the composition An uncured thermosetting resin particle (C) is contained in the product, and the uncured thermosetting resin particle (C) is at least one selected from the following. .
<Thermoplastic resin (B)>
Polyolefin resin and modified products thereof, polyester resin, (meth) acrylic resin, styrene resin, polyamide resin, thermoplastic elastomer, thermoplastic polyimide resin, diene rubber and hydrogenated product thereof, olefin rubber <uncured thermosetting Resin particles (C)>
Epoxy resin, bismaleimide resin
＜熱可塑性樹脂（Ｂ）＞
ポリオレフィン樹脂及びその変性物、ポリエステル樹脂、（メタ）アクリル樹脂、スチレン樹脂、ポリアミド樹脂、熱可塑性エラストマー、熱可塑性ポリイミド樹脂、ジエン系ゴム及びその水添物、オレフィン系ゴム
＜未硬化の熱硬化性樹脂粒子（Ｃ）＞
エポキシ樹脂、ビスマレイミド樹脂 A method for producing a thermosetting adhesive sheet, comprising a thermosetting resin (A), one or more thermoplastic resins (B) selected from the following, and at least one uncured selected from the following: Thermosetting resin particles (C) and liquid thermosetting containing a solvent that dissolves the thermosetting resin (A) and the thermoplastic resin (B) and does not dissolve the uncured thermosetting resin particles (C). A method for producing a thermosetting adhesive sheet, comprising: preparing a thermosetting adhesive composition, applying the liquid thermosetting adhesive composition on a substrate, and then drying to obtain a thermosetting adhesive sheet .
<Thermoplastic resin (B)>
Polyolefin resin and modified products thereof, polyester resin, (meth) acrylic resin, styrene resin, polyamide resin, thermoplastic elastomer, thermoplastic polyimide resin, diene rubber and hydrogenated product thereof, olefin rubber <uncured thermosetting Resin particles (C)>
Epoxy resin, bismaleimide resin
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