JP2011079959A - Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same and reinforced flexible printed wiring board - Google Patents
Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same and reinforced flexible printed wiring board Download PDFInfo
- Publication number
- JP2011079959A JP2011079959A JP2009233278A JP2009233278A JP2011079959A JP 2011079959 A JP2011079959 A JP 2011079959A JP 2009233278 A JP2009233278 A JP 2009233278A JP 2009233278 A JP2009233278 A JP 2009233278A JP 2011079959 A JP2011079959 A JP 2011079959A
- Authority
- JP
- Japan
- Prior art keywords
- thermosetting adhesive
- epoxy resin
- adhesive composition
- mass
- epoxy
- 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 116
- 239000000853 adhesive Substances 0.000 title claims abstract description 94
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 150000007524 organic acids Chemical class 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012790 adhesive layer Substances 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 230000003014 reinforcing effect Effects 0.000 claims description 8
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- RXFZJKXZSLVQJV-UHFFFAOYSA-N icosa-8,12-dienedihydrazide Chemical compound NNC(=O)CCCCCCC=CCCC=CCCCCCCC(=O)NN RXFZJKXZSLVQJV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 23
- 229920001721 polyimide Polymers 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011521 glass Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- -1 acryl Chemical group 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 238000007796 conventional method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RDIGYBZNNOGMHU-UHFFFAOYSA-N 3-amino-2,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound OC1=CC(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 RDIGYBZNNOGMHU-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- PJPRFQPMDKJMRW-UHFFFAOYSA-N hexadecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCCCCCC(=O)NN PJPRFQPMDKJMRW-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- HATIEXJZXOLRAO-UHFFFAOYSA-N octanedihydrazide Chemical compound NNC(=O)CCCCCCC(=O)NN HATIEXJZXOLRAO-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
-
- 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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- 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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
- H05K1/0281—Reinforcement details thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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Abstract
Description
本発明は、アクリル系共重合体、エポキシ樹脂及びエポキシ樹脂用硬化剤を含有する熱硬化性接着組成物に関する。 The present invention relates to a thermosetting adhesive composition containing an acrylic copolymer, an epoxy resin, and a curing agent for epoxy resin.
ポリイミドフィルムからなるフレキシブルプリント配線板の端子部等をポリイミドフィルムやガラスエポキシ板、金属板で裏打ちし、その強度を高めることが行われている。このような場合、補強板とフレキシブルプリント配線板のポリイミドとの間の接着は、それらで挟持した熱硬化性接着剤層を硬化させて接着することが一般的である。このような熱硬化性接着剤層としては、フレキシブルプリント配線板分野においては主として液状エポキシ樹脂と固形エポキシ樹脂とそれらの硬化剤とからなるエポキシ樹脂系接着剤が広く使用されている（特許文献１）。 A terminal portion or the like of a flexible printed wiring board made of a polyimide film is lined with a polyimide film, a glass epoxy board, or a metal plate to increase its strength. In such a case, the adhesion between the reinforcing plate and the polyimide of the flexible printed wiring board is generally performed by curing the thermosetting adhesive layer sandwiched between them and bonding them. As such a thermosetting adhesive layer, an epoxy resin adhesive mainly composed of a liquid epoxy resin, a solid epoxy resin, and a curing agent thereof is widely used in the field of flexible printed wiring boards (Patent Document 1). ).
しかし、このようなエポキシ樹脂系接着剤は、エポキシ樹脂と硬化剤との配合割合が多いため、常温保管中に徐々に硬化反応が進行してしまうという問題があり、常温保管特性に問題があった。そこで、常温保管特性を向上させるために、エポキシ樹脂の配合量を抑制し、反射的にアクリル系ポリマーを主要成分として使用したアクリル系熱硬化性接着組成物が提案されている（特許文献２、特に実施例２）。 However, since such an epoxy resin adhesive has a large blending ratio of epoxy resin and curing agent, there is a problem that the curing reaction gradually proceeds during normal temperature storage, and there is a problem in normal temperature storage characteristics. It was. Therefore, in order to improve the room temperature storage characteristics, an acrylic thermosetting adhesive composition that suppresses the amount of the epoxy resin and uses an acrylic polymer as a main component in a reflective manner has been proposed (Patent Document 2,). Especially Example 2).
しかしながら、特許文献２のアクリル系熱硬化性接着組成物の場合、特許文献１のような従来のエポキシ樹脂系接着剤に比べ、常温保存性は向上するものの、常温で数ヶ月という長期に亘り保管し、その後にフレキシブルプリント基板と樹脂シート、金属補強板あるいはガラスエポキシ板との接合に使用すると接着性（剥離強度）及びリフロー半田耐熱性が低下する場合があり、その改善が求められていた。 However, in the case of the acrylic thermosetting adhesive composition of Patent Document 2, the storage stability at room temperature is improved compared to the conventional epoxy resin adhesive as in Patent Document 1, but it is stored for a long period of several months at room temperature. However, if it is subsequently used for joining a flexible printed circuit board to a resin sheet, a metal reinforcing plate or a glass epoxy plate, the adhesiveness (peeling strength) and the reflow soldering heat resistance may be lowered.
本発明の目的は、以上の従来の技術の課題を解決しようとするものであり、フレキシブルプリント基板等の分野における接着に使用するアクリル系熱硬化性接着組成物であって、ポリイミドフィルム等の樹脂基板と、ポリイミドフィルム、金属補強板あるいはガラスエポキシ基板との間を良好に接着し、数ヶ月という長期に亘って良好な常温保管特性を示すことができるアクリル系熱硬化性接着組成物を提供することである。 The object of the present invention is to solve the above-mentioned problems of the prior art, and is an acrylic thermosetting adhesive composition used for bonding in the field of flexible printed circuit boards, which is a resin such as a polyimide film. Provided is an acrylic thermosetting adhesive composition that can satisfactorily bond between a substrate and a polyimide film, a metal reinforcing plate, or a glass epoxy substrate and can exhibit good room temperature storage characteristics over a long period of several months. That is.
本発明者は、エポキシ樹脂系接着剤の常温保管性を改善するためのエポキシ樹脂用硬化剤として、有機溶剤に溶解し難く常温では固体であるためエポキシ樹脂と反応せず、加熱によりエポキシ樹脂と溶融混合して反応が開始する有機酸ジヒドラジドに着目し、アクリル系共重合体にエポキシ樹脂、エポキシ樹脂用硬化剤として有機酸ジヒドラジドを配合することを研究した。一般に、フィルム状接着シートの製造方法として、上記配合物をメチルエチルケトン等の有機溶剤に溶解・分散し、塗布して製造する方法が採用されているが、有機酸ジヒドラジドの硬化剤粒子は有機溶剤に溶解し難いとはいえ、有機溶剤中では徐々に溶解し、溶解した硬化剤がエポキシ樹脂にも溶解してしまうために反応が進行してしまうという問題があった。このような知見の下、有機酸ジヒドラジドの平均粒径を特定の粒径範囲に制御することにより、常温保管時における有機酸ジヒドラジドの有機溶剤への溶解の抑制と、熱硬化反応の速やかな進行とをバランスよく実現でき、更に、アクリル系共重合体として、特定範囲量のエポキシ基非含有（メタ）アクリル酸エステルモノマーとアクリロニトリルモノマーとエポキシ基含有（メタ）アクリル酸エステルモノマーとの共重合体を採用することにより、上述の目的を達成できることを見出し、本願発明を完成させた。 The present inventor is an epoxy resin curing agent for improving the storage stability of an epoxy resin adhesive at room temperature and does not react with the epoxy resin because it is difficult to dissolve in an organic solvent and is solid at room temperature. Focusing on organic acid dihydrazide, which starts reaction after being melt-mixed, we studied the blending of organic acid dihydrazide as an epoxy resin and a curing agent for epoxy resin in acrylic copolymers. In general, as a method for producing a film-like adhesive sheet, a method in which the above-mentioned compound is dissolved and dispersed in an organic solvent such as methyl ethyl ketone and applied is used. However, the curing agent particles of organic acid dihydrazide are used in an organic solvent. Although it is difficult to dissolve, there is a problem that the reaction progresses because it dissolves gradually in an organic solvent and the dissolved curing agent also dissolves in the epoxy resin. Under such knowledge, by controlling the average particle size of the organic acid dihydrazide to a specific particle size range, the dissolution of the organic acid dihydrazide in the organic solvent during normal temperature storage and the rapid progress of the thermosetting reaction In addition, a copolymer of a specific range amount of an epoxy group-free (meth) acrylate monomer, an acrylonitrile monomer, and an epoxy group-containing (meth) acrylate monomer as an acrylic copolymer. By adopting the above, it was found that the above-mentioned object can be achieved, and the present invention was completed.
即ち、本発明は、アクリル系共重合体（Ａ）、エポキシ樹脂（Ｂ）及びエポキシ樹脂用硬化剤（Ｃ）を含有する熱硬化性接着組成物であって、
該アクリル系共重合体（Ａ）が、エポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）６５〜７５質量％、アクリロニトリルモノマー（ｂ）２０〜３５質量％及びエポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）１〜１０質量％を共重合させたものであり、
該エポキシ樹脂用硬化剤が、平均粒子径０．５〜１５μｍの有機酸ジヒドラジド粒子である熱硬化性接着組成物を提供する。なお、本明細書において、「（メタ）アクリル」なる用語は、「メタクリル又はアクリル」という意味で用いている。
That is, the present invention is a thermosetting adhesive composition containing an acrylic copolymer (A), an epoxy resin (B), and a curing agent for epoxy resin (C),
The acrylic copolymer (A) is an epoxy group-free (meth) acrylic acid ester monomer (a) 65 to 75% by mass, an acrylonitrile monomer (b) 20 to 35% by mass and an epoxy group-containing (meth) acrylic acid. Ester monomer (c) 1-10% by weight copolymerized,
Provided is a thermosetting adhesive composition in which the epoxy resin curing agent is organic acid dihydrazide particles having an average particle size of 0.5 to 15 μm. In the present specification, the term “(meth) acryl” is used to mean “methacryl or acryl”.
また、本発明は、基材フィルム上に、この熱硬化性接着組成物からなる熱硬化性接着層が形成されてなる熱硬化性接着シートを提供する。 Moreover, this invention provides the thermosetting adhesive sheet by which the thermosetting adhesive layer which consists of this thermosetting adhesive composition is formed on a base film.
更に、本発明は、この熱硬化性接着シートの製造方法であって、上述の本発明の熱硬化性接着組成物を有機溶剤に投入し、エポキシ樹脂用硬化剤（Ｃ）を有機溶媒中に分散させ、他方アクリル共重合体（Ａ）及びエポキシ樹脂（Ｂ）を有機溶剤中に溶解させることにより熱硬化性接着層形成用塗料を調製する工程、及び
熱硬化性接着層形成用塗料を、基材フィルム上に塗布し、乾燥することにより熱硬化性接着層を形成する工程
を含んでなる製造方法を提供する。
Furthermore, this invention is a manufacturing method of this thermosetting adhesive sheet, Comprising: The thermosetting adhesive composition of the above-mentioned this invention is thrown into an organic solvent, The hardening | curing agent (C) for epoxy resins is put in an organic solvent. Dispersing the acrylic copolymer (A) and the epoxy resin (B) on the other hand in an organic solvent to prepare a thermosetting adhesive layer forming coating, and a thermosetting adhesive layer forming coating, Provided is a production method comprising a step of forming a thermosetting adhesive layer by applying on a substrate film and drying.
本発明の熱硬化性接着組成物は、ポリイミドフィルム等の樹脂基板と、ポリイミドフィルム、ガラスエポキシ、ステンレス等の金属板との間を良好に接着し（好ましくは１５Ｎ／ｃｍ以上）、しかも数ヶ月という長期に亘って良好なフィルム常温保管特性を示す。また、２６０℃以上のリフロー処理後においても、吸湿のために膨れが生じないという特性も示す。 The thermosetting adhesive composition of the present invention adheres well between a resin substrate such as a polyimide film and a metal plate such as a polyimide film, glass epoxy, and stainless steel (preferably 15 N / cm or more), and for several months. The film shows good room temperature storage characteristics over a long period of time. In addition, even after a reflow treatment at 260 ° C. or higher, there is also a characteristic that swelling does not occur due to moisture absorption.
本発明の熱硬化性接着組成物は、アクリル系共重合体（Ａ）、エポキシ樹脂（Ｂ）及びエポキシ樹脂用硬化剤（Ｃ）を含有する。 The thermosetting adhesive composition of the present invention contains an acrylic copolymer (A), an epoxy resin (B), and a curing agent for epoxy resin (C).
本発明において、アクリル系共重合体（Ａ）は、フィルム成形時に成膜性をもたせ、硬化物に可撓製、強靭性をもたせるためのものであり、エポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）、アクリロニトリルモノマー（ｂ）及びエポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）を共重合させたものである。 In the present invention, the acrylic copolymer (A) is for imparting film-forming properties at the time of film formation, and for making the cured product flexible and tough, and does not contain an epoxy group (meth) acrylic ester. A monomer (a), an acrylonitrile monomer (b), and an epoxy group-containing (meth) acrylic acid ester monomer (c) are copolymerized.
エポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）としては、電子部品分野に適用されている従来のアクリル系熱硬化性接着剤で使用されているものから適宜選択して使用することができ、例えば、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、ｎ−ブチルアクリレート、ｉ−ブチルアクリレート、ｎ−ヘキシルアクリレート、ｎ−オクチルアクリレート、ｉ−オクチルアクリレート、２−エチルヘキシルアクリレート、ｉ−ノニルアクリレート、ステアリルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、ｉ−ブチルメタクリレート、ｎ−ヘキシルメタクリレート、ｎ−オクチルメタクリレート、ｉ−オクチルメタリレート、２−エチルヘキシルメタリレート、ｉ−ノニルメタクリレート、ｎ−ドデシルメタクリレート、ｉ−ドデシルメタクリレート、ステアリルメタクリレート等が挙げられる。中でもブチルアクリレート、エチルアクリレートを使用することが好ましい。 The epoxy group-free (meth) acrylic acid ester monomer (a) can be appropriately selected from those used in conventional acrylic thermosetting adhesives applied in the field of electronic components. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, stearyl Acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate , I- nonyl methacrylate, n- dodecyl methacrylate, i- dodecyl methacrylate, stearyl methacrylate, and the like. Of these, butyl acrylate and ethyl acrylate are preferably used.
アクリル系共重合体（Ａ）を調製する際に使用する全モノマーにおけるエポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）の使用量は、少なすぎると基本特性が低下し、多すぎると耐熱性が低下する傾向があるので、好ましくは６５〜７５質量％、より好ましくは６５〜７０質量％である。 When the amount of the epoxy group-free (meth) acrylic acid ester monomer (a) used in the preparation of the acrylic copolymer (A) is too small, the basic characteristics are lowered. Since there exists a tendency for property to fall, Preferably it is 65-75 mass%, More preferably, it is 65-70 mass%.
アクリロニトリルモノマー（ｂ）は、耐熱性を向上するために使用されている。 Acrylonitrile monomer (b) is used to improve heat resistance.
アクリル系共重合体（Ａ）を調製する際に使用する全モノマーにおけるアクリロニトリルモノマー（ｂ）の使用量は、少なすぎると耐熱性が低下し、多すぎると溶剤に溶解し難くなる傾向があるので、好ましくは２０〜３５質量％、より好ましくは２５〜３０質量％である。 When the amount of the acrylonitrile monomer (b) used in preparing all the acrylic copolymers (A) is too small, the heat resistance is lowered, and when it is too much, it tends to be difficult to dissolve in the solvent. , Preferably 20 to 35% by mass, more preferably 25 to 30% by mass.
エポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）は、エポキシ樹脂用硬化剤と反応し、熱硬化性接着組成物の硬化物に３次元架橋構造を形成するために使用されている。３次元架橋構造が形成されると硬化物の耐湿性及び耐熱性が向上し、例えば、熱硬化性接着組成物の硬化物でフレキシブルプリント配線板に接着固定された補強樹脂シートからなる補強フレキシブルプリント配線板を、２２０℃以上でのハンダ処理（例えばハンダリフロー処理）を行った場合でも、その接着固定部に、吸湿を原因とする膨れ現象が発生することを防止することが可能となる。このようなエポキシ基含有（メタ）アクリル酸エステルモノマー（ａ）としては、電子部品分野に適用されている従来のアクリル系熱硬化性接着剤で使用されているものから適宜選択して使用することができ、例えば、グリシジルアクリレート（ＧＭＡ）、グリシジルメタクリレート（ＧＭＡ）等が挙げられる。中でも、安全性、市場入手容易性の点からグルシジルメタクリレート（ＧＭＡ）を使用することが好ましい。 The epoxy group-containing (meth) acrylic acid ester monomer (c) is used for reacting with a curing agent for epoxy resin to form a three-dimensional cross-linked structure in the cured product of the thermosetting adhesive composition. When a three-dimensional cross-linked structure is formed, the moisture resistance and heat resistance of the cured product are improved. For example, a reinforced flexible print made of a reinforced resin sheet bonded and fixed to a flexible printed wiring board with a cured product of a thermosetting adhesive composition. Even when the wiring board is subjected to a soldering process (for example, a solder reflow process) at 220 ° C. or higher, it is possible to prevent a swelling phenomenon due to moisture absorption from occurring in the adhesive fixing portion. Such an epoxy group-containing (meth) acrylic acid ester monomer (a) is appropriately selected from those used in conventional acrylic thermosetting adhesives applied in the field of electronic components. Examples thereof include glycidyl acrylate (GMA) and glycidyl methacrylate (GMA). Among these, glycidyl methacrylate (GMA) is preferably used from the viewpoint of safety and market availability.
アクリル系共重合体（Ａ）を調製する際に使用する全モノマーにおけるエポキシ基含有（メタ）アクリル酸エステルモノマー（ａ）の使用量は、少なすぎると耐熱性が低下し、多すぎると剥離強度が低下する傾向があるので、好ましくは１〜１０質量％、より好ましくは３〜７質量％である。 When the amount of the epoxy group-containing (meth) acrylic acid ester monomer (a) used in the preparation of the acrylic copolymer (A) is too small, the heat resistance is lowered. Therefore, it is preferably 1 to 10% by mass, more preferably 3 to 7% by mass.
以上説明したエポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）、アクリロニトリルモノマー（ｂ）及びエポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）からアクリル系共重合体の調製は、公知の共重合方法を適用して行うことができる。 Preparation of an acrylic copolymer from the epoxy group-free (meth) acrylic acid ester monomer (a), acrylonitrile monomer (b) and epoxy group-containing (meth) acrylic acid ester monomer (c) described above is a known copolymer. The polymerization method can be applied.
本発明において使用するアクリル系共重合体（Ａ）は、その重量平均分子量が小さすぎると剥離強度並びに耐熱性が低下し、大きすぎると溶液粘度が上がり、塗布性が悪化する傾向があるので、好ましくは５０００００〜７０００００、より好ましくは５５００００〜６５００００の重量平均分子量を有することが好ましい。 If the acrylic copolymer (A) used in the present invention has a weight-average molecular weight that is too small, the peel strength and heat resistance will decrease, and if it is too large, the solution viscosity will increase, and the applicability will tend to deteriorate. Preferably it has a weight average molecular weight of 500,000 to 700,000, more preferably 550000 to 650000.
本発明の熱硬化性接着組成物を構成するエポキシ樹脂（Ｂ）は、３次元網目構造を形成し、耐熱性、接着性を良好にするために使用されるものである。 The epoxy resin (B) constituting the thermosetting adhesive composition of the present invention is used for forming a three-dimensional network structure and improving heat resistance and adhesiveness.
エポキシ樹脂（Ｂ）としては、電子部品分野に適用されている従来のエポキシ樹脂系熱硬化性接着剤で使用されている液状あるいは固体状のエポキシ樹脂から適宜選択して使用することができ、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ポリアルキレンポリオール（ネオペンチルグリコールなど）ポリグリシジエーテル、テトラグリシジルジアミノジフェニルメタン、トリグリシジル−ｐ−アミノフェノール、トリグリシジル−ｍ−アミノフェノール、テトラグリシジル−ｍ−キシレンジアミン、ジグリシジルフタレート、ジグリシジルヘキサヒドロフタレート、ジグリシジルテトラヒドロフタレート、ビニルシクロヘキセンジオキシド、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、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート等が挙げられる。 As the epoxy resin (B), it can be appropriately selected from liquid or solid epoxy resins used in conventional epoxy resin-based thermosetting adhesives applied in the field of electronic components. For example, Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, polyalkylene polyol (such as neopentyl glycol) polyglycol Sidiether, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-m-xylenediamine, diglycidyl phthalate, diglycidyl hexahi Rofutareto, diglycidyl tetrahydrophthalate, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexyl methyl) adipate, and the like.
本発明の熱硬化性接着組成物におけるエポキシ樹脂（Ｂ）の使用量は、少なすぎると耐熱性が低下し、多すぎると接着性が低下する傾向があるので、アクリル系共重合体（Ａ）１００質量部に対し、好ましくは５〜３０質量部、より好ましくは１０〜２０質量部である。 When the amount of the epoxy resin (B) used in the thermosetting adhesive composition of the present invention is too small, the heat resistance is lowered, and when it is too much, the adhesiveness tends to be lowered. Therefore, the acrylic copolymer (A) Preferably it is 5-30 mass parts with respect to 100 mass parts, More preferably, it is 10-20 mass parts.
本発明の熱硬化性接着組成物は、エポキシ樹脂（Ｂ）及びアクリル系共重合体（Ａ）を調製する際に使用されたエポキシ基含有（メタ）アクリル酸エステルモノマーに由来するエポキシ基と反応するエポキシ樹脂硬化剤（Ｃ）として、平均粒子径０．５〜１５μｍ、好ましくは１〜５μｍの有機酸ジヒドラジド粒子を使用する。有機酸ジヒドラジドを使用する理由は、それが常温で固体であるため熱硬化性接着組成物の常温保管特性を向上させることができるためである。また、有機酸ジヒドラジド粒子の平均粒子径を０．５〜１５μｍとした理由は、０．５μｍ未満であると熱硬化性接着組成物の塗布のために有機溶剤を使用した場合に、有機酸ジヒドラジド粒子が溶解する可能性が高まり、常温保管特性が低下することが危惧されるからであり、逆に１５μｍより大きいと熱硬化性接着組成物の塗布性が低下し、また、粒度が大きい為にアクリルポリマーやエポキシ樹脂との溶融時に十分に混合できなくなることが懸念されるからである。 The thermosetting adhesive composition of the present invention reacts with an epoxy group derived from an epoxy group-containing (meth) acrylic acid ester monomer used in preparing the epoxy resin (B) and the acrylic copolymer (A). As the epoxy resin curing agent (C) to be used, organic acid dihydrazide particles having an average particle diameter of 0.5 to 15 μm, preferably 1 to 5 μm are used. The reason for using the organic acid dihydrazide is that it is solid at room temperature, so that the room temperature storage characteristics of the thermosetting adhesive composition can be improved. The reason why the average particle diameter of the organic acid dihydrazide particles is 0.5 to 15 μm is that when the organic solvent is used for application of the thermosetting adhesive composition, the organic acid dihydrazide is less than 0.5 μm. This is because the possibility of dissolution of the particles is increased, and there is a concern that the storage property at room temperature may be deteriorated. Conversely, if the particle size is larger than 15 μm, the applicability of the thermosetting adhesive composition is deteriorated, and the acrylic particle size is increased due to the large particle size. This is because there is a concern that the polymer and the epoxy resin cannot be sufficiently mixed when melted.
このような有機酸ジヒドラジドとしては、従来よりエポキシ樹脂の硬化剤として使用されている有機酸ジヒドラジドの中から適宜選択して使用することができ、例えば、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、イミノジ酢酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカンジオヒドラジド、ヘキサデカンジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、ジグリコール酸ジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６−ナフトエ酸ジヒドラジド、４，４’−ビスベンゼンジヒドラジド、１，４−ナフトエ酸ジヒドラジド、アミキュアＶＤＨ、アミキュアＵＤＨ（商品名、味の素（株）製）、クエン酸トリヒドラジド等が挙げられる。これらは１種単独であるいは２種以上組み合わせても使用することができる。これらの中でも比較的低融点であり、硬化性のバランスに優れ、入手が容易であるという点から、アジピン酸ジヒドラジドまたは７，１１−オクタデカジエン−１，１８−ジカルボヒドラジドを使用することが好ましい。 Such an organic acid dihydrazide can be appropriately selected from organic acid dihydrazides conventionally used as curing agents for epoxy resins. For example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide , Iminodiacetic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, hexadecanedihydrazide, maleic acid dihydrazide, diglycolic acid diglycolic acid diglycolic acid diglycolic acid diglycolic acid Dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphtho Acid dihydrazide, Amicure VDH, Amicure UDH (trade name, manufactured by Ajinomoto Co.), trihydrazide etc. citric acid. These can be used alone or in combination of two or more. Among these, adipic acid dihydrazide or 7,11-octadecadien-1,18-dicarbohydrazide is used because it has a relatively low melting point, excellent balance of curability, and is easily available. preferable.
本発明の熱硬化性接着組成物におけるエポキシ樹脂用硬化剤（Ｃ）の使用量は、少なすぎると未反応のエポキシ基が残り、架橋も十分でないため、耐熱性、接着性が低下し、多すぎると過剰の硬化剤が未反応のまま残るため、耐熱性、接着性が低下する傾向があるので、アクリル系共重合体（Ａ）及びエポキシ樹脂（Ｂ）の合計１００質量部に対し、好ましくは４〜２０質量部、より好ましくは６〜１５質量部である。 If the amount of the curing agent for epoxy resin (C) used in the thermosetting adhesive composition of the present invention is too small, unreacted epoxy groups remain and crosslinking is not sufficient, resulting in a decrease in heat resistance and adhesiveness. Too much curing agent remains unreacted, and heat resistance and adhesiveness tend to decrease. Therefore, it is preferable for a total of 100 parts by mass of the acrylic copolymer (A) and the epoxy resin (B). Is 4 to 20 parts by mass, more preferably 6 to 15 parts by mass.
本発明の熱硬化性接着組成物は、以上説明した成分に加えて、本発明の効果を損なわない範囲で必要に応じ、有機酸ジヒドラジドの溶解を促進させないような金属不活性剤、消泡剤、防錆剤、分散剤等の公知の添加剤を配合することができる。 The thermosetting adhesive composition of the present invention includes, in addition to the components described above, a metal deactivator and an antifoaming agent that do not promote the dissolution of the organic acid dihydrazide as necessary within the range not impairing the effects of the present invention. Well-known additives such as a rust inhibitor and a dispersant can be blended.
本発明の熱硬化性接着組成物は、アクリル系共重合体（Ａ）、エポキシ樹脂（Ｂ）、エポキシ樹脂用硬化剤（Ｃ）及びその他の添加剤を、常法により均一に混合することにより調製することができる。その形態としては、ペースト、フィルム、分散液状などとすることができる。中でも、保管性や使用時のハンドリング性などの観点から、ポリエチレンテレフタレートフィルム、ポリイミドフィルム等に必要に応じてシリコーン等で剥離処理した基材フィルム（剥離基材）に、本発明の熱硬化性接着組成物からなる熱硬化性接着層が１０〜５０μｍの厚さで形成されてなる熱硬化性接着シートの態様として使用することが好ましい。 The thermosetting adhesive composition of the present invention is obtained by uniformly mixing an acrylic copolymer (A), an epoxy resin (B), a curing agent for epoxy resin (C), and other additives by a conventional method. Can be prepared. The form can be a paste, a film, a dispersed liquid, or the like. Above all, from the viewpoints of storability and handling at the time of use, the thermosetting adhesion of the present invention is applied to a base film (peeling base) that is peeled off with silicone or the like as necessary on a polyethylene terephthalate film, a polyimide film or the like. It is preferable that the thermosetting adhesive layer made of the composition is used as an embodiment of a thermosetting adhesive sheet formed with a thickness of 10 to 50 μm.
このような熱硬化性接着シートの製造方法は、以下の熱硬化性接着層形成用塗料調製工程及び熱硬化性接着層形成工程を含む。 Such a method for producing a thermosetting adhesive sheet includes the following thermosetting adhesive layer forming coating preparation step and thermosetting adhesive layer forming step.
＜熱硬化性接着層形成用塗料調製工程＞
まず、本発明の熱硬化性接着組成物をメチルエチルケトン、トルエン等の有機溶剤に塗布法に応じた粘度となるように投入し、エポキシ樹脂用硬化剤（Ｃ）を有機溶剤中に分散させ、他方アクリル共重合体（Ａ）及びエポキシ樹脂（Ｂ）を有機溶剤中に溶解させることにより熱硬化性接着層形成用塗料を調製する。この場合、室温下で全有機酸ジヒドラジド粒子の７０質量％が熱硬化性接着層形成用塗料中に固体粒子として分散していることが好ましい。熱硬化性接着シートの常温保管性を高めるためである。
<The coating preparation process for thermosetting adhesive layer formation>
First, the thermosetting adhesive composition of the present invention is charged into an organic solvent such as methyl ethyl ketone and toluene so as to have a viscosity corresponding to the coating method, and the epoxy resin curing agent (C) is dispersed in the organic solvent. A thermosetting adhesive layer-forming coating material is prepared by dissolving the acrylic copolymer (A) and the epoxy resin (B) in an organic solvent. In this case, it is preferable that 70% by mass of the total organic acid dihydrazide particles are dispersed as solid particles in the thermosetting adhesive layer-forming coating material at room temperature. This is for improving the room temperature storage property of the thermosetting adhesive sheet.
＜熱硬化性接着層形成工程＞
次に、熱硬化性接着層形成用塗料を、基材フィルム上にバーコーター、ロールコーターにより乾燥厚が１０〜５０μｍとなるように塗布し、常法により乾燥することにより熱硬化性接着層を形成する。これにより熱硬化性接着シートを得ることができる。
<Thermosetting adhesive layer forming step>
Next, the thermosetting adhesive layer-forming coating material is applied on the base film with a bar coater or roll coater so that the dry thickness is 10 to 50 μm, and dried by a conventional method to form the thermosetting adhesive layer. Form. Thereby, a thermosetting adhesive sheet can be obtained.
以上説明した熱硬化性接着組成物及び熱硬化性接着シートは、電子部品分野に好ましく適用できる。特に、上述の熱硬化性接着シートは、フレキシブルプリント配線板の端子部等と、その裏打ちするためのポリエチレンテレフタレート、ポリイミド、ガラスエポキシ、ステンレス、アルミニウム等の厚さ５０μｍ〜２ｍｍの補強用樹脂シートとを接着固定するために好ましく適用でき、その適用により、フレキシブルプリント配線板の端子部と補強用樹脂シートとが、本発明の熱硬化性接着シートの基材フィルムを除いた熱硬化性接着層の熱硬化物で接着固定されてなる補強フレキシブルプリント配線板が得られる。 The thermosetting adhesive composition and the thermosetting adhesive sheet described above can be preferably applied to the field of electronic components. In particular, the thermosetting adhesive sheet described above includes a terminal portion of a flexible printed wiring board and a reinforcing resin sheet having a thickness of 50 μm to 2 mm, such as polyethylene terephthalate, polyimide, glass epoxy, stainless steel, and aluminum for backing the flexible printed wiring board. Can be preferably applied to bond and fix the terminal portion of the flexible printed wiring board and the reinforcing resin sheet of the thermosetting adhesive layer excluding the base film of the thermosetting adhesive sheet of the present invention. A reinforced flexible printed wiring board obtained by bonding and fixing with a thermosetting material is obtained.
以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples.
実施例１〜１０，比較例１〜８
（１）アクリル系共重合体の調製
表１及び表２に示したモノマーからなるアクリル系共重合体を用意した。これらのアクリル系共重合体の重量平均分子量を表１及び表２に示した。
Examples 1-10, Comparative Examples 1-8
(1) Preparation of acrylic copolymer An acrylic copolymer composed of the monomers shown in Tables 1 and 2 was prepared. The weight average molecular weights of these acrylic copolymers are shown in Tables 1 and 2.
（２）熱硬化接着層形成用塗料の調製
得られたアクリル系共重合体溶液に、表１及び表２の配合割合でエポキシ樹脂（Ｂ）及びエポキシ樹脂用硬化剤（Ｃ）として有機酸ジヒドラジドとを添加し、均一に混合することにより熱硬化性接着組成物として、熱硬化性接着層形成用塗料を調製した。得られた塗料の粘度をＢ型粘度計により測定し、表１及び表２に示した。
(2) Preparation of paint for forming thermosetting adhesive layer In the obtained acrylic copolymer solution, organic acid dihydrazide as epoxy resin (B) and epoxy resin curing agent (C) in the blending ratios of Tables 1 and 2 Was added and mixed uniformly to prepare a thermosetting adhesive layer-forming coating material as a thermosetting adhesive composition. The viscosities of the obtained paints were measured with a B-type viscometer and are shown in Tables 1 and 2.
（３）熱硬化性接着シートの作製
得られた熱硬化性接着層形成用塗料を、剥離処理が施されたポリエチレンテレフタレートフィルムに塗布し、５０〜１３０℃の乾燥炉中で乾燥し、３５μｍ厚の熱硬化性接着層を形成することにより、熱硬化性接着シートを作成した。
(3) Production of thermosetting adhesive sheet The obtained thermosetting adhesive layer-forming coating material was applied to a polyethylene terephthalate film that had been subjected to a release treatment, dried in a drying oven at 50 to 130 ° C., and 35 μm thick. A thermosetting adhesive sheet was prepared by forming a thermosetting adhesive layer.
（４）熱硬化性接着層形成用塗料の塗布性の評価
上述の熱硬化性接着シートの作製の際、熱硬化性接着層形成用塗料の塗布性について、以下の基準に従って評価した。得られた評価結果を表１及び表２に示す。
(4) Evaluation of applicability of the thermosetting adhesive layer-forming coating material When the thermosetting adhesive sheet was prepared, the applicability of the thermosetting adhesive layer-forming coating material was evaluated according to the following criteria. The obtained evaluation results are shown in Tables 1 and 2.
AA：接着剤厚みが均一で塗布中に筋を引かず、外観においても硬化剤粒子が観察されない場合
Ａ：塗布中に筋は引かないが、乾燥後のフィルムに硬化剤粒子が観察される場合
Ｂ：塗布筋があり、厚みも不均一である場合
Ｃ：溶液がゲル状となり、塗布が不可能な場合
AA: When the adhesive thickness is uniform, no streaks are drawn during application, and no hardener particles are observed in appearance. A: No streaks are drawn during application, but hardener particles are observed in the dried film. B: When there are application stripes and the thickness is non-uniform C: When the solution becomes a gel and application is impossible
（５）剥離強度の評価
得られた直後の熱硬化性接着シートを所定の大きさの短冊（５ｃｍ×１０ｃｍ）にカットし、その熱硬化性接着層を、１７５μｍ厚のポリイミドフィルム（１７５ＡＨ、カネカ（株）製）に８０℃に設定したラミネーターで仮貼りした後、基材フィルムを取り除いて熱硬化性接着層を露出させた。露出した熱硬化性接着層に対し、同じ大きさの５０μｍ厚のポリイミドフィルム（２００Ｈ、デュポン社）を上から重ね合わせ、１７０℃で２．０ＭＰａの圧力で６０秒間加熱加圧した後、１４０℃のオーブン中に６０分間保持した。
(5) Evaluation of peel strength The thermosetting adhesive sheet immediately after being obtained is cut into a strip (5 cm × 10 cm) of a predetermined size, and the thermosetting adhesive layer is formed into a 175 μm-thick polyimide film (175AH, Kaneka). After being temporarily attached to a manufactured product) with a laminator set at 80 ° C., the base film was removed to expose the thermosetting adhesive layer. A 50 μm thick polyimide film (200H, DuPont) of the same size is superimposed on the exposed thermosetting adhesive layer from above, heated and pressurized at 170 ° C. and a pressure of 2.0 MPa for 60 seconds, and then 140 ° C. In an oven for 60 minutes.
また、短冊（５ｃｍ×１０ｃｍ）にカットした熱硬化性接着シートの熱硬化性接着層を、０．５ｍｍのＳＵＳ３０４板または厚さ１ｍｍのガラスエポキシ板に押し当てて仮貼りした後、基材フィルムを取り除いて熱硬化性接着層を露出させた。露出した熱硬化性接着層に対し、短冊状の厚さ５０μｍのポリイミドフィルム（５ｃｍ×１０ｃｍ）を上から重ね合わせ、１７０℃で２．０ＭＰａの圧力で６０秒間加熱加圧した後、１４０℃のオーブン中に６０分間保持した。 In addition, after the thermosetting adhesive layer of the thermosetting adhesive sheet cut into a strip (5 cm × 10 cm) is pressed against a 0.5 mm SUS304 plate or a 1 mm thick glass epoxy plate, the substrate film is temporarily attached. Was removed to expose the thermosetting adhesive layer. A strip-shaped polyimide film (5 cm × 10 cm) having a thickness of 50 μm is superimposed on the exposed thermosetting adhesive layer, heated and pressurized at 170 ° C. and a pressure of 2.0 MPa for 60 seconds, and then heated at 140 ° C. Hold in oven for 60 minutes.
その後、ポリイミドフィルムに対し、剥離速度５０ｍｍ／ｍｉｎで９０度剥離試験を行い、引き剥がすに要した力を測定した。得られた結果を表１及び表２に示す。剥離強度は実用上１０Ｎ／ｃｍであることが望まれている。また、常温６ヶ月保管後の剥離強度と初期の剥離強度との差が−３０％未満であることが望まれている。従って、差が２Ｎ／ｃｍ未満の場合を常温保管特性が良好とし、超えると不良とした。 Thereafter, a 90 ° peel test was performed on the polyimide film at a peel speed of 50 mm / min, and the force required for peeling was measured. The obtained results are shown in Tables 1 and 2. Peel strength is desired to be 10 N / cm practically. Moreover, it is desired that the difference between the peel strength after storage at room temperature for 6 months and the initial peel strength is less than -30%. Therefore, when the difference is less than 2 N / cm, the room temperature storage characteristics are good, and when it exceeds, the result is bad.
また、２５℃で５ヶ月間常温保管した熱硬化性接着シートについても、同様の剥離強度の評価を行った。得られた結果を表１及び表２に示す。
The same peel strength was also evaluated for the thermosetting adhesive sheet stored at room temperature for 5 months at 25 ° C. The obtained results are shown in Tables 1 and 2.
＊４：グリシジルメタクリレート、＊５：２−ヒドロキシエチルメタクリレート、＊６：アクリル酸、
＊７：アジピン酸ジヒドラジド、＊８：７，１１−オクタデカジエン−１，１８−ジカルボヒドラジド
＊９：ｊＥＲ８２８、ジャパンエポキシレジン社、＊１０：ｊＥＲ１５４、ジャパンエポキシレジン社
* 7: Adipic acid dihydrazide, * 8: 7,11-octadecadien-1,18-dicarbohydrazide * 9: jER828, Japan Epoxy Resin, * 10: jER154, Japan Epoxy Resin
＜表１及び表２の結果の考察＞
実施例１〜７の熱硬化性接着シートは、アクリル系共重合体（Ａ）が、エポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）６５〜７５質量％、アクリロニトリルモノマー（ｂ）２０〜３５質量％及びエポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）１〜１０質量％を共重合させたものであり、エポキシ樹脂用硬化剤が、平均粒子径０．５〜１５μｍの有機酸ジヒドラジド粒子であるので、塗布性も初期剥離強度、常温保管特性も満足のいくものであった。
<Consideration of results in Tables 1 and 2>
In the thermosetting adhesive sheets of Examples 1 to 7, the acrylic copolymer (A) is an epoxy group-free (meth) acrylic acid ester monomer (a) 65 to 75% by mass, and an acrylonitrile monomer (b) 20 to 20%. An organic acid dihydrazide obtained by copolymerizing 35% by mass and 1-10% by mass of an epoxy group-containing (meth) acrylic acid ester monomer (c) and having an average particle diameter of 0.5 to 15 μm. Since it was a particle, the applicability, the initial peel strength, and the room temperature storage characteristics were satisfactory.
なお、実施例８の熱硬化性接着シートは、アクリル系共重合体（Ａ）の重量平均分子量が３０万と実施例１〜７の熱硬化性接着シートに比べて低いため、常温保管特性は良好なものの、全体的に剥離強度及び耐熱性が低めであった。 In addition, since the thermosetting adhesive sheet of Example 8 has a low weight average molecular weight of 300,000 of the acrylic copolymer (A) as compared with the thermosetting adhesive sheets of Examples 1 to 7, room temperature storage characteristics are Although good, the overall peel strength and heat resistance were low.
実施例９の熱硬化性接着シートは、アクリル系共重合体（Ａ）の重量平均分子量が９０万と実施例１〜７の熱硬化性接着シートに比べて高いため、有機溶剤で更に希釈する必要があったが、常温保管特性は良好なものであった。ただ、希釈しているため全体的に剥離強度が低めであった。 The thermosetting adhesive sheet of Example 9 is further diluted with an organic solvent because the weight average molecular weight of the acrylic copolymer (A) is 900,000, which is higher than those of Examples 1-7. Although necessary, the room temperature storage characteristics were good. However, the peel strength was generally low due to dilution.
実施例１０の熱硬化性接着シートの場合、有機酸ジヒドラジドの平均粒径が実施例１〜７の熱硬化性接着シートに比べて大きいため、塗布性が若干低下し、また、常温保管特性は良好なものであったが、全体的に剥離強度が低めであった。また、ヒドラジド粒子が大きすぎるため反応性が低下し、剥離強度、耐熱性が十分でなかった。 In the case of the thermosetting adhesive sheet of Example 10, since the average particle size of the organic acid dihydrazide is larger than that of the thermosetting adhesive sheets of Examples 1 to 7, the applicability is slightly reduced, and the room temperature storage characteristics are Although it was good, the peel strength was generally low. Moreover, since the hydrazide particle | grains were too large, the reactivity fell, and peeling strength and heat resistance were not enough.
それに対し、比較例１の熱硬化性接着シートは、アクリル系共重合体における成分（ａ）が少なすぎ、成分（ｂ）が多すぎるので、有機溶剤に十分に溶解せず、ゲル化してしまった。 On the other hand, since the thermosetting adhesive sheet of Comparative Example 1 has too little component (a) and too much component (b) in the acrylic copolymer, it does not sufficiently dissolve in the organic solvent and gels. It was.
比較例２の熱硬化性接着シートは、アクリル系共重合体における成分（ａ）が多すぎ、成分（ｂ）が少なすぎるので、常温保管特性は良好なものであったが、初期剥離強度が実用に適さない低いレベルであった。 Since the thermosetting adhesive sheet of Comparative Example 2 has too much component (a) and too little component (b) in the acrylic copolymer, the room temperature storage characteristics were good, but the initial peel strength was The level was not suitable for practical use.
比較例３の熱硬化性接着シートは、アクリル系共重合体における成分（ｃ）が少なすぎるので、常温保管特性は良好なものであったが、初期剥離強度が実用に適さない低いレベルであった。 Since the thermosetting adhesive sheet of Comparative Example 3 had too little component (c) in the acrylic copolymer, the room temperature storage characteristics were good, but the initial peel strength was a low level not suitable for practical use. It was.
比較例４の熱硬化性接着シートは、アクリル系共重合体における成分（ｃ）が多すぎるので、常温保管特性は良好なものであったが、初期剥離強度が実用に適さない低いレベルであった。 Since the thermosetting adhesive sheet of Comparative Example 4 had too much component (c) in the acrylic copolymer, the room temperature storage characteristics were good, but the initial peel strength was a low level not suitable for practical use. It was.
比較例５の熱硬化性接着シートは、有機酸ジヒドラジドの平均粒径が大きすぎるので、初期剥離強度が実用に適さない低いレベルであった。 In the thermosetting adhesive sheet of Comparative Example 5, the average particle size of the organic acid dihydrazide was too large, so the initial peel strength was at a low level not suitable for practical use.
比較例６〜８の熱硬化性接着シートは、アクリル系共重合体に水酸基またはカルボキシル基が存在するため、常温保管特性が不良であった。 The thermosetting adhesive sheets of Comparative Examples 6 to 8 had poor room temperature storage characteristics because of the presence of hydroxyl groups or carboxyl groups in the acrylic copolymer.
実施例１１
実施例１〜１０及び比較例２〜８の熱硬化性接着シートを使用して以下に説明するように補強フレキシブルプリント配線板を作製した。
Example 11
Reinforcing flexible printed wiring boards were produced using the thermosetting adhesive sheets of Examples 1 to 10 and Comparative Examples 2 to 8 as described below.
＜吸湿リフロー半田耐熱性試験＞
短冊（２ｃｍ×２ｃｍ）にカットした熱硬化性接着シートの熱硬化性接着層を、１７５μｍ厚のポリイミドフィルム（アピカル１７５ＡＨ、カネカ（株）製）に８０℃に設定したラミネーターで仮張りした後、剥離基材を取り除いて熱硬化性接着層を露出させた。露出した熱硬化性接着層に対し、同じ大きさの厚さ５０μｍ厚のポリイミドフィルム（カプトン２００Ｈ、デュポン社製）を上から重ね合わせ、１７０℃で２．０ＭＰａの圧力で６０秒間加熱加圧した後、１４０度のオーブン中で６０分間保持した。その後、加熱硬化した試験片を４０℃、９０％ＲＨの湿熱オーブン中で９６時間放置した。
<Hygroscopic reflow solder heat resistance test>
After the thermosetting adhesive layer of the thermosetting adhesive sheet cut into a strip (2 cm × 2 cm) was temporarily attached to a 175 μm-thick polyimide film (Apical 175AH, manufactured by Kaneka Corporation) with a laminator set at 80 ° C., The release substrate was removed to expose the thermosetting adhesive layer. On the exposed thermosetting adhesive layer, a polyimide film (Kapton 200H, manufactured by DuPont) having the same size and a thickness of 50 μm was superimposed from above and heated and pressurized at 170 ° C. and a pressure of 2.0 MPa for 60 seconds. Thereafter, it was kept in an oven at 140 degrees for 60 minutes. Thereafter, the heat-cured test piece was left in a wet heat oven at 40 ° C. and 90% RH for 96 hours.
湿熱処理直後の試験片をトップ温度２６０℃×３０秒に設定したリフロー炉を通過させ、通過後の試験片に膨れ、剥がれ等の外観異常がないかを目視観察し、外観に全く異常がない場合を“Ａ”と評価し、試験片に膨れがわずかに観察されるが実用上問題がない場合を“Ｂ”と評価し、試験片に発泡によるフクレが観察される場合を“Ｃ”と評価した。得られた結果を表３及び表４に示す。 The test piece immediately after the wet heat treatment is passed through a reflow furnace set at a top temperature of 260 ° C. × 30 seconds, and the test piece after passing is visually observed for abnormal appearance such as swelling and peeling, and there is no abnormality in the appearance. The case was evaluated as “A”, the swelling was observed slightly on the test piece, but the case where there was no practical problem was evaluated as “B”, and the case where blistering due to foaming was observed on the test piece as “C” evaluated. The obtained results are shown in Tables 3 and 4.
吸湿リフロー半田耐熱性試験の結果、実施例１〜１０の熱硬化性接着シートを使用した補強フレキシブルプリント配線板は、外観に異常が全く観察されないか、または試験片に膨れがわずかに観察されたが実用上問題がなかった。特に、実施例１〜７の熱硬化性接着シートを使用した補強フレキシブルプリント配線板は、アクリル共重合体−エポキシ樹脂−ヒドラジド架橋構造のバランスがよく、未反応の原料が殆ど残存しないために、外観に異常が全く観察されなかった。 As a result of the moisture absorption reflow soldering heat resistance test, the reinforced flexible printed wiring board using the thermosetting adhesive sheets of Examples 1 to 10 showed no abnormality in appearance, or slight swelling was observed on the test piece. There was no problem in practical use. In particular, the reinforced flexible printed wiring board using the thermosetting adhesive sheets of Examples 1 to 7 has a good balance of acrylic copolymer-epoxy resin-hydrazide cross-linked structure, and almost no unreacted raw material remains. No abnormality was observed in the appearance.
他方、比較例２〜８の場合、比較例４を除き、２５℃／６ヶ月後には、試験片に発泡によるフクレが観察された。なお比較例４の場合、良好な架橋構造のために吸湿リフロー半田耐熱性は良好ではあったが、前述したように、初期剥離強度が実用に適さない低いレベルであった。 On the other hand, in the case of Comparative Examples 2 to 8, except for Comparative Example 4, after 25 ° C / 6 months, swelling due to foaming was observed on the test piece. In the case of Comparative Example 4, although the moisture absorption reflow solder heat resistance was good due to a good cross-linked structure, the initial peel strength was at a low level not suitable for practical use as described above.
本発明の熱硬化性接着組成物及び熱硬化性接着シートは、ポリイミドフィルム等の樹脂基板と、ポリイミドフィルム、ステンレス板あるいはガラスエポキシ基板との間を、良好に接着でき、しかも数ヶ月という長期に亘って良好な常温保管特性を示す。また、２６０℃リフロー処理しても、吸湿のために膨れが生じないようにできる。従って、ポリイミド材料を多用する電子部品分野における接着剤として有用である。 The thermosetting adhesive composition and thermosetting adhesive sheet of the present invention can satisfactorily bond between a resin substrate such as a polyimide film and a polyimide film, a stainless steel plate or a glass epoxy substrate, and for a long period of several months. It exhibits good room temperature storage characteristics. Moreover, even if it carries out a 260 degreeC reflow process, it can prevent that a swelling arises for moisture absorption. Therefore, it is useful as an adhesive in the field of electronic components that frequently use polyimide materials.
Claims (9)
該アクリル系共重合体（Ａ）が、エポキシ基非含有（メタ）アクリル酸エステルモノマー（ａ）６５〜７５質量％、アクリロニトリルモノマー（ｂ）２０〜３５質量％及びエポキシ基含有（メタ）アクリル酸エステルモノマー（ｃ）１〜１０質量％を共重合させたものであり、
該エポキシ樹脂用硬化剤が、平均粒子径０．５〜１５μｍの有機酸ジヒドラジド粒子である熱硬化性接着組成物。 A thermosetting adhesive composition containing an acrylic copolymer (A), an epoxy resin (B), and a curing agent for epoxy resin (C),
The acrylic copolymer (A) is an epoxy group-free (meth) acrylic acid ester monomer (a) 65 to 75% by mass, an acrylonitrile monomer (b) 20 to 35% by mass and an epoxy group-containing (meth) acrylic acid. Ester monomer (c) 1-10% by weight copolymerized,
A thermosetting adhesive composition, wherein the epoxy resin curing agent is organic acid dihydrazide particles having an average particle size of 0.5 to 15 µm.
請求項１〜６のいずれかに記載の熱硬化性接着組成物を有機溶剤に投入し、エポキシ樹脂用硬化剤（Ｃ）を有機溶媒中に分散させ、他方アクリル共重合体（Ａ）及びエポキシ樹脂（Ｂ）を有機溶剤中に溶解させることにより熱硬化性接着層形成用塗料を調製する工程、及び
熱硬化性接着層形成用塗料を、基材フィルム上に塗布し、乾燥することにより熱硬化性接着層を形成する工程
を含んでなる製造方法。 A method for producing a thermosetting adhesive sheet according to claim 7,
The thermosetting adhesive composition according to any one of claims 1 to 6 is charged into an organic solvent, and the epoxy resin curing agent (C) is dispersed in the organic solvent, while the acrylic copolymer (A) and the epoxy are dispersed. The step of preparing a thermosetting adhesive layer-forming coating material by dissolving the resin (B) in an organic solvent, and applying the thermosetting adhesive layer-forming coating material on the substrate film and drying to heat A production method comprising a step of forming a curable adhesive layer.
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| JP2009233278A JP5728804B2 (en) | 2009-10-07 | 2009-10-07 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same, and reinforced flexible printed wiring board |
| CN201080045247.5A CN102549097B (en) | 2009-10-07 | 2010-07-26 | Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
| CN201510763270.2A CN105331308B (en) | 2009-10-07 | 2010-07-26 | Thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
| PCT/JP2010/062492 WO2011043119A1 (en) | 2009-10-07 | 2010-07-26 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing same, and reinforced flexible printed wiring board |
| KR1020127009008A KR101702694B1 (en) | 2009-10-07 | 2010-07-26 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing same, and reinforced flexible printed wiring board |
| TW099126891A TWI565772B (en) | 2009-10-07 | 2010-08-12 | Thermosetting followed by composition, thermosetting followed by sheet, method for producing the same, and a reinforcing flexible printed wiring board |
| HK12109993.4A HK1169135A1 (en) | 2009-10-07 | 2012-10-10 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing same, and reinforced flexible printed wiring board |
| HK16109624.7A HK1221481A1 (en) | 2009-10-07 | 2016-08-12 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing same, and reinforced flexible printed wiring board |
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| WO2013183486A1 (en) * | 2012-06-06 | 2013-12-12 | デクセリアルズ株式会社 | Thermosetting resin composition, heat-curable adhesive sheet, and process for producing heat-curable adhesive sheet |
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| KR20170063820A (en) * | 2014-11-12 | 2017-06-08 | 데쿠세리아루즈 가부시키가이샤 | Heat-curable adhesive composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201113340A (en) | 2011-04-16 |
| KR20120092594A (en) | 2012-08-21 |
| CN105331308B (en) | 2017-11-28 |
| WO2011043119A1 (en) | 2011-04-14 |
| CN102549097A (en) | 2012-07-04 |
| TWI565772B (en) | 2017-01-11 |
| JP5728804B2 (en) | 2015-06-03 |
| HK1221481A1 (en) | 2017-06-02 |
| HK1169135A1 (en) | 2013-01-18 |
| KR101702694B1 (en) | 2017-02-06 |
| CN102549097B (en) | 2015-12-02 |
| CN105331308A (en) | 2016-02-17 |
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