JP2003313526A - Adhesive composition for flexible printed wiring board lamination and adhesive film - Google Patents
Adhesive composition for flexible printed wiring board lamination and adhesive filmInfo
- Publication number
- JP2003313526A JP2003313526A JP2002153114A JP2002153114A JP2003313526A JP 2003313526 A JP2003313526 A JP 2003313526A JP 2002153114 A JP2002153114 A JP 2002153114A JP 2002153114 A JP2002153114 A JP 2002153114A JP 2003313526 A JP2003313526 A JP 2003313526A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- adhesive
- adhesive film
- printed wiring
- flexible printed
- 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.)
- Pending
Links
- 239000002313 adhesive film Substances 0.000 title claims abstract description 36
- 239000000853 adhesive Substances 0.000 title claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000003475 lamination Methods 0.000 title abstract 3
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 21
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 15
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000010030 laminating Methods 0.000 claims description 5
- 230000037303 wrinkles Effects 0.000 abstract description 11
- 230000008961 swelling Effects 0.000 abstract description 10
- 239000012787 coverlay film Substances 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- -1 ethyl methacrylate Chemical compound 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006082 mold release agent Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000000576 coating method 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
- 239000013557 residual solvent Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-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
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はプレス加工性、耐熱
性、接着性に優れるフレキシブルプリント配線板（以下
ＦＰＣ）積層用接着剤組成物及び接着フィルムに関す
る。TECHNICAL FIELD The present invention relates to an adhesive composition and an adhesive film for flexible printed wiring board (FPC) laminating, which are excellent in press workability, heat resistance and adhesiveness.
【０００２】[0002]
【従来の技術】近年、電子機器の高性能化、高機能化、
小型化の要求から、ＦＰＣが多く使用され、特に、民生
機器に多用されている。そのＦＰＣに使用される接着フ
ィルムについても接着性、はんだ耐熱性、電気絶縁性、
屈曲性など高性能のものが求められるようになってき
た。また、ＦＰＣの形成時において、接着フィルムとカ
バーレイフィルム面や回路面との間に脹れや熱収縮によ
るしわが発生するなど、作業性や加工性が問題になって
きている。特に、熱プレスでＦＰＣを成形する場合、Ｆ
ＰＣ全面に均等な圧力と熱を加えるため、従来の接着フ
ィルムでは流動しやすく、脹れや熱収縮によるしわが発
生しやすいという問題がある。2. Description of the Related Art In recent years, electronic devices have been improved in performance and function,
Due to the demand for miniaturization, FPCs are often used, and in particular, they are widely used for consumer equipment. Regarding the adhesive film used for the FPC, adhesiveness, solder heat resistance, electrical insulation,
Higher performance such as flexibility has been demanded. In addition, workability and workability are becoming a problem when wrinkles are generated between the adhesive film and the coverlay film surface or the circuit surface due to swelling or heat shrinkage during the formation of the FPC. Especially when FPC is formed by hot press, F
Since a uniform pressure and heat are applied to the entire surface of the PC, there is a problem that the conventional adhesive film easily flows and wrinkles easily occur due to swelling or heat shrinkage.
【０００３】このような背景から、諸特性とともに、プ
レス加工時において、接着フィルムとカバーレイフィル
ム面や回路面との間に脹れや熱収縮によるしわの発生を
抑制したＦＰＣ用接着フィルムが要求されるようになっ
てきた。From such a background, in addition to various characteristics, there is a demand for an adhesive film for FPC which suppresses the generation of wrinkles due to swelling or thermal contraction between the adhesive film and the coverlay film surface or the circuit surface during press working. It has started to be done.
【０００４】従来、ＦＰＣ接着フィルム用の接着剤とし
ては、アクリロニトリルブタジエンゴム／フェノール樹
脂、アクリロニトリルブタジエンゴム／エポキシ樹脂／
フェノール樹脂、アクリロニトリルブタジエンゴム／エ
ポキシ樹脂、エポキシ樹脂／ポリエステル樹脂、エポキ
シ樹脂／アクリル樹脂、アクリル樹脂等が用いられる。
しかし、これらの接着剤は、一長一短があり、必ずしも
前記諸特性を満足しておらず、混合組成のバラツキや、
硬化の不均一性などの点から、プレス加工時において、
脹れや熱収縮によるしわが発生しやすくなるなど、従来
の接着剤では、プレス加工性を満足するものが少なかっ
た。Conventionally, as an adhesive for an FPC adhesive film, acrylonitrile butadiene rubber / phenol resin, acrylonitrile butadiene rubber / epoxy resin /
Phenol resin, acrylonitrile butadiene rubber / epoxy resin, epoxy resin / polyester resin, epoxy resin / acrylic resin, acrylic resin and the like are used.
However, these adhesives have merits and demerits, and do not necessarily satisfy the above various characteristics, and variations in the mixed composition,
Due to non-uniformity of curing, etc.
There are few conventional adhesives that satisfy the press workability, such as wrinkles due to swelling and heat shrinkage.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記諸欠点
を解消して、諸特性とともに、プレス加工時において、
接着フィルムとカバーレイフィルム面や回路面との間
に、脹れや熱収縮によるしわの発生を抑制したＦＰＣ用
接着フィルムを提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned various drawbacks and, together with various characteristics, during press working,
It is an object of the present invention to provide an adhesive film for FPC in which generation of wrinkles due to swelling or heat shrinkage is suppressed between the adhesive film and the coverlay film surface or the circuit surface.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
を解決するために、鋭意研究を行った結果、低分子量ア
クリル樹脂を添加することで、硬化時の熱収縮や相溶性
を大幅に向上することが可能となり、膨れやしわの発生
を抑制することを見いだし、本発明に至ったものであ
る。すなわち、本発明によれば、ＦＰＣ用接着フィルム
において、接着剤組成物が、カルボン酸を官能基として
含有する高分子量アクリルゴム（Ａ）、低分子量アクリ
ル樹脂（Ｂ）、エポキシ樹脂（Ｃ）、フェノール樹脂
（Ｄ）、硬化剤または硬化触媒（Ｅ）からなることを特
徴とするフレキシブルプリント配線板積層用接着剤組成
物にある。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the addition of a low molecular weight acrylic resin significantly reduces heat shrinkage and compatibility during curing. Therefore, the present invention has been found to be possible to suppress the occurrence of blisters and wrinkles, and has reached the present invention. That is, according to the present invention, in the FPC adhesive film, the adhesive composition has a high molecular weight acrylic rubber (A) containing a carboxylic acid as a functional group, a low molecular weight acrylic resin (B), an epoxy resin (C), A flexible printed wiring board laminating adhesive composition comprising a phenol resin (D), a curing agent or a curing catalyst (E).
【０００７】[0007]
【発明実施の形態】本発明の詳細を以下に説明する。DETAILED DESCRIPTION OF THE INVENTION The details of the present invention will be described below.
【０００８】本発明の接着剤組成物に用いるカルボキシ
ル基含有アクリルゴム（Ａ）とは、少なくとも１分子中
にカルボキシル基を１個以上有するアクリルゴムであ
り、アクリル酸アルキルエステル（メタアクリル酸エス
テルも含む、以下同様）を主成分とし、カルボキシル基
を有するビニル単量体と必要に応じてアクリロニトリ
ル、スチレン等を含む共重合体である。アクリル酸アル
キルエステルとしては例えば、アクリル酸エチル（メタ
クリル酸エチルも含む、以下同様）、アクリル酸プロピ
ル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル
酸オクチル、アクリル酸２−エチルヘキシル、アクリル
酸ウンデシル、アクリル酸ラウリル、等の単量体及び、
アクリル酸２−ヒドロキシエチル、アクリル酸２ヒドロ
キシルプロピル、アリルアルコール等の水酸基を有する
単量体、グリシジルアクリレート、ジメチルアミノエチ
ルアクリレート等のエピクロルヒドリン変成物のエポキ
シ基を有する単量体等があげられる。これらのなかか
ら、１種類または２種類以上を選択して使用できる。カ
ルボキシル基を有するビニル単量体としては例えば、ア
クリル酸、メタクリル酸、イタコン酸、クロトン酸、マ
レイン酸、無水マレイン酸があげられるが、これらに限
定されるものではない。The carboxyl group-containing acrylic rubber (A) used in the adhesive composition of the present invention is an acrylic rubber having at least one carboxyl group in at least one molecule, and is an alkyl acrylate (also methacrylic acid ester). A copolymer containing a vinyl monomer having a carboxyl group and, if necessary, acrylonitrile, styrene, etc. as a main component. Examples of alkyl acrylates include ethyl acrylate (including ethyl methacrylate, the same applies below), propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, undecyl acrylate, acrylic acid. Monomers such as lauryl, and
Examples thereof include monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and allyl alcohol, and monomers having an epoxy group of epichlorohydrin modified compound such as glycidyl acrylate and dimethylaminoethyl acrylate. From these, one kind or two or more kinds can be selected and used. Examples of vinyl monomers having a carboxyl group include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and maleic anhydride.
【０００９】アクリルゴム（Ａ）の重合方法としては塊
状重合、溶液重合、乳化重合、懸濁重合があげられる
が、塩析工程を必要とせず、マイグレーションの低下の
原因となる乳化剤の影響を受けにくい懸濁重合が好まし
い。The acrylic rubber (A) can be polymerized by bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, but it does not require a salting-out step and is affected by an emulsifier which causes a decrease in migration. The difficult suspension polymerization is preferred.
【００１０】本発明の接着剤組成物に用いるアクリルゴ
ム（Ａ）は、ＧＰＣによる数平均分子量が５０〜１１０
万であるであることが好ましい。５０万より小さいと、
リフローはんだ耐熱性が得られず、また、１１０万より
大きいと、溶液粘度が高く、接着フィルム形成時に加工
性が悪いという問題を生じる。The acrylic rubber (A) used in the adhesive composition of the present invention has a number average molecular weight by GPC of 50 to 110.
It is preferable that it is ten thousand. If it is less than 500,000,
If the reflow soldering heat resistance cannot be obtained, and if it is more than 1.1 million, the solution viscosity is high and the workability is poor at the time of forming the adhesive film.
【００１１】本発明の接着剤組成物に低分子量アクリル
樹脂（Ｂ）は、（メタ）アクリル酸エステルを主成分と
する重合性不飽和結合を有するモノマーを重合させるこ
とにより形成される。このような（メタ）アクリル酸エ
ステルの例としては、（メタ）アクリル酸メチル、（メ
タ）アクリル酸エチル、（メタ）アクリル酸プロピル、
（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチ
ル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸
−２−エチルヘキシル、（メタ）アクリル酸オクチル、
（メタ）アクリル酸ノニル、（メタ）アクリル酸デシ
ル、（メタ）アクリル酸ドデシルのような（メタ）アク
リル酸アルキルエステル、また、シクロヘキシル（メ
タ）アクリレートのような（メタ）アクリル酸の脂環属
アルコールとのエステル、さらに、（メタ）アクリル酸
フェニル、（メタ）アクリル酸ベンジルのような（メ
タ）アクリル酸アリールエステルを挙げることができ
る。このような（メタ）アクリル酸エステルは、単独で
あるいは組み合わせて使用することができる。The low molecular weight acrylic resin (B) in the adhesive composition of the present invention is formed by polymerizing a monomer having a polymerizable unsaturated bond containing (meth) acrylic acid ester as a main component. Examples of such (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, Pentyl (meth) acrylate, Hexyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, Octyl (meth) acrylate,
Alkyl ester of (meth) acrylic acid such as nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and alicyclic group of (meth) acrylic acid such as cyclohexyl (meth) acrylate Mention may be made of esters with alcohols as well as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. Such (meth) acrylic acid ester can be used alone or in combination.
【００１２】本発明の接着剤組成物に低分子量アクリル
樹脂（Ｂ）は、ＧＰＣによる数平均分子量が４千〜１万
であるであることが好ましい。４千より小さいと、エポ
キシ樹脂やフェノール樹脂の分子量に近くなり、また、
１万より大きいと、アクリルゴムの分子量に近くなり、
いずれも、硬化段階で、均一に反応し難くなり、プレス
加工性において、膨れやしわが発生するという問題を生
じる。The low molecular weight acrylic resin (B) in the adhesive composition of the present invention preferably has a number average molecular weight by GPC of 4,000 to 10,000. If it is less than 4,000, it will be close to the molecular weight of epoxy resin or phenol resin,
If it is more than 10,000, it will be close to the molecular weight of acrylic rubber,
In both cases, it becomes difficult to react uniformly during the curing stage, and in press workability, problems such as swelling and wrinkling occur.
【００１３】本発明の熱硬化性接着剤に用いるエポキシ
樹脂（Ｃ）は、多官能エポキシ樹脂であり、１分子中に
エポキシ基を２個以上有するものであれば良く、特に限
定されるものではないが、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、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
ノールノボラック型等のノボラック型エポキシ樹脂、グ
リシジルアミン型エポキシ樹脂等が挙げられる。また、
これらのエポキシ樹脂は、単独で、あるいは必要に応じ
て２種以上併用して用いることができる。エポキシ樹脂
の配合量は、カルボキシル基含有アクリルゴム１００重
量部に対し、１０〜９０重量部が好ましく、１０重量部
未満では、架橋密度の低下から、リフローはんだ付け耐
熱性が低下し、また、９０重量部を越えると、接着強さ
が低下する等の問題を生じる。The epoxy resin (C) used in the thermosetting adhesive of the present invention is a polyfunctional epoxy resin, as long as it has two or more epoxy groups in one molecule, and is not particularly limited. Examples thereof include novolak type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type, cresol novolac type and bisphenol novolac type, and glycidyl amine type epoxy resin. Also,
These epoxy resins can be used alone or in combination of two or more as required. The compounding amount of the epoxy resin is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber, and when the amount is less than 10 parts by weight, the reflow soldering heat resistance is decreased due to the decrease of the crosslink density, and 90 If it exceeds the weight part, problems such as a decrease in adhesive strength occur.
【００１４】本発明の接着剤組成物に用いるフェノール
樹脂（Ｄ）は、レゾール型のものであれば良く、フェノ
ール樹脂の分子量、軟化点、ＯＨ当量は特に制限されな
い。レゾール型フェノール樹脂の配合量は、カルボキシ
ル基含有アクリルゴム１００重量部に対し、５〜５０重
量部が好ましく、５重量部未満では、架橋密度が低下
し、リフローはんだ付け耐熱性が低下する。また、５０
重量部を越えると、フィルムとしての貯蔵安定性が損な
われ、接着強さが低下する等の問題を生じる。The phenol resin (D) used in the adhesive composition of the present invention may be of a resol type, and the molecular weight, softening point and OH equivalent of the phenol resin are not particularly limited. The amount of the resol-type phenolic resin to be blended is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber, and if it is less than 5 parts by weight, the crosslink density is lowered and the reflow soldering heat resistance is lowered. Also, 50
If it exceeds the weight part, the storage stability of the film is impaired and the adhesive strength is lowered.
【００１５】硬化剤（Ｅ）は、公知のエポキシ樹脂の硬
化剤として用いられるものであれば良く、特に限定され
るものではないが、例えば、脂肪族アミン系硬化剤、芳
香族アミン系硬化剤、酸無水物系硬化剤、ジシアンジア
ミド、三沸化硼素アミン錯塩、イミダゾール化合物等が
例示される。これらの硬化剤の配合量は、エポキシ樹脂
１００重量部に対して０．１〜１０重量部が必要であ
り、好ましくは１〜５重量部である。０．１重量部未満
では、エポキシ樹脂の十分な硬化が得られず、リフロー
はんだ付け耐熱性、電気特性が低下し、１０重量部を越
えると接着性が低下し、貯蔵安定性が悪くなる等の問題
を生じる。The curing agent (E) is not particularly limited as long as it is used as a known curing agent for epoxy resins, and examples thereof include aliphatic amine curing agents and aromatic amine curing agents. , Acid anhydride-based curing agents, dicyandiamide, boron trifluoride amine complex salts, imidazole compounds and the like. The blending amount of these curing agents is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 0.1 parts by weight, the epoxy resin cannot be sufficiently cured and the heat resistance and electric properties of reflow soldering are deteriorated. If the amount is more than 10 parts by weight, the adhesiveness is decreased and the storage stability is deteriorated. Cause problems.
【００１６】無機充てん剤としては、例えば、水酸化ア
ルミニウム、水酸化マグネシウム等の金属水酸化物、酸
化アルミニウム、酸化カルシウム等の金属酸化物、その
他、シリカ、マイカ、タルク、クレー等が挙げられる。
これらは、単独あるいは必要に応じて２種以上併用して
用いることができる。これらの無機充てん剤の配合量
は、１〜５０重量部が好ましく、１重量部未満では、フ
ィルムに粘性が残り、フィルム打ち抜き加工性が低下す
る。また、５０重量部以上では、フィルムに脆性が現
れ、接着強さが低下する等の問題を生じる。Examples of the inorganic fillers include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, metal oxides such as aluminum oxide and calcium oxide, and silica, mica, talc, clay and the like.
These may be used alone or in combination of two or more as required. The blending amount of these inorganic fillers is preferably from 1 to 50 parts by weight, and when the amount is less than 1 part by weight, the film remains viscous and the film punching processability is deteriorated. On the other hand, if the amount is 50 parts by weight or more, the film becomes brittle and the adhesive strength is lowered.
【００１７】これらの成分はメチルエチルケトン、トル
エン、メタノール、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジ
メチルホルムアミド等の有機溶剤に溶解して使用され
る。These components are used by dissolving them in an organic solvent such as methyl ethyl ketone, toluene, methanol, N-methylpyrrolidone and N, N-dimethylformamide.
【００１８】無機充填剤を添加した場合は、ボールミル
等を用いて、粒径を１０μｍ以下に調整する。１０μｍ
より大きいと、接着フィルムとした時、フィルム表面に
凹凸が発生し、接着性、はんだ耐熱性の低下及び外観性
を損ねる。When an inorganic filler is added, the particle size is adjusted to 10 μm or less using a ball mill or the like. 10 μm
When it is larger than the above range, when the adhesive film is formed, unevenness is generated on the film surface, which deteriorates adhesiveness, solder heat resistance and appearance.
【００１９】本発明に用いられる離型紙としては、特に
限定されるものではないが、例えば、上質紙、クラフト
紙、ロール紙、グラシン紙などの紙の両面に、クレー、
ポリエチレン、ポリプロピレンなどの目止剤の塗布層を
設け、さらにその各塗布層の上にシリコーン系、フッ素
系、アルキド系の離型剤が塗布されたもの、及び、ポリ
エチレン、ポリプロピレン、エチレン−α−オレフィン
共重合体、プロピレン−α−オレフィン共重合体等の各
種オレフィンフィルム単独、及びポリエチレンテレフタ
レート等のフィルム上に上記離型剤を塗布したものが挙
げられるが、塗布された接着剤層との離型力、シリコー
ンが電気特性に悪影響を与える等の理由から、上質紙の
両面にポリプロピレン目止処理しその上にアルキド系離
型剤を用いたもの、ポリエチレンテレフタレート上にア
ルキド系離型剤を用いたものが好ましい。The release paper used in the present invention is not particularly limited, and examples thereof include fine paper, kraft paper, roll paper, glassine paper, and the like.
A coating layer of a sealing agent such as polyethylene or polypropylene is provided, and a silicone-based, fluorine-based or alkyd-based mold release agent is further coated on each coating layer, and polyethylene, polypropylene, ethylene-α- Olefin copolymers, various olefin films such as propylene-α-olefin copolymers alone, and those obtained by coating the release agent on a film such as polyethylene terephthalate, but the release from the coated adhesive layer. For reasons such as mold force and silicone adversely affecting the electrical characteristics, polypropylene sealing treatment is applied to both sides of high-quality paper, and an alkyd-based mold release agent is used on top of it, and an alkyd-based mold release agent is used on polyethylene terephthalate. Those that have been used are preferred.
【００２０】接着フィルムは接着剤溶液を離型紙上に直
接コーティングし、有機溶剤を乾燥することで得られ
る。コーティング方法としては、特に限定されないが、
コンマコーター、リバースロールコーター等が挙げられ
る。乾燥後の接着フィルム厚みは、必要に応じて、適宜
変更されるが、好ましくは５〜２００μｍの範囲であ
る。接着フィルム厚が５μｍ未満では、層間絶縁の信頼
性が低下する。２００μｍ以上では乾燥が不十分で、残
留溶剤が多くなり、ＦＰＣ製造のプレス時にフクレを生
じるという問題点が挙げられる。乾燥条件は特に限定さ
れないが、乾燥後の残留溶剤率は１％以下が好ましい。
１％以上では、ＦＰＣプレス時に残留溶剤が発泡して、
フクレを生じるという問題点が挙げられる。The adhesive film is obtained by directly coating the release agent paper with the adhesive solution and drying the organic solvent. The coating method is not particularly limited,
Examples include a comma coater and a reverse roll coater. The thickness of the adhesive film after drying is appropriately changed as necessary, but is preferably in the range of 5 to 200 μm. When the thickness of the adhesive film is less than 5 μm, the reliability of interlayer insulation decreases. When the thickness is 200 μm or more, there is a problem that the drying is insufficient, the residual solvent increases, and blisters occur during pressing in FPC production. The drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% or less.
If it is 1% or more, residual solvent foams during FPC pressing,
The problem is that it causes blisters.
【００２１】[0021]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００２２】（実施例１）
（１）低分子量アクリル樹脂〔Ｉ］の調整
滴下ロート、攪拌機、温度計、窒素ガス導入管、及び冷
却管を備えたフラスコに、ラジカル重合開始剤として反
応するアゾビスイソブチロニトリル０．２８ｇを用い、
重合単量体としてメタクリル酸ブチル３３１ｇ、アクリ
ル酸２−ヒドロキシエチル２０．８ｇ投入し、窒素ガス
雰囲気下で内温が９０℃に上昇するまで攪拌しながら重
合し、数平均分子量が４，６００の低分子量アクリル樹
脂〔Ｉ〕を得た。Example 1 (1) Preparation of Low Molecular Weight Acrylic Resin [I] Azo that reacts as a radical polymerization initiator in a flask equipped with a dropping funnel, stirrer, thermometer, nitrogen gas introducing tube, and cooling tube. Using 0.28 g of bisisobutyronitrile,
Butyl methacrylate (331 g) and 2-hydroxyethyl acrylate (20.8 g) were added as polymerization monomers and polymerized while stirring under a nitrogen gas atmosphere until the internal temperature rose to 90 ° C., and the number average molecular weight was 4,600. A low molecular weight acrylic resin [I] was obtained.
【００２３】（２）接着剤溶液の調整
懸濁重合によってえられたカルボキル基含有のアクリル
ゴムＷＳ０２３ＤＲ（帝国化学産業製）を１００重量部
に対し、数平均分子量が４，６００の低分子量アクリル
樹脂〔Ｉ〕を２５重量部、クレゾールノボラック型エポ
キシ樹脂のＥＳＣＮ２２０Ｓ（住友化学株式会社製）を
５０重量部、レゾール型フェノール樹脂のヒタノールＨ
２１８１（日立化成工業製）１０重量部、硬化剤として
ジシアンジアミド１重量部、無機充填剤として酸化珪素
のアエロジル２００（日本アエロジル社製）２０重量部
をメチルエチルケトンに溶解、分散し、不揮発分２０％
溶液とした。この溶液を、ボールミルを用いて無機充填
剤を十分に分散して接着剤溶液とした。接着剤溶液の固
形分比を(2) Preparation of Adhesive Solution A low molecular weight acrylic resin having a number average molecular weight of 4,600 per 100 parts by weight of a carboxyl group-containing acrylic rubber WS023DR (manufactured by Teikoku Kagaku Sangyo) obtained by suspension polymerization. [I] 25 parts by weight, cresol novolac type epoxy resin ESCN220S (manufactured by Sumitomo Chemical Co., Ltd.) 50 parts by weight, resol type phenolic resin Hitanol H
2181 (manufactured by Hitachi Chemical Co., Ltd.), 1 part by weight of dicyandiamide as a curing agent, and 20 parts by weight of Aerosil 200 of silicon oxide (manufactured by Nippon Aerosil Co., Ltd.) as an inorganic filler are dissolved and dispersed in methyl ethyl ketone to give a nonvolatile content of 20%.
It was a solution. The inorganic filler was sufficiently dispersed in this solution using a ball mill to prepare an adhesive solution. The solid content ratio of the adhesive solution
【表１】に示した。The results are shown in [Table 1].
【００２４】[0024]
【表１】 [Table 1]
【００２５】（３）接着フィルムの作成
１３０μｍ厚の上質紙の両面にポリプロピレン目止処理
しその上にアルキド系離型剤を用いたものに乾燥後の接
着剤厚みが２５μｍになるように接着剤溶液を塗付し、
熱風乾燥機中で９０℃３分乾燥して接着フィルムとし
た。(3) Preparation of Adhesive Film A high-quality paper having a thickness of 130 μm was subjected to polypropylene sealing treatment on both sides, and an alkyd-based mold release agent was further applied to the adhesive so that the adhesive thickness after drying would be 25 μm. Apply the solution,
An adhesive film was obtained by drying in a hot air drier at 90 ° C. for 3 minutes.
【００２６】（特性の評価） （１）プレス加工性
２５μｍポリイミドフィルムＫａｐｔｏｎ１００Ｈ（デ
ュポン社製）２枚の間に接着フィルムを挟み込んだ試験
片をプレス温度１７０℃、圧力１ＭＰａ、時間３分間、
加熱圧着して、表面の膨れやしわを観察した。
（２）接着強さ
２５μｍポリイミドフィルムＫａｐｔｏｎ１００Ｈ（デ
ュポン社製）と、３０μｍの圧延銅箔の間に、接着フィ
ルムを挟み込み、真空プレスを用いて、プレス温度１７
０℃、圧力１ＭＰａ、時間３分間加熱圧着した後、１５
０℃２時間後硬化した試験片をＪＩＳＣ６４８１に準拠
し、９０°剥離強度を測定した。
（３）流れ出し性
３０μｍ圧延銅箔２枚の間に接着フィルムを挟み込んだ
試験片に直径３０ｍｍの円を打ち抜き、これをプレス温
度１７０℃、圧力３ＭＰａ、時間３分間圧着して、端部
からの流れ出し量を観察した。(Evaluation of characteristics) (1) Press workability A test piece in which an adhesive film was sandwiched between two 25 μm polyimide films Kapton 100H (manufactured by DuPont) was pressed at a temperature of 170 ° C., a pressure of 1 MPa, and a time of 3 minutes.
The surface was swollen and wrinkled by hot pressing. (2) Adhesive strength 25 μm Polyimide film Kapton 100H (manufactured by DuPont) and rolled copper foil of 30 μm, the adhesive film is sandwiched, and the press temperature is 17 using a vacuum press.
After thermocompression bonding at 0 ° C, pressure 1 MPa, time 3 minutes, 15
The 90 ° peel strength of the test piece after 2 hours of curing at 0 ° C was measured according to JIS C6481. (3) Flowability A circle having a diameter of 30 mm was punched out from a test piece in which an adhesive film was sandwiched between two rolled 30 μm rolled copper foils, and the test piece was pressure-bonded at a press temperature of 170 ° C., a pressure of 3 MPa for a time of 3 minutes, and pressed from an end portion. The flow rate was observed.
【００２７】特性の評価結果をThe evaluation result of the characteristics
【表２】に示した。実施例１の接着フィルムは、接着強
さ、流れ出し性を損なうことなく、プレス加工性が良好
であった。The results are shown in [Table 2]. The adhesive film of Example 1 had good press workability without impairing the adhesive strength and flowability.
【００２８】[0028]
【表２】 [Table 2]
【００２９】（実施例２）実施例１において、数平均分
子量が４，６００の低分子量アクリル樹脂〔Ｉ〕を１
２．５重量部とした以外は、実施例１と同様に行った。
実施例２で調整した接着剤溶液の固形分比を(Example 2) In Example 1, the low molecular weight acrylic resin [I] having a number average molecular weight of 4,600 was
Example 1 was repeated except that the amount was 2.5 parts by weight.
The solid content ratio of the adhesive solution prepared in Example 2 was
【表１】に示した。特性の評価結果をThe results are shown in [Table 1]. The evaluation results of the characteristics
【表２】に示した。実施例２の接着フィルムは、接着強
さ、流れ出し性を損なうことなく、プレス加工性が良好
であった。The results are shown in [Table 2]. The adhesive film of Example 2 had good press workability without impairing the adhesive strength and the flowability.
【００３０】（比較例１）
（１）低分子量アクリル樹脂〔ＩＩ〕の調整
実施例１と同様の容器に、ラジカル重合開始剤として反
応するアゾビスイソブチロニトリルを０．１４ｇとした
以外は、実施例１と同様に重合し、数平均分子量が２，
６００の低分子量アクリル樹脂〔ＩＩ〕を得た。(Comparative Example 1) (1) Preparation of low molecular weight acrylic resin [II] In the same container as in Example 1, except that 0.14 g of azobisisobutyronitrile which reacts as a radical polymerization initiator was used. Polymerized in the same manner as in Example 1 and having a number average molecular weight of 2,
600 low molecular weight acrylic resins [II] were obtained.
【００３１】実施例１において、数平均分子量が２，６
００の低分子量アクリル樹脂〔ＩＩ〕を用いた以外は、
実施例１と同様に行った。比較例１で調整した接着剤溶
液の固形分比をIn Example 1, the number average molecular weight was 2,6.
Except that a low molecular weight acrylic resin [II] of 00 was used.
The same procedure as in Example 1 was performed. The solid content ratio of the adhesive solution prepared in Comparative Example 1 was
【表１】に示した。特性の評価結果をThe results are shown in [Table 1]. The evaluation results of the characteristics
【表２】に示した。比較例１の接着フィルムは、プレス
加工時に、接着フィルムとカバーレイフィルム面や回路
面との間に、膨れや熱収縮によるしわの発生がみられ、
良好なプレス加工性が得られなかった。The results are shown in [Table 2]. In the adhesive film of Comparative Example 1, wrinkles due to swelling or heat shrinkage were observed between the adhesive film and the coverlay film surface or the circuit surface during pressing.
Good press workability was not obtained.
【００３２】（比較例２）実施例１において、低分子量
アクリル樹脂を除いた以外は、実施例１と同様に行っ
た。比較例２で調整した接着剤溶液の固形分比を(Comparative Example 2) The procedure of Example 1 was repeated, except that the low molecular weight acrylic resin was omitted. The solid content ratio of the adhesive solution prepared in Comparative Example 2 was
【表１】に示した。特性の評価結果をThe results are shown in [Table 1]. The evaluation results of the characteristics
【表２】に示した。比較例２の接着フィルムは、プレス
加工時に、接着フィルムとカバーレイフィルム面や回路
面との間に、膨れや熱収縮によるしわの発生がみられ、
良好なプレス加工性が得られなかった。The results are shown in [Table 2]. In the adhesive film of Comparative Example 2, wrinkles due to swelling and heat shrinkage were observed between the adhesive film and the coverlay film surface or the circuit surface during pressing.
Good press workability was not obtained.
【００３３】（比較例３）実施例１において、数平均分
子量が４，６００の低分子量アクリル樹脂〔Ｉ〕を４
０．０重量部とした以外は、実施例１と同様に行った。
比較例３で調整した接着剤溶液の固形分比を(Comparative Example 3) A low molecular weight acrylic resin [I] having a number average molecular weight of 4,600 was prepared in the same manner as in Example 1.
Example 1 was repeated except that the amount was 0.0 part by weight.
The solid content ratio of the adhesive solution prepared in Comparative Example 3 was
【表１】に示した。特性の評価結果をThe results are shown in [Table 1]. The evaluation results of the characteristics
【表２】に示した。比較例３の接着フィルムは、プレス
加工時に、接着フィルムとカバーレイフィルム面や回路
面との間に、膨れや熱収縮によるしわの発生がみられ、
良好なプレス加工性が得られなかった。また、接着強さ
が低下し、流れ出し性が大きくなった。The results are shown in [Table 2]. In the adhesive film of Comparative Example 3, wrinkles due to swelling and heat shrinkage were observed between the adhesive film and the coverlay film surface or the circuit surface during pressing.
Good press workability was not obtained. In addition, the adhesive strength was reduced and the flowability was increased.
【００３４】[0034]
【発明の効果】本発明によれば、アクリルゴム、アクリ
ル樹脂、フェノール樹脂、エポキシ樹脂、硬化剤、無機
充てん剤を所定の割合で配合し、さらに、アクリルゴム
の数平均分子量が５０〜１１０万、低分子量アクリル樹
脂の数平均分子量が４千〜１万であることで、プレス加
工時において、混合組成のバラツキや、硬化の不均一性
がなく、接着フィルムとカバーレイフィルム面や回路面
との間で、膨れや熱収縮によるしわが、全くない、ＦＰ
Ｃ用接着剤組成物および接着フィルムを得ることができ
た。According to the present invention, acrylic rubber, acrylic resin, phenol resin, epoxy resin, curing agent and inorganic filler are blended in a predetermined ratio, and the number average molecular weight of the acrylic rubber is 50 to 1.1 million. Since the number average molecular weight of the low molecular weight acrylic resin is 4,000 to 10,000, there is no variation in the mixed composition and unevenness of curing during press working, and the adhesive film and the coverlay film surface and the circuit surface are There are no wrinkles due to blistering or heat shrinkage between
An adhesive composition for C and an adhesive film could be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 3/38 Ｈ０５Ｋ 3/38 Ｅ Ｆターム(参考） 4J004 AA02 AA10 AA12 AA13 AA17 BA02 DB03 FA05 4J040 DF041 DF042 DF051 DF052 DF061 DF062 EB031 EB032 EC061 EC062 EC071 EC072 EC121 EC122 GA07 GA12 JA09 KA14 KA16 LA01 LA06 LA08 NA20 5E343 AA02 AA12 AA18 AA33 BB05 BB24 BB67 CC02 CC03 CC17 DD51 EE21 GG02 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H05K 3/38 H05K 3/38 EF term (reference) 4J004 AA02 AA10 AA12 AA13 AA17 BA02 DB03 FA05 4J040 DF041 DF042 DF051 DF052 DF061 DF062 EB031 EB032 EC061 EC062 EC071 EC072 EC121 EC122 GA07 GA12 JA09 KA14 KA16 LA01 LA06 LA08 NA20 5E343 AA02 AA12 AA18 AA33 BB05 BB24 BB67 CC02 CC03 CC17 DD51 EE21 GG02
Claims (4)
量アクリルゴム（Ａ）、低分子量アクリル樹脂（Ｂ）、
エポキシ樹脂（Ｃ）、フェノール樹脂（Ｄ）、硬化剤ま
たは硬化触媒（Ｅ）からなることを特徴とするフレキシ
ブルプリント配線板積層用接着剤組成物。1. A high molecular weight acrylic rubber (A) containing a carboxylic acid as a functional group, a low molecular weight acrylic resin (B),
An adhesive composition for laminating a flexible printed wiring board, comprising an epoxy resin (C), a phenol resin (D), a curing agent or a curing catalyst (E).
量アクリルゴム（Ａ）の数平均分子量が５０〜１１０
万、低分子量アクリル樹脂（Ｂ）の数平均分子量が４千
〜１万である請求項１記載のフレキシブルプリント配線
板積層用接着剤組成物。2. A high molecular weight acrylic rubber (A) containing a carboxylic acid as a functional group has a number average molecular weight of 50 to 110.
The adhesive composition for laminating flexible printed wiring boards according to claim 1, wherein the low molecular weight acrylic resin (B) has a number average molecular weight of 4,000 to 10,000.
量アクリルゴム（Ａ）１００重量部に対し、低分子量ア
クリル樹脂（Ｂ）の添加量が１〜３０重量部であること
を特徴とする請求項１記載のフレキシブルプリント配線
板積層用接着剤組成物。3. A low molecular weight acrylic resin (B) is added in an amount of 1 to 30 parts by weight based on 100 parts by weight of a high molecular weight acrylic rubber (A) containing a carboxylic acid as a functional group. Item 2. The adhesive composition for laminating a flexible printed wiring board according to Item 1.
剤組成物を用いた接着フィルム層及び、離型紙を積層し
てなるフレキシブルプリント配線板積層用接着フィル
ム。4. An adhesive film for laminating a flexible printed wiring board, which comprises an adhesive film layer using the adhesive composition according to claim 1, claim 2 and claim 3 and a release paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002153114A JP2003313526A (en) | 2002-04-19 | 2002-04-19 | Adhesive composition for flexible printed wiring board lamination and adhesive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002153114A JP2003313526A (en) | 2002-04-19 | 2002-04-19 | Adhesive composition for flexible printed wiring board lamination and adhesive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003313526A true JP2003313526A (en) | 2003-11-06 |
Family
ID=29545422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002153114A Pending JP2003313526A (en) | 2002-04-19 | 2002-04-19 | Adhesive composition for flexible printed wiring board lamination and adhesive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003313526A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139387A (en) * | 2003-11-10 | 2005-06-02 | Shin Etsu Chem Co Ltd | Acrylic adhesive sheet |
| JP2005298781A (en) * | 2004-04-06 | 2005-10-27 | Hitachi Kasei Polymer Co Ltd | Adhesive composition for flexible wiring circuit board and adhesive film |
| JP2005314604A (en) * | 2004-04-30 | 2005-11-10 | Shin Etsu Chem Co Ltd | Flame-retardant adhesive composition and adhesive sheet using the same |
| JP2006124651A (en) * | 2004-09-29 | 2006-05-18 | Shin Etsu Chem Co Ltd | Acrylic flame retardant adhesive composition and acrylic flame retardant adhesive sheet |
| JP2011068822A (en) * | 2009-09-28 | 2011-04-07 | Hitachi Kasei Polymer Co Ltd | Adhesive film with separator |
| JP2011202185A (en) * | 2004-03-02 | 2011-10-13 | Nitto Denko Corp | Thermosetting adhesive tape or sheet and production method therefor |
| CN112088089A (en) * | 2018-05-11 | 2020-12-15 | 昭和电工材料株式会社 | Conductor substrate, wiring substrate, stretchable element, and method for manufacturing wiring substrate |
| CN115260963A (en) * | 2022-09-27 | 2022-11-01 | 武汉市三选科技有限公司 | Thin-film die-bonding adhesive for low-modulus vertical stack packaging, preparation method and application thereof |
-
2002
- 2002-04-19 JP JP2002153114A patent/JP2003313526A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139387A (en) * | 2003-11-10 | 2005-06-02 | Shin Etsu Chem Co Ltd | Acrylic adhesive sheet |
| JP2011202185A (en) * | 2004-03-02 | 2011-10-13 | Nitto Denko Corp | Thermosetting adhesive tape or sheet and production method therefor |
| JP2005298781A (en) * | 2004-04-06 | 2005-10-27 | Hitachi Kasei Polymer Co Ltd | Adhesive composition for flexible wiring circuit board and adhesive film |
| JP2005314604A (en) * | 2004-04-30 | 2005-11-10 | Shin Etsu Chem Co Ltd | Flame-retardant adhesive composition and adhesive sheet using the same |
| JP2006124651A (en) * | 2004-09-29 | 2006-05-18 | Shin Etsu Chem Co Ltd | Acrylic flame retardant adhesive composition and acrylic flame retardant adhesive sheet |
| JP2011068822A (en) * | 2009-09-28 | 2011-04-07 | Hitachi Kasei Polymer Co Ltd | Adhesive film with separator |
| CN112088089A (en) * | 2018-05-11 | 2020-12-15 | 昭和电工材料株式会社 | Conductor substrate, wiring substrate, stretchable element, and method for manufacturing wiring substrate |
| CN115260963A (en) * | 2022-09-27 | 2022-11-01 | 武汉市三选科技有限公司 | Thin-film die-bonding adhesive for low-modulus vertical stack packaging, preparation method and application thereof |
| CN115260963B (en) * | 2022-09-27 | 2022-12-27 | 武汉市三选科技有限公司 | Low-modulus vertical stack packaging film die attach adhesive, and preparation method and application thereof |
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