JP5077840B2 - Coverlay - Google Patents
Coverlay Download PDFInfo
- Publication number
- JP5077840B2 JP5077840B2 JP2006204788A JP2006204788A JP5077840B2 JP 5077840 B2 JP5077840 B2 JP 5077840B2 JP 2006204788 A JP2006204788 A JP 2006204788A JP 2006204788 A JP2006204788 A JP 2006204788A JP 5077840 B2 JP5077840 B2 JP 5077840B2
- Authority
- JP
- Japan
- Prior art keywords
- dianhydride
- polyimide film
- film
- weight
- mol
- 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.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 claims description 62
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 26
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 23
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 21
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 239000009719 polyimide resin Substances 0.000 claims description 5
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 45
- 229920005575 poly(amic acid) Polymers 0.000 description 31
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 26
- 239000010408 film Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- -1 β-picoline Chemical class 0.000 description 22
- 239000010410 layer Substances 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 229920002120 photoresistant polymer Polymers 0.000 description 15
- 108010025899 gelatin film Proteins 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 238000005530 etching Methods 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- MPXKIFWZOQVOLN-UHFFFAOYSA-N 1-(1-adamantyl)adamantane Chemical compound C1C(C2)CC(C3)CC2CC13C(C1)(C2)CC3CC2CC1C3 MPXKIFWZOQVOLN-UHFFFAOYSA-N 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- ZRJAHFLFCRNNMR-UHFFFAOYSA-N 3-amino-2-(4-aminophenyl)benzoic acid Chemical compound C1=CC(N)=CC=C1C1=C(N)C=CC=C1C(O)=O ZRJAHFLFCRNNMR-UHFFFAOYSA-N 0.000 description 1
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- OSGFBINRYVUILV-UHFFFAOYSA-N 4-[(4-aminophenyl)-diethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](CC)(CC)C1=CC=C(N)C=C1 OSGFBINRYVUILV-UHFFFAOYSA-N 0.000 description 1
- NMLVVZNIIWJNTI-UHFFFAOYSA-N 4-[(4-aminophenyl)-ethylphosphoryl]aniline Chemical compound C=1C=C(N)C=CC=1P(=O)(CC)C1=CC=C(N)C=C1 NMLVVZNIIWJNTI-UHFFFAOYSA-N 0.000 description 1
- KTZLSMUPEJXXBO-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylphosphoryl]aniline Chemical compound C1=CC(N)=CC=C1P(=O)(C=1C=CC(N)=CC=1)C1=CC=CC=C1 KTZLSMUPEJXXBO-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- HWKHQQCBFMYAJZ-UHFFFAOYSA-N 4-amino-n-(3-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC(N)=C1 HWKHQQCBFMYAJZ-UHFFFAOYSA-N 0.000 description 1
- YFBMJEBQWQBRQJ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=CC=C1 YFBMJEBQWQBRQJ-UHFFFAOYSA-N 0.000 description 1
- MMDNZKASBVVBBC-UHFFFAOYSA-N 5-(4-amino-3-methylphenyl)-2-methylaniline Chemical group C1=C(N)C(C)=CC=C1C1=CC=C(N)C(C)=C1 MMDNZKASBVVBBC-UHFFFAOYSA-N 0.000 description 1
- IIEKUGPEYLGWQQ-UHFFFAOYSA-N 5-[4-(4-amino-2-methylpentyl)phenyl]-4-methylpentan-2-amine Chemical compound CC(N)CC(C)CC1=CC=C(CC(C)CC(C)N)C=C1 IIEKUGPEYLGWQQ-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- FOLJMFFBEKONJP-UHFFFAOYSA-N adamantane-1,3-diamine Chemical compound C1C(C2)CC3CC1(N)CC2(N)C3 FOLJMFFBEKONJP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 230000005606 hygroscopic expansion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- VQXBKCWOCJSIRT-UHFFFAOYSA-N octadecane-1,12-diamine Chemical compound CCCCCCC(N)CCCCCCCCCCCN VQXBKCWOCJSIRT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Description
本発明は、カバーレイに関するものであり、更に詳しくはポリイミドフィルムを基材として、その片面に接着剤層を形成することにより得られるカバーレイに関するものである。 The present invention relates to a cover lay, and more particularly to a cover lay obtained by forming an adhesive layer on one side of a polyimide film as a base material.
プリント配線板は広く電子・電機機器に使用されている。中でも、折り曲げ可能なフレキシブルプリント配線板は、パーソナルコンピューターや携帯電話等の折り曲げ部分、ハードディスク等の屈曲が必要な部分に広く使用されている。フレキシブルプリント配線板の配線回路は耐熱性樹脂一体的に積層された金属箔を科学的にエッチングして形成されるが、この配線回路の表面は酸化されやすいので、その上を覆う保護層が設けられ、この保護層を通常カバーレイと称している。このようなフレキシブルプリント配線板の基材、及び配線板を保護するためのカバーレイの基材としては、通常各種のポリイミドフィルムが使用されている。 Printed wiring boards are widely used in electronic and electrical equipment. Among them, a flexible printed wiring board that can be bent is widely used in bent portions of personal computers and mobile phones, and in portions that require bending such as hard disks. The wiring circuit of the flexible printed wiring board is formed by scientific etching of a metal foil laminated integrally with a heat-resistant resin. The surface of this wiring circuit is easily oxidized, so a protective layer is provided to cover it. This protective layer is usually called a coverlay. As the base material of such a flexible printed wiring board and the base material of a coverlay for protecting the wiring board, various polyimide films are usually used.
ポリイミドフィルムの代表的なものは、酸二無水物成分としてピロメリット酸ニ無水物を用い、ジアミン成分として４，４’−ジアミノジフェニルエーテルを用いるポリイミドフィルムが挙げられる。このようなポリイミドフィルムは機械的、熱的特性のバランスに優れた構造を有しており、汎用の製品として広く工業的に用いられている。しかしながら、ピロメリット酸二無水物と４，４’−ジアミノジフェニルエーテルとからなるポリイミドフィルムは曲げやすい長所を有する反面、カバーレイとして用いる場合には柔らかすぎてしわが発生しやすい。しわが発生すると、その部分に空気を噛み込み、配線の腐食等が起こり、結果として配線に不良を引き起こす問題があった。 A typical polyimide film includes a polyimide film using pyromellitic dianhydride as the acid dianhydride component and 4,4'-diaminodiphenyl ether as the diamine component. Such a polyimide film has a structure with an excellent balance between mechanical and thermal properties, and is widely used industrially as a general-purpose product. However, a polyimide film composed of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether has an advantage that it is easy to bend. However, when used as a coverlay, it is too soft and tends to generate wrinkles. When wrinkles are generated, air is caught in the portions, and the wiring is corroded. As a result, there is a problem that the wiring is defective.
また、ピロメリット酸二無水物と４，４’−ジアミノジフェニルエーテルとからなるポリイミドフィルムは、熱膨張係数（ＣＴＥ）や吸湿膨張係数（ＣＨＥ）が大きく、吸水率も高い為、熱や吸水による寸法変化が大きい。その為、カバーレイとして使用した場合、配線板との寸法変化にずれが起こり、貼り合わせた時に反りが生じる問題点を有していた。 In addition, polyimide film consisting of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether has a large coefficient of thermal expansion (CTE) and hygroscopic expansion coefficient (CHE), and a high water absorption rate. The change is great. For this reason, when used as a cover lay, there has been a problem in that the dimensional change with the wiring board is shifted, and warping occurs when bonded.
このような問題を解決する為、ポリイミドフィルム以外の寸法変化が小さい基材、例えば液晶フィルム等を用いてカバーレイを形成する方法（例えば特許文献１参照）等が開示されているが、液晶フィルムはポリイミドフィルムに比べて耐熱性が劣っており、半田付けの際に基材が変形するという問題を有していた。とりわけ近年は環境の問題から鉛を使用しない鉛フリー半田が広がっているが、鉛フリー半田のほとんどは融点が鉛含有半田よりも高い為、液晶フィルムの基材変形の問題は一層深刻となっていた。
したがって、本発明の目的は、かかるカバーレイの寸法変化と耐熱性の両方の問題を解決し、鉛フリー半田を用いたフレキシブルプリント配線板と貼り合わせるのに適したカバーレイを提供することにある。 Accordingly, an object of the present invention is to provide a cover lay suitable for bonding to a flexible printed wiring board using lead-free solder, which solves both problems of dimensional change and heat resistance of the cover lay. .
本発明は、上記の目的を達成するため、以下の構成を採用する。
（１）ジアミン成分として１０〜４０モル％のパラフェニレンジアミン及び６０〜９０モル％の４，４’−ジアミノジフェニルエーテル、酸二無水物成分としてピロメリット酸二無水物５０〜９９モル％及び３，３’，４，４’−ビフェニルテトラカルボン酸二無水物１〜５０モル％とから主としてなるポリイミドフィルムを用い、ポリイミドフィルムの弾性率が３〜７ＧＰａ、５０〜２００℃での線膨張係数が５〜２０ｐｐｍ／℃、湿度膨張係数が２５ｐｐｍ／％ＲＨ以下、吸水率が３％以下、２００℃１時間での加熱収縮率が０．１０％以下であり、このポリイミドフィルムの片面に、接着剤層を形成してなるカバーレイ。
（２）接着剤がエポキシ樹脂、アクリル樹脂、及びポリイミド樹脂から選ばれる少なくとも１種から主としてなることを特徴とする（１）に記載のカバーレイ。
In order to achieve the above object, the present invention employs the following configuration.
(1) 10 to 40 mol% of paraphenylenediamine and 60 to 90 mol% of 4,4'-diaminodiphenyl ether as a diamine component, 50 to 99 mol% of pyromellitic dianhydride as an acid dianhydride component, and 3, Using a polyimide film mainly composed of 1 to 50 mol% of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, the elastic modulus of the polyimide film is 3 to 7 GPa and the linear expansion coefficient at 50 to 200 ° C. is 5 ~ 20ppm / ° C, coefficient of humidity expansion is 25ppm /% RH or less, water absorption is 3% or less, and heat shrinkage at 200 ° C for 1 hour is 0.10% or less. Coverlay formed .
(2 ) The coverlay according to (1 ) , wherein the adhesive mainly comprises at least one selected from an epoxy resin, an acrylic resin, and a polyimide resin.
本発明によれば、鉛フリー半田を用いても変形しないカバーレイを提供することができる。 According to the present invention, it is possible to provide a coverlay that does not deform even when lead-free solder is used.
本発明のカバーレイは、フレキシブルプリント配線板の基材及び配線板を保護するためのものであり、その基材としてポリイミドフィルムを用い、このポリイミドフィルムの片面に接着剤を形成したものである。 The coverlay of this invention is for protecting the base material and wiring board of a flexible printed wiring board, uses a polyimide film as the base material, and forms the adhesive agent on the single side | surface of this polyimide film.
ここで、基材のポリイミドフィルムとしては、ジアミン成分としてパラフェニレンジアミン及び４，４’−ジアミノジフェニルエーテル、酸二無水物成分としてピロメリット酸二無水物及び３，３’，４，４’−ビフェニルテトラカルボン酸二無水物とから主としてなるポリイミドフィルムである。すなわち、パラフェニレンジアミン、４、４’−ジアミノジフェニルエーテル、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物の４種類を必須成分とし、これら４種類のみ、あるいはこれら４種類に加えて少量の別成分を加えることにより得られるポリイミドフィルムである。ジアミン成分として１０〜４０モル％のパラフェニレンジアミン及び６０〜９０モル％の４，４’−ジアミノジフェニルエーテルを用い、酸二無水物成分としてピロメリット酸二無水物５０〜９９モル％及び３，３’，４，４’−ビフェニルテトラカルボン酸二無水物１〜５０モル％を用いてなるポリイミドフィルムであって、弾性率が３〜７ＧＰａ、５０〜２００℃での線膨張係数が５〜２０ｐｐｍ／℃、湿度膨張係数が２５ｐｐｍ／％ＲＨ以下、吸水率が３％以下、２００℃１時間での加熱収縮率が０．１０％以下であるポリイミドフィルムである。パラフェニレンジアミンが多すぎると硬くなり、少なすぎると柔らかすぎるので、好ましくは１５〜４０モル％、より好ましくは２０〜４０モル％である。４，４’−ジアミノジフェニルエーテルが多すぎると柔らかくなり、少なすぎると硬くなるので、好ましくは６０〜８５モル％、好ましくは６０〜８０モル％である。ピロメリット酸二無水物が多すぎると硬くなり、少なすぎると柔らかくなるので、好ましくは５５〜９５モル％、より好ましくは６０〜９０モル％である。３，３’，４，４’−ビフェニルテトラカルボン酸二無水物が多すぎると柔らかくなり、少なすぎると硬くなるので、好ましくは５〜４５モル％、より好ましくは１５〜３５モル％である。硬さの指標である弾性率は３〜７ＧＰａであり、７ＧＰａを超えると硬すぎ、３ＧＰａより小さいと柔らかすぎる。線膨張係数は５〜２０ｐｐｍ／℃であり、２０ｐｐｍ／℃を超えると熱による寸法変化が大き過ぎ、５ｐｐｍ／℃より小さくなると、配線に使用される金属との線膨張係数との差が大きくなるため反りが生じてしまう。湿度膨張係数が２５ｐｐｍ／％ＲＨを超えると湿度による寸法変化が大き過ぎるので、湿度膨張係数は２５ｐｐｍ／％ＲＨ以下である。吸水率が３％を超えると、吸い込んだ水の影響でフィルムの寸法変化が大きくなるので３％以下である。２００℃１時間の加熱収縮率が０．１０％を超えるとやはり熱による寸法変化が大きくなるので、加熱収縮率は０．１０％以下である。 Here, as the polyimide film of the base material, paraphenylenediamine and 4,4′-diaminodiphenyl ether as diamine components, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyl as acid dianhydride components It is a polyimide film mainly composed of tetracarboxylic dianhydride. That is, four types of paraphenylenediamine, 4,4′-diaminodiphenyl ether, pyromellitic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are essential components, and only these four types are included. Or it is a polyimide film obtained by adding a small amount of another component in addition to these four types . With 10-40 mol% of paraphenylenediamine and 60 to 90 mole% of 4,4'-diaminodiphenyl ether as a di-amine component, pyromellitic dianhydride as dianhydride component 50-99 mol%, and 3, 3 ', I polyimide film der made using 50 mol% 4,4'-biphenyltetracarboxylic acid dianhydride, the elastic modulus 3～7GPa,. 5 to the linear expansion coefficient at 50 to 200 ° C. It is a polyimide film having 20 ppm / ° C., a humidity expansion coefficient of 25 ppm /% RH or less, a water absorption rate of 3% or less, and a heat shrinkage at 200 ° C. for 1 hour of 0.10% or less. Becomes hard and paraphenylenediamine is too large, since too soft too small, the good Mashiku 15-40 mol%, more preferably 20 to 40 mol%. It softens when 4,4'-diaminodiphenyl ether is too high, since hard and too small, good Mashiku is 60-85 mol%, favorable Mashiku is 60 to 80 mol%. Becomes hard and pyromellitic dianhydride is too large, since the tender is too small, good Mashiku is 55 to 95 mol%, more preferably 60 to 90 mol%. 3,3 ', softens the 4,4'-biphenyltetracarboxylic dianhydride is too large, since the hard and too small, the good Mashiku 5 to 45 mol%, more preferably 15 to 35 mol% is there. The elastic modulus, which is an index of hardness , is 3 to 7 GPa. If it exceeds 7 GPa, it is too hard , and if it is less than 3 GPa, it is too soft. The linear expansion coefficient was 5 to 20 ppm / ° C., 20 ppm / ° C. greater than the dimensional change is too large due to heat, becomes smaller than 5 ppm / ° C., the difference between the linear expansion coefficient between the metal used in the wiring is increased Therefore, warping occurs. When the humidity expansion coefficient exceeds 25 ppm /% RH, the dimensional change due to humidity is too large, so the humidity expansion coefficient is 25 ppm /% RH or less . When water absorption is more than 3%, 3% or less because the dimensional change of the film is increased by the influence of water sucked. Since heat shrinkage of 200 ° C. 1 hour dimensional change becomes large due to too heat exceeds 0.10%, heat shrinkage is 0.10% or less.
本発明におけるポリイミドフィルムには、上述の通り、パラフェニレンジアミンや４，４’―ジアミノジフェニルエーテル以外に少量のジアミンを添加してもよい。また、ピロメリット酸二無水物や３，３’，４，４’−ビフェニルテトラカルボン酸二無水物以外に少量の酸二無水物を添加してもよい。具体的なジアミン及び酸二無水物としては以下のものが挙げられるが、これらに限定されない。 As described above, a small amount of diamine other than paraphenylenediamine or 4,4′-diaminodiphenyl ether may be added to the polyimide film of the present invention. In addition to pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, a small amount of acid dianhydride may be added. Specific examples of diamines and acid dianhydrides include, but are not limited to:
（１）酸二無水物
２，３’，３，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，３，６，７−ナフタレンジカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）エーテル、ピリジン−２，３，５，６−テトラカルボン酸二無水物、１，２，４，５−ナフタレンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、１，４，５，８−デカヒドロナフタレンテトラカルボン酸二無水物、４，８−ジメチル−１，２，５，６−ヘキサヒドロナフタレンテトラカルボン酸二無水物、２，６−ジクロロ−１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，７−ジクロロ−１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−テトラクロロ−１，４，５，８−ナフタレンテトラカルボン酸二無水物、１，８，９，１０−フェナントレンテトラカルボン酸二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、３，４，３’，４’−ベンゾフェノンテトラカルボン酸二無水物等。
(1) Acid dianhydride 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,6,7 -Naphthalenedicarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ether, pyridine-2,3,5,6-tetracarboxylic dianhydride, 1,2,4,5-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,8-decahydronaphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2 , 5,6-hexahydronaphthalenetetracarboxylic dianhydride, 2,6-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8 -Naphthalenetetracarboxylic dianhydride 2,3,6,7-tetrachloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 2,2-bis ( 2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene-1, 2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride and the like.
（２）ジアミン
３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、メタフェニレンジアミン、４，４’−ジアミノジフェニルプロパン、３，４’−ジアミノジフェニルプロパン、３，３’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルメタン、ベンチジン、４，４’−ジアミノジフェニルサルファイド、３，４’−ジアミノジフェニルサルファイド、３，３’−ジアミノジフェニルサルファイド、４，４’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、２，６−ジアミノピリジン、ビス−（４−アミノフェニル）ジエチルシラン、３，３’−ジクロロベンチジン、ビス−（４−アミノフェニル）エチルホスフィノキサイド、ビス−（４−アミノフェニル）フェニルホスフィノキサイド、ビス−（４−アミノフェニル）−Ｎ−フェニルアミン、ビス−（４−アミノフェニル）−Ｎ−メチルアミン、１，５−ジアミノナフタレン、３，３’−ジメチル−４，４’−ジアミノビフェニル、３，４’−ジメチル−３’，４−ジアミノビフェニル３，３’−ジメトキシベンチジン、２，４−ビス（ｐ−β−アミノ−ｔ−ブチルフェニル）エーテル、ビス（ｐ−β−アミノ−ｔ−ブチルフェニル）エーテル、ｐ−ビス（２−メチル−４−アミノペンチル）ベンゼン、ｐ−ビス−（１，１−ジメチル−５−アミノペンチル）ベンゼン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、１，３−ジアミノアダマンタン、３，３’−ジアミノ−１，１’−ジアミノアダマンタン、３，３’−ジアミノメチル１，１’−ジアダマンタン、ビス（ｐ−アミノシクロヘキシル）メタン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、３−メチルヘプタメチレンジアミン、４，４’−ジメチルヘプタメチレンジアミン、２，１１−ジアミノドデカン、１，２−ビス（３−アミノプロポキシ）エタン、２，２−ジメチルプロピレンジアミン、３−メトキシヘキサエチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、２，５−ジメチルヘプタメチレンジアミン、５−メチルノナメチレンジアミン、１，４−ジアミノシクロヘキサン、１，１２−ジアミノオクタデカン、２，５−ジアミノ−１，３，４−オキサジアゾール、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、Ｎ−（３−アミノフェニル）−４−アミノベンズアミド、４−アミノフェニル−３−アミノベンゾエート等。
(2) Diamine 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, metaphenylenediamine, 4,4′-diaminodiphenylpropane, 3,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'- Diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 2,6-diaminopyridine, bis- (4-aminophenyl) diethylsilane, 3, , 3'-Dichlorobenzidine Bis- (4-aminophenyl) ethylphosphinoxide, bis- (4-aminophenyl) phenylphosphinoxide, bis- (4-aminophenyl) -N-phenylamine, bis- (4-aminophenyl) ) -N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-dimethyl-3 ', 4-diaminobiphenyl 3,3'-dimethoxybench Gin, 2,4-bis (p-β-amino-t-butylphenyl) ether, bis (p-β-amino-t-butylphenyl) ether, p-bis (2-methyl-4-aminopentyl) benzene P-bis- (1,1-dimethyl-5-aminopentyl) benzene, m-xylylenediamine, p-xylylenediamine, 1,3-diaminoadamantane, 3, '-Diamino-1,1'-diaminoadamantane, 3,3'-diaminomethyl 1,1'-diadamantane, bis (p-aminocyclohexyl) methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylene Diamine, decamethylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine 3-methoxyhexaethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,12-diaminooctadecane, 2,5- Diamino-1,3 , 4-oxadiazole, 2,2-bis (4-aminophenyl) hexafluoropropane, N- (3-aminophenyl) -4-aminobenzamide, 4-aminophenyl-3-aminobenzoate and the like.
ポリイミドフィルムを製造する際には、通常まずジアミンと酸二無水物とを重合してポリイミドの前駆体であるポリアミック酸を合成し、しかる後にフィルム状にしながら、或いはフィルム状にした後にイミド化してポリイミドフィルムとする。本発明においては、ジアミン成分を最低２種類、酸二無水物を最低２種類用いるが、これらの成分を一度に混合してランダムに重合させてもよく、また適当な組み合わせで順に混合し、ブロック重合してもよい。例えば、まずパラフェニレンジアミンとピロメリット酸二無水物とを反応させ、しかる後に４，４’−ジアミノジフェニルエーテルと３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を加えるブロック重合、あるいはまず４，４’−ジアミノジフェニルエーテルとピロメリット酸二無水物とを反応させ、しかる後にパラフェニレンジアミンと３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を加えるブロック重合などが挙げられる。重合の際に用いる溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−メチルホルムアミド、ジメチルスルホキシドなどが挙げられるが、これらに限定されない。また、β−ピコリンのような第三級アミン類に代表される各種触媒、無水酢酸のような有機カルボン酸無水物に代表される各種脱水剤などを適宜使用してもよい。更に、フィルムの滑り性を向上させる目的でシリカやアルミナ、リン酸水素カルシウム、リン酸カルシウム等の各種フィラーを添加してもよい。 When producing a polyimide film, usually a diamine and acid dianhydride are first polymerized to synthesize a polyamic acid which is a polyimide precursor, and then imidized while forming a film or after forming a film. A polyimide film is used. In the present invention, at least two kinds of diamine components and at least two kinds of acid dianhydrides are used. These components may be mixed at once and polymerized at random, or may be mixed in an appropriate combination in order and blocked. Polymerization may be performed. For example, block polymerization in which paraphenylenediamine and pyromellitic dianhydride are first reacted, and then 4,4′-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are added. Alternatively, block polymerization in which 4,4′-diaminodiphenyl ether and pyromellitic dianhydride are reacted and then paraphenylenediamine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are added. Can be mentioned. Examples of the solvent used in the polymerization include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylformamide, dimethyl sulfoxide and the like. Further, various catalysts typified by tertiary amines such as β-picoline, various dehydrating agents typified by organic carboxylic acid anhydrides such as acetic anhydride, and the like may be used as appropriate. Furthermore, various fillers such as silica, alumina, calcium hydrogen phosphate, and calcium phosphate may be added for the purpose of improving the slipperiness of the film.
重合方法は公知のいずれの方法で行ってもよく、例えば（１）〜（５）が挙げられる。
（１）先に芳香族ジアミン成分全量を溶媒中に入れ、その後芳香族テトラカルボン酸類成分を芳香族ジアミン成分全量と当量になるよう加えて重合する方法。
（２）先に芳香族テトラカルボン酸類成分全量を溶媒中に入れ、その後芳香族ジアミン成分を芳香族テトラカルボン酸類成分と等量になるよう加えて重合する方法。
（３）一方の芳香族ジアミン化合物を溶媒中に入れた後、反応成分に対して芳香族テトラカルボン酸類化合物が９５〜１０５モル％となる比率で反応に必要な時間混合した後、もう一方の芳香族ジアミン化合物を添加し、続いて芳香族テトラカルボン酸類化合物を全芳香族ジアミン成分と全芳香族テトラカルボン酸類成分とがほぼ等量になるよう添加して重合する方法。
（４）芳香族テトラカルボン酸類化合物を溶媒中に入れた後、反応成分に対して一方の芳香族ジアミン化合物が９５〜１０５モル％となる比率で反応に必要な時間混合した後、芳香族テトラカルボン酸類化合物を添加し、続いてもう一方の芳香族ジアミン化合物を全芳香族ジアミン成分と全芳香族テトラカルボン酸類成分とがほぼ等量になるよう添加して重合する方法。
（５）溶媒中で一方の芳香族ジアミン成分と芳香族テトラカルボン酸類をどちらかが過剰になるよう反応させてポリアミド酸溶液（Ａ）を調整し、別の溶媒中でもう一方の芳香族ジアミン成分と芳香族テトラカルボン酸類をどちらかが過剰になるよう反応させポリアミド酸溶液（Ｂ）を調整する。こうして得られた各ポリアミド酸溶液（Ａ）と（Ｂ）を混合し、重合を完結する方法。この時ポリアミド酸溶液（Ａ）を調整するに際し芳香族ジアミン成分が過剰の場合、ポリアミド酸溶液（Ｂ）では芳香族テトラカルボン酸成分を過剰に、またポリアミド酸溶液（Ａ）で芳香族テトラカルボン酸成分が過剰の場合、ポリアミド酸溶液（Ｂ）では芳香族ジアミン成分を過剰にし、ポリアミド酸溶液（Ａ）と（Ｂ）を混ぜ合わせこれら反応に使用される全芳香族ジアミン成分と全芳香族テトラカルボン酸類成分とがほぼ等量になるよう調整する。
The polymerization method may be performed by any known method, and examples thereof include (1) to (5).
(1) A method in which the total amount of the aromatic diamine component is first put in a solvent, and then the aromatic tetracarboxylic acid component is added so as to be equivalent to the total amount of the aromatic diamine component and polymerized.
(2) A method in which the total amount of the aromatic tetracarboxylic acid component is first put in a solvent, and then the aromatic diamine component is added in an amount equivalent to that of the aromatic tetracarboxylic acid component for polymerization.
(3) After one aromatic diamine compound is put in a solvent, the aromatic tetracarboxylic acid compound is mixed at a ratio of 95 to 105 mol% with respect to the reaction components, and then mixed for the other time. A method in which an aromatic diamine compound is added, and then an aromatic tetracarboxylic acid compound is added and polymerized so that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are approximately equal.
(4) After putting the aromatic tetracarboxylic acid compound in the solvent, the aromatic tetracarboxylic acid compound is mixed for a time required for the reaction at a ratio of 95 to 105 mol% of one aromatic diamine compound with respect to the reaction component, and then aromatic tetra A method in which a carboxylic acid compound is added, and then the other aromatic diamine compound is added and polymerized so that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are approximately equal.
(5) A polyamic acid solution (A) is prepared by reacting one aromatic diamine component and an aromatic tetracarboxylic acid in a solvent so that either one becomes excessive, and the other aromatic diamine in another solvent. The polyamic acid solution (B) is prepared by reacting the component and the aromatic tetracarboxylic acid so that either one becomes excessive. A method of mixing the polyamic acid solutions (A) and (B) thus obtained to complete the polymerization. At this time, when adjusting the polyamic acid solution (A), if the aromatic diamine component is excessive, the polyamic acid solution (B) contains excessive aromatic tetracarboxylic acid component, and the polyamic acid solution (A) contains aromatic tetracarboxylic acid. When the acid component is excessive, the polyamic acid solution (B) makes the aromatic diamine component excessive, and the polyamic acid solutions (A) and (B) are combined to form the wholly aromatic diamine component and wholly aromatic compound used in these reactions. Adjustment is made so that the amount of the tetracarboxylic acid component is approximately equal.
なお、重合方法はこれらに限定されることはなく、その他公知の方法を用いてもよい。 The polymerization method is not limited to these, and other known methods may be used.
こうして得られるポリアミック酸溶液は、固形分を５〜４０重量％、好ましくは１０〜３０重量％を含有しており、またその粘度はブルックフィールド粘度計による測定値で１０〜２０００Ｐａ・ｓ、好ましくは、１００〜１０００Ｐａ・ｓのものが、安定した送液のために好ましく使用される。また、有機溶媒溶液中のポリアミック酸は部分的にイミド化されていてもよい。 The polyamic acid solution thus obtained contains a solid content of 5 to 40% by weight, preferably 10 to 30% by weight, and its viscosity is 10 to 2000 Pa · s as measured by a Brookfield viscometer, preferably 100-1000 Pa · s is preferably used for stable liquid feeding. Moreover, the polyamic acid in the organic solvent solution may be partially imidized.
ポリイミドフィルムの厚みについては特に限定されないが、好ましくは１〜２２５μｍ、より好ましくは３〜１７５μｍ、更に好ましくは５〜１２５μｍである。厚すぎるとロール状にした際に巻きずれが発生しやすくなり、薄すぎるとしわなどが入りやすくなる。 Although it does not specifically limit about the thickness of a polyimide film, Preferably it is 1-225 micrometers, More preferably, it is 3-175 micrometers, More preferably, it is 5-125 micrometers. When it is too thick, it becomes easy to cause winding slip when it is made into a roll, and when it is too thin, wrinkles and the like are likely to enter.
上記のようなポリイミドフィルムの片面に、接着剤を介し、カバーレイを形成する。接着剤としてはエポキシ樹脂、アクリル樹脂、及びポリイミド樹脂から選ばれる少なくとも１種が好ましい。これらの接着剤には、柔軟性を持たせるなどの目的で、各種ゴム、可塑剤、硬化剤、リン系等の難燃剤、その他の各種添加物が付与されていてもよい。また、ポリイミド樹脂は主として熱可塑性ポリイミドが用いられることが多いが、熱硬化性ポリイミドでもよい。ポリイミド樹脂の場合、通常は溶媒不要な場合が多いが、適当な有機溶媒に可溶なポリイミドを用いてもよい。 A coverlay is formed on one side of the polyimide film as described above via an adhesive. As the adhesive, at least one selected from an epoxy resin, an acrylic resin, and a polyimide resin is preferable. These adhesives may be provided with various rubbers, plasticizers, curing agents, phosphorus-based flame retardants, and other various additives for the purpose of imparting flexibility. The polyimide resin is mainly thermoplastic polyimide, but may be thermosetting polyimide. In the case of a polyimide resin, a solvent is usually unnecessary, but a polyimide soluble in an appropriate organic solvent may be used.
接着剤の厚みとしては、フレキシブル配線板の配線を十分に埋め込むことができ、配線を保護できる厚みであれば特に限定されないが、例えば配線厚みが１８μｍの場合には１０〜１００μｍの接着剤厚みが好ましく、１５〜５０μｍの接着剤厚みが好ましい。また例えば配線厚みが８μｍの場合には５〜５０μｍの接着剤厚みが好ましく、１２．５〜２５μｍの接着剤厚みがより好ましい。接着剤が薄すぎると配線間を十分に埋め込むことができず、空気を噛み込む恐れがある。また接着剤が厚すぎると基材のポリイミドフィルムの寸法変化に影響を及ぼすので、上記範囲の厚みが選ばれる。 The thickness of the adhesive is not particularly limited as long as the wiring of the flexible wiring board can be sufficiently embedded and the wiring can be protected. For example, when the wiring thickness is 18 μm, the adhesive thickness is 10 to 100 μm. An adhesive thickness of 15-50 μm is preferred. For example, when the wiring thickness is 8 μm, an adhesive thickness of 5 to 50 μm is preferable, and an adhesive thickness of 12.5 to 25 μm is more preferable. If the adhesive is too thin, it may not be possible to sufficiently embed between the wirings, and air may be caught. Further, if the adhesive is too thick, it affects the dimensional change of the polyimide film of the base material, so the thickness in the above range is selected.
このようにしてできたカバーレイは、接着剤を保護する目的で、フレキシブル配線板と貼り合わせる直前まで保護シートを付けておくことが好ましい。保護シートとしては、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム。ポリ塩化ビニルフィルムなどが挙げられ、これらのフィルムに公知の微粘着剤が塗布されたものが使用される。 The cover lay thus formed is preferably provided with a protective sheet until just before being bonded to the flexible wiring board for the purpose of protecting the adhesive. As protective sheets, polyester film, polyethylene film, polypropylene film. A polyvinyl chloride film etc. are mentioned, and what coated the well-known slight adhesive on these films is used.
本発明のカバーレイは、フレキシブルプリント配線板と貼り合わせることで使用される。配線板の配線形成の方法としては、サブトラクティブ法、セミアディティブ法、フルアディティブ法等が挙げられる。サブトラクティブ法とは、接着剤を介してポリイミドフィルム上に銅箔を貼り、銅箔を配線パターン状にエッチング処理することで配線を形成する方法、或いは接着剤を介さずに直接銅層をポリイミドフィルム上に形成し、銅層を配線パターン状にエッチング処理することで配線を形成する方法を意味する。銅箔を貼り付ける場合、銅箔としては圧延銅箔又は電解銅箔が用いられる。また、配線を形成する際には、通常フォトレジスト層を銅箔上に形成し、このフォトレジスト層を選択露光及び現像処理することで配線状にパターニングし、パターニングしたフォトレジスト層をエッチングマスクとして銅をエッチング処理し、その後にフォトレジスト層を完全に除去する。ここでフォトレジストとしては液状あるいはドライフィルムレジストが用いられ、エッチング液としては、塩化鉄系、塩化銅系、過酸系等の溶液が用いられる。
セミアディティブ法とは、まずポリイミドフィルム上に直接、或いは接着剤を介してシード層となる金属層を形成し、このシード層の上にフォトレジスト層を形成し、フォトレジスト層を選択露光及び現像処理することで配線状にパターニングし、パターニングしたフォトレジスト層を鍍金マスクとしてシード層上に無電解鍍金或いは電解鍍金にて配線を形成し、その後にフォトレジストを完全に除去し、最後に配線以外の部分のシード層をエッチング除去する方法を意味する。ここで、シード層金属としては、ニッケル、クロム、アルミニウム、鉛、銅、錫、亜鉛、鉄、銀、金等が単独或いは合金として使用される。また、フォトレジストとしては液状あるいはドライフィルムレジストが用いられ、無電解鍍金或いは電解鍍金の金属としては鉛、銅、ニッケル、クロム、錫、亜鉛、銀、金等が用いられ、エッチング液としては、シード層の金属に合わせたエッチング液が用いられる。
The coverlay of this invention is used by bonding with a flexible printed wiring board. Examples of the method for forming wiring on the wiring board include a subtractive method, a semi-additive method, and a full additive method. The subtractive method is a method of forming a wiring by attaching a copper foil on a polyimide film via an adhesive and etching the copper foil into a wiring pattern. Alternatively, the copper layer is polyimide directly without using an adhesive. It means a method of forming a wiring by forming on a film and etching a copper layer into a wiring pattern. When affixing a copper foil, a rolled copper foil or an electrolytic copper foil is used as the copper foil. Also, when forming wiring, a photoresist layer is usually formed on a copper foil, and this photoresist layer is subjected to selective exposure and development to be patterned into a wiring shape, and the patterned photoresist layer is used as an etching mask. The copper is etched and then the photoresist layer is completely removed. Here, a liquid or dry film resist is used as the photoresist, and a solution such as iron chloride, copper chloride, or peracid is used as the etchant.
In the semi-additive method, a metal layer to be a seed layer is first formed directly on a polyimide film or via an adhesive, a photoresist layer is formed on the seed layer, and the photoresist layer is selectively exposed and developed. By patterning into a wiring shape by processing, using the patterned photoresist layer as a plating mask, wiring is formed on the seed layer by electroless plating or electrolytic plating, and then the photoresist is completely removed, and finally other than wiring This means that the seed layer is removed by etching. Here, as the seed layer metal, nickel, chromium, aluminum, lead, copper, tin, zinc, iron, silver, gold or the like is used alone or as an alloy. In addition, a liquid or dry film resist is used as a photoresist, lead, copper, nickel, chromium, tin, zinc, silver, gold or the like is used as a metal for electroless plating or electrolytic plating, and as an etching solution, An etchant that matches the metal of the seed layer is used.
フルアディティブ法とは、ポリイミドフィルム上に直接、或いは接着剤の上にフォトレジスト層を形成し、フォトレジスト層を選択露光及び現像処理することで配線状にパターニングし、パターニングしたフォトレジスト層を鍍金マスクとして無電解鍍金にて配線を形成し、その後にフォトレジストを完全に除去する方法を意味する。ここでフォトレジストとしては液状あるいはドライフィルムレジストが用いられ、無電解鍍金の金属としては銅、ニッケル、鉛、クロム、錫、亜鉛、銀、金等が用いられる。 In the full additive method, a photoresist layer is formed directly on a polyimide film or on an adhesive, and the photoresist layer is subjected to selective exposure and development to pattern it into a wiring, and the patterned photoresist layer is plated. It means a method of forming a wiring by electroless plating as a mask and then completely removing the photoresist. Here, a liquid or dry film resist is used as the photoresist, and copper, nickel, lead, chromium, tin, zinc, silver, gold or the like is used as the electroless plating metal.
上記のような各種配線形成の方法に用いられる金属としては、主として銅が好ましい。形成された配線は電気・電子回路として用いられるが、銅よりも抵抗の高い金属だと電気伝導性が悪くなるので好ましくない。また、銅に比べて密度が疎になる金属だとやはり電気伝導性が悪くなるので、好ましくない。但し、銅は錆びやすく腐食されやすい欠点も有しているので、銅を保護する目的で錫や鉛、アルミニウム、ニッケル、銀、金等の金属を銅の上に形成することは任意である。また、銅はポリイミドフィルム中に拡散しやすいため、銅の拡散を防ぐ目的でニッケルやクロム、銀、金、錫等をポリイミドフィルムと銅との間にバリア層として噛ませることも任意である。 As a metal used for the above-mentioned various wiring formation methods, copper is mainly preferred. The formed wiring is used as an electric / electronic circuit, but a metal having a higher resistance than copper is not preferable because the electric conductivity deteriorates. In addition, it is not preferable that the metal has a lower density than copper because the electrical conductivity is deteriorated. However, since copper has a drawback that it is easily rusted and corroded, it is optional to form a metal such as tin, lead, aluminum, nickel, silver, or gold on the copper for the purpose of protecting the copper. Further, since copper easily diffuses into the polyimide film, nickel, chromium, silver, gold, tin, or the like may be arbitrarily bitten as a barrier layer between the polyimide film and copper in order to prevent copper diffusion.
以下、実施例にて具体的に説明する。なお、実施例で用いるポリイミドフィルムは合成例１〜５の方法により製膜したものを用いるが、これらに限定されない。また、比較例１〜２で用いるポリイミドフィルムは合成例６〜７により製膜したものを用いる。更に、実施例で用いる接着剤としては合成例８〜９により調合したものを用いるが、これらに限定されない。なお、フィルム厚さ、線膨張係数、弾性率、湿度膨張係数、吸水率、加熱収縮率については以下の（１）〜（６）の方法で測定した。
（１）フィルム厚
Ｍｉｔｕｔｏｙｏ製ライトマチック（Series318 ）を使用して測定した。
（２）線膨張係数
島津製作所製ＴＭＡ−５０を使用し、測定温度範囲：５０〜２００℃、昇温速度：１０℃／分の条件で測定した。
（３）弾性率
エー・アンド・デイ製ＲＴＭ−２５０を使用し、引張速度：１００ｍｍ／ｍｉｎの条件で測定した。
（４）湿度膨張係数
２５℃にてＴＭ７０００炉内にフィルムを取り付け、炉内にドライガスを送り込んで乾燥させた後、ＨＣ−１型水蒸気発生装置からの給気によりＴＭ７０００炉内を９０％ＲＨに加湿させ、その間の寸法変化から湿度膨張係数を求めた。
（５）吸水率
９８％ＲＨ雰囲気下のデシケーター内に２日間静置し、乾燥時重量に対しての増加重量％で評価した。
（６）加熱収縮率
２０ｃｍ×２０ｃｍのフィルムを用意し、２５℃、６０％ＲＨに調整された部屋に２日間放置した後のフィルム寸法（Ｌ１）を測定し、続いて２００℃６０分間加熱した後再び２５℃、６０％ＲＨに調整された部屋に２日間放置した後フィルム寸法（Ｌ２）を測定し、下記式計算により評価した。
加熱収縮率 ＝ −（Ｌ２−Ｌ１）／Ｌ１×１００
Hereinafter, specific examples will be described. In addition, although the polyimide film used by the Example uses what was formed by the method of the synthesis examples 1-5, it is not limited to these. Moreover, what was formed into a film by the synthesis examples 6-7 is used for the polyimide film used by Comparative Examples 1-2. Furthermore, as adhesives used in the examples, those prepared in Synthesis Examples 8 to 9 are used, but are not limited thereto. The film thickness, linear expansion coefficient, elastic modulus, humidity expansion coefficient, water absorption rate, and heat shrinkage rate were measured by the following methods (1) to (6).
(1) Film thickness It measured using the lightmatic (Series318) made from Mitutoyo.
(2) Linear expansion coefficient TMA-50 manufactured by Shimadzu Corporation was used, and measurement was performed under the conditions of measurement temperature range: 50 to 200 ° C and temperature increase rate: 10 ° C / min.
(3) Elastic modulus RTM-250 manufactured by A & D was used, and measurement was performed under the condition of a tensile speed of 100 mm / min.
(4) Humidity expansion coefficient A film was installed in a TM7000 furnace at 25 ° C., dried by sending dry gas into the furnace, and then the inside of the TM7000 furnace was 90% RH by supplying air from an HC-1 type steam generator. The humidity expansion coefficient was determined from the dimensional change during the period.
(5) Water absorption rate It left still in the desiccator of 98% RH atmosphere for 2 days, and evaluated by the weight increase with respect to the weight at the time of drying.
(6) Heat shrinkage rate A film of 20 cm × 20 cm was prepared, and the film size (L1) after being left in a room adjusted to 25 ° C. and 60% RH for 2 days was measured, followed by heating at 200 ° C. for 60 minutes. Thereafter, the film size (L2) was measured after being left in a room adjusted to 25 ° C. and 60% RH for 2 days, and evaluated by the following formula calculation.
Heat shrinkage rate = − (L2−L1) / L1 × 100
（合成例１）
ピロメリット酸二無水物（分子量２１８．１２）／３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）／パラフェニレンジアミン（分子量１０８．１４）をモル比で３／１／３／１の割合で混合し、ＤＭＡｃ（Ｎ，Ｎ−ジメチルアセトアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイより回転する１００℃のステンレス製ドラム上にキャストし、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをドラムから引き剥がし、その両端を把持し、加熱炉にて２００℃×３０秒、３５０℃×３０秒、５５０℃×３０秒処理し、厚さ２５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 1)
Pyromellitic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) / Paraphenylenediamine (molecular weight 108.14) is mixed at a molar ratio of 3/1/3/1 and polymerized to a 18.5 wt% solution of DMAc (N, N-dimethylacetamide), and the polyamic acid is Obtained. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a stainless steel drum at 100 ° C. rotated by a T-shaped slit die to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. This gel film was peeled off from the drum, and both ends thereof were gripped and treated in a heating furnace at 200 ° C. for 30 seconds, 350 ° C. for 30 seconds, and 550 ° C. for 30 seconds to obtain a polyimide film having a thickness of 25 μm. The physical properties are shown in Table 1.
（合成例２）
ピロメリット酸二無水物（分子量２１８．１２）／３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）／パラフェニレンジアミン（分子量１０８．１４）をモル比で３／２／４／１の割合で混合し、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。この際、まずピロメリット酸二無水物とパラフェニレンジアミンとを先に反応させ、しかる後に４，４’−ジアミノジフェニルエーテルと３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を添加するブロック重合を行った。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイより回転する１００℃のステンレス製ドラム上にキャストし、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをドラムから引き剥がし、その両端を把持し、加熱炉にて２００℃×３０秒、３５０℃×３０秒、５５０℃×３０秒処理し、厚さ１２．５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 2)
Pyromellitic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) / Paraphenylenediamine (molecular weight 108.14) is mixed at a molar ratio of 3/2/4/1 and polymerized in a DMF (N, N-dimethylformamide) 18.5% by weight solution to form a polyamic acid. Obtained. In this case, pyromellitic dianhydride and paraphenylenediamine are first reacted, and then 4,4′-diaminodiphenyl ether and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are added. Block polymerization was performed. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a stainless steel drum at 100 ° C. rotated by a T-shaped slit die to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. The gel film was peeled off from the drum, and both ends thereof were gripped and treated in a heating furnace at 200 ° C. for 30 seconds, 350 ° C. for 30 seconds, 550 ° C. for 30 seconds to obtain a polyimide film having a thickness of 12.5 μm. . The physical properties are shown in Table 1.
（合成例３）
ピロメリット酸二無水物（分子量２１８．１２）／３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）／パラフェニレンジアミン（分子量１０８．１４）をモル比で３／２／２／３の割合で混合し、ＤＭＡｃ（Ｎ，Ｎ−ジメチルアセトアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。この際、まずピロメリット酸二無水物と４，４’−ジアミノジフェニルエーテルとを先に反応させ、しかる後にパラフェニレンジアミンと３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を添加するブロック重合を行った。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイよりエンドレスベルト上にキャストし、７０℃の熱風にて加熱し、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをエンドレスベルトから引き剥がし、その両端を把持し、加熱炉にて２００℃×６０秒、３５０℃×６０秒、５５０℃×４５秒処理し、厚さ１２５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 3)
Pyromellitic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) / Paraphenylenediamine (molecular weight 108.14) is mixed at a molar ratio of 3/2/2/3 and polymerized to a 18.5 wt% solution of DMAc (N, N-dimethylacetamide). Obtained. At this time, pyromellitic dianhydride and 4,4′-diaminodiphenyl ether are first reacted, and then paraphenylenediamine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are added. Block polymerization was performed. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on an endless belt from a T-shaped slit die and heated with hot air at 70 ° C. to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. This gel film was peeled off from the endless belt, and both ends thereof were gripped and treated in a heating furnace at 200 ° C. for 60 seconds, 350 ° C. for 60 seconds, and 550 ° C. for 45 seconds to obtain a 125 μm thick polyimide film. The physical properties are shown in Table 1.
（合成例４）
ピロメリット酸二無水物（分子量２１８．１２）／３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（分子量２１８．１２）／３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（分子量３２２．２０）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）／パラフェニレンジアミン（分子量１０８．１４）をモル比で１１９／３９／２／１２０／４０の割合で混合し、ＤＭＡｃ（Ｎ，Ｎ−ジメチルアセトアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイよりエンドレスベルト上にキャストし、５０℃の熱風にて加熱し、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをエンドレスベルトから引き剥がし、その両端を把持し、加熱炉にて１５０℃×３０秒、３００℃×３０秒、４００℃×２０秒、５５０℃×２０秒処理し、厚さ１２．５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 4)
Pyromellitic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-benzophenonetetracarboxylic Acid dianhydride (molecular weight 322.20) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) / paraphenylenediamine (molecular weight 108.14) in a molar ratio of 119/39/2/120/40 The mixture was mixed and polymerized to a 18.5 wt% solution of DMAc (N, N-dimethylacetamide) to obtain a polyamic acid. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on an endless belt from a T-shaped slit die and heated with hot air at 50 ° C. to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. This gel film is peeled off from the endless belt, both ends thereof are gripped, and processed in a heating furnace at 150 ° C. × 30 seconds, 300 ° C. × 30 seconds, 400 ° C. × 20 seconds, 550 ° C. × 20 seconds, and a thickness of 12. A 5 μm polyimide film was obtained. The physical properties are shown in Table 1.
（合成例５）
ピロメリット酸二無水物（分子量２１８．１２）／３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）／パラフェニレンジアミン（分子量１０８．１４）／メタフェニレンジアミン（分子量１０８．１４）をモル比で７５／２５／７９／１９／２の割合で混合し、ＤＭＡｃ（Ｎ，Ｎ−ジメチルアセトアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイよりエンドレスベルト上にキャストし、５０℃の熱風にて加熱し、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをエンドレスベルトから引き剥がし、その両端を把持し、加熱炉にて１５０℃×３０秒、３００℃×３０秒、４００℃×２０秒、５５０℃×２０秒処理し、厚さ６．２μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 5)
Pyromellitic dianhydride (molecular weight 218.12) / 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) / Paraphenylenediamine (molecular weight 108.14) / metaphenylenediamine (molecular weight 108.14) in a molar ratio of 75/25/79/19/2, and DMAc (N, N-dimethylacetamide) 18. Polymerization was performed with a 5% by weight solution to obtain a polyamic acid. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on an endless belt from a T-shaped slit die and heated with hot air at 50 ° C. to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. This gel film is peeled off from the endless belt, both ends thereof are gripped, and processed in a heating furnace at 150 ° C. × 30 seconds, 300 ° C. × 30 seconds, 400 ° C. × 20 seconds, 550 ° C. × 20 seconds, and a thickness of 6. A 2 μm polyimide film was obtained. The physical properties are shown in Table 1.
（合成例６）
ピロメリット酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）をモル比で１／１の割合で混合し、ＤＭＡｃ（Ｎ，Ｎ−ジメチルアセトアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイより回転する１００℃のステンレス製ドラム上にキャストし、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをドラムから引き剥がし、その両端を把持し、加熱炉にて２００℃×３０秒、３５０℃×３０秒、５５０℃×３０秒処理し、厚さ２５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 6)
Pyromellitic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) is mixed at a molar ratio of 1/1, and DMAc (N, N-dimethylacetamide) 18. Polymerization was performed with a 5% by weight solution to obtain a polyamic acid. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a stainless steel drum at 100 ° C. rotated by a T-shaped slit die to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. This gel film was peeled off from the drum, and both ends thereof were gripped and treated in a heating furnace at 200 ° C. for 30 seconds, 350 ° C. for 30 seconds, and 550 ° C. for 30 seconds to obtain a polyimide film having a thickness of 25 μm. The physical properties are shown in Table 1.
（合成例７）
ピロメリット酸二無水物（分子量２１８．１２）／４，４’−ジアミノジフェニルエーテル（分子量２００．２０）をモル比で１／１の割合で混合し、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）１８．５重量％溶液にして重合し、ポリアミド酸を得た。無水酢酸（分子量１０２．０９）とイソキノリンからなる転化剤をポリアミド酸溶液に対し５０重量％の割合で混合、攪拌した。この時、ポリアミド酸のアミド酸基に対し、無水酢酸及びイソキノリンがそれぞれ２．０及び０．４モル当量になるように調製した。得られた混合物を、Ｔ型スリットダイより回転する１００℃のステンレス製ドラム上にキャストし、残揮発成分が６０重量％の自己支持性を有するゲルフィルムを得た。このゲルフィルムをドラムから引き剥がし、その両端を把持し、加熱炉にて２００℃×３０秒、３５０℃×３０秒、５５０℃×３０秒処理し、厚さ１２．５μｍのポリイミドフィルムを得た。物性を表１に示す。
(Synthesis Example 7)
Pyromellitic dianhydride (molecular weight 218.12) / 4,4′-diaminodiphenyl ether (molecular weight 200.20) is mixed at a molar ratio of 1/1 to obtain DMF (N, N-dimethylformamide) 18. Polymerization was performed with a 5% by weight solution to obtain a polyamic acid. A conversion agent consisting of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a stainless steel drum at 100 ° C. rotated by a T-shaped slit die to obtain a gel film having a self-supporting property with a residual volatile component of 60% by weight. The gel film was peeled off from the drum, and both ends thereof were gripped and treated in a heating furnace at 200 ° C. for 30 seconds, 350 ° C. for 30 seconds, 550 ° C. for 30 seconds to obtain a polyimide film having a thickness of 12.5 μm. . The physical properties are shown in Table 1.
（合成例８）
昭和電工（株）製水酸化アルミニウムＨ−４３を１９重量部、油化シェル（株）製エポキシ樹脂「エピコート」８２８を９重量部、東都化成（株）リン含有エポキシ樹脂ＦＸ２７９ＢＥＫを３５重量部、住友化学（株）製硬化剤４，４’−ＤＤＳ（４，４’−ジアミノジフェニルスルホン）を３．５重量部、ＪＳＲ（株）ＮＢＲ（ＰＮＲ−１Ｈ）２６重量部をメチルイソブチルケトン２００重量部に３０℃で攪拌、混合し、接着剤溶液を得た。
(Synthesis Example 8)
19 parts by weight of aluminum hydroxide H-43 manufactured by Showa Denko KK, 9 parts by weight of epoxy resin “Epicoat” 828 manufactured by Yuka Shell Co., Ltd., 35 parts by weight of phosphorus-containing epoxy resin FX279BEK manufactured by Toto Kasei Co., Ltd. 3.5 parts by weight of curing agent 4,4′-DDS (4,4′-diaminodiphenyl sulfone) manufactured by Sumitomo Chemical Co., Ltd., and 26 parts by weight of JSR NBR (PNR-1H) 200 parts by weight of methyl isobutyl ketone The mixture was stirred and mixed at 30 ° C. to obtain an adhesive solution.
（合成例９）
油化シェル（株）製エポキシ樹脂「エピコート」８３４を９重量部、東都化成（株）リン含有エポキシ樹脂ＺＸ−１５４８−３を１７重量部、住友化学（株）製硬化剤４，４‘−ＤＤＳを３．５重量部、ＪＳＲ（株）ＮＢＲ（ＰＮＲ−１Ｈ）２６重量部、昭和電工（株）製水酸化アルミニウムＨ−４３を２０重量部をメチルエチルケトン２００重量部に３０℃で攪拌、混合し、接着剤溶液を得た。
(Synthesis Example 9)
9 parts by weight of epoxy resin “Epicoat” 834 manufactured by Yuka Shell Co., Ltd., 17 parts by weight of phosphorus-containing epoxy resin ZX-1548-3 manufactured by Toto Kasei Co., Ltd., curing agent 4,4′- manufactured by Sumitomo Chemical Co., Ltd. Stir and mix 3.5 parts by weight of DDS, 26 parts by weight of NSR (PNR-1H), 20 parts by weight of aluminum hydroxide H-43 manufactured by Showa Denko KK at 200 ° C. with 200 parts by weight of methyl ethyl ketone. As a result, an adhesive solution was obtained.
（実施例１）
合成例１で製膜したポリイミドフィルムを用い、この片面に合成例８の接着剤を塗布し、１５０℃×５分間加熱乾燥し、乾燥膜厚２５μｍの接着剤層を形成し、カバーレイを得た。
Example 1
Using the polyimide film formed in Synthesis Example 1, the adhesive of Synthesis Example 8 was applied to one side of the film and dried by heating at 150 ° C. for 5 minutes to form an adhesive layer having a dry film thickness of 25 μm to obtain a coverlay. It was.
ニッカン工業（株）製フレキシブルプリント回路用銅張積層板Ｆ−３０ＶＣ１を用い、銅箔面とカバーレイの接着剤層とを１００℃、０．２７ＭＰａで貼り合わせた。このようにして貼り合わせた銅張積層板とカバーレイを用い、引き剥がし強度（ピール強度）、半田耐熱性、ＵＬに基づく難燃性を評価した。結果を表２に示す。 Using a copper-clad laminate F-30VC1 for flexible printed circuits manufactured by Nikkan Kogyo Co., Ltd., the copper foil surface and the adhesive layer of the coverlay were bonded at 100 ° C. and 0.27 MPa. Using the copper-clad laminate and coverlay bonded together in this way, peel strength (peel strength), solder heat resistance, and flame retardance based on UL were evaluated. The results are shown in Table 2.
（比較例１）
実施例１において、合成例１で製膜したポリイミドフィルムを合成例６で製膜したポリイミドフィルムに変更する以外は全て実施例１と同様にしてカバーレイを形成し、実施例１と同様の評価を実施した。結果を表２に示す。
(Comparative Example 1)
In Example 1, a coverlay was formed in the same manner as in Example 1 except that the polyimide film formed in Synthesis Example 1 was changed to the polyimide film formed in Synthesis Example 6, and the same evaluation as in Example 1 was performed. Carried out. The results are shown in Table 2.
（実施例２）
合成例２で製膜したポリイミドフィルムを用い、この片面に合成例９の接着剤を塗布し、１５０℃×５分間加熱乾燥し、乾燥膜厚１５μｍの接着剤層を形成し、カバーレイを得た。
(Example 2)
Using the polyimide film formed in Synthesis Example 2, the adhesive of Synthesis Example 9 was applied to one side of the film and dried by heating at 150 ° C. for 5 minutes to form an adhesive layer having a dry film thickness of 15 μm to obtain a coverlay. It was.
ニッカン工業（株）製フレキシブルプリント回路用銅張積層板Ｆ−３０ＶＣ１を用い、銅箔面とカバーレイの接着剤層とを１００℃、０．２７ＭＰａで貼り合わせた。このようにして貼り合わせた銅張積層板とカバーレイを用い、引き剥がし強度（ピール強度）、半田耐熱性、ＵＬに基づく難燃性、粘着性を評価した。結果を表２に示す。 Using a copper-clad laminate F-30VC1 for flexible printed circuits manufactured by Nikkan Kogyo Co., Ltd., the copper foil surface and the adhesive layer of the coverlay were bonded at 100 ° C. and 0.27 MPa. Using the copper-clad laminate and coverlay bonded in this manner, the peel strength (peel strength), solder heat resistance, flame retardance based on UL, and adhesiveness were evaluated. The results are shown in Table 2.
（比較例２）
実施例２において、合成例２で製膜したポリイミドフィルムを合成例７で製膜したポリイミドフィルムに変更する以外は全て実施例２と同様にしてカバーレイを形成し、実施例２と同様の評価を実施した。結果を表２に示す。
(Comparative Example 2)
In Example 2, a coverlay was formed in the same manner as in Example 2 except that the polyimide film formed in Synthesis Example 2 was changed to the polyimide film formed in Synthesis Example 7, and the same evaluation as in Example 2 was performed. Carried out. The results are shown in Table 2.
（実施例３）
実施例１において、合成例１で製膜したポリイミドフィルムを合成例３で製膜したポリイミドフィルムに変更する以外は全て実施例１と同様にしてカバーレイを形成し、実施例２と同様の評価を実施した。結果を表２に示す。
(Example 3)
In Example 1, except that the polyimide film formed in Synthesis Example 1 was changed to the polyimide film formed in Synthesis Example 3, a coverlay was formed in the same manner as in Example 1, and the same evaluation as in Example 2 was performed. Carried out. The results are shown in Table 2.
（実施例４）
実施例２において、合成例２で製膜したポリイミドフィルムを合成例４で製膜したポリイミドフィルムに変更する以外は全て実施例２と同様にしてカバーレイを形成し、実施例２と同様の評価を実施した。結果を表２に示す。
Example 4
In Example 2, a coverlay was formed in the same manner as in Example 2 except that the polyimide film formed in Synthesis Example 2 was changed to the polyimide film formed in Synthesis Example 4, and the same evaluation as in Example 2 was performed. Carried out. The results are shown in Table 2.
（実施例５）
実施例１において、合成例１で製膜したポリイミドフィルムを合成例５で製膜したポリイミドフィルムに変更する以外は全て実施例１と同様にしてカバーレイを形成し、実施例２と同様の評価を実施した。結果を表２に示す。
(Example 5)
In Example 1, a coverlay was formed in the same manner as in Example 1 except that the polyimide film formed in Synthesis Example 1 was changed to the polyimide film formed in Synthesis Example 5, and the same evaluation as in Example 2 was performed. Carried out. The results are shown in Table 2.
本発明によれば、寸法安定性や耐熱性に優れたカバーレイの提供が可能になる。 According to the present invention, it is possible to provide a coverlay excellent in dimensional stability and heat resistance.
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006204788A JP5077840B2 (en) | 2006-07-27 | 2006-07-27 | Coverlay |
| KR1020070075278A KR101463220B1 (en) | 2006-07-27 | 2007-07-26 | Coverlay |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006204788A JP5077840B2 (en) | 2006-07-27 | 2006-07-27 | Coverlay |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008031251A JP2008031251A (en) | 2008-02-14 |
| JP5077840B2 true JP5077840B2 (en) | 2012-11-21 |
Family
ID=39121033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006204788A Active JP5077840B2 (en) | 2006-07-27 | 2006-07-27 | Coverlay |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5077840B2 (en) |
| KR (1) | KR101463220B1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8071273B2 (en) | 2008-03-31 | 2011-12-06 | Dai Nippon Printing Co., Ltd. | Polyimide precursor, resin composition comprising the polyimide precursor, pattern forming method using the resin composition, and articles produced by using the resin composition |
| JP5251211B2 (en) * | 2008-03-31 | 2013-07-31 | 大日本印刷株式会社 | Photosensitive resin composition and pattern forming method |
| JP5253315B2 (en) * | 2009-07-27 | 2013-07-31 | 大成プラス株式会社 | Solvent type epoxy adhesive and bonding method |
| JP6639249B2 (en) * | 2016-02-03 | 2020-02-05 | 東レ・デュポン株式会社 | Polyimide film with adhesive |
| JP6802131B2 (en) * | 2016-09-29 | 2020-12-16 | 東レ・デュポン株式会社 | Polyimide film with adhesive |
| JP7077064B2 (en) * | 2018-03-02 | 2022-05-30 | 東レ・デュポン株式会社 | Polyimide film |
| JP7235356B2 (en) * | 2018-12-24 | 2023-03-08 | ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド | Polyamic acid composition for manufacturing display substrate and method for manufacturing display substrate using the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03291986A (en) * | 1990-04-09 | 1991-12-24 | Sumitomo Bakelite Co Ltd | Manufacture of board for flexible printed circuit with cover coating |
| JP2815668B2 (en) * | 1990-04-20 | 1998-10-27 | 住友ベークライト株式会社 | Manufacturing method of flexible printed circuit board with cover coat |
| JP3945642B2 (en) * | 2002-08-28 | 2007-07-18 | 信越化学工業株式会社 | Coverlay |
| JP4126432B2 (en) * | 2003-10-17 | 2008-07-30 | 東レ・デュポン株式会社 | Method for producing polyimide film |
| JP4428016B2 (en) * | 2003-10-17 | 2010-03-10 | 東レ・デュポン株式会社 | Method for producing polyimide film |
-
2006
- 2006-07-27 JP JP2006204788A patent/JP5077840B2/en active Active
-
2007
- 2007-07-26 KR KR1020070075278A patent/KR101463220B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR101463220B1 (en) | 2014-11-19 |
| KR20080011095A (en) | 2008-01-31 |
| JP2008031251A (en) | 2008-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2004189981A (en) | Thermoplastic polyimide resin material and laminated body, and manufacturing method of printed wiring board | |
| WO2004055110A1 (en) | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same | |
| JP5077840B2 (en) | Coverlay | |
| JP5131519B2 (en) | Coverlay | |
| JP4994992B2 (en) | Laminate for wiring board and flexible wiring board for COF | |
| JP2009021350A (en) | Cover lay | |
| JP2007194603A (en) | Flexible printed wiring board, and manufacturing method thereof | |
| JP2008166556A (en) | Flexible printed wiring board | |
| JP4876890B2 (en) | Copper plate | |
| JP3090768B2 (en) | Laminate | |
| JP2007196671A (en) | Copper clad plate | |
| JP2007313738A (en) | Metal clad plate | |
| JP2007201442A (en) | Chip-on film | |
| JP2007173260A (en) | Flexible printed wiring board | |
| JP2008034527A (en) | Cover lay | |
| JP2007168370A (en) | Copper plated board | |
| JP3781381B2 (en) | Laminated body and wiring board using the same | |
| KR20070065237A (en) | Flexible printed circuit board and method of manufacturing the same | |
| JP5126735B2 (en) | Flexible printed wiring board | |
| JP2007194602A (en) | Flexible printed wiring board, and manufacturing method thereof | |
| JP2008034526A (en) | Cover lay | |
| JP2005135985A (en) | Manufacturing method for printed wiring board | |
| JP5004074B2 (en) | Chip on film | |
| JP2009019096A (en) | Cover-lay | |
| JP2008166555A (en) | Flexible printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090507 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100301 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20100301 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120522 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20120614 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20120614 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120625 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120814 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120820 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150907 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5077840 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |