JPH03100076A - Manufacture of thin polyimide film - Google Patents
Manufacture of thin polyimide filmInfo
- Publication number
- JPH03100076A JPH03100076A JP23843189A JP23843189A JPH03100076A JP H03100076 A JPH03100076 A JP H03100076A JP 23843189 A JP23843189 A JP 23843189A JP 23843189 A JP23843189 A JP 23843189A JP H03100076 A JPH03100076 A JP H03100076A
- Authority
- JP
- Japan
- Prior art keywords
- water
- electrodeposition coating
- bis
- dianhydride
- organic group
- 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
- 229920001721 polyimide Polymers 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 19
- 239000011342 resin composition Substances 0.000 claims abstract description 15
- 125000000962 organic group Chemical group 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 27
- 239000004642 Polyimide Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 26
- -1 amine compound Chemical class 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 abstract 2
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 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 description 42
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 229940124530 sulfonamide Drugs 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- KJRQMXRCZULRHF-UHFFFAOYSA-N 2-(4-cyanoanilino)acetic acid Chemical compound OC(=O)CNC1=CC=C(C#N)C=C1 KJRQMXRCZULRHF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RTIXKCRFFJGDFG-UHFFFAOYSA-N chrysin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- ZCOGQSHZVSZAHH-UHFFFAOYSA-N n,n-dimethylaziridine-1-carboxamide Chemical compound CN(C)C(=O)N1CC1 ZCOGQSHZVSZAHH-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 1
- LVUQCTGSDJLWCE-UHFFFAOYSA-N 1-benzylpyrrolidin-2-one Chemical compound O=C1CCCN1CC1=CC=CC=C1 LVUQCTGSDJLWCE-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RSVLLJMCLGUKLM-UHFFFAOYSA-N 10-isocyanatodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCN=C=O RSVLLJMCLGUKLM-UHFFFAOYSA-N 0.000 description 1
- QXOJEFDVHQCJNH-UHFFFAOYSA-N 10-isocyanatodecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCN=C=O QXOJEFDVHQCJNH-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- YBJCHCCHVQKFCL-UHFFFAOYSA-N 18-isocyanatooctadecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCCCCCCCCCN=C=O YBJCHCCHVQKFCL-UHFFFAOYSA-N 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 description 1
- NJJQKUCTKNDSPO-UHFFFAOYSA-N 2,4-diamino-1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=C(N)C(=O)C(N)=CC1=CC=CC=C1 NJJQKUCTKNDSPO-UHFFFAOYSA-N 0.000 description 1
- HFXFYWMYAYUJAA-UHFFFAOYSA-N 2,5-diaminobenzenesulfonamide Chemical compound NC1=CC=C(N)C(S(N)(=O)=O)=C1 HFXFYWMYAYUJAA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- MXOAZJGPKQBDJY-UHFFFAOYSA-N 2-(4-bromo-n-ethylanilino)acetic acid Chemical compound OC(=O)CN(CC)C1=CC=C(Br)C=C1 MXOAZJGPKQBDJY-UHFFFAOYSA-N 0.000 description 1
- LEERKBXWSSFGHA-UHFFFAOYSA-N 2-(4-chloro-n-ethylanilino)acetic acid Chemical compound OC(=O)CN(CC)C1=CC=C(Cl)C=C1 LEERKBXWSSFGHA-UHFFFAOYSA-N 0.000 description 1
- XRHNNBAYEDHJFF-UHFFFAOYSA-N 2-(4-chloro-n-propylanilino)acetic acid Chemical compound CCCN(CC(O)=O)C1=CC=C(Cl)C=C1 XRHNNBAYEDHJFF-UHFFFAOYSA-N 0.000 description 1
- RGADKZXRWFOTFV-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(C)(CO)CO RGADKZXRWFOTFV-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- MAKLMMYWGTWPQM-UHFFFAOYSA-N 2-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCC)=CC=C3C(=O)C2=C1 MAKLMMYWGTWPQM-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
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Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、目的とするパターンのポリイミド薄膜を導電
性基体に形成するポリイミド薄膜の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a polyimide thin film in which a polyimide thin film having a desired pattern is formed on a conductive substrate.
(従来の技術)
従来、光硬化性樹脂組成物はハケ塗り、デイツプコート
、ロールコート、カーテンコート等の方法で塗装され、
感光層を基体の上に形成していた。(Prior Art) Conventionally, photocurable resin compositions have been applied by methods such as brush coating, dip coating, roll coating, and curtain coating.
A photosensitive layer was formed on the substrate.
しかしこれらの方法では、膜厚の均一性が不十分(特に
複雑な形状の場合には膜厚を均一にすることは不可能に
近い)、膜厚の制御が困難、ビンホ(但し9式中、RQ
は4価の有機基でラシ、へは2ている(特公昭52−2
1526号公報参照)。However, with these methods, the uniformity of the film thickness is insufficient (particularly in the case of complex shapes, it is almost impossible to make the film thickness uniform), it is difficult to control the film thickness, and the film thickness is difficult to control. , RQ
is a tetravalent organic group, and he is a 2-valent organic group.
(See Publication No. 1526).
この方法によれば、■基板表面の凹凸への感光層の追従
性が良好であること、■短時間で形状が複雑なものでも
均一な感光層を形成できる。■溶液が水溶液のため作業
環境の汚染が防止でき防災上にも問題がない等の利点が
ある。According to this method, (1) the ability of the photosensitive layer to follow irregularities on the surface of the substrate is good, and (2) a uniform photosensitive layer can be formed in a short time even if the shape is complex. ■Since the solution is an aqueous solution, it has the advantage of preventing contamination of the working environment and causing no problems in terms of disaster prevention.
(発明が解決しようとする課題)
しかし従来から用いていた感光性樹脂組成物がアクリル
樹脂系、エポキシ樹脂系、アルキド樹脂系等の通常の有
機樹脂であるため、電着塗装後の光硬化物の耐熱性や耐
溶剤性が低いため、高温で長時間さらされる環境下では
劣化が著しく、そのため電気特性1機械特性、耐食性等
の各種物性の低下が問題となったり、ま念、その後、エ
ツチング処理やメツキ処理をする場合の耐エツチング液
性や耐メツキ液性が低いという問題があった。(Problem to be solved by the invention) However, since the photosensitive resin compositions conventionally used are ordinary organic resins such as acrylic resins, epoxy resins, and alkyd resins, photocured products after electrodeposition coating Due to its low heat resistance and solvent resistance, it deteriorates significantly in environments where it is exposed to high temperatures for long periods of time.As a result, deterioration of various physical properties such as electrical properties 1 mechanical properties and corrosion resistance may become a problem. There was a problem in that the resistance to etching liquids and plating liquids during processing and plating was low.
(課題を解決するための手段)
そこで本発明者らは、鋭意検討した結果、いったん感光
性のポリアミド酸を合成し、これに塩基を加えて水分散
性を向上させて感光性電着浴を作製し、この中に導電性
基体を浸漬して電着塗装し。(Means for solving the problem) As a result of intensive studies, the present inventors synthesized a photosensitive polyamic acid, added a base to it to improve its water dispersibility, and created a photosensitive electrodeposition bath. A conductive substrate is immersed in this material and then electrodeposition coated.
さらに露光、現像工程を経たのち、加熱処理することに
より耐熱性や耐溶剤性が良好で強じんなポリイミド薄膜
のパターンを導電性基体上に形成する方法を見い出した
。Furthermore, we have discovered a method of forming a strong polyimide thin film pattern with good heat resistance and solvent resistance on a conductive substrate by carrying out an exposure and development process followed by heat treatment.
すなわち9本発明は、一般式(I)で表わされる繰り返
し単位を有する感光性ポリアミド酸及び非水溶性光開始
剤を含有してなる感光性樹脂組成物に塩基及び水を加え
て水溶性もしくけ水分散性の電着塗装浴を作製し、該浴
に導電性基体を陽極として浸漬し2通電により電着塗装
して導電性基体上に電着塗装膜を形成し、その後活性光
線を前記電着塗装膜に#J儂上に照射し、露光部を光硬
化させ。That is, the present invention provides a photosensitive resin composition containing a photosensitive polyamic acid having a repeating unit represented by the general formula (I) and a water-insoluble photoinitiator, to which a base and water are added. A water-dispersible electrodeposition coating bath is prepared, a conductive substrate is immersed in the bath as an anode, and electrodeposition is applied by applying two currents to form an electrodeposition coating film on the conductive substrate. Irradiate #J on the coated film and photo-cure the exposed area.
未震光部を現像により除去した後、加熱処理することに
より、導電性基体上に目的とするパターンのポリイミド
薄膜を形成することを特徴とするポリイミド薄膜の製造
法に関する。The present invention relates to a method for producing a polyimide thin film, which is characterized in that a polyimide thin film having a desired pattern is formed on a conductive substrate by heat treatment after removing the non-shocked areas by development.
(但し9式中、R1は4価の有機基であすr ”2は2
価の有機基であり、Yは1価のエチレン性不飽和基を有
する有機基であり+mはOまたVil、nは1または2
で、かつm+n=2となるように選ばれる)。(However, in formula 9, R1 is a tetravalent organic group and ``2'' is 2
is a valent organic group, Y is an organic group having a monovalent ethylenically unsaturated group, +m is O or Vil, and n is 1 or 2
and m+n=2).
本発明によれば電着塗装の利点を生かし、密着性が良好
で均一な感光層を形成でき、かつ加熱処理後には、耐熱
性や耐溶剤性が良好で強じんなポリイミド薄膜のパター
ンを得ることができる。According to the present invention, by taking advantage of the advantages of electrodeposition coating, a uniform photosensitive layer with good adhesion can be formed, and after heat treatment, a strong polyimide thin film pattern with good heat resistance and solvent resistance can be obtained. be able to.
以下に本発明について詳述する。The present invention will be explained in detail below.
本発明に用いられる一般式(I)で表わされる繰り返し
単位を有する感光性ポリアミド酸は2例えば。Examples of the photosensitive polyamic acid having a repeating unit represented by the general formula (I) used in the present invention include 2.
下記一般式(It)iたはall)で表わされる化合物
(以下。A compound represented by the following general formula (It) i or all) (hereinafter referred to as a compound).
単に化合物■と呼ぶ)とアミン化合物(以下、単に化合
物■と呼ぶ)とを重合することによって得られる。(hereinafter simply referred to as compound (2)) and an amine compound (hereinafter simply referred to as compound (2)).
(但し2式中、馬およびR4は4価の有機基であり、X
はハロゲン原子またはヒドロキシ基、Yは1価のエチレ
ン性不飽和基を有する有機基である)。(However, in formula 2, horse and R4 are tetravalent organic groups, and
is a halogen atom or a hydroxy group, and Y is an organic group having a monovalent ethylenically unsaturated group).
化合物■と化合物■との反応は、不活性な有機溶媒中で
0−100℃の温度で行なわれることが好ましく、5〜
60℃の温度で行なわれることがより好ましい。また、
化合物■と化合物■との反応は、カルボジイミド聾脱水
縮合剤9例えば、ジシクロへキシルカルボジイミドなど
やアミン類等の脱ハロゲン化剤2例えばピリジンやトリ
エチルアミン等を触媒的に用いることにより促進される
。The reaction between compound (1) and compound (2) is preferably carried out in an inert organic solvent at a temperature of 0 to 100°C, and at a temperature of 5 to 100°C.
More preferably, it is carried out at a temperature of 60°C. Also,
The reaction between compound (1) and compound (2) is promoted by catalytically using a carbodiimide dehydration condensing agent 9 such as dicyclohexylcarbodiimide and a dehalogenating agent 2 such as amines such as pyridine or triethylamine.
上記反応に用いる有機溶媒としては、生成する一般式(
I)で表わされる繰り返し単位を有する感光性ポリアミ
ド酸を完全に溶解する極性溶媒が一般に好ましく2例え
ば、N−メチル−2−ピロリドン、 N、N−ジメチル
アセトアミド、 N、N−ジメチルホルムアミド、ジメ
チルスルホキシド、テトラメチル尿素、ヘキサメチルリ
ン酸ドリアもド、γ−ブチロラクトン、 N、N−ジメ
チルプロピレンウレア、 N、N−ジメチルエチレンウ
1/ア等が挙げられる。As the organic solvent used in the above reaction, the general formula (
Polar solvents that completely dissolve the photosensitive polyamic acid having the repeating unit represented by I) are generally preferred.2 For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide. , tetramethylurea, hexamethylphosphate, γ-butyrolactone, N,N-dimethylpropyleneurea, N,N-dimethylethyleneurea, and the like.
また、場合により上記の反応混合物から感光性ポリアミ
ド酸を単離するには、アルコール類または水に反応混合
物を少量ずつ加える方法が好ましい。このようにして得
られた固体を、再度、前記反応に用いる有機溶媒に溶解
し、アルコール類または水に加えて再沈澱させることを
繰り返すことにより精製することができる。Further, in order to isolate the photosensitive polyamic acid from the above reaction mixture in some cases, it is preferable to add the reaction mixture to alcohol or water little by little. The solid thus obtained can be purified by repeating dissolving it in the organic solvent used in the reaction, adding it to alcohol or water, and reprecipitating it.
化合物■は、テトラカルボン酸二無水物をエチレン性不
飽和基を有するヒドロキシ化合物で全てまたは部分的に
開環させて半エステル化することにより、またはさらに
前記半エステル化物を塩化チオニルや五塩化リンなどで
酸ノ10ゲン化することにより得ることができる。上記
のテトラカルボン酸二無水物とエチレン性不飽和基を有
する化合物との反応は1例えば、ピリジン、ジメチルア
ミノピリジンなどを添加することKよシ促進できる。Compound (1) can be obtained by half-esterifying the tetracarboxylic dianhydride by completely or partially ring-opening the tetracarboxylic dianhydride with a hydroxy compound having an ethylenically unsaturated group, or by further converting the half-esterified product into thionyl chloride or phosphorus pentachloride. It can be obtained by converting it into an acid 10-genated compound using a method such as the following. The reaction between the above-mentioned tetracarboxylic dianhydride and a compound having an ethylenically unsaturated group can be accelerated by adding, for example, pyridine, dimethylaminopyridine, or the like.
また9本発明に用いられる一般式(I)で表わされる繰
り返し単位を有する感光性ポリアミド酸は。Furthermore, the photosensitive polyamic acid having a repeating unit represented by the general formula (I) used in the present invention is.
例えば、一般式(IV)で表わされる繰り返し単位を有
するポリアミド酸と
(但し9式中、馬は一般式(I)におけるR、と同意義
であり、R6は一般式(I)における鳥と同意義である
)エチレン性不飽和基を有するイソシアナート化合物と
の反応によっても得られる。For example, a polyamic acid having a repeating unit represented by the general formula (IV) (in formula 9, horse has the same meaning as R in the general formula (I), and R6 has the same meaning as the bird in the general formula (I)) It can also be obtained by reaction with isocyanate compounds having ethylenically unsaturated groups.
一般式(Iv)で表わされる繰り返しを単位を有するポ
リアミド酸とエチレン性不飽和基を有するインシアナー
ト化合物との反応は、不活性な有機溶媒中で、0〜10
0℃で行なわれることが好ましく。The reaction between the polyamic acid having a repeating unit represented by the general formula (Iv) and the incyanato compound having an ethylenically unsaturated group is carried out in an inert organic solvent from 0 to 10
Preferably it is carried out at 0°C.
20〜70℃の温度で行なうことがより好ましい。It is more preferable to carry out the reaction at a temperature of 20 to 70°C.
エチレン性不飽和基を有するイソシアナート化合物の一
般式(!Vlで表わされる繰り返し単位を有するポリア
ミド酸に対する割合は、感度およびポリイミド薄膜の耐
熱性の点から、上記ポリアミド酸中のカルボキシル基1
当量に対して0.01〜0.8当量反応させることが好
ましく、o、i〜0.5当量反応させることがよシ好ま
しい。The ratio of the isocyanate compound having an ethylenically unsaturated group to the polyamic acid having a repeating unit represented by the general formula (!Vl) is determined from the viewpoint of sensitivity and heat resistance of the polyimide thin film.
It is preferable to react in an amount of 0.01 to 0.8 equivalents, and more preferably in an amount of o, i to 0.5 equivalents.
さらに、エチレン性不飽和基を有するイソシアナート化
合物と一般弐■で表わされる繰り返し単位を有するポリ
アミド酸との反応は、トリエチルアミン、1,4−ジア
ゾビシクロ[2,2,2]オクタン等のアミン、ジブチ
ルスズジラウレート、ジブチルスズジアセテート等のス
ズ化合物を触媒的に用いると容易となる。Furthermore, the reaction between an isocyanate compound having an ethylenically unsaturated group and a polyamic acid having a repeating unit represented by 2) can be performed using amines such as triethylamine, 1,4-diazobicyclo[2,2,2]octane, etc. This can be facilitated by using a tin compound such as dibutyltin dilaurate or dibutyltin diacetate as a catalyst.
一般式(財)で表される繰り返し単位を有するポリアミ
ド酸は、テトラカルボン酸二無水物と前記化合物■を出
発原料として公知の方法によね得ることができる。A polyamic acid having a repeating unit represented by the general formula (I) can be obtained by a known method using tetracarboxylic dianhydride and the above-mentioned compound (2) as starting materials.
上記においてテトラカルボン酸二無水物と化合物■との
反応は、不活性な有機溶媒中で0〜100℃。In the above, the reaction between the tetracarboxylic dianhydride and compound (1) is carried out at 0 to 100°C in an inert organic solvent.
好ましくは10〜80℃の温度で行なわれ、ポリアミド
酸の有機溶媒液として得ることができる。It is preferably carried out at a temperature of 10 to 80°C, and can be obtained as an organic solvent solution of polyamic acid.
これらのテトラカルボン酸二無水物と化合物■は。These tetracarboxylic dianhydrides and compound ■.
前者/後者が0.8 / 1〜1.2/1(モル比)の
割合で使用するのが好ましく2等モルで使用するのがよ
り好ましい。また、上記テトラカルボン酸二無水物と化
合物■との反応に用いる有機溶媒としては、最終的に生
成する一般式(I)で表わされる繰り返し単位を有する
重合体を完全に溶解する極性溶媒が一般に好ましく2例
えば、N−メチル−2−ピロリドン、 N、N−ジメチ
ルアセトアミド、 N、N−ジメチルホルムアミド、ジ
メチルスルホキシド、テトラメチル尿素、ヘキサメチル
リン酸トリアミド、γ−ブチロラクトン、 N、N−ジ
メチルプロピレンウレア。The former/latter is preferably used in a ratio of 0.8/1 to 1.2/1 (molar ratio), more preferably 2 equimolar. In addition, as the organic solvent used for the reaction between the tetracarboxylic dianhydride and compound (1), a polar solvent that completely dissolves the finally produced polymer having the repeating unit represented by the general formula (I) is generally used. Preferably 2, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, N,N-dimethylpropyleneurea .
N、N−ジメチルエチレンウレア等が挙げられる。Examples include N,N-dimethylethyleneurea.
本発明に用いられるテトラカルボン酸二無水物としては
0例えば、ピロメリット酸二無水物、λλ′44′−ベ
ンゾフェノンテトラカルボン酸二無水物、&λJ 4.
4/−ビフェニルテトラカルボン酸二無水物、メタ−タ
ーフェニル−a t 4.4’−テトラカルボン酸二無
水物、パラ−ターフェニル−a、 3:4゜41−テト
ラカルボン酸二無水物、1,2,5.6−ナフタレンテ
トラカルボン酸二無水物、2,3,6.7−ナフタレン
テトラカルボン酸二無水物、4本5.6−ピリジンテト
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、3,49.10−ペリレンテ
トラカルボン酸二無水物、、4.4’−スルホニルシフ
タル酸二無水物、ビス(λ4−ジカルボキシフェニル)
エーテル二m水物、 λ2−ビス(:3.4−ジカル
ボキシフェニル)プロパン二無水物。ブタンテトラカル
ボン酸二無水物、ペンタンテトラカルボン酸二無水物、
ヘキサンテトラカルボン酸二無水物、シクロペンタンテ
トラカルボン酸二無水物、ビシクロヘキセンテトラカル
ボン酸二無水物、シクロヘキサンテトラカルボン酸二無
水物、ビシクロ−(2,2,2)−オクト−クエン−4
へ5.6−テトラカルボン酸二無水物、5−(λ5−ジ
オキソテトラヒドロフリル)−3−メチル−3−シクロ
ヘキセン−1,2−ジカルボン酸無水物、ジシクロへキ
シルーミ4.■4′−テトラカルボン酸二無水物、エチ
レンビストリメリテート二無水物、トリメチレンビスト
リメリテートニ無水物、テトラメチレンビストリメリテ
ートニ無水物、ペンタメチレンビストリメリテートニ無
水物。Examples of the tetracarboxylic dianhydride used in the present invention include pyromellitic dianhydride, λλ'44'-benzophenonetetracarboxylic dianhydride, &λJ 4.
4/-biphenyltetracarboxylic dianhydride, meta-terphenyl-at 4.4'-tetracarboxylic dianhydride, para-terphenyl-a, 3:4゜41-tetracarboxylic dianhydride, 1,2,5.6-naphthalenetetracarboxylic dianhydride, 2,3,6.7-naphthalenetetracarboxylic dianhydride, 4 5.6-pyridinetetracarboxylic dianhydride, 1,4. 5.8-Naphthalenetetracarboxylic dianhydride, 3,49.10-perylenetetracarboxylic dianhydride, 4.4'-sulfonylsiphthalic dianhydride, bis(λ4-dicarboxyphenyl)
Ether dimhydrate, λ2-bis(:3,4-dicarboxyphenyl)propane dianhydride. Butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride,
Hexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclohexenetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, bicyclo-(2,2,2)-octo-quene-4
5.6-Tetracarboxylic dianhydride, 5-(λ5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyluminum4. (2) 4'-Tetracarboxylic dianhydride, ethylene bistrimelitate dianhydride, trimethylene bistrimelitate dianhydride, tetramethylene bistrimelitate dianhydride, pentamethylene bistrimelitate dianhydride.
ヘキサメチレンビストリメリテートニ無水物、オクタメ
チレンビストリメリテートニ無水物、2.2−ビス14
−ジカルボキシフェニル)へキサフルオロプロパンニ無
水物、λ2−ビス(4−(λ4−ジカルボキシフェノキ
シ)フェニル〕へキサフルオロプロパン二m水物、2.
2−ビス〔4−(2,3−ジカルボキシフェノキシ)フ
ェニル〕へキサフルオロプロパン二無水物。cトリフル
オロメチル)ピロメリット酸二無水物、ビス(トリフル
オロメチル)ピロメリット酸二無水物、3.3’−ビス
(トリフルオロメチル) −4,4; 5.5’−テト
ラカルボキシビフェニルニ無水物、2.2:5.5’−
テトラキス(トリフルオロメチル)−3,3:4.4’
−テトラカルボキシビフェニルニ無水物、3.3’−ビ
ス(トリフルオロメチル) −44; 5.5’−テト
ラカルボキシビフェニルエーテルニ無水物、2.2’−
ビス(トリフルオロメチル) −4,4; 5.5’−
テトラヵルボキシビフェニルエーテルニ無水物、3.3
’−ビス(トリフルオロメチル) −4,4; 5.5
’−テトラカルポキシペンゾフエノンニ無水物、 2
.2’−ビス(トリフルオロメチル) −4,4:5.
5’−テトラカルボキシベンゾフエノンニ無水物、1.
4−ビス〔3−(トリフルオロメチル’) −4,5−
ジカルボキシフェノキシ〕ベンゼンニ無水物、 1.
4−ビス〔2−(トリフルオロメチル)−4,5−ジカ
ルボキシフェノキシフベンゼン二m水物、 4.4’−
ビス〔3−(トリフルオロメチル) −4,5−ジカル
ボキシフェノキシ〕ビフェニルニ無水物、1−)リフル
オロメチル−λ5−ビスC3−() リフルオロメチル
)−4,5−ジカルボキシフェノキシ〕ベンゼンニ無水
物、 1.1’−ビス(トリフルオロメチル)−λ3
′−ビスI:3−()リフルオロメチル) −4,5−
ジカルボキシフェノキシ〕ビフェニルニ無水物、4゜4
′−ビス〔3−(トリフルオロメチル) −4,5−ジ
カルボキシフェノキシ〕ビフェニルエーテルニfg水物
、1−トリフルオロメチル−3,5−ビス(3,4−ジ
カルボキシフェニル)ベンゼン二無水物、1.4−ビス
(トリフルオロメチル)−3,5−ビス(3,4−ジカ
ルボキシフェニル)ベンゼン二m水物、 1,2,4
.6−テトラキス(トリフルオロメチル)−3,5−ビ
ス(λ4−ジカルボキシフェニル)ヘンゼンニ無水物、
1.1−一ビス(トリフルオロメチル)−3,3’−(
3,4−ジカルボキシフェノキシ)ビフェニルニ無水物
、 1,1:4,4’−テトラキス(トリフルオロメ
チル)λ3’−(3,4−ジカルボキシフェノキシ)ビ
フェニル二無水物。2.2−ビス(4−(λ3−ジカル
ボキシベンゾイルオキシ)フェニル〕へキサフルオロプ
ロパン二m水物。Hexamethylene bistrimelitate dianhydride, octamethylene bistrimelitate dianhydride, 2.2-bis14
-dicarboxyphenyl)hexafluoropropane dianhydride, λ2-bis(4-(λ4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2.
2-bis[4-(2,3-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride. c trifluoromethyl)pyromellitic dianhydride, bis(trifluoromethyl)pyromellitic dianhydride, 3.3'-bis(trifluoromethyl)-4,4;5.5'-tetracarboxybiphenyl dianhydride Anhydride, 2.2:5.5'-
Tetrakis(trifluoromethyl)-3,3:4.4'
-Tetracarboxybiphenyl dianhydride, 3.3'-bis(trifluoromethyl) -44; 5.5'-tetracarboxybiphenyl ether dianhydride, 2.2'-
Bis(trifluoromethyl) -4,4; 5.5'-
Tetracarboxybiphenyl ether dianhydride, 3.3
'-bis(trifluoromethyl) -4,4; 5.5
'-tetracarpoxypenzophenone dianhydride, 2
.. 2'-bis(trifluoromethyl)-4,4:5.
5'-Tetracarboxybenzophenone dianhydride, 1.
4-bis[3-(trifluoromethyl') -4,5-
Dicarboxyphenoxy benzene anhydride, 1.
4-bis[2-(trifluoromethyl)-4,5-dicarboxyphenoxybenzene dihydrate, 4.4'-
Bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]biphenyl dianhydride, 1-)lifluoromethyl-λ5-bisC3-()lifluoromethyl)-4,5-dicarboxyphenoxy] Benzene dianhydride, 1.1'-bis(trifluoromethyl)-λ3
'-Bis I:3-()lifluoromethyl)-4,5-
Dicarboxyphenoxy]biphenyl dianhydride, 4゜4
'-Bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]biphenylethernifg hydrate, 1-trifluoromethyl-3,5-bis(3,4-dicarboxyphenyl)benzene dianhydride 1,4-bis(trifluoromethyl)-3,5-bis(3,4-dicarboxyphenyl)benzene dihydrate, 1,2,4
.. 6-tetrakis(trifluoromethyl)-3,5-bis(λ4-dicarboxyphenyl) anhydride,
1.1-bis(trifluoromethyl)-3,3'-(
3,4-dicarboxyphenoxy)biphenyl dianhydride, 1,1:4,4'-tetrakis(trifluoromethyl)λ3'-(3,4-dicarboxyphenoxy)biphenyl dianhydride. 2.2-bis(4-(λ3-dicarboxybenzoyloxy)phenyl)hexafluoropropane dihydrate.
2.2−ビス〔3−メチル−4−(λ3−ジカルボキシ
ベンゾイルオキシ)フェニル〕へキサフルオロプロパン
ニ無水物、ス2−ビス(4−(2−トリフルオロメチル
−3,4−ジカルボキシベンゾイルオキシ)フェニル〕
へキサフルオロプロパンニ無水物、1,5−ビスl:
4− (3,4−ジカルボキシヘンソイルオキシ)フェ
ニル〕デカフルオロペンタンニ無水物、1.3−ビス[
4−(3,4−ジカルボキシベンゾイルオキシ)フェニ
ル〕へキサフルオロプロパンニ無水物、1.6−ピスC
4−(3,4−ジカルボキシベンゾイルオキシ)フェニ
ル〕ドデカフルオロヘキサンニ無水物、λ2−ビス〔3
゜5−ジメチル−4−(λ4−ジカルボキシフェノキシ
)フェニル〕へキサフルオロブロバンニ無水物、2.2
−ビスC4−(3,4−ジカルボキシフェノキシ)フェ
ニル〕オクタフルオロブタンニ無水物j λ2−ビス(
4−(2−トリフルオロメチル−へ4−ジカルボキシ)
フェニル〕へキサフルオロフロパン二m水物、1.3−
ビス(4−(&4−ジカルボキシフェノキシ)フェニル
〕ヘキサフルオロプロパンニ無水物、1.5−ビスC4
−(3,4−ジカルボキシフェノキシ)フェニル〕テカ
フルオロペンタンニ無水物、1.6−ビス(4−(3,
4−ジカルボキシフェノキシ)フェニル〕ドデヵフルオ
ロプロパンニ無水物。2.2-bis[3-methyl-4-(λ3-dicarboxybenzoyloxy)phenyl]hexafluoropropanide anhydride, 2-bis(4-(2-trifluoromethyl-3,4-dicarboxy) benzoyloxy)phenyl]
Hexafluoropropanihydride, 1,5-bisl:
4-(3,4-dicarboxyhensoyloxy)phenyl]decafluoropentane dianhydride, 1,3-bis[
4-(3,4-dicarboxybenzoyloxy)phenyl]hexafluoropropanihydride, 1,6-pisC
4-(3,4-dicarboxybenzoyloxy)phenyl]dodecafluorohexane dianhydride, λ2-bis[3
゜5-dimethyl-4-(λ4-dicarboxyphenoxy)phenyl]hexafluorobrovanni anhydride, 2.2
-bisC4-(3,4-dicarboxyphenoxy)phenyl]octafluorobutani dianhydride j λ2-bis(
4-(2-trifluoromethyl-to-4-dicarboxy)
phenyl]hexafluorofuropane dihydrate, 1.3-
Bis(4-(&4-dicarboxyphenoxy)phenyl)hexafluoropropanihydride, 1.5-bisC4
-(3,4-dicarboxyphenoxy)phenyl]tecafluoropentanihydride, 1,6-bis(4-(3,
4-Dicarboxyphenoxy)phenyl]dodecafluoropropanihydride.
などが挙けられる。Examples include.
本発明に用いられる化合物■としては2例えば。Examples of the compound ① used in the present invention include 2.
4.4′−ジアミノジフェニルエーテル、441−ジア
ミノジフェニルエーテル、4.4’−ジアミノジフェニ
ルメタン、44’−ジアミノジフェニルスルホン。4.4'-diaminodiphenyl ether, 441-diaminodiphenyl ether, 4.4'-diaminodiphenylmethane, 44'-diaminodiphenyl sulfone.
44′−ジアミノジフェニルスルフィド、ベンジジン、
メタ−フェニレンジアミン、バラーフ二二レンジアミン
、1,5−ナフタレンジアミン、λ6−ナフタレンジア
ミン、2.2−ビス(4−アミノフェノキシフェニル)
プロパン、ビス(4−アミノフェノキシフェニル)スル
ホン、 2.2−ビス(4−アミノフェニル)へキサ
フルオロプロパン、2゜2−ビス(3−アミノ−4−メ
チルフェニル)へキサフルオロプロパン、2.2−ビス
(3−メチル−4−アミノフェニル)へキサフルオロプ
ロパン。44'-diaminodiphenyl sulfide, benzidine,
Meta-phenylene diamine, baraf 22 diamine, 1,5-naphthalene diamine, λ6-naphthalene diamine, 2,2-bis(4-aminophenoxyphenyl)
Propane, bis(4-aminophenoxyphenyl)sulfone, 2.2-bis(4-aminophenyl)hexafluoropropane, 2°2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2. 2-bis(3-methyl-4-aminophenyl)hexafluoropropane.
2.2−ビス(3,5−ジメチル−4−アミノフェニル
)へキサフルオロプロパン、ス2−ビス〔4−(4−ア
ミノフェノキシ)フェニル〕へキサフルオロプロパン、
ス2−ビス[:4−(3−アミノフェノキシ)フェニル
〕ヘキサフルオロプロパン。2.2-bis(3,5-dimethyl-4-aminophenyl)hexafluoropropane, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
2-bis[:4-(3-aminophenoxy)phenyl]hexafluoropropane.
″2.2−ビス(4−(2−アミノフェノキシ)フェニ
ル〕へキサフルオロプロパン、 2.2−ビス〔亀5
−ジメチル−4−(4−アミノフェノキシ)フェニル〕
へキサフルオロプロパン、1.4−ビス(2−()リフ
ルオロメチル)−4−アミノフェノキシ〕ベンゼン、4
.4’−ビス(2−()リフルオロメチル)−4−アミ
ノフェノキシ)ビフェニル、4.4’−ビス〔2−(ト
リフルオロメチル)−4−アミノフェノキシ〕ジフェニ
5ルスルホン、4゜4’−ビスC4−(4−アミノフェ
ニルチオ)−フェニル〕ビフェニル、212′−ビス(
4−(4−アミノフェニルチオ)−フェニル〕へキサフ
ルオロプロパン、2.2’−ビス[:4−(2−)リフ
ルオロメチル−4−アミノフェノキシ)フェニル〕へキ
サフルオロプロパン。″2.2-bis(4-(2-aminophenoxy)phenyl)hexafluoropropane, 2.2-bis[turtle 5
-dimethyl-4-(4-aminophenoxy)phenyl]
Hexafluoropropane, 1,4-bis(2-()lifluoromethyl)-4-aminophenoxy]benzene, 4
.. 4'-bis(2-()lifluoromethyl)-4-aminophenoxy)biphenyl, 4.4'-bis[2-(trifluoromethyl)-4-aminophenoxy]diphenylsulfone, 4°4'- BisC4-(4-aminophenylthio)-phenyl]biphenyl, 212'-bis(
4-(4-aminophenylthio)-phenyl]hexafluoropropane, 2,2'-bis[:4-(2-)lifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane.
などが挙げられる。Examples include.
これらは、単独でも2糧類以上を組合せても使用するこ
とができる。These can be used alone or in combination of two or more.
また、この他に一般式(V)で表わされるジアミノアミ
ド化合物も併用することができる。In addition, a diaminoamide compound represented by general formula (V) can also be used in combination.
(ただし、Arは芳香族基、2はSO意またけCOを示
し、1個のアミノ基とZ −N H,とは互いにオルト
位に位置する)。(However, Ar is an aromatic group, 2 represents SO and CO, and one amino group and Z - NH, are located at the ortho position to each other).
この化合物としては2例えば、4.4’−ジアミノジフ
ェニルエーテル−3−スルホンアミド、λ4′−ジアミ
ノジフェニルエーテル−4−スルホンアミド、3.4’
−ジアミノジフェニルエーテル−35−スルホンアミド
、λ3′−ジアミノジフェニルエーテル−4−スルホン
アミド、4.4’−ジアミノジフェニルメタンー3−ス
ルホンアミ)”、 3.4’−ジアミノジフェニルメタ
ン−4−スルホンアミド、3゜4′−ジアミノジフェニ
ルメタン−3′−スルホンアミド、λ3’−’)7Z/
)フェニルメタン−4−スルホンアミド、4.4’−ジ
アミノジフェニルスルホン−3−スルホンアミド、3,
4’−ジアミノジフェニルスルホン−4−スルホンアミ
ド、3.4’−ジアミノジフェニルスルホン−31−ス
ルホンアミド。Examples of this compound include 4,4'-diaminodiphenyl ether-3-sulfonamide, λ4'-diaminodiphenyl ether-4-sulfonamide, 3.4'
-diaminodiphenyl ether-35-sulfonamide, λ3'-diaminodiphenyl ether-4-sulfonamide, 4.4'-diaminodiphenylmethane-3-sulfonamide), 3.4'-diaminodiphenylmethane-4-sulfonamide, 3゜4 '-Diaminodiphenylmethane-3'-sulfonamide, λ3'-')7Z/
) phenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,
4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-31-sulfonamide.
33’−ジアミノジフェニルスルホン−4−スルホンア
ミド、4.4’−ジアミノジフェニルサルファイド−3
−スルホンアミド、141−ジアミノ、ジフェニルサル
ファイド−4−スルホンアミド、3.3’−ジアミノジ
フェニルサルファイド−4−スルホンアミド、λ4−−
ジアミノジフェニルサルファイド−3′−スルホンアミ
ド、1.4−ジアミノベンゼン−2−スルホンアミド、
4.4’−ジアミノジフェニルエ・−チル−3−カルボ
ンアミドj3.4’−ジアミノジフェニルエーテル−4
−カルボンアミド、3゜4’ −ジアミノジフェニルエ
ーテル−3′−カルボンアミド、亀3’−ジアミノジフ
ェニルエーテル−4−カルボンアミド、4.4’−ジア
ミノジフェニルメタン−3−カルボンアミド、λ4′−
ジアミノジフ工二ルメタン−4−カルボンアミド、&4
′−ジアミノジフェニルメタン−31−カルボンアミド
、13′−ジアミノジフェニルメタン−4−カルボンア
ミドj4.4’−ジアミノジフェニルスルホン−3−カ
ルボンアミド、亀4′−ジアミノジフェニルスルホン−
4−カルボンアミド、入4′−ジアミノジフェニルスル
ホン−35−カルボンアミド、へ3I−ジアミノジフェ
ニルスルホン−4−カルボンアミド。33'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3
-Sulfonamide, 141-diamino, diphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-sulfonamide, λ4--
Diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide,
4.4'-Diaminodiphenylether-3-carbonamidej3.4'-Diaminodiphenyl ether-4
-carbonamide, 3゜4'-diaminodiphenyl ether-3'-carbonamide, tome 3'-diaminodiphenyl ether-4-carbonamide, 4.4'-diaminodiphenylmethane-3-carbonamide, λ4'-
Diaminodiphenylmethane-4-carbonamide, &4
'-Diaminodiphenylmethane-31-carbonamide, 13'-diaminodiphenylmethane-4-carbonamidej4.4'-diaminodiphenylsulfone-3-carbonamide, turtle 4'-diaminodiphenylsulfone-
4-carbonamide, 4'-diaminodiphenylsulfone-35-carbonamide, and 3I-diaminodiphenylsulfone-4-carbonamide.
44’−ジアミノジフェニルサルファイド−3−カルボ
ンアミド、亀4′−ジアミノジフェニルサルファイド−
4−カルボンアミドj3.3’−ジアミノジフェニルサ
ルファイド−4−カルボンアミド、3゜4′−ジアミノ
ジフェニルサルファイド−31−スルホンアミド、lI
4−ジアミノベンゼン−2−カルボンアミド等が挙げら
れる。44'-diaminodiphenyl sulfide-3-carbonamide, tome 4'-diaminodiphenyl sulfide-
4-Carbonamide j3.3'-diaminodiphenyl sulfide-4-carbonamide, 3゜4'-diaminodiphenyl sulfide-31-sulfonamide, lI
Examples include 4-diaminobenzene-2-carbonamide.
本発明に用いられるエチレン性不飽和基を有するヒドロ
キシ化合物としては2例えば、トリメチロールプロパン
ジアクリレート、トリメチロールプロパンジメタクリレ
ート、トリメチロールエタンジアクリレート、トリメチ
ロールエタンジメタクリレート、ペンタエリスリトール
トリアクリレート、ペンタエリスリトールトリメタクリ
レート。Examples of the hydroxy compound having an ethylenically unsaturated group used in the present invention include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, pentaerythritol triacrylate, and pentaerythritol. trimethacrylate.
2−ヒドロキシエチルアクリ1/−ト、2−ヒドロキシ
エチルメタクリレート、2−ヒドロキシプロピルアクリ
レート、2−ヒドロキシプロピルメタクリレート、2−
ヒドロキシ−3−フェノキシプロヒルアクリレート、2
−ヒドロキシ−3−フェノキシプロピルメタクリレート
、アリルアルコール、グリセリンジアリルエーテル、ト
リメチロールプロパンジアリルエーテル、トリメチロー
ルエタンジアリルエーテル、ペンタエリスリトールジア
リルエーテル、エチレングリコールモノアリルエーテル
、ジエチレングリコールモノアリルエーテル、シクリセ
ロールトリアリルエーテル、クロチルアルコール、ビニ
ルフェノール、シンナミルアルコール、アリルフェノー
ル、O−シンナミルフェノール。2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-
Hydroxy-3-phenoxyprohylacrylate, 2
-Hydroxy-3-phenoxypropyl methacrylate, allyl alcohol, glycerin diallyl ether, trimethylolpropane diallyl ether, trimethylolethane diallyl ether, pentaerythritol diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, cyclycerol triallyl ether, Crotyl alcohol, vinylphenol, cinnamyl alcohol, allylphenol, O-cinnamylphenol.
(RはHまたはCH3である)。(R is H or CH3).
(RはH捷たはCH3である) 等が挙げられる。(R is H or CH3) etc.
これらのエチレン性不飽和基を有するヒドロキシ化合物
は、単独でも2種類以上を組合せても使用することがで
きる。These hydroxy compounds having an ethylenically unsaturated group can be used alone or in combination of two or more.
本発明に用いられるエチレン性不飽和基を有するイソシ
アナート化合物としては1例えば、イソシアナートエチ
ルアクリレート、イソシアナートプロピルアクリレート
、イソシアナートブチルアクリレート、イソシアナート
ペンチルアクリレート、イソシアナートヘキシルアクリ
レート、イソシアナートオクチルアクリレート、イソシ
アナートデシルアクリレート、イソシアナートオクタデ
シルアクリレート、イソシアナートエチルメタクリレー
ト、インシアナートプロピルメタクリレート、インシア
ナートブチルメタクリレート、インシアナートペンチル
メタクリレート、イソシアナ−トへキシルメタクリレー
ト、イソシアナートオクチルメタクリレート、イソシア
ナートデシルメタクリレート、イソシアナートオクタデ
シルメタクリレート、イソシアナートエチルクロトネー
ト。Examples of the isocyanate compound having an ethylenically unsaturated group used in the present invention include isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, isocyanatopentyl acrylate, isocyanatohexyl acrylate, isocyanatooctyl acrylate, Isocyanatodecyl acrylate, isocyanatooctadecyl acrylate, isocyanatoethyl methacrylate, incyanatopropyl methacrylate, incyanatobutyl methacrylate, incyanatopentyl methacrylate, isocyanatohexyl methacrylate, isocyanatooctyl methacrylate, isocyanatodecyl methacrylate, Isocyanate octadecyl methacrylate, isocyanate ethyl crotonate.
インシアナートプロピルクロトネート、イソシア等が挙
げられる。イソシアナートエチルメタクリレートは市販
品として1例えばダウ・ケミカル社。Incyanatopropylcrotonate, isocyanate, and the like. Isocyanate ethyl methacrylate is commercially available, such as from Dow Chemical Company.
昭和ロープイア化学社等から入手することが可能である
。It can be obtained from Showa Ropeia Chemical Co., Ltd., etc.
本発明に用いられる非水溶性光開始剤としては。The water-insoluble photoinitiator used in the present invention includes:
例えば、ミヒラーズヶトン、ベンゾイン、2−メチルベ
ンツイン、ベンゾインメチルエーテル、ベンゾインエチ
ルエーテル、ベンゾインイソプロピルエーテル、ベンゾ
インブチルエーテル、2−を−ブチルアントラキノン、
1.2−ベン:/−9,10−アントラキノン、アント
ラキノン、メチルアントラキノン、4.4’−ビス(ジ
エチルアミノ)ベンゾフェノン、アセトフェノン、ベン
ゾフェノン。For example, Michlerskaton, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-butylanthraquinone,
1.2-ben:/-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone.
チオキサントン、214−ジエチルチオキサントン。Thioxanthone, 214-diethylthioxanthone.
1.5−アセナフテン、ス2−ジメトキシー2−フェニ
ルアセトフェノン、1−ヒドロキシシクロへキシルフェ
ニルケトン、2−メチル−(4−(メチルチオ)フェニ
ル)−2−モルフォリノ−1−プロパノン、ジアセチル
、ベンジル、ベンジルジメチルケタール、ベンジルジエ
チルケタール、ジフェニルジスルフィド、アントラセン
、フェナンスレンキノン、リボフラビンテトラブチレー
ト。1.5-acenaphthene, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-(4-(methylthio)phenyl)-2-morpholino-1-propanone, diacetyl, benzyl, benzyl Dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate.
アクリルオレンジ、エリスロシン、フェナンスレンキノ
ン、2−イソプロピルチオキサントン、3゜3−カルボ
ニル−ビス(7−ジエチルアミノ)クマリン、216.
−ビス(p−ジエチルアミノベンジリデン)−4−メチ
ル−4−アザシクロへキサノン。Acrylic orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 3°3-carbonyl-bis(7-diethylamino)coumarin, 216.
-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone.
6−ビス(p−ジメチルアミノベンジリデン)−シクロ
ペンタノン、2.6−ビス(p−ジエチルアミノベンジ
リデン)−4−フェニルシクロヘキサノン、下記の式で
表わされるアミノスチリルケトン等を挙げることができ
る。Examples include 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2.6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, and aminostyryl ketone represented by the following formula.
これらの非水溶性光開始剤は、単独でも2種類以上を組
合せても使用することができる。These water-insoluble photoinitiators can be used alone or in combination of two or more.
これらの光開始剤に、光開始助剤であるアミン類やアミ
ノ酸を併用することもできる。These photoinitiators can also be used in combination with photoinitiation aids such as amines and amino acids.
アミン類としては9例えば、p−ジメチルアミノ安息香
酸エチル、p−ジエチルアミノ安息香酸メチル、p−ジ
エチルアミノ安息香酸エチル、p−ジメチルアミノ安息
香酸エチル、p−ジメチルアミノ安息香酸インアミル、
p−ジメチルアミノベンゾニトリル、 N、N−ジメチ
ルアントラニル酸エチル等を挙げることができる。Examples of amines include ethyl p-dimethylaminobenzoate, methyl p-diethylaminobenzoate, ethyl p-diethylaminobenzoate, ethyl p-dimethylaminobenzoate, inamyl p-dimethylaminobenzoate,
Examples include p-dimethylaminobenzonitrile and ethyl N,N-dimethylanthranilate.
アミノ酸としては1例えば。N−フェニルグリシン、N
−メチル−N−(p−/、ロロフェニル)グリシン、N
−エチル−N−(p−クロロフェニル)グリシン、N−
(n−プロピル)−N−(p−クロロフェニル)グリシ
ン、N−メチル−N−(p−−fロモフェニル)クリシ
ン、N−エチル−N−(p−ブロモフェニル)グリシン
、N−(p−シアノフェニル)グリシンeN−(p−ク
ロロフェニル)クリシン、N−(p−ブロモフェニル)
グリシン等を挙げることができる。For example, as an amino acid. N-phenylglycine, N
-Methyl-N-(p-/, lorophenyl)glycine, N
-ethyl-N-(p-chlorophenyl)glycine, N-
(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p--fromophenyl)chrycine, N-ethyl-N-(p-bromophenyl)glycine, N-(p-cyano phenyl)glycine eN-(p-chlorophenyl)chrysine, N-(p-bromophenyl)
Examples include glycine and the like.
これらの非水溶性光開始剤、光開始助剤であるアミン類
およびアミノ酸の使用量は。感光性樹脂組成物の感度お
よび塗膜の耐熱性の点から、一般式(I3で表わされる
繰り返し単位を有する感光性ポリアミド酸100重量部
に対して9通常0.01〜30重量部、好ましく If
io、 1〜10重量部とされる。What are the amounts of these water-insoluble photoinitiators, amines and amino acids used as photoinitiation aids? From the viewpoint of the sensitivity of the photosensitive resin composition and the heat resistance of the coating film, 9 is usually 0.01 to 30 parts by weight, preferably 0.01 to 30 parts by weight, preferably If
io, 1 to 10 parts by weight.
また。これらの光開始剤、アミン類およびアミノ酸は、
単独でも2種類以上を組合せても使用することかできる
。Also. These photoinitiators, amines and amino acids are
They can be used alone or in combination of two or more.
本発明になる感光性樹脂組成物には、さらに分子内に光
重合性の不飽和基を1つ以上有するエチレン性不飽和化
合物を含有させることができる。The photosensitive resin composition of the present invention can further contain an ethylenically unsaturated compound having one or more photopolymerizable unsaturated groups in the molecule.
このエチレン性不飽和化合物としては2例えば。Examples of this ethylenically unsaturated compound include 2.
多価アルコールにα、β−不飽和カルボン酸を付加して
得られる化合物9例えば、トリメチロールプロパンジ(
メタ)アクリ1/−ト、トリメチロールプロパントリ(
メタ)アクリレート、テトラメチロールプロパントリ(
メタ)アクリレート、ペンタエリスリトールトリ(メタ
)アクリレート。Compound 9 obtained by adding α,β-unsaturated carboxylic acid to polyhydric alcohol For example, trimethylolpropanedi(
meth)acrylate, trimethylolpropane tri(
meth)acrylate, tetramethylolpropane tri(
meth)acrylate, pentaerythritol tri(meth)acrylate.
ペンタエリスリトールテトラ(メタ)アクリレート、ジ
ペンタエリスリトールペンタ(メタ)アクリレート、ジ
ペンタエリスリトールヘキサ(メタ)アクリレート等、
グリシジル基含有化合物にα。Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.
α for glycidyl group-containing compounds.
β−不飽和カルボン酸を付加して得られる化合物。A compound obtained by adding β-unsaturated carboxylic acid.
例、l’、)リメチロールブロバントリグリシジルエー
テルトリアクリレート、ビスフェノール人ジグリシジル
エーテルジ(メタ)アクリレート等。Examples, l',) Limethylolbroban triglycidyl ether triacrylate, bisphenol diglycidyl ether di(meth)acrylate, etc.
多価カルボン酸9例えば、無水フタル酸等と水酸基及び
エチレン性不飽和基を有する物質1例えば。Polycarboxylic acid 9 For example, phthalic anhydride etc. and substance 1 having a hydroxyl group and an ethylenically unsaturated group.
β−ヒドロキシエチル(メタ)アクリレート等とのエス
テル化物、アクリル酸またはメタクリル酸のアルキルエ
ステル、例えば、(メタ)アクリル酸メチル、(メタ)
アクリル酸プロピル、(メタ)アクリル酸ブチル等が用
いられ、トリメチルへキサメチレンジイソシアネート、
2価アルコール及び2価アルコールの(メタ)アクリル
酸のモノエステルを反応させて得られるウレタンジアク
リレート化合物等も用いられる。これらの化合物は2種
以上用いてもよい。また、このエチレン性不飽和化合物
の使用量は、前記の感光性ポリアミド酸100重量部に
対して50重量部以下が好ましい。Esterified products with β-hydroxyethyl (meth)acrylate etc., alkyl esters of acrylic acid or methacrylic acid, such as methyl (meth)acrylate, (meth)
Propyl acrylate, butyl (meth)acrylate, etc. are used, and trimethylhexamethylene diisocyanate,
A urethane diacrylate compound obtained by reacting a dihydric alcohol and a monoester of (meth)acrylic acid of the dihydric alcohol can also be used. Two or more types of these compounds may be used. The amount of the ethylenically unsaturated compound used is preferably 50 parts by weight or less based on 100 parts by weight of the photosensitive polyamic acid.
エチレン性不飽和化合物の使用量が50重量部を越える
と、加熱処理して得られるポリイミド薄膜の耐熱性が低
下する。When the amount of the ethylenically unsaturated compound used exceeds 50 parts by weight, the heat resistance of the polyimide thin film obtained by heat treatment decreases.
また9本発明になる感光性樹脂組成物には、p−メトキ
シフェノール、ハイドロキノン、ピロガロール、フェノ
チアジンなどの熱重合抑制剤を含有させることができる
。Further, the photosensitive resin composition of the present invention may contain a thermal polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, and phenothiazine.
さらに本発明になる感光性樹脂組成物には、染料、jl
lI料等の着色剤、可塑剤、接着促進剤、タルク等を添
加してもよい。Furthermore, the photosensitive resin composition of the present invention includes a dye, jl
Coloring agents such as II additives, plasticizers, adhesion promoters, talc, etc. may be added.
これら感光性樹脂組成物は前記した有機溶媒に均一に溶
解されることが望ましい。It is desirable that these photosensitive resin compositions be uniformly dissolved in the above-mentioned organic solvent.
次にこの溶液に塩基を加えて感光性樹脂組成物の水溶化
または水分散化を容易にする。ここで用いる塩基として
は、特に制限はないが9例えば。Next, a base is added to this solution to facilitate water solubilization or water dispersion of the photosensitive resin composition. The base used here is not particularly limited, but for example, 9.
トリエチルアミン、モノエタノールアミン、ジェタノー
ルアミン、イソプロピルアミン、ジメチルアミノエタノ
ール、モルホリン、アンモニア、水酸化ナトリウム等が
挙げられる。これらは単独もしくは2種類以上を混合し
て用いることができる。Examples include triethylamine, monoethanolamine, jetanolamine, isopropylamine, dimethylaminoethanol, morpholine, ammonia, and sodium hydroxide. These can be used alone or in combination of two or more.
これら塩基の使用量は感光性ポリアミド酸のカルボキシ
ル基1当量に対して0.4〜1.0当量が好ましい。0
.4当量未満では電着塗装浴の水分散性や安全性が低下
し、1.0当量を越えると電着塗装後の塗膜厚が薄くな
り、貯蔵安定性が低下する傾向がある。The amount of these bases used is preferably 0.4 to 1.0 equivalents per equivalent of carboxyl group of the photosensitive polyamic acid. 0
.. If the amount is less than 4 equivalents, the water dispersibility and safety of the electrodeposition coating bath will decrease, and if it exceeds 1.0 equivalents, the coating thickness after electrodeposition will become thinner, and storage stability will tend to decrease.
次に水を加えて感光性樹脂組成物を水に溶解もしくは分
散させて電着塗装浴を作製する。電着塗装浴の固形分は
5〜20重量%、またpHは5.0〜9.0の範囲が好
ましい。この範囲外では膜形成が阻害されるおそれがあ
る。pHを上記の好ましい範囲に合わせるために後から
前記の塩基を加えて調整してもよい。Next, water is added to dissolve or disperse the photosensitive resin composition in water to prepare an electrodeposition coating bath. The solid content of the electrodeposition coating bath is preferably 5 to 20% by weight, and the pH is preferably in the range of 5.0 to 9.0. Outside this range, film formation may be inhibited. In order to adjust the pH to the above-mentioned preferred range, the above-mentioned base may be added later to adjust the pH.
また、感光性樹脂組成物の水分散性や分散安定性を高め
るために非イオン性界面活性剤、陽イオン界面活性剤、
陰イオン界面活性剤等を適宜加えることもできる。In addition, nonionic surfactants, cationic surfactants,
Anionic surfactants and the like can also be added as appropriate.
さらに、電着塗装時の塗布量を多くするために。Furthermore, in order to increase the amount of coating during electrodeposition coating.
トルエン、キシレン、2−エチルヘキシルアルコール等
の疎水性溶媒も適宜加えることができる。Hydrophobic solvents such as toluene, xylene, and 2-ethylhexyl alcohol can also be added as appropriate.
このようKして得られた電着塗装浴を用いて導電性基体
に電着塗装するには、導電性の基体を電着塗装浴中に浸
漬し、これを陽極として通常50〜400Vの直流電圧
を10秒〜5分間印加して行なわれる。得られた塗膜の
膜厚は5〜80μmであることが好ましい。このときの
電着塗装浴の温度は15〜30℃に管理することが望ま
しい。In order to perform electrodeposition coating on a conductive substrate using the electrodeposition coating bath obtained in this way, the conductive substrate is immersed in the electrodeposition coating bath, and this is used as an anode to apply a direct current of usually 50 to 400 V. This is done by applying a voltage for 10 seconds to 5 minutes. The thickness of the resulting coating film is preferably 5 to 80 μm. At this time, the temperature of the electrodeposition coating bath is desirably controlled at 15 to 30°C.
本発明に用いる導電性基体としては2例えば。Examples of the conductive substrate used in the present invention include two examples.
鋼、アルミニウム、鉄、亜鉛、その他各種合金などの金
属のみからなるものや、樹脂やガラスなどの表面に金属
箔をはシ合わせたシ、蒸着、めっき及びその他の導電処
理を施すなどして表面を導電性にしたものなどが好まし
く、また基体の形状は板状、筒状、その他種々の立体構
造をもったものなどとされ特に制限はない。Items made only of metal such as steel, aluminum, iron, zinc, and various other alloys, or those made of resin or glass with metal foil attached to the surface, or those that have been subjected to vapor deposition, plating, or other conductive treatment. It is preferable to use conductive materials, and the shape of the substrate is not particularly limited, and may be plate-like, cylindrical, or have various three-dimensional structures.
電着塗装後、電着塗装浴から被塗物を引き上げ水洗、水
切シした後、熱風等で乾燥される。この際、乾燥温度が
高いと塗膜(感光層)が熱硬化し。After electrodeposition coating, the object to be coated is taken out of the electrodeposition coating bath, washed with water, drained, and then dried with hot air or the like. At this time, if the drying temperature is high, the coating film (photosensitive layer) will be thermally cured.
露光後の現像工程で一部が現像残シとなるため。This is because part of the image remains as a development residue during the development process after exposure.
通常110℃以下で乾燥することが好ましい。It is usually preferable to dry at 110°C or lower.
このようにして得られた塗膜の上に、会務0榛巷半次の
露光時の酸素による硬化阻害を防止するために、ビニル
系、アクリル系、ポリエステル系等の一般的な樹脂の皮
膜を1〜10μm程度の膜厚で形成してもよい。On top of the coating film obtained in this way, a film of a general resin such as vinyl, acrylic, or polyester is applied to prevent curing inhibition due to oxygen during exposure. It may be formed with a film thickness of about 1 to 10 μm.
ついで該塗膜に活性光線を照射し、露光部を光硬化させ
、現像により光硬化物のパターンを得ることができる。Next, the coating film is irradiated with actinic rays to photocure the exposed areas, and a pattern of the photocured product can be obtained by development.
活性光線の光源としては、波長300〜450 nmの
光線を発するもの9例えば。Examples of active light sources include those that emit light with a wavelength of 300 to 450 nm.
水銀蒸気アーク、カーボンアーク、キセノンアーク等が
好ましく用いられる。Mercury vapor arc, carbon arc, xenon arc, etc. are preferably used.
現像は、現像液で未露光部分を溶解除去してパターンを
得るための工程である。ここで用いる現像液としては9
例えば、N−メチル−2−ピロリドン、N−アセチル−
2−ピロリドン、 N、N−ジメチルホルムアミド、
N、N−ジメチルアセトアミド、ジメチルスルホキシド
、ヘキサメチルホスホルトリアミド、ジメチルイミダゾ
リジノン、N−ベンジル−2−ピロリドン、N−アセチ
ル−ε−カプロラクタム、 N、N−ジメチルプロピレ
ンウレア、 N、N−ジメチルエチレンウレア等の極性
溶媒が単独で、またはポリアミド酸の非溶媒9例えばメ
タノール、エタノール、イソプロピルアルコール、ベン
ゼン、アセトン、メチルエチルケトン。Development is a process for obtaining a pattern by dissolving and removing unexposed areas with a developer. The developer used here is 9
For example, N-methyl-2-pyrrolidone, N-acetyl-
2-pyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, N-benzyl-2-pyrrolidone, N-acetyl-ε-caprolactam, N,N-dimethylpropyleneurea, N,N-dimethyl A polar solvent such as ethylene urea alone or a non-solvent of the polyamic acid 9 such as methanol, ethanol, isopropyl alcohol, benzene, acetone, methyl ethyl ketone.
シクロヘキサノン、シクロペンタノン、トルエン。Cyclohexanone, cyclopentanone, toluene.
キシレン、メチルセロソルブ、水、塩基性化合物。Xylene, methyl cellosolve, water, basic compounds.
塩基性水溶液等との混合液を用いることができる。A mixed solution with a basic aqueous solution or the like can be used.
また、塩基性水溶液単独もしくは塩基性水溶液に上記の
ポリアミド酸の非溶媒であるメタノール。In addition, methanol, which is a non-solvent for the above-mentioned polyamic acid, may be used alone or in a basic aqueous solution.
エタノール、アセトン、トルエン、メチルセロソルブ等
を混合した液も用いることができる。A mixture of ethanol, acetone, toluene, methyl cellosolve, etc. can also be used.
塩基性化合物として1例えば、モノエタノールアミン、
ジェタノールアミン、トリエタノールアミン、テトラメ
チルアンモニウムヒドロキシド。As a basic compound, for example, monoethanolamine,
Jetanolamine, triethanolamine, tetramethylammonium hydroxide.
炭酸ナトリウム、炭酸カリウム、リン酸ナト1ノウム等
が挙げられる。Examples include sodium carbonate, potassium carbonate, and sodium phosphate.
塩基性水溶液を調整する場合、塩基性化合物の使用量は
。水100重量部に対して通常0.0001〜30重量
部用いることが好ましく、0.05〜5重量部用いるこ
とがより好ましい。When preparing a basic aqueous solution, what is the amount of basic compound used? It is generally preferable to use 0.0001 to 30 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of water.
次いで、現像により形成されたパターンを、リンス液に
より洗浄し、現像溶液を除去することが好ましい。Next, it is preferable to wash the pattern formed by the development with a rinsing liquid to remove the developing solution.
リンス液としては、現傷液との混和性のよいポリアミド
酸の非溶媒が用いられ2例えば、メタノール、エタノー
ル、イソプロピルアルコール、ベンゼン、トルエン、キ
シレン、メチルセロソルブ。As the rinsing liquid, a polyamic acid non-solvent having good miscibility with the wound liquid is used, such as methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, and methyl cellosolve.
水等が挙げられる。Examples include water.
上記処理により得られるパターンは、ポリイミドの前駆
体であり、150〜450℃の加熱処理によジイミド結
合を有するポリイミドのパターンとなる。The pattern obtained by the above treatment is a polyimide precursor, and becomes a polyimide pattern having diimide bonds by heat treatment at 150 to 450°C.
(実施例) 以下9本発明を実施例によって説明する。(Example) The present invention will be explained below with reference to nine examples.
実施例1
温度計及び攪拌装置を付した1000−のフラスコに4
3:44’−ベンゾフェノンテトラカルボン酸二無水物
64.4gK、N−メチル−2−ピロリドン400g及
び2−ヒドロキシエチルメタクリレート529を加えて
室温にて12時間攪拌した。この溶液に氷冷下、塩化チ
オニル709を1時間かけて滴下し、その後室温で2時
間攪拌を行なった。この溶液K 4.4’−ジアミノジ
フェニルエーテル40.09を加えて8時間攪拌した。Example 1 In a 1000-cm flask equipped with a thermometer and a stirring device, 4
3: 64.4 g of 44'-benzophenone tetracarboxylic dianhydride, 400 g of N-methyl-2-pyrrolidone, and 529 g of 2-hydroxyethyl methacrylate were added, and the mixture was stirred at room temperature for 12 hours. Thionyl chloride 709 was added dropwise to this solution over 1 hour under ice cooling, and then stirred at room temperature for 2 hours. This solution K 40.09% of 4'-diaminodiphenyl ether was added and stirred for 8 hours.
さらに、エタノール80mJ!を加えて3時間攪拌し、
その後8Eの水中にゆるやかに注入したところ2重合体
が固形物として析出した。Furthermore, ethanol 80mJ! Add and stir for 3 hours,
Thereafter, when the mixture was slowly poured into 8E water, the dipolymer precipitated as a solid.
この重合体1009に対して、スロービス(p−ジエチ
ルアミノベンジリデン)−4−メチル−4−アザシクロ
へキサン1g、N−(p−シアノフェニル)グリシン5
9.ネオペンチルグリコールジアクリレート259及び
N−メチル−2−ピロリドン2009を加え、攪拌混合
して均一な感光性樹脂組成物の溶液を得た。さらに中和
剤としてトリエチルアミン289を溶解させ之後、固形
分含有率が10重量%になるように水を加えて電着塗装
浴を作製した(pH6,3)。For this polymer 1009, 1 g of slow bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexane, 5 g of N-(p-cyanophenyl)glycine,
9. Neopentyl glycol diacrylate 259 and N-methyl-2-pyrrolidone 2009 were added and mixed with stirring to obtain a uniform photosensitive resin composition solution. Furthermore, after dissolving triethylamine 289 as a neutralizing agent, water was added so that the solid content was 10% by weight to prepare an electrodeposition coating bath (pH 6.3).
この電着塗装浴中にアルミニウム板(形状200gX
75mmX iIIIm)を陽極として、ステンレス板
(SU8304)(形状200mmX 75nmX 1
mm)を陰極として浸漬し、25℃の温度で150Vの
直流電圧を2分間印加し、上記アルミニウム板の表面に
電着塗装膜(感光膜)を形成した。この後。In this electrodeposition coating bath, an aluminum plate (shape 200g
A stainless steel plate (SU8304) (shape 200 mm x 75 nm x 1
mm) was used as a cathode, and a DC voltage of 150 V was applied for 2 minutes at a temperature of 25° C. to form an electrodeposition coating film (photoresist film) on the surface of the aluminum plate. After this.
水洗、水切り後80℃で15分乾燥した(乾燥後の膜厚
20μm)。After washing with water and draining water, it was dried at 80° C. for 15 minutes (film thickness after drying: 20 μm).
このものにネガマスクを介して3kW超高圧水銀灯で6
00 mJ/cm”の光量を画像状に露光した後。A 3kW ultra-high pressure mercury lamp was applied to this item through a negative mask.
After imagewise exposure to a light amount of 00 mJ/cm''.
N−メチル−2−ピロリドンとp−キシレンの1対1(
重量比)混合液を用いて現像した結果、ステップタブレ
ット(光学密度0.0・5を1段目とし。1:1 of N-methyl-2-pyrrolidone and p-xylene (
As a result of development using the mixed solution (weight ratio), a step tablet (optical density of 0.0.5 was set as the first stage) was developed.
1段ごとに光学密度が0.15ずつ増加するネガマスク
を1吏用)6段の光感度と100μmの解像度を得た。Using a negative mask in which the optical density increases by 0.15 for each step, a 6-step photosensitivity and a resolution of 100 μm were obtained.
このあと、100℃、200℃及び350℃でそれぞれ
1時間の加熱を順に行なった結果。The results were then heated at 100°C, 200°C, and 350°C for 1 hour each.
レジスト膜厚11μmのポリイミドパターンを得ること
ができ九。A polyimide pattern with a resist film thickness of 11 μm could be obtained.
このポリイミドパターンを表面に形成したアルミニウム
板をN−メチル−2−ピロリドン中に室温下で1時間浸
漬したが、パターンの溶解及びはく離等は聴められず、
耐溶剤性が極めて高いことが分かった。The aluminum plate with this polyimide pattern formed on its surface was immersed in N-methyl-2-pyrrolidone for 1 hour at room temperature, but no dissolution or peeling of the pattern was observed.
It was found that the solvent resistance was extremely high.
またポリイミドパターンを機械的に削り、その粉末10
■を用いて示差熱天秤で空気中昇温10’C/minの
条件で重量減少開始温度を測定した結果、410℃の値
を得、耐熱性も高いことが分かつ九。In addition, the polyimide pattern was mechanically shaved, and the powder 10
As a result of measuring the weight loss onset temperature using a differential thermal balance in the air at a heating rate of 10'C/min, a value of 410°C was obtained, indicating that the heat resistance is also high.
実施例2
温度計及び攪拌装置を付した3 000rn1のフラx
コに、4’l、−ビス(3,4−ジカルボキシフェニル
)へキサフルオロプロパンニ無・水物444gをN−メ
チル−2−ピロリドン15009に溶解し。Example 2 3 000rn1 flax equipped with thermometer and stirring device
Separately, 444 g of 4'l,-bis(3,4-dicarboxyphenyl)hexafluoropropanide anhydride was dissolved in 15009 N-methyl-2-pyrrolidone.
4.4′−ジアミノジフェニルエーテル2009を加え
て室温で4時間攪拌した。4.4'-Diaminodiphenyl ether 2009 was added and stirred at room temperature for 4 hours.
つぎに、イソシアナートエチルメタクリレート779を
加えて室温で10時間攪拌した。この溶液3409に対
して、ス4−ジエチルチオキサントン29.p−ジメチ
ルアミノ安息香酸エチル39及びネオペンチルグリコー
ルジアクリレート259を加え、攪拌混合して均一な感
光性樹脂組成物を得た。さらに中和剤としてトリエチル
アミン20gを溶解させた後、固形分含有率が10重量
%になるように水を加えて電着塗装浴を作製した(PH
7,0)。Next, isocyanate ethyl methacrylate 779 was added and stirred at room temperature for 10 hours. For 3409 of this solution, 29. 39 ethyl p-dimethylaminobenzoate and 259 neopentyl glycol diacrylate were added and mixed with stirring to obtain a uniform photosensitive resin composition. Furthermore, after dissolving 20 g of triethylamine as a neutralizing agent, water was added so that the solid content was 10% by weight to prepare an electrodeposition coating bath (PH
7,0).
この電着塗装浴中に実施例1と同様なアルミニウム板と
ステンレス板を浸漬し、25℃の温度で100Vの直流
電圧を3分間印加し、上記アルミニウム板の表面に電着
塗装膜を形成し九。この後。An aluminum plate and a stainless steel plate similar to those in Example 1 were immersed in this electrodeposition coating bath, and a DC voltage of 100V was applied for 3 minutes at a temperature of 25°C to form an electrodeposition coating film on the surface of the aluminum plate. Nine. After this.
水洗、水切シ後80℃で15分乾燥した(乾燥後の膜厚
17μm)。After washing with water and draining, it was dried at 80° C. for 15 minutes (film thickness after drying: 17 μm).
とのものにネガマスクを介して3に!超高圧水銀灯で6
00 mJ/cm”の光量を画像状に露光した後。3 through the negative mask! 6 with ultra-high pressure mercury lamp
After imagewise exposure to a light amount of 00 mJ/cm''.
実施例1と同じ現像液を用いて現像した結果、6.5段
の光感度と90μmの解像度を得意。このあと100℃
、200℃及び350℃でそれぞれ1時間の加熱を順に
行なった結果、レジスト膜厚9μmのポリイミドパター
ンを得ることができた。As a result of developing using the same developer as in Example 1, it achieved a photosensitivity of 6.5 steps and a resolution of 90 μm. 100℃ after this
, 200° C. and 350° C. for 1 hour each, and as a result, a polyimide pattern with a resist film thickness of 9 μm could be obtained.
このポリイミドパターンを表面に形成したアルミニウム
板をN−メチル−2−ピロリドン中に室温下で1時間浸
漬し九が、実施例1の場合と同様。The aluminum plate with the polyimide pattern formed on its surface was immersed in N-methyl-2-pyrrolidone for 1 hour at room temperature.
パターンの溶解及びはく離等は認められず、耐溶剤性が
極めて高いことが分かった。No dissolution or peeling of the pattern was observed, indicating extremely high solvent resistance.
ま九、実施例1と同様にポリイミドパターンの重量減少
開始温度を測定した結果、400℃の値を得、耐熱性も
高いことが分かった。Finally, as in Example 1, the weight loss start temperature of the polyimide pattern was measured, and a value of 400° C. was obtained, indicating that the heat resistance was also high.
実施例3
温度計及び攪拌装置を付した3000mgのフラスコに
5−(g3−ジオキソテトラヒドロ7リル)−3−メチ
ル−3−シクロヘキセン−1,2−ジカルボン酸無水物
264gをN−メチル−2−ピロリドン11009に溶
解し、44I−ジアミノジフェニルエーテル200gを
加えて室温で4時間攪拌した。Example 3 In a 3000 mg flask equipped with a thermometer and a stirrer, 264 g of 5-(g3-dioxotetrahydro7lyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride was added to N-methyl-2 -Dissolved in pyrrolidone 11009, added 200 g of 44I-diaminodiphenyl ether, and stirred at room temperature for 4 hours.
つぎに、イソシアナートエチルメタクリレート779を
加えて室温で10時間攪拌した。この溶gasogに対
してλ4−ジエチルチオキサントン29.P−ジメチル
アミノ安息香酸エチル3g及びネオペンチルグリコール
ジアクリレート259を加え、攪拌混合して均一な感光
性樹脂組成物を得た。さらに中和剤としてトリエチルア
ミン229を溶解させた後、固形分含有率が10重量%
になるように水を加えて電着塗装浴を作製した(PH6
,1)。Next, isocyanate ethyl methacrylate 779 was added and stirred at room temperature for 10 hours. For this dissolved gasog, λ4-diethylthioxanthone 29. 3 g of ethyl P-dimethylaminobenzoate and 259 g of neopentyl glycol diacrylate were added and mixed with stirring to obtain a uniform photosensitive resin composition. Furthermore, after dissolving triethylamine 229 as a neutralizing agent, the solid content was 10% by weight.
An electrodeposition coating bath was prepared by adding water so that the pH was 6.
,1).
この電着塗装浴中に実施例1と同様なアルミニウム板と
ステンレス板を浸漬し、25℃の温度で120vの直流
電圧を3分間印加し、上記アルミニウム板の表面に電着
塗装膜を形成した。この後。An aluminum plate and a stainless steel plate similar to those in Example 1 were immersed in this electrodeposition coating bath, and a DC voltage of 120V was applied for 3 minutes at a temperature of 25°C to form an electrodeposition coating film on the surface of the aluminum plate. . After this.
水洗、水切り後80℃で15分乾燥した(乾燥後の膜厚
21μm)。After washing with water and draining, it was dried at 80° C. for 15 minutes (film thickness after drying: 21 μm).
とのものにネガマスクを介して3kW超高圧水銀灯で6
00mJ/crrr’の光量を画像状に露光した後。6 with a 3kW ultra-high pressure mercury lamp through a negative mask.
After imagewise exposure to a light amount of 00 mJ/crrr'.
2sの炭酸ソーダ水溶液を用いて現像した結果。Result of development using 2s of sodium carbonate aqueous solution.
5段の光感度と100μmの解像度を得た。このあと、
100℃、200’C及び300℃でそれぞれ1時間の
加熱を順に行なった結果、レジスト膜厚11μmのポリ
イミドパターンを得ることができた。A 5-step photosensitivity and a resolution of 100 μm were obtained. after this,
As a result of successively heating at 100° C., 200° C. and 300° C. for 1 hour each, a polyimide pattern with a resist film thickness of 11 μm could be obtained.
このポリイミドパターンを表面に形成したアルミニウム
板をN−メチル−2−ピロリドン中に室温下で1時間浸
漬したが、実施例1の場合と同様。The aluminum plate with this polyimide pattern formed on its surface was immersed in N-methyl-2-pyrrolidone at room temperature for 1 hour, but in the same manner as in Example 1.
パターンの溶解及びはく離等は認められず耐溶剤性が極
めて高いことが分かった。No dissolution or peeling of the pattern was observed, indicating extremely high solvent resistance.
また、実施例1と同様にポリイミドパターンの重量開始
温度を測定した結果、330℃の値を得。Further, as in Example 1, the weight onset temperature of the polyimide pattern was measured and a value of 330°C was obtained.
耐熱性も高いことが分かった。It was also found to have high heat resistance.
(発明の効果) 本発明によって、基材の凹凸の追従性が良好で。(Effect of the invention) According to the present invention, the ability to follow the irregularities of the base material is good.
複雑な形状の基材の表面にも短時間で感光膜を形成でき
、また、その後、露光、現偉及び加熱処理により任意の
パターンを高感度で精度よく形成でき、しかもそのパタ
ーンがポリイミド薄膜のため従来になく高ノ耐溶剤性、
耐熱性等の優れた物性を有するパターンを得ることがで
きる。A photoresist film can be formed on the surface of a base material with a complex shape in a short time, and any pattern can then be formed with high sensitivity and precision through exposure, development, and heat treatment. Due to its unprecedented high solvent resistance,
A pattern having excellent physical properties such as heat resistance can be obtained.
Claims (1)
感光性ポリアミド酸及び非水溶性光開始剤を含有してな
る感光性樹脂組成物に塩基及び水を加えて水溶性もしく
は水分散性の電着塗装浴を作製し、該浴に導電性基体を
陽極として浸漬し、通電により電着塗装して導電性基体
上に電着塗装膜を形成し、その後、活性光線を前記電着
塗装膜に画像状に照射し、露光部を光硬化させ、未露光
部を現像により除去した後、加熱処理することにより、
導電性基体上に目的とするパターンのポリイミド薄膜を
形成することを特徴とするポリイミド薄膜の製造法 ▲数式、化学式、表等があります▼( I ) (但し、式中、R_1は4価の有機基であり、R_2は
2価の有機基であり、Yは1価のエチレン性不飽和基を
有する有機基であり、mは0または1、nは1または2
で、かつm+n=2となるように選ばれる)。[Claims] 1. A base and water are added to a photosensitive resin composition containing a photosensitive polyamic acid having a repeating unit represented by the general formula (I) and a water-insoluble photoinitiator to make it water-soluble. Alternatively, a water-dispersible electrodeposition coating bath is prepared, a conductive substrate is immersed in the bath as an anode, electrodeposition is applied by applying electricity to form an electrodeposition coating film on the conductive substrate, and then active light is applied. By irradiating the electrodeposition coating film in an imagewise manner, photocuring the exposed areas, removing the unexposed areas by development, and then heat-treating.
A polyimide thin film manufacturing method characterized by forming a polyimide thin film with a desired pattern on a conductive substrate ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (However, in the formula, R_1 is a tetravalent organic group, R_2 is a divalent organic group, Y is an organic group having a monovalent ethylenically unsaturated group, m is 0 or 1, and n is 1 or 2.
and m+n=2).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23843189A JPH03100076A (en) | 1989-09-14 | 1989-09-14 | Manufacture of thin polyimide film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23843189A JPH03100076A (en) | 1989-09-14 | 1989-09-14 | Manufacture of thin polyimide film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03100076A true JPH03100076A (en) | 1991-04-25 |
Family
ID=17030110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23843189A Pending JPH03100076A (en) | 1989-09-14 | 1989-09-14 | Manufacture of thin polyimide film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03100076A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001010964A1 (en) * | 1999-08-06 | 2001-02-15 | Pi R & D Co., Ltd. | Composition for polyimide electrodeposition and method of forming patterned polyimide film with the same |
JP2001139881A (en) * | 1999-11-12 | 2001-05-22 | Sankyo Seiki Mfg Co Ltd | Electrodeposition coating material, sliding member, and bearing device |
JP2014031445A (en) * | 2012-08-03 | 2014-02-20 | Ube Ind Ltd | Process for producing polyamide coating film |
-
1989
- 1989-09-14 JP JP23843189A patent/JPH03100076A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001010964A1 (en) * | 1999-08-06 | 2001-02-15 | Pi R & D Co., Ltd. | Composition for polyimide electrodeposition and method of forming patterned polyimide film with the same |
JP4958355B2 (en) * | 1999-08-06 | 2012-06-20 | 株式会社ピーアイ技術研究所 | Composition for electrodeposition of polyimide and method for producing patterned polyimide film using the same |
JP2001139881A (en) * | 1999-11-12 | 2001-05-22 | Sankyo Seiki Mfg Co Ltd | Electrodeposition coating material, sliding member, and bearing device |
JP2014031445A (en) * | 2012-08-03 | 2014-02-20 | Ube Ind Ltd | Process for producing polyamide coating film |
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