JPS63202740A - Photosensitive resin composition and laminated body using same - Google Patents
Photosensitive resin composition and laminated body using sameInfo
- Publication number
- JPS63202740A JPS63202740A JP3655787A JP3655787A JPS63202740A JP S63202740 A JPS63202740 A JP S63202740A JP 3655787 A JP3655787 A JP 3655787A JP 3655787 A JP3655787 A JP 3655787A JP S63202740 A JPS63202740 A JP S63202740A
- Authority
- JP
- Japan
- Prior art keywords
- group
- resin composition
- photosensitive resin
- weight
- formula
- 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
- 239000011342 resin composition Substances 0.000 title claims description 46
- 229920005684 linear copolymer Polymers 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 39
- -1 urethane dimethacrylate compound Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 238000010030 laminating Methods 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052802 copper Inorganic materials 0.000 abstract description 13
- 239000010949 copper Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 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 6
- 239000002253 acid Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- RLOIVWPKZYTEIK-UHFFFAOYSA-N 2-[2-[2-[2-[2-[4-[2-[4-[2-[2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C(=O)(C=C)OCCOCCOCCOCCOCCOC1=CC=C(C(C)(C)C2=CC=C(OCCOCCOCCOCCOCCOC(=O)C=C)C=C2)C=C1 RLOIVWPKZYTEIK-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
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CNCAHWAKBQIUMY-UHFFFAOYSA-N tribromo(tribromomethylsulfonyl)methane Chemical compound BrC(Br)(Br)S(=O)(=O)C(Br)(Br)Br CNCAHWAKBQIUMY-UHFFFAOYSA-N 0.000 description 2
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 2
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- FQKSRGCBHCFRTN-UHFFFAOYSA-N (4-nonylphenyl) prop-2-enoate Chemical compound CCCCCCCCCC1=CC=C(OC(=O)C=C)C=C1 FQKSRGCBHCFRTN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- DVFAVJDEPNXAME-UHFFFAOYSA-N 1,4-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2C DVFAVJDEPNXAME-UHFFFAOYSA-N 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- CRDHCRAGZZULOI-UHFFFAOYSA-N 1-[2-(diethylamino)phenyl]-2-hydroxy-2-phenylethanone Chemical compound CCN(CC)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 CRDHCRAGZZULOI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- PZJFUNZDCRKXPZ-UHFFFAOYSA-N 2,5-dihydro-1h-tetrazole Chemical class C1NNN=N1 PZJFUNZDCRKXPZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- YQZHOBBQNFBTJE-UHFFFAOYSA-N 2-chloro-3-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(Cl)=C2 YQZHOBBQNFBTJE-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- OKJSFKIUVDXFMS-UHFFFAOYSA-N 4-[bis[4-(diethylamino)-2-methylphenyl]methyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=C(N(CC)CC)C=C1C OKJSFKIUVDXFMS-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- UUQJMSSFMULZHR-UHFFFAOYSA-N [4,5,5,6,6-pentaethoxy-4-[2-[1,5,5,6,6-pentaethoxy-4-(2-methylprop-2-enoyloxy)cyclohex-2-en-1-yl]propan-2-yl]cyclohex-2-en-1-yl] 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OC1C(C(C(C=C1)(C(C)(C)C1(C(C(C(C=C1)OC(C(=C)C)=O)(OCC)OCC)(OCC)OCC)OCC)OCC)(OCC)OCC)(OCC)OCC UUQJMSSFMULZHR-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- WKRKXDRSJVDMGO-UHFFFAOYSA-N ethyl 2-(diethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(CC)CC WKRKXDRSJVDMGO-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- XHDKYWMKOLURNK-UHFFFAOYSA-N n,n-diethylhexan-1-amine Chemical compound CCCCCCN(CC)CC XHDKYWMKOLURNK-UHFFFAOYSA-N 0.000 description 1
- WSTNFGAKGUERTC-UHFFFAOYSA-N n-ethylhexan-1-amine Chemical compound CCCCCCNCC WSTNFGAKGUERTC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、感光性樹脂組成物および感光性樹脂組成物積
層体に関し、さらに詳しくは銅への密着力、像形成能、
屈曲性および耐酸性に優れ、かつ感光層のしみ出しが少
なく、アルカリ現像可能な、エツチングレジストまたは
めっきレジスト材料として好適な感光性樹脂組成物およ
び感光性樹脂組成物積層体に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photosensitive resin composition and a photosensitive resin composition laminate, and more particularly, to adhesion to copper, image forming ability,
The present invention relates to a photosensitive resin composition and a photosensitive resin composition laminate that have excellent flexibility and acid resistance, have little oozing of the photosensitive layer, are developable with alkali, and are suitable as an etching resist or plating resist material.
（従来の技術）
印刷配線板の製造、金属の精密加工等の分野において、
エツチング、めっき等の化学的・電気的手法に用いられ
るレジスト材料として、感光性樹脂組成物およびこれを
用いて得られる感光性樹脂組成物積層体（以下、感光性
フィルムとも称する）が広（用いられている。(Prior technology) In the fields of printed wiring board manufacturing, metal precision processing, etc.
Photosensitive resin compositions and photosensitive resin composition laminates (hereinafter also referred to as photosensitive films) obtained using the same are widely used as resist materials used in chemical and electrical methods such as etching and plating. It is being
近年印刷配線板の分野ではカメラ、自動車等の電気回路
材としてフレキシブルな配線材料が要求されており、こ
の製造に際してはロール状のフレキシブル銅張り積層板
（以下、フレキ板とも称する）を各工程ごとに連続的に
引き出して作業することが行なわれており、このフレキ
板に用いられる感光性フィルムにもエツチング等の強酸
高温、高湿度下での銅に対する密着力と屈曲性が要求さ
れている。In recent years, in the field of printed wiring boards, flexible wiring materials have been required as electrical circuit materials for cameras, automobiles, etc., and during the production of these materials, roll-shaped flexible copper-clad laminates (hereinafter also referred to as flexible boards) are required for each process. The photosensitive film used for this flexible board is also required to have adhesion and flexibility to copper under strong acid, high temperature, and high humidity conditions such as etching.
従来鋼に対する密着力に関しては種々研究されており、
例えば特開昭５４−１５３６２４号公報、特開昭５４−
１５３６２５号公報等にウレタン結合を有する附加重合
性化合物を含有する感光性フィルムが開示されているが
、これらは耐めっき性等の耐酸性等に注目しているのみ
で屈曲性に関しては何ら考慮されていない、一方、屈曲
性を良好にするために可塑剤等を多く添加するとロール
状に保存した場合に端面から感光層がしみ出すというコ
ールドフローが発生し、感光層の積層が困難になり、耐
電気めっき性が低下し、また光硬化後のレジストの耐現
像液性が低下するという欠点があった。Various studies have been conducted regarding adhesion to conventional steel.
For example, JP-A-54-153624, JP-A-54-
A photosensitive film containing an addition polymerizable compound having a urethane bond is disclosed in Japanese Patent No. 153625, but these only focus on acid resistance such as plating resistance, and no consideration is given to flexibility. On the other hand, if a large amount of plasticizer, etc. is added to improve flexibility, cold flow occurs when the photosensitive layer oozes out from the edge when stored in roll form, making it difficult to stack the photosensitive layers. There were disadvantages in that the electroplating resistance was reduced and the developer resistance of the resist after photocuring was reduced.
附加重合性化合物としてペンタエトキシジアクリレート
等のカルボキシル基含有線状共重合体と相溶性の良好な
物質を用いて得られる感光性樹脂組成物では、一般に耐
電気めっき性が低く、硬化後の可とう性が著しく低い。Photosensitive resin compositions obtained using substances with good compatibility with carboxyl group-containing linear copolymers such as pentaethoxy diacrylate as addition-polymerizable compounds generally have low electroplating resistance and are difficult to coat after curing. Resilience is extremely low.
また可塑剤等には硬化後の可とう性を良好にする物質も
あるが、これらを用いる場合には耐現像液性が低下した
り、レジストの硬度が低下するという欠点があった。In addition, there are plasticizers and the like that improve flexibility after curing, but when these are used, there are drawbacks such as a decrease in developer resistance and a decrease in the hardness of the resist.
（発明が解決しようとする問題点）
本発明の目的は、前記従来技術の欠点を除去し、銅への
密着力、像形成能、屈曲性および耐酸性に優れ、かつ感
光層のしみ出しが少なく、アルカリ現像可能な感光性樹
脂組成物を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the prior art, to provide excellent adhesion to copper, image forming ability, flexibility, and acid resistance, and to prevent seepage of the photosensitive layer. The object of the present invention is to provide a photosensitive resin composition that can be developed with alkali.
（問題点を解決するための手段）
本発明は、（ａ）一般式（Ｉ）で表わされる附加重合性
化合物、
（式中Ｒ１およびＲ２は水素原子またはメチル基を意味
し、これらは而−でも異なっていてもよく、Ｒ３はフェ
ニル基、ナフチル基、ピリジル基またはフリル基を意味
し、これらの基はハロゲン原子、炭素数１〜１０のアル
キル基、炭素数１〜１０のアルコキシ基、フェニル基、
アミノ基または炭素数１〜３のアルキル基の一または二
で置換されたアルキル置換アミノ基の一または二辺上で
置換されていてもよく、ｎは１〜１０の正の整数を意味
する）、（ｂ）２価アルコール、アルキレンジイソシア
ナートおよび２価アルコールのアクリル酸モノエステル
またはメタクリル酸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またはウレタンジメタク
リレート化合物、（Ｃ）一般式（ｎ）で表わされる附加
重合性化合物、以下余白
（式中Ｒ４、Ｒ１，、Ｒ６およびＲ７は水素原子または
メチル基を意味し、これらは同一でも異なっていてもよ
く、ｎおよびｍはｎ＋ｍ＝８〜１２を満足する正の整数
を意味する）、（ｄ）光重合開始剤ならびに（ｅ）カル
ボキシル基含有量１７〜５０モル％、吸水率４〜３０重
量％および重量平均分子量３０．０００〜４００，００
０の線状共重合体を含有してなる感光性樹脂組成物なら
びに感光性樹脂組成物層の少な（とも一方の面にフィル
ム状支持体を積層してなる感光性樹脂組成物積層体にお
いて、該感光性樹脂組成物層が、（ａ）一般式（Ｉ）で
表わされる附加重合性化合物、（式中Ｒ１およびＲ２は
水素原子またはメーチル基を意味し、これらは同一でも
異なっていてもよく、Ｒ３はフェニル基、ナフチル基、
ピリジル基またはフリル基を意味し、これらの基はハロ
ゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１
０のアルコキシ基、フェニル基、アミノ基または炭素数
１〜３のアルキル基の一または二で置換されたアルキル
置換アミノ基の一または二辺上で置換されていてもよく
、ｎは１〜１０の正の整数を意味する）、（ｂ）２価ア
ルコール、アルキレンジイソシアナートおよび２価アル
コールのアクリル酸モノエステルまたはメタクリル酸モ
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
ト化合物またはウレタンジメタクリレート化合物、（Ｃ
）一般式（ｎ）で表わされる附加重合性化合物、以下余
白
（式中Ｒ４、Ｒ５、Ｒ６およびＲ７は水素原子またはメ
チル基を意味し、これらは同一でも異なっていてもよく
、ｎおよびｍはｎ＋ｍ＝３〜１２を満足する正の整数を
意味する）、（ｄ）光重合開始剤ならびに（ｅ）カルボ
キシル基含有量１７〜５０モル％、吸水率４〜３０重量
％および重量平均分子量３０，０００〜４００，０００
の線状共重合体を含有してなる感光性樹脂組成物積層体
に関する。(Means for Solving the Problems) The present invention provides (a) an addition-polymerizable compound represented by the general formula (I), in which R1 and R2 represent a hydrogen atom or a methyl group; R3 means a phenyl group, a naphthyl group, a pyridyl group, or a furyl group, and these groups include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. basis,
An alkyl-substituted amino group substituted with one or two amino groups or alkyl groups having 1 to 3 carbon atoms may be substituted on one or two sides, n means a positive integer of 1 to 10) , (b) urethane diacrylate compound or urethane dimethacrylate compound obtained by reacting dihydric alcohol, alkylene diisocyanate, and acrylic acid monoester or methacrylic acid monoester of dihydric alcohol, (C) General formula (n) An addition polymerizable compound represented by ), (d) a photopolymerization initiator and (e) a carboxyl group content of 17 to 50 mol%, a water absorption rate of 4 to 30% by weight, and a weight average molecular weight of 30.000 to 400,00.
In a photosensitive resin composition containing a linear copolymer of 0 and a photosensitive resin composition laminate having a small number of photosensitive resin composition layers (both with a film support laminated on one side, The photosensitive resin composition layer comprises (a) an addition polymerizable compound represented by the general formula (I), (wherein R1 and R2 mean a hydrogen atom or a methyl group, and these may be the same or different. , R3 is a phenyl group, a naphthyl group,
It means a pyridyl group or a furyl group, and these groups are halogen atoms, alkyl groups having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
It may be substituted on one or two sides of an alkyl-substituted amino group substituted with one or two alkoxy groups, phenyl groups, amino groups, or alkyl groups having 1 to 3 carbon atoms, and n is 1 to 10. ), (b) a urethane diacrylate compound or a urethane dimethacrylate compound obtained by reacting a dihydric alcohol, an alkylene diisocyanate, and an acrylic acid monoester or methacrylic acid monoester of the dihydric alcohol, (C
) An addition-polymerizable compound represented by the general formula (n), below in the blanks (in the formula, R4, R5, R6 and R7 mean a hydrogen atom or a methyl group, which may be the same or different, and n and m are n + m = a positive integer satisfying 3 to 12), (d) a photopolymerization initiator and (e) a carboxyl group content of 17 to 50 mol%, a water absorption rate of 4 to 30% by weight, and a weight average molecular weight of 30, 000~400,000
The present invention relates to a photosensitive resin composition laminate containing a linear copolymer.
本発明の感光性樹脂組成物において、前記一般式（Ｉ）
で表わされる附加重合性化合物（以下、成分ａと称する
）、上記のウレタンジアクリレート化合物またはウレタ
ンジメタクリレート化合物（以下成分すと称する）、一
般式（ｎ）で表わされる附加重合性化合物（以下、成分
Ｃと称する）および上記の線状共重合体（以下、成分ｅ
と称する）の全量１００重量部に対し、成分ａを１〜１
５重量部、成分すを５〜３０重量部、成分Ｃを３〜１５
重量部および成分ｅを４０〜７０重量部含有してなる樹
脂組成が好ましい。In the photosensitive resin composition of the present invention, the general formula (I)
The addition polymerizable compound represented by formula (n) (hereinafter referred to as component a), the above urethane diacrylate compound or urethane dimethacrylate compound (hereinafter referred to as component a), the addition polymerizable compound represented by general formula (n) (hereinafter referred to as component a) (hereinafter referred to as component C) and the above linear copolymer (hereinafter referred to as component e)
1 to 1 part of component a to 100 parts by weight of the total amount of
5 parts by weight, 5 to 30 parts by weight of component C, 3 to 15 parts by weight of component C
A resin composition containing 40 to 70 parts by weight of component e is preferred.
本発明において成分ａとしては、例えばフェノキシジェ
トキシアクリレート（Ｍ−１０１、東亜合成化学（株）
製油品名）、フェノキシポリエトキシアクリレート（Ａ
ＭＰ−６０Ｇ、新中村化学工業（株）製油品名）、フェ
ノキシジェトキシメタクリレート、フェノキシヘキサエ
トキシメタクリレート、ｐ−ノニルフェノキシジェトキ
シアクリレ−） （Ｍ−１１１、東亜合成化学（株）製
油品名）等が挙げられる。In the present invention, component a is, for example, phenoxyjethoxy acrylate (M-101, manufactured by Toagosei Kagaku Co., Ltd.).
(oil product name), phenoxypolyethoxy acrylate (A
MP-60G, Shin Nakamura Chemical Co., Ltd. (oil product name), phenoxyjetoxy methacrylate, phenoxyhexaethoxy methacrylate, p-nonylphenoxyjetoxy acrylate) (M-111, Toagosei Kagaku Co., Ltd. (oil product name)), etc. can be mentioned.
成分ａの配合量は、硬化物の耐現像液性等の点を考慮し
て成分ａ、ｂＳｃ、後述の所望により含有される附加重
合圧化合物およびｅの全量１００重量部に対して好まし
くは１〜１５重量部、より好ましくは３〜１５重量部で
ある。Considering the developer resistance of the cured product, the blending amount of component a is preferably 1 part by weight per 100 parts by weight of the total amount of components a, bSc, the additional polymerization pressure compound and e that are optionally contained as described below. ~15 parts by weight, more preferably 3 to 15 parts by weight.
本発明の感光性樹脂組成物における成分すとしては、例
えばシクロヘキサン−１，４−ジメタツールとトリメチ
ルへキサメチレンジイソシアナートと２−ヒドロキシル
アクリレートとの２：１：４モル比反応物、シクロヘキ
サン−１，６−ジメタツールとトリメチルへキサメチレ
ンジイソシアナートと２−ヒドロキシメチルアクリレー
トとの０．２４ ： １．０ ： ０．７４モル比反応
物、１．２−プロピレンジオールとトリメチルへキサメ
チレンジイソシアナートと２−ヒドロキシメチルメタク
リレートとの０．５ ： １．０ ： １．０モル比反
応物等が用いられる。Components in the photosensitive resin composition of the present invention include, for example, a reaction product of cyclohexane-1,4-dimetatool, trimethylhexamethylene diisocyanate, and 2-hydroxyl acrylate in a molar ratio of 2:1:4, cyclohexane-1 , 0.24: 1.0: 0.74 molar ratio reactants of 6-dimetatool, trimethylhexamethylene diisocyanate and 2-hydroxymethyl acrylate, 1.2-propylene diol and trimethylhexamethylene diisocyanate and 2-hydroxymethyl methacrylate in a molar ratio of 0.5:1.0:1.0.
成分すは既に公知の化合物であり、その製法等に特に制
限はない。The components are already known compounds, and there are no particular restrictions on the method for producing them.
成分すの配合量は得られる硬化物の屈曲性の点から成分
ａ、ｂ、ｃ、後述の所望により含有される附加重合性化
合物およびｅの全量１００重量部に対して好ましくは５
〜３０重量部、より好ましくは５〜２０重量部である。From the viewpoint of the flexibility of the cured product obtained, the amount of component (a) is preferably 5 parts by weight per 100 parts by weight of the total amount of components (a), (b), (c), optional addition polymerizable compounds (described later), and (e).
~30 parts by weight, more preferably 5 to 20 parts by weight.
また本発明の感光性樹脂組成物の成分Ｃとしては、例え
ば２．２−ビス（４−メタクリロキシペンタエトキシフ
ェニル）プロパン、ビスフェノールＡのエチレンオキシ
ド付加物のメタクリレート（ＢＰＥ−１０、新中村化学
工業（株）製油品名）等が用いられる。In addition, as component C of the photosensitive resin composition of the present invention, for example, 2,2-bis(4-methacryloxypentaethoxyphenyl)propane, methacrylate of ethylene oxide adduct of bisphenol A (BPE-10, Shin Nakamura Chemical Co., Ltd.) Co., Ltd. (oil product name) etc. are used.
成分Ｃの配合量は硬化物の耐現像液性の点から成分ａ、
ｂ、ｃ、後述の所望により含有される附加重合性化合物
およびｅの全量１００重量部に対して好ましくは３〜１
５重量部、より好ましくは５〜１５重量部である。The blending amount of component C is determined from the viewpoint of developer resistance of the cured product.
Preferably 3 to 1 parts by weight based on 100 parts by weight of the total amount of b, c, addition polymerizable compound contained as desired below, and e.
It is 5 parts by weight, more preferably 5 to 15 parts by weight.
本発明の感光性樹脂組成物は、前記成分ａ ”−ｃの附
加重合性化合物の他に、さらに少なくとも１個の光重合
し得るエチレン性不飽和結合を有する附加重合性化合物
を所望により含有することもできる。The photosensitive resin composition of the present invention optionally further contains an addition polymerizable compound having at least one photopolymerizable ethylenically unsaturated bond in addition to the addition polymerizable compounds of components a'' to c. You can also do that.
所望により含有される附加重合性化合物としては、例え
ば多価アルコールにα、β−不飽和カルボン酸を付加し
て得られるもの、例えばテトラエチレングリコールジ（
メタ）アクリレート（アクリレートまたはメタクリレー
トを意味する。以下同じ）、ポリエチレングリコールジ
（メタ）アクリレート（エチレン基の数が２〜１４のも
の）、トリメチロールプロパンジ（メタ）アクリレート
、トリメチロールプロパントリ （メタ）アクリレート
、テトラメチロールメタントリ （メタ）アクリレート
、テトラメチロールメタンテトラ（メタ）アクリレート
、ポリプロピレングリコールジ（メタ）アクリレート（
プロピレン基の数が２〜１４のもの）、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、２．２−ビス（
４−メタクリロキシジェトキシフェニル）プロパン、グ
リシジル基含有化合物にα、β−不飽和カルボン酸を付
加して得られるもの、例えばトリメチロールプロパント
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Ａジグリシジルエーテルジアクリレート等、例えば無
水フタル酸等の多価カルボン酸と、例えばβ−ヒドロキ
シエチル（メタ）アクリレート等の水酸基およびエチレ
ン性不飽和基を有する物質とのエステル化物などが挙げ
られる。Examples of the optional addition polymerizable compound include those obtained by adding an α,β-unsaturated carboxylic acid to a polyhydric alcohol, such as tetraethylene glycol di(
meth)acrylate (means acrylate or methacrylate; the same applies hereinafter), polyethylene glycol di(meth)acrylate (those with 2 to 14 ethylene groups), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate ) acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, polypropylene glycol di(meth)acrylate (
2-14 propylene groups), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(
4-methacryloxyjethoxyphenyl)propane, those obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, such as trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc. Examples include esterification products of polyhydric carboxylic acids such as phthalic anhydride and substances having hydroxyl groups and ethylenically unsaturated groups such as β-hydroxyethyl (meth)acrylate.
これらの所望により含有される附加重合性化合物のみで
は、耐電気めっき性や耐現像液性は得られるが、感光層
の一定の硬さが得られる量にした場合の銅への密着力が
劣り、硬化後の可とう性が低く、作業性の低下を招く。Electroplating resistance and developer resistance can be obtained with only these addition polymerizable compounds contained as desired, but the adhesion to copper is poor when the amount is set to provide a certain hardness of the photosensitive layer. , the flexibility after curing is low, leading to a decrease in workability.
本発明においては、これらと成分ａ、ｂ、ｃの附加重合
性化合物を併用することにより、単独で使用した場合よ
りも一定の可とう性や感光層の硬さを保持しながら銅へ
の密着力が格段に増加する。In the present invention, by using these together with addition-polymerizable compounds of components a, b, and c, it is possible to maintain a certain level of flexibility and hardness of the photosensitive layer than when used alone, while adhering to copper. Power increases significantly.
本発明の感光性樹脂組成物において、成分ａ〜Ｃの附加
重合性化合物および所望により用いられる附加重合性化
合物の全量は感度および接着力の低下防止、コールドフ
ローの防止等の点から附加重合性化合物と線状共重合体
との全量１００重量部に対して３０〜６０重量部が好ま
しく、３０〜４５重量部が特に好ましい。この量は感光
性フィルムをロール状に製造し、保存した場合の端面か
らの感光層のしみ出しくコールドフローの発生）と密接
に関係し、通常低粘度の附加重合性化合物を使用する場
合には附加重合性化合物の量も低減させる必要がある。In the photosensitive resin composition of the present invention, the total amount of the addition-polymerizable compounds of components a to C and the addition-polymerizable compound used as desired is determined from the viewpoint of preventing decreases in sensitivity and adhesive strength, prevention of cold flow, etc. It is preferably 30 to 60 parts by weight, particularly preferably 30 to 45 parts by weight, based on 100 parts by weight of the total amount of the compound and linear copolymer. This amount is closely related to the occurrence of cold flow when the photosensitive film is manufactured in roll form and stored, causing the photosensitive layer to seep out from the end surface. It is also necessary to reduce the amount of addition polymerizable compounds.
本発明に用いられる成分ｄとしては、２００℃以下の温
度では熱的に活性化しない物質で、例えば紫外線等の活
性光線により活性化する物質が好ましい。これらの物質
としては、例えば２−エチルアントラキノン、２−ｔ−
ブチルアントラキノン、オクタメチルアントラキノン、
１，２−ベンズアントラキノン、２．３−ベンズアント
ラキノン、２−フェニルアントラキノン、２，３−ジフ
ェニルアントラキノン、１−クロロアントラキノン、２
〜クロロアントラキノン、２−メチルアントラキノン、
１．４−ナツタキノン、９．１０−フエナントラキノン
、１，４−ジメチルアントラキノン、２．３−ジメチル
アントラキノン、３−クロロ−２−メチルアントラキノ
ン等の置換まだは非置換の多核キノン類、例えばベンゾ
フェノン、ジメチルアミノベンゾフェノン、ミヒラーケ
トン（４，４’−ビス（ジメチルアミノ）ベンゾフェノ
ン）、４．４’−ビス（ジエチルアミノ）ベンゾフェノ
ン、４−メトキシ−４１−ジメチルアミノベンゾフェノ
ン等の芳香族ケトン、ベンゾイン、例エバベンゾインメ
チルエーテル、ベンゾインエチルエーテル、ベンゾイン
フェニルエーテル等のベンゾインエーテル、メチルベン
ゾイン、エチルベンゾインなどが挙げられる。さらに２
，４．５−トリアリールイミダゾールニ量体と２−メル
カプトベンゾキサゾール、ロイコクリスタルバイオレッ
ト、トリス（４−ジエチルアミノ−２−メチルフェニル
）メタン等との組合わせ、２．４−ジエチルチオキサン
トンとジエチルアミノ安息香酸イソアミルまたはジエチ
ルアミノ安息香酸エチル等との組合わせなども用いられ
る。Component d used in the present invention is preferably a substance that is not thermally activated at a temperature of 200° C. or lower, but is activated by actinic light such as ultraviolet rays. These substances include, for example, 2-ethylanthraquinone, 2-t-
Butylanthraquinone, octamethylanthraquinone,
1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2
~chloroanthraquinone, 2-methylanthraquinone,
Substituted or unsubstituted polynuclear quinones such as 1.4-natsutaquinone, 9.10-phenanthraquinone, 1,4-dimethylanthraquinone, 2.3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, e.g. Aromatic ketones such as benzophenone, dimethylaminobenzophenone, Michler's ketone (4,4'-bis(dimethylamino)benzophenone), 4,4'-bis(diethylamino)benzophenone, 4-methoxy-41-dimethylaminobenzophenone, benzoin, e.g. Examples include benzoin ethers such as evabenzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, methylbenzoin, and ethylbenzoin. 2 more
, combination of 4.5-triarylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet, tris(4-diethylamino-2-methylphenyl)methane, etc., 2.4-diethylthioxanthone and diethylaminobenzoin A combination with isoamyl acid or ethyl diethylaminobenzoate is also used.
成分ｄの配合量は、光硬化性、耐性、解像度、安定性等
の点から、成分ａ、ｂ、ｃ、前述の所望により含有され
る附加重合性化合物およびｅの全量１００重量部に対し
て好ましくは０．５〜２０重量部、より好ましくは１〜
１０重量部である。From the viewpoint of photocurability, resistance, resolution, stability, etc., the amount of component d is determined based on 100 parts by weight of the total amount of components a, b, c, the addition polymerizable compound contained as desired, and e. Preferably 0.5 to 20 parts by weight, more preferably 1 to 20 parts by weight
It is 10 parts by weight.
本発明の感光性樹脂組成物は、成分ｅを必須成分として
含有する。The photosensitive resin composition of the present invention contains component e as an essential component.
本発明におけるフォトレジスト像の電気めっきへの優れ
た耐性およびめっき前処理液等に対する耐性、さらには
基板との密着性、現像性等の一般特性は、前記附加重合
性化合物とこの線状共重合体との双方により達成される
。The general properties of the photoresist image in the present invention, such as excellent resistance to electroplating and resistance to plating pretreatment liquids, as well as adhesion with the substrate and developability, are due to the addition polymerizable compound and this linear copolymerizable compound. This is achieved by both combining and combining.
成分ｅは２種または３種以上の単量体を共重合させるこ
とにより得られ、この際用いられる単量体は２種類に大
別される。第１の単量体は該線状共重合体に現像性を付
与するために用いられ、不飽和基を１個有するカルボン
酸または酸無水物、例えばアクリル酸、メタクリル酸、
フマル酸、ケイ皮酸、プロピオール酸、イタコン酸、マ
レイン酸、マレインＭ 無水物、マレイン酸半エステル
等が用いられ、アクリル酸またはメタクリル酸が好まし
い。Component e is obtained by copolymerizing two or more types of monomers, and the monomers used in this case are roughly classified into two types. The first monomer is used to impart developability to the linear copolymer, and is a carboxylic acid or acid anhydride having one unsaturated group, such as acrylic acid, methacrylic acid,
Fumaric acid, cinnamic acid, propiolic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid half ester, etc. are used, and acrylic acid or methacrylic acid is preferred.
第２の単量体はフォトレジスト像が耐めっき性、耐エツ
チング性を保持するため、また耐現像液性、可とう性お
よび可塑性を保持するために用いられ、不飽和基を１個
有するものが用いられ、その単量体への２０℃における
水の熔解性が２重量％以下であるようなものが好ましい
が、２重量％を越えるような親水性の単量体を少量用い
ても生成された線状共重合体の吸水率が前記の範囲であ
れば差しつかえない。第２の単量体の分子量は現像性の
点から３００以下が好ましい。第２の単量体としては、
例えばメチルアクリレート、メチルメタクリレート、エ
チルアクリレート、エチルメタクリレート、ブチルアク
リレート、ブチルメタクリレート、２−エチルへキシル
アクリレート、２−エチルへキシルメタクリレート等の
アルキルアクリレートまたはアルキルメタクリレート、
例えばビニル−ｎ−ブチルエーテル等のビニルアルコー
ルのエステル類、α−位もしくは芳香族環において置換
されている重合可能なスチレン誘導体またはスチレンな
どが用いられ、アルキルアクリレートまたはアルキルメ
タクリレートが好ましい。The second monomer is used to maintain plating resistance, etching resistance, developer resistance, flexibility, and plasticity of the photoresist image, and has one unsaturated group. It is preferable that the solubility of the monomer in water at 20°C is 2% by weight or less; There is no problem as long as the water absorption rate of the linear copolymer obtained is within the above range. The molecular weight of the second monomer is preferably 300 or less from the viewpoint of developability. As the second monomer,
Alkyl acrylates or alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,
For example, esters of vinyl alcohol such as vinyl-n-butyl ether, polymerizable styrene derivatives or styrene substituted at the α-position or the aromatic ring, etc. are used, and alkyl acrylates or alkyl methacrylates are preferred.
成分ｅは既に公知の化合物であり、その製法等には特に
制限はない。Component e is a known compound, and there are no particular restrictions on its manufacturing method.
本発明に用いられる成分ｅは、前記第１の単量体と第２
の単量体とを共重合することにより得られる。第１およ
び第２の単量体の種類および使用量は該線状共重合体の
カルボキシル基含有量が１７〜５０モル％、吸水率が４
〜３０重量％となるように選択使用される。この際カル
ボキシル基含有量とは線状共重合体に使用される全単量
体のモル数に対する前記第１の単量体のモル数の百分率
（モル％）をいう。また吸水率はＪＩＳ Ｋ ６９
１１に示された規格、すなわち直径５０±１１１゜厚さ
３±０．２鶴の試料を２３℃の水に２４時間浸漬したと
きの重量増加率で示される。Component e used in the present invention comprises the first monomer and the second monomer.
It can be obtained by copolymerizing the monomers. The types and amounts of the first and second monomers are such that the linear copolymer has a carboxyl group content of 17 to 50 mol% and a water absorption rate of 4.
It is selectively used so that the amount is 30% by weight. In this case, the carboxyl group content refers to the percentage (mol %) of the number of moles of the first monomer relative to the number of moles of all monomers used in the linear copolymer. Also, the water absorption rate is JIS K 69.
11, that is, the weight increase rate when a sample with a diameter of 50±111° and a thickness of 3±0.2° is immersed in water at 23° C. for 24 hours.
前記線状共重合体の種々の処理液に対する耐性は、その
カルボキシル基含有量または吸水率（親水性）の一方に
より一義的に決定されるものではな（、その両者により
決定され、両者はそれぞれ前記範囲内になければならな
い。仮にカルボキシル基含有量が１７〜５０モル％の範
囲内にあっても、第２の単量体として極端に疎水性の単
量体が選ばれ、該線状共重合体の吸水率が４重量％未満
の場合には、現像は困難となり、一方吸水率が３０重量
％を越える場合には、露光部では親水性の限界を越え、
フォトレジスト像はその端部（露光部と未露光部の境界
）で最も著しく現像液に侵され、画像の切れが悪く、解
像度が低下し、結果的に見掛は上の感光度も低下し、さ
らにめっき液やエツチング液に対する耐性も低下し、剥
離等の現象を生じる。The resistance of the linear copolymer to various processing solutions is not uniquely determined by its carboxyl group content or water absorption rate (hydrophilicity) (but is determined by both of them, and both of them are different from each other). Even if the carboxyl group content is within the range of 17 to 50 mol%, an extremely hydrophobic monomer is selected as the second monomer, and the linear covalent If the water absorption rate of the polymer is less than 4% by weight, development will be difficult, while if the water absorption rate exceeds 30% by weight, the hydrophilicity limit will be exceeded in the exposed areas,
A photoresist image is most severely attacked by the developer at its edges (the border between exposed and unexposed areas), resulting in poor image sharpness, reduced resolution, and, as a result, apparent sensitivity. Furthermore, resistance to plating solutions and etching solutions is also reduced, resulting in phenomena such as peeling.
また吸水率が４〜３０重量％の範囲内にあっても、カル
ボキシル基含有量が１７モル％未満の場合には現像がで
きず、一方カルボキシル基含有量が５０モル％を越える
場合には、レジスト像の表面光沢がなくなり耐性が低下
する。Further, even if the water absorption rate is within the range of 4 to 30% by weight, if the carboxyl group content is less than 17 mol%, development cannot be performed, while if the carboxyl group content exceeds 50 mol%, The surface gloss of the resist image is lost and the resistance is reduced.
本発明に用いられる線状共重合体の重量平均分子量は３
０，０００〜４００，０００、好ましくはｓｏ、ｏｏｏ
〜２００．０００である。重量平均分子量が３０，００
０未満の場合には、フィルム形成性が損なわれ、現像液
を含む処理液に対する耐性が低下する。一方４００，０
００を越える場合には、フィルム形成性および耐性は良
好であるが、現像性が低下する。The weight average molecular weight of the linear copolymer used in the present invention is 3
0,000-400,000, preferably so, ooo
~200.000. Weight average molecular weight is 30,00
When it is less than 0, film forming properties are impaired and resistance to processing solutions including developing solutions is reduced. On the other hand 400,0
If it exceeds 00, the film forming properties and resistance are good, but the developability deteriorates.
成分ｅの配合量は、成分ａ ％ ｂ ｓ Ｃ１前述の所
望により含有される附加重合性化合物およびｅの全ｆｆ
１１００．ｆｉｆｆｉ部に対して好ましくは４０〜７０
重量部、より好ましくは５０〜６５重量部である。The blending amount of component e is as follows: component a % b s C1 the addition polymerizable compound contained as desired above and the total ff of e.
1100. Preferably 40 to 70 to fiffi part
Parts by weight, more preferably 50 to 65 parts by weight.
４０重量部未満の場合には、感光層が軟化し、保存時に
コールドフローが発生し、一方７０重量部を越える場合
には、感光層が硬くなり、ラミネート時にはがれやすく
なる。When the amount is less than 40 parts by weight, the photosensitive layer becomes soft and cold flow occurs during storage, while when it exceeds 70 parts by weight, the photosensitive layer becomes hard and easily peels off during lamination.
本発明の感光性樹脂組成物は密着性付与剤を含有するこ
とが好ましい。密着性付与剤としては、例えばベンゾト
リアゾール、トリルトリアゾール、アミノベンズチアゾ
ール、テトラゾリン誘導体、イミダゾール誘導体、ベン
ゾトリアゾール等にホルムアルデヒドと２置換のアルキ
ルアミンとを脱水縮合して得られるジアルキルアミノメ
チレンベンゾトリアゾール誘導体などの金属の防錆剤が
用いられ、これらはめっき性およびエツチング後の密着
性に効果がある。これらの化合物のうちジアルキルアミ
ノメチレンベンゾトリアゾール誘導体が特に好ましい。The photosensitive resin composition of the present invention preferably contains an adhesion imparting agent. Examples of the adhesion imparting agent include dialkylaminomethylene benzotriazole derivatives obtained by dehydrating formaldehyde and a di-substituted alkylamine to benzotriazole, tolyltriazole, aminobenzthiazole, tetrazoline derivatives, imidazole derivatives, benzotriazole, etc. Rust inhibitors for metals are used, and these are effective in improving plating properties and adhesion after etching. Among these compounds, dialkylaminomethylenebenzotriazole derivatives are particularly preferred.
密着性付与剤の使用量はめっき性、密着性、安定性、剥
離時間の点から、成分ａ、ｂ、ｃ、前述の所望により含
有される附加重合性化合物およびｅの全量１００重量部
に対して０．０１〜２重量部が好ましく、０．０５〜０
．５ ｆｆｉ量部がより好ましい。From the viewpoint of plating properties, adhesion, stability, and peeling time, the amount of adhesion imparting agent to be used is based on 100 parts by weight of the total amount of components a, b, c, the addition polymerizable compound contained as described above, and e. It is preferably 0.01 to 2 parts by weight, and 0.05 to 0 parts by weight.
．． 5 ffi parts is more preferred.
これらの密着性付与剤は附加重合性化合物の種類および
量と密接な関係があり、本発明の感光性樹脂組成物では
安定性の低下が少ない。These adhesion-imparting agents are closely related to the type and amount of the addition-polymerizable compound, and the photosensitive resin composition of the present invention exhibits little decrease in stability.
本発明の感光性樹脂組成物は感光層の反応性を向上させ
るため有機ハロゲン化合物等の連鎖移動剤を含有するこ
とが好ましい。有機ハロゲン化合物等の連鎖移動剤とし
ては、例えば四塩化炭素、トリブロモメチルフェニルス
ルホン、ジ（トリブロモメチル）スルホン等が用いられ
、トリブロモメチルフェニルスルホンが特に好ましい。The photosensitive resin composition of the present invention preferably contains a chain transfer agent such as an organic halogen compound in order to improve the reactivity of the photosensitive layer. As the chain transfer agent such as an organic halogen compound, carbon tetrachloride, tribromomethylphenylsulfone, di(tribromomethyl)sulfone, etc. are used, and tribromomethylphenylsulfone is particularly preferred.
連鎖移動剤の使用量は附加重合性化合物（成分ａ ％
Ｃ）と線状共重合体の全量１００重量部に対して０．０
１〜５重量部が好ましい。The amount of chain transfer agent used is the addition polymerizable compound (component a%
C) and the total amount of 100 parts by weight of the linear copolymer: 0.0
1 to 5 parts by weight is preferred.
本発明の感光性樹脂組成物は染料、顔料、熱重合禁止剤
、粘着性付与剤、難燃化剤、成膜性付与剤等を含有して
いてもよい。The photosensitive resin composition of the present invention may contain dyes, pigments, thermal polymerization inhibitors, tackifiers, flame retardants, film-forming agents, and the like.
本発明の第２の発明は、上記の感光性樹脂組成物を用い
た感光性樹脂組成物積層体を提供するものである。感光
性樹脂組成物積層体は、上記の感光性樹脂組成物の溶液
をポリエチレンテレフタレート（ポリエステル）、ポリ
プロピレン、ポリビニルエーテル等のフィルム状支持体
上に第１図に示される装置等により、塗布、乾燥させて
得られ、さらにポリエチレンテレフタレート（ポリエス
テル）、ポリビニルアルコール、ポリスチレン、ポリエ
チレン等の１種または２種以上を積層してもよい。また
紫外線吸収層、酸素透過限外層を設けることもできる。A second aspect of the present invention provides a photosensitive resin composition laminate using the above photosensitive resin composition. The photosensitive resin composition laminate is produced by applying a solution of the above photosensitive resin composition onto a film support such as polyethylene terephthalate (polyester), polypropylene, polyvinyl ether, etc. using an apparatus shown in FIG. In addition, one or more of polyethylene terephthalate (polyester), polyvinyl alcohol, polystyrene, polyethylene, etc. may be laminated. Further, an ultraviolet absorbing layer and an oxygen permeable ultralayer can also be provided.
（発明の効果）
本発明の感光性樹脂組成物は銅への密着力、像形成能、
屈曲性および耐酸性に優れ、かつ感光層のしみ出しが少
なく、アルカリ現像可能なものである。(Effects of the invention) The photosensitive resin composition of the present invention has excellent adhesion to copper, image forming ability,
It has excellent flexibility and acid resistance, has little seepage of the photosensitive layer, and can be developed with alkali.
本発明の感光性樹脂組成物および感光性樹脂組成物積層
体は、エツチングレジストまたはめっきレジスト材料と
して好適なものであり、印刷配線板の製造、金属の精密
加工等の分野に広く用いることができる。The photosensitive resin composition and photosensitive resin composition laminate of the present invention are suitable as etching resist or plating resist materials, and can be widely used in fields such as manufacturing printed wiring boards and precision processing of metals. .
（実施例）
以下、実施例により本発明を説明する。部とあるのは重
量部である。(Example) The present invention will be explained below with reference to Examples. Parts are by weight.
実施例１
（ａ）感光性樹脂組成物の調製
次に示す化合物を、次に示す配合割合で配合して感光性
樹脂組成物の溶液を得た。Example 1 (a) Preparation of photosensitive resin composition The following compounds were blended in the following proportions to obtain a solution of a photosensitive resin composition.
アクリルポリマー（メタクリル酸／メタクリル酸メチル
／メタクリル酸ブチル／アクリル酸２−エチルへキシル
＝２３１５１／６／２０重量部比の共重合体、重量平均
分子量約７０，０００）の４０％エチルセロソルブ溶液
（ＰＭ−１） １５０部ウレ
タンジアクリレート（シクロヘキサン−１，６−ジメタ
ノール／トリメチルへキサメチレンジイソシアナート／
２−ヒドロキシメチルアクリレート＝０．２４／１．０
１０．７４モル比の反応物）の７５％トルエン溶液（Ｔ
Ｍ−１）３０部
モノアクリレート化合物ＡＭＰ−６０Ｇ（ｆｒ中村化学
工業（株）製部品名、フェノールのエチレンオキシド付
加物、平均付加数４のアクリレート）
５部ＢＰＥ−１０（新中村化学工業（
株）製部品名、ビスフェノールＡのエチレンオキシド付
加物のメタクリレート） １０部ジメ
チルアミノベンゾフェノン（ＭＫ）０、２部
ベンゾフェノン（ＢＰ） ６．０部ＢＴ−Ｌ
Ｘ （城北化学工業（株）製部品名、１．２．３−ベン
ゾトリアゾールとホルムアルデヒドとＮ、Ｎ−ジ（２−
エチル）ヘキシルアミンとの縮合物）０．２部
ビクトリアピュアブルー（ＶＰＢ）
０．４部
メチルエチルケトン ３０部トリブロモメ
チルスルホン（ＴＢＳ）
１．０部
（ｂ）感光性フィルムの調製および特性の評価第１図に
示す装置を用いて（ａ）で得られた感光性樹脂組成物の
溶液を、２５μｍ厚さのポリエチレンテレフタレートフ
ィルム（ポリエステルフィルム）２上に均一に塗布し、
８０〜１００℃の熱風対流式乾燥機３で約１０分間乾燥
した。感光性樹脂組成物の層の乾燥後の厚さは約５０μ
ｍであった。感光性樹脂組成物の層の上には、さらに第
１図のようにして厚さ約２５μｍのポリエチレンフィル
ム４を保護膜として張り合わせた。第１図において、５
はポリエチレンテレフタレートフィルム（ポリエステル
フィルム）繰す出シロール、６．７．８はロール、９は
ナイフ、１０はポリエチレンフィルム繰り出しロール、
１１．１２はロール、１３は感光性フィルム巻き取りロ
ールである。A 40% ethyl cellosolve solution of acrylic polymer (copolymer of methacrylic acid/methyl methacrylate/butyl methacrylate/2-ethylhexyl acrylate = 23151/6/20 parts by weight ratio, weight average molecular weight approximately 70,000) ( PM-1) 150 parts urethane diacrylate (cyclohexane-1,6-dimethanol/trimethylhexamethylene diisocyanate/
2-hydroxymethyl acrylate = 0.24/1.0
10.74 molar ratio of reactants) in 75% toluene solution (T
M-1) 30 parts monoacrylate compound AMP-60G (fr Nakamura Chemical Industry Co., Ltd. part name, ethylene oxide adduct of phenol, acrylate with an average addition number of 4)
Part 5 BPE-10 (Shin Nakamura Chemical Industry (
Co., Ltd. part name, methacrylate of ethylene oxide adduct of bisphenol A) 10 parts dimethylaminobenzophenone (MK) 0, 2 parts Benzophenone (BP) 6.0 parts BT-L
X (Johoku Chemical Industry Co., Ltd., 1.2.3 -Benzotoriazole and formaldehyde and N -N -(2-)
Condensate with ethylhexylamine) 0.2 parts Victoria Pure Blue (VPB) 0.4 parts Methyl ethyl ketone 30 parts Tribromomethylsulfone (TBS) 1.0 parts (b) Preparation of photosensitive film and evaluation of properties Using the apparatus shown in Figure 1, the solution of the photosensitive resin composition obtained in (a) was uniformly applied onto a 25 μm thick polyethylene terephthalate film (polyester film) 2.
It was dried for about 10 minutes in a hot air convection dryer 3 at 80 to 100°C. The thickness of the photosensitive resin composition layer after drying is approximately 50μ
It was m. On the layer of the photosensitive resin composition, a polyethylene film 4 having a thickness of about 25 μm was further laminated as a protective film as shown in FIG. In Figure 1, 5
is a polyethylene terephthalate film (polyester film) feeding roll, 6.7.8 is a roll, 9 is a knife, 10 is a polyethylene film feeding roll,
11 and 12 are rolls, and 13 is a photosensitive film winding roll.
このようにして得られた感光性フィルムを、銅パターン
（銅厚さ約７０μｍ）の形成された試験用フレキシブル
配線板（ポリエステル基板、基材厚さ０．２ｍｍ）上に
、日立化成工業（株）製ラミネータ（銅厚１８μｍ、ラ
ミネート温度１００℃、ラミネートスピード１ｍ／分）
を用い、保護膜を剥離しながら感光性樹脂組成物面を基
板側にして加熱・加圧積層した。室温で１時間放置した
後試験用ネガマスクを通して１５０ｍＪ／−の露光量の
紫外線を照射した。室温で１５分放置後、３０℃の１％
炭酸ソーダ水溶液をスプレー圧力１．５ ｋｇ／ｄで７
０秒間スプレーし、良好な像を得た。このフレキシブル
基板に５０℃で塩化第二銅液をスプレー圧力１．５ ｋ
ｇ ／ ｃｎ！で５０秒間スプレーし、レジストが被覆
されていない部分の銅を除去して回路を得た。得られた
像についてマンドレル試験（ＪＩＳ Ｋ５４００）を
行なった結果、３φでもレジストの浮きは観測されなか
った。また試験板を湿度９０％、温度４０℃に３日放置
後マンドレル試験を行なったが、３φまで良好であった
。これらの結果を第１表に示す。The photosensitive film thus obtained was placed on a test flexible wiring board (polyester substrate, base material thickness 0.2 mm) on which a copper pattern (copper thickness approximately 70 μm) was formed. ) laminator (copper thickness 18μm, lamination temperature 100℃, lamination speed 1m/min)
The photosensitive resin composition surface was placed on the substrate side and laminated under heat and pressure while peeling off the protective film. After being left at room temperature for 1 hour, it was irradiated with ultraviolet rays at an exposure dose of 150 mJ/- through a test negative mask. After leaving at room temperature for 15 minutes, 1% of 30℃
Spray sodium carbonate aqueous solution at a pressure of 1.5 kg/d.
It was sprayed for 0 seconds and a good image was obtained. Spray cupric chloride solution onto this flexible substrate at 50°C at a pressure of 1.5 k.
g/cn! The copper was sprayed for 50 seconds to remove the copper in the areas not covered with the resist, thereby obtaining a circuit. As a result of performing a mandrel test (JIS K5400) on the obtained image, no lifting of the resist was observed even at 3φ. In addition, a mandrel test was performed after the test plate was left at a humidity of 90% and a temperature of 40° C. for 3 days, and it was good up to 3φ. These results are shown in Table 1.
実施例２
第１表に示す組成（但しアクリルポリマー、光重合開始
剤および溶剤については実施例１のとおり）の感光性樹
脂組成物の溶液を調製し、実施例１と同様にして感光性
フィルムを調製し、特性の評価を行なった。その結果を
第１表に示す。Example 2 A solution of a photosensitive resin composition having the composition shown in Table 1 (acrylic polymer, photoinitiator, and solvent are as in Example 1) was prepared, and a photosensitive film was prepared in the same manner as in Example 1. was prepared and its properties were evaluated. The results are shown in Table 1.
以下余白
（註）
＊１ ウレタンジアクリレート（シクロヘキサン−１，
６−ジメタノール／トリメチルへキサメチレンジイソシ
アナート／２−ヒドロキシメチルアクリレート＝０．２
４／１．０１０．７４モル比反応物）の７５％トルエン
溶液
＊２ ウレタンジメタクリレート （Ｉ，２−プロピレ
ンジオール／トリメチルへキサメチレンジイソシアナー
ト／２−ヒドロキシメチルメタクリレート−０，５／
１．０ ／ １．０モル比反応物）の７５％トルエン溶
液
＊３ ビスフェノールＡのエチレンオキシド付加物のメ
タクリレ−１・（新中村化学工業（株）製部品名）
＊４ フェノールのエチレンオキシド付加物のモノアク
リレート（平均付加モル数４、新中村化学工業（株）製
部品名）
＊５ 同上（平均付加モル数５）
＊６ 同上（平均付加モル数７）
＊７ 同上（平均付加モル数１．５、東亜合成化学（株
）′！Ａ商品名）
＊８ ｐ−ノニルフェノールのエチレンオキシド付加物
のモノアクリレート（平均付加モル数１．５、東亜合成
化学（株）製部品名）＊９ ｐ−ノニルフェノールのエ
チレンオキシド付加物のモノアクリレート（平均付加モ
ル数３、東亜合成化学（株）製部品名）
＊１０ トリメチロールプロパントリアクリレート
＊１１ テトラエチレングリコールジアクリレート
＊１２１，２．３−ベンゾトリアゾールとホルムアルデ
ヒドとＮ、Ｎ−ジ（２−エチル）へキシルアミンとの縮
合物（城北化学工業（株）製部品名）
第１表の結果から本発明の感光性樹脂組成物が屈曲性に
優れた感光材料であることが示される。Below margin (note) *1 Urethane diacrylate (cyclohexane-1,
6-dimethanol/trimethylhexamethylene diisocyanate/2-hydroxymethyl acrylate = 0.2
75% toluene solution of 4/1.010.74 molar ratio reactants*2 Urethane dimethacrylate (I,2-propylene diol/trimethyl hexamethylene diisocyanate/2-hydroxymethyl methacrylate-0,5/
75% toluene solution of 1.0/1.0 molar ratio reactant) *3 Methacrylate-1, an ethylene oxide adduct of bisphenol A (part name manufactured by Shin-Nakamura Chemical Co., Ltd.) *4 An ethylene oxide adduct of phenol Monoacrylate (average number of added moles: 4, part name manufactured by Shin-Nakamura Chemical Co., Ltd.) *5 Same as above (average number of added moles: 5) *6 Same as above (average number of added moles: 7) *7 Same as above (average number of added moles: 1. 5. Toagosei Kagaku Co., Ltd. '!A product name) *8 Monoacrylate of ethylene oxide adduct of p-nonylphenol (average number of moles added 1.5, part name manufactured by Toagosei Kagaku Co., Ltd.) *9 p-nonylphenol Monoacrylate of ethylene oxide adduct (average addition mole number 3, part name manufactured by Toagosei Kagaku Co., Ltd.) *10 Trimethylolpropane triacrylate *11 Tetraethylene glycol diacrylate *12 1,2.3-benzotriazole and formaldehyde Condensate with N,N-di(2-ethyl)hexylamine (part name manufactured by Johoku Kagaku Kogyo Co., Ltd.) From the results in Table 1, the photosensitive resin composition of the present invention is a photosensitive material with excellent flexibility. It is shown that something is true.
第１図は、実施例で用いた感光性フィルムの製造装置の
概略図である。
１・・・感光性樹脂組成物の溶液、２・・・ポリエチレ
ンテレフタレートフィルム（ポリエステルフィルム）、
３・・・乾燥機、４・・・ポリエチレンフィルム、５・
・・ポリエステルフィルム繰り出しロール、６．７．８
・・・ロール、９・・・ナイフ、１０・・・ポリエチレ
ンフィルム繰り出しロール、１１．１２・・・ロール、
１３・・・感光性フィルム巻き取りロール。FIG. 1 is a schematic diagram of a photosensitive film manufacturing apparatus used in Examples. 1... Solution of photosensitive resin composition, 2... Polyethylene terephthalate film (polyester film),
3... Dryer, 4... Polyethylene film, 5...
・・Polyester film feeding roll, 6.7.8
...Roll, 9...Knife, 10...Polyethylene film feeding roll, 11.12...Roll,
13... Photosensitive film winding roll.
Claims (1)
物、 ▲数式、化学式、表等があります▼（１） （式中Ｒ＿１およびＲ＿２は水素原子またはメチル基を
意味し、これらは同一でも異なっていてもよく、Ｒ＿３
はフェニル基、ナフチル基、ピリジル基またはフリル基
を意味し、これらの基はハロゲン原子、炭素数１〜１０
のアルキル基、炭素数１〜１０のアルコキシ基、フェニ
ル基、アミノ基または炭素数１〜３のアルキル基の一ま
たは二で置換されたアルキル置換アミノ基の一または二
以上で置換されていてもよく、ｎは１〜１０の正の整数
を意味する）、 （ｂ）２価アルコール、アルキレンジイソシアナートお
よび２価アルコールのアクリル酸モノエステルまたはメ
タクリル酸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またはウレタンジメタクリレート
化合物、 （ｃ）一般式（II）で表わされる附加重合性化合物、 ▲数式、化学式、表等があります▼（II） （式中Ｒ＿４、Ｒ＿５、Ｒ＿６およびＲ＿７は水素原子
またはメチル基を意味し、これらは同一でも異なってい
てもよく、ｎおよびｍはｎ＋ｍ＝８〜１２を満足する正
の整数を意味する）、 （ｄ）光重合開始剤ならびに （ｅ）カルボキシル基含有量１７〜５０モル％、吸水率
４〜３０重量％および重量平均分子量３０，０００〜４
００，０００の線状共重合体を含有してなる感光性樹脂
組成物。 ２、感光性樹脂組成物層の少なくとも一方の面にフィル
ム状支持体を積層してなる感光性樹脂組成物積層体にお
いて、該感光性樹脂組成物層が、（ａ）一般式（ I ）
で表わされる附加重合性化合物、 ▲数式、化学式、表等があります▼（ I ） （式中Ｒ＿１およびＲ＿２は水素原子またはメチル基を
意味し、これらは同一でも異なっていてもよく、Ｒ＿３
はフェニル基、ナフチル基、ピリジル基またはフリル基
を意味し、これらの基はハロゲン原子、炭素数１〜１０
のアルキル基、炭素数１〜１０のアルコキシ基、フェニ
ル基、アミノ基または炭素数１〜３のアルキル基の一ま
たは二で置換されたアルキル置換アミノ基の一または二
以上で置換されていてもよく、ｎは１〜１０の正の整数
を意味する）、 （ｂ）２価アルコール、アルキレンジイソシアナートお
よび２価アルコールのアクリル酸モノエステルまたはメ
タクリル酸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またはウレタンジメタクリレート
化合物、 （ｃ）一般式（II）で表わされる附加重合性化合物、 ▲数式、化学式、表等があります▼（II） （式中Ｒ＿４、Ｒ＿５、Ｒ＿６およびＲ＿７は水素原子
またはメチル基を意味し、これらは同一でも異なってい
てもよく、ｎおよびｍはｎ＋ｍ＝８〜１２を満足する正
の整数を意味する）、 （ｄ）光重合開始剤ならびに （ｅ）カルボキシル基含有量１７〜５０モル％、吸水率
４〜３０重量％および重量平均分子量３０，０００〜４
００，０００の線状共重合体を含有してなる感光性樹脂
組成物積層体。[Claims] 1. (a) An addition polymerizable compound represented by the general formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R_1 and R_2 represent a hydrogen atom or a methyl group. and these may be the same or different, R_3
means a phenyl group, a naphthyl group, a pyridyl group, or a furyl group, and these groups include a halogen atom and a carbon number of 1 to 10.
an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, an amino group, or an alkyl substituted amino group substituted with one or two alkyl groups having 1 to 3 carbon atoms. (b) urethane diacrylate obtained by reacting a dihydric alcohol, an alkylene diisocyanate and an acrylic acid monoester or methacrylic acid monoester of the dihydric alcohol; compound or urethane dimethacrylate compound, (c) An addition polymerizable compound represented by the general formula (II), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_4, R_5, R_6 and R_7 are hydrogen atoms or methyl group, which may be the same or different, n and m are positive integers satisfying n+m=8 to 12), (d) photopolymerization initiator and (e) carboxyl group-containing amount 17-50 mol%, water absorption rate 4-30% by weight and weight average molecular weight 30,000-4
A photosensitive resin composition containing a linear copolymer of 0.00,000. 2. In a photosensitive resin composition laminate formed by laminating a film support on at least one surface of the photosensitive resin composition layer, the photosensitive resin composition layer has (a) general formula (I)
There are addition polymerizable compounds represented by ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 mean a hydrogen atom or a methyl group, and they may be the same or different, and R_3
means a phenyl group, a naphthyl group, a pyridyl group, or a furyl group, and these groups include a halogen atom and a carbon number of 1 to 10.
an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, an amino group, or an alkyl substituted amino group substituted with one or two alkyl groups having 1 to 3 carbon atoms. (b) urethane diacrylate obtained by reacting a dihydric alcohol, an alkylene diisocyanate and an acrylic acid monoester or methacrylic acid monoester of the dihydric alcohol; compound or urethane dimethacrylate compound, (c) An addition polymerizable compound represented by the general formula (II), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_4, R_5, R_6 and R_7 are hydrogen atoms or methyl group, which may be the same or different, n and m are positive integers satisfying n+m=8 to 12), (d) photopolymerization initiator and (e) carboxyl group-containing amount 17-50 mol%, water absorption rate 4-30% by weight and weight average molecular weight 30,000-4
A photosensitive resin composition laminate containing a linear copolymer of 0.00,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3655787A JPS63202740A (en) | 1987-02-19 | 1987-02-19 | Photosensitive resin composition and laminated body using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3655787A JPS63202740A (en) | 1987-02-19 | 1987-02-19 | Photosensitive resin composition and laminated body using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63202740A true JPS63202740A (en) | 1988-08-22 |
Family
ID=12473057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3655787A Pending JPS63202740A (en) | 1987-02-19 | 1987-02-19 | Photosensitive resin composition and laminated body using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63202740A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723260A (en) * | 1995-09-18 | 1998-03-03 | Mitsubishi Chemical Corporation | Unsaturated group-containing urethane compound, photopolymerizable composition containing it, and photosensitive lithographic printing plate |
| JP2001305730A (en) * | 2000-04-25 | 2001-11-02 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern and method for producing printed wiring board |
| JP2002099082A (en) * | 2000-09-25 | 2002-04-05 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the composition, method of producing resist pattern and method of producing printed-wiring board |
| JP2010189533A (en) * | 2009-02-18 | 2010-09-02 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition for optical lens sheet and cured product thereof |
| JP2018072789A (en) * | 2015-12-25 | 2018-05-10 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, production method of resin pattern, production method of cured film pattern, and display device |
-
1987
- 1987-02-19 JP JP3655787A patent/JPS63202740A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723260A (en) * | 1995-09-18 | 1998-03-03 | Mitsubishi Chemical Corporation | Unsaturated group-containing urethane compound, photopolymerizable composition containing it, and photosensitive lithographic printing plate |
| JP2001305730A (en) * | 2000-04-25 | 2001-11-02 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern and method for producing printed wiring board |
| JP2002099082A (en) * | 2000-09-25 | 2002-04-05 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the composition, method of producing resist pattern and method of producing printed-wiring board |
| JP2010189533A (en) * | 2009-02-18 | 2010-09-02 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition for optical lens sheet and cured product thereof |
| JP2018072789A (en) * | 2015-12-25 | 2018-05-10 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, production method of resin pattern, production method of cured film pattern, and display device |
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