JPH0228651A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
- Publication number
- JPH0228651A JPH0228651A JP17842488A JP17842488A JPH0228651A JP H0228651 A JPH0228651 A JP H0228651A JP 17842488 A JP17842488 A JP 17842488A JP 17842488 A JP17842488 A JP 17842488A JP H0228651 A JPH0228651 A JP H0228651A
- Authority
- JP
- Japan
- Prior art keywords
- group
- photosensitive composition
- compound
- unevenness
- component
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 3
- 239000010954 inorganic particle Substances 0.000 abstract 2
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003505 polymerization initiator Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- -1 ethylene glycol Chemical class 0.000 description 19
- 229910000679 solder Inorganic materials 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 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 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 125000005529 alkyleneoxy group Chemical group 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 241000951471 Citrus junos Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 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 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- 241000270708 Testudinidae Species 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 210000001685 thyroid gland Anatomy 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YQZZHMXSIYMFDK-UHFFFAOYSA-N 2-[bis(2-prop-2-enoyloxyethoxy)phosphoryloxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOP(=O)(OCCOC(=O)C=C)OCCOC(=O)C=C YQZZHMXSIYMFDK-UHFFFAOYSA-N 0.000 description 1
- JSMXLCYHZRBRHW-UHFFFAOYSA-N 2-[phenoxy(2-prop-2-enoyloxyethoxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound [O-][P+](OCCOC(=O)C=C)(OCCOC(=O)C=C)Oc1ccccc1 JSMXLCYHZRBRHW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- WVSFUMAHZBOQGJ-UHFFFAOYSA-N phosphono 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOP(O)(O)=O WVSFUMAHZBOQGJ-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、感光性組成物に係り、更に詳しくは、塗布む
らを生ずることなくプリント配線板上に塗布することの
できるフォトソルダーレジストとして好適な感光性組成
物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive composition, and more specifically, it is suitable as a photo solder resist that can be coated onto a printed wiring board without causing uneven coating. The present invention relates to a photosensitive composition.
プリント配線板製造の際のソルダーレジスト形成方法と
しては、従来、スクリーン印刷により画像形成する方法
が用いられてきたが、解像性の改良のためにフォトレジ
スト法が用いられるようになった。この方法は、液状感
光性組成物を回路形成された基板上に全面塗布し、必要
に応じて溶媒を加熱除去した後、マスクを通して像露光
して、現像処理によりレジスト形成する方法である。Conventionally, a method of forming an image by screen printing has been used as a method of forming a solder resist when manufacturing printed wiring boards, but a photoresist method has come to be used to improve resolution. In this method, a liquid photosensitive composition is applied over the entire surface of a circuit-formed substrate, the solvent is removed by heating if necessary, image exposure is carried out through a mask, and a resist is formed by a development process.
しかしながら、上記のような従来のレジスト形成方法で
は、いわゆるスジ状むら、ピンホル、ユズ膚、濃淡むら
、及び特に無機微粒子を含有する感光性組成物に生じや
すい凹凸のある約０．７ ｍの亀の甲状むら等を有する
不均一な感光層のできることがあり、これは外観上商品
としての価値を損なうばかりでなく、感度、回路被覆性
、半田耐熱性等の特性における不安定性の原因ともなる
、という問題点があった。However, in the conventional resist forming method as described above, a tortoise shell of approximately 0.7 m with so-called streak-like unevenness, pinholes, citrus skin, uneven shading, and unevenness that tends to occur especially in photosensitive compositions containing inorganic fine particles is produced. A non-uniform photosensitive layer may be formed with irregularities, etc., which not only impairs the value of the product in terms of appearance, but also causes instability in characteristics such as sensitivity, circuit coverage, and soldering heat resistance. There was a problem.
本発明は、上記のような従来の課題のすべてを解決して
、上記のむら等が全くない均一な乾燥塗布面（感光層）
を得ることのできる新規な感光性組成物の提供を目的と
する。The present invention solves all of the conventional problems as described above, and provides a uniform dry coating surface (photosensitive layer) without any of the above-mentioned unevenness.
The object of the present invention is to provide a novel photosensitive composition that can be obtained.
本発明者らは、かかる目的を達成すべく鋭意研究を進め
た結果、本発明に到達した。すなわち、本発明の要旨と
するところは、（５）重合性不飽和基を有する化合物、
但）光重合開始剤、Ｃ）無機微粒子及び０ フッ素系界
面活性剤よりなることを特徴とする感光性組成物にある
。The present inventors have conducted extensive research to achieve this objective, and as a result, have arrived at the present invention. That is, the gist of the present invention is (5) a compound having a polymerizable unsaturated group;
However, it is a photosensitive composition characterized by comprising: a) photopolymerization initiator, C) inorganic fine particles, and a fluorine-based surfactant.
かかる本発明の感光性組成物を構成する第１の成分は、
（５）の重合性不飽和基を有する化合物である。The first component constituting the photosensitive composition of the present invention is:
(5) This is a compound having a polymerizable unsaturated group.
上記のような囚成分の化合物は、ポリマオリゴマー モ
ノマーのいずれでもよいのであるが、ポリマーとしては
、例えばヒドロキシエチルメタクリレート、ヒドロキシ
エチルアクリレート、ヒドロキシエチルアクリレート又
はヒドロキシプロピルアクリレートを単独又は共量体と
して含むメタクリル系又はアクリル系ポリマーにメタク
リル酸又はアクリル酸をエステル化導入したポリマー
フェノキシ樹脂の水酸基にメタクリル酸又はアクリル酸
をエステル化導入したポリマー 同水酸基にメタクリル
基又はアクリル基をエーテル化導入したポリマー同水酸
基にグリシジルメタクリレート又はグリ／ジルアクリレ
−トを付加変性したポリマージアリル（イソ）フタレー
ト及び／又はトリアリルイソシアヌレートの（共）重合
ポリマーグリシジルメタクリレート又はグリ／ジルアク
リレートの（共）重合ポリマーにメタクリル酸又はアク
リル酸をエステル化導入したポリマーカルボキシル基含
有ポリマーにグリシジルメタクリレート又はグリシジル
アクリレートを付加導入したポリマー 無水マレイン酸
の共重合体に水酸基とメタクリル基又はアクリル基との
両者を含む化合物を付加反応させたポリマー 部分加水
分解し７た酢酸ビニルポリマーにメタクリル酸又はアク
リル酸をエステル化導入したポリマー等が挙げられる。The above-mentioned compound as a prisoner component may be any polymer oligomer monomer, but examples of the polymer include methacrylate containing hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, or hydroxypropyl acrylate alone or as a comer. Polymers in which methacrylic acid or acrylic acid is esterified into acrylic or acrylic polymers
A polymer in which methacrylic acid or acrylic acid is esterified into the hydroxyl group of a phenoxy resin. A polymer in which a methacrylic or acrylic group is etherified into the hydroxyl group. A polymer in which glycidyl methacrylate or glycidyl acrylate is added and modified to the same hydroxyl group Diallyl (iso) A polymer obtained by esterifying methacrylic acid or acrylic acid into a (co)polymerized polymer of phthalate and/or triallyl isocyanurate or a (co)polymerized polymer of glycidyl methacrylate or glycidyl acrylate.Glycidyl methacrylate or glycidyl acrylate is added to a carboxyl group-containing polymer. Addition-introduced polymer A polymer obtained by addition-reacting a compound containing both a hydroxyl group and a methacrylic group or an acrylic group to a copolymer of maleic anhydride.Methacrylic acid or acrylic acid is esterified and introduced into a partially hydrolyzed vinyl acetate polymer. Polymers such as
また、モノマー、オリゴマーとしては、ジオール類、例
えば、エチレングリコール、＋ｌラエチレンクリコール
、ノナエチレングリコール、ホリエチレングリコール、
プロピレングリコール、ブタンジオール、ヘキサンジオ
ール、ヘキサメチレングリコール、ビスフェノールＡの
ジヒドロキシエチルエーテル、四臭化ビスフェノールＡ
１それのジヒドロキシエチルエーテル、シクロヘキサン
ジメタツール等のアクリル酸ジエステル又はメタクリル
酸ジエステル；トリメチロールプロパン、ペンタエリス
リトール、ジペンタエリスリトール又はその誘導体、グ
リセロール、トリヒドロキシエチルイソシアヌレート又
はその誘導体等２価以上のポリオール類のメタクリル酸
エステル又はアクリル酸エステル；多価エポキシ化合物
、例えば、ビスフェノールＡ型エポキシ化合物、フェノ
ールノボラック型エポキシ化合物、クレゾールノボラッ
ク型エポキシ化合物とメタクリル酸又はアクリル酸との
反応生成物、ビスフェノールＡ型エポキシアクリレート
の水酸基にカルボン酸無水物を反応させた化合物、ノボ
ラックエポキシアクリレート樹脂の水酸基にカルボン酸
無水物を反応させた化合物；ジイソシアネート化合物と
ジオールモノアクリレート又はジオールモノメタクリレ
ートとの反応生成物、ジインシアネート化合物とジオー
ル化合物とジオールモノメタクリレート又はジオールモ
ノアクリレートとの反応生成物、ジイソシアネート化合
物とジオール化合物とトリオールジメタクリレート又は
トリオールジアクリレートとの反応生成物；リン酸エス
テル基を有するメタクリレート化合物又は了クリレート
化合物、具体的には、ビスメタクリロキシエチルフォス
フェート又はビスアクリロキンエチルフォスフェート、
ビス（アクリロキシエチル）フェニルフォスフェート、
ビス（メタクリロキシエチル）ブチルフォスフェート、
トリ、２メタクリロキシエチルフオスフエート又はトリ
スアクリロキシエチルフォスフェート；シリコーン系メ
タクリレート又はアクリレート等が挙げられる。In addition, examples of monomers and oligomers include diols, such as ethylene glycol, +l-ethylene glycol, nonaethylene glycol, polyethylene glycol,
Propylene glycol, butanediol, hexanediol, hexamethylene glycol, dihydroxyethyl ether of bisphenol A, bisphenol A tetrabromide
1 Acrylic acid diesters or methacrylic acid diesters such as dihydroxyethyl ether and cyclohexane dimetatool; divalent or higher valences such as trimethylolpropane, pentaerythritol, dipentaerythritol or derivatives thereof, glycerol, trihydroxyethyl isocyanurate or derivatives thereof Methacrylic acid ester or acrylic acid ester of polyols; polyhydric epoxy compounds such as bisphenol A type epoxy compounds, phenol novolac type epoxy compounds, reaction products of cresol novolac type epoxy compounds and methacrylic acid or acrylic acid, bisphenol A type A compound obtained by reacting the hydroxyl group of epoxy acrylate with a carboxylic anhydride, a compound obtained by reacting the hydroxyl group of a novolac epoxy acrylate resin with a carboxylic acid anhydride; a reaction product of a diisocyanate compound and diol monoacrylate or diol monomethacrylate, diincyanate A reaction product of a compound, a diol compound, and a diol monomethacrylate or a diol monoacrylate; a reaction product of a diisocyanate compound, a diol compound, and a triol dimethacrylate or a triol diacrylate; a methacrylate compound or an acrylate compound having a phosphate ester group; Specifically, bismethacryloxethyl phosphate or bisacryloquine ethyl phosphate,
bis(acryloxyethyl) phenyl phosphate,
bis(methacryloxyethyl)butyl phosphate,
Tri, 2-methacryloxyethyl phosphate or tris-acryloxyethyl phosphate; silicone-based methacrylate or acrylate, and the like.
これらの中から１つ又は２つ以上が用いられる。One or more of these may be used.
さらにメタクリロキシエチルフォスフェート又はアクリ
ロキシエチルフォスフェートナト（Ｄメタクリル基又は
アクリル基を１個有するリン酸メタクリレート又はアク
リレ−ト化合物の添加も好適である。Furthermore, it is also suitable to add methacryloxyethyl phosphate or acryloxyethyl phosphate (D phosphoric acid methacrylate or acrylate compound having one methacryl group or acrylic group).
上述の本発明における（３）成分の化合物の中でも特に
好適なものとしては１．下記−数式ＣＩ）（式中 Ｒ１
及びＲ２は異なっていてもよい水素原子又はメチル基を
示し、Ｒ３は−ＣＨ２０ＨＣＨ２ＯＨ
−ＣＨ２ＣＨ２−又は−ＣＨ２ＣＨ−を示す。）で表わ
さＯＨ３
れる重合単位を含むメタクリル系若しくはアクリル系ポ
リマー カルボキシル基含有ポリマーにグリシジルアク
リレート若しくはグリジルメタクリレートを導入したポ
リマー 又は、無水マレイン酸を含有するポリマーに水
酸基と１個以上のアクリル基若しくはメタクリル基をも
った化合物を反応させたポリマーの中から選ばれるポリ
マーに対して、２個以上の末端アクリル基若しくはメタ
クリル基を有する重合性単量体を組合せたものなどが挙
げられる。Among the compounds of component (3) in the above-mentioned present invention, particularly preferred are 1. Below - formula CI) (in the formula R1
and R2 represent a hydrogen atom or a methyl group which may be different, and R3 represents -CH20HCH2OH -CH2CH2- or -CH2CH-. ) A methacrylic or acrylic polymer containing a polymerized unit represented by OH3 A polymer obtained by introducing glycidyl acrylate or glycidyl methacrylate into a carboxyl group-containing polymer Or a polymer containing maleic anhydride containing a hydroxyl group and one or more acrylic or methacrylic groups Examples include a combination of a polymer selected from polymers obtained by reacting a compound having a group with a polymerizable monomer having two or more terminal acrylic or methacrylic groups.
本発明の感光性組成物の第２の成分は、（Ｂ）の光重合
開始剤である。The second component of the photosensitive composition of the present invention is the photopolymerization initiator (B).
上記のようなＣＢ）成分の化合物としては、具体的ニハ
ヘンゾイン、ペンツインアルキルエーテル類、アントラ
キノン誘導体、ベンゾフェノン誘導体、２．２−ジメト
キシ−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）フェニルツー２−モルフォリノ−１−プロパ
ノン、ヘンシル誘導体、ベンゾフェノン誘導体、４．４
’−ビス−ジメチルアミンベンゾフェノン、キサントン
誘導体、チオキサントン誘導体、ビイミダゾール類、ト
リクロロメチル−５−）リアジン類、３．４．３’ 、
４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベ
ンゾフェノン、ジ−ｔ−ブチルパーオキシイソフタレー
ト、及びこれらと色素類、アミン化合物例えばジアルキ
ルアミノ安息香酸アルキルエステル、アリルチオ尿素、
Ｎ−フェニルグリシンなどとの組合せが挙げられる。Examples of the above-mentioned compounds of the CB) component include nihahenzoin, pentuin alkyl ethers, anthraquinone derivatives, benzophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2- Methyl-[4-(methylthio)phenyl-2-morpholino-1-propanone, Hensyl derivative, benzophenone derivative, 4.4
'-bis-dimethylamine benzophenone, xanthone derivatives, thioxanthone derivatives, biimidazoles, trichloromethyl-5-)riazines, 3.4.3',
4'-tetra(t-butylperoxycarbonyl)benzophenone, di-t-butylperoxyisophthalate, and pigments with these, amine compounds such as dialkylaminobenzoic acid alkyl ester, allylthiourea,
Examples include combinations with N-phenylglycine and the like.
本発明の感光性組成物の第３の成分は、（Ｃ）の無機微
粒子である。The third component of the photosensitive composition of the present invention is (C) inorganic fine particles.
上記０成分の無機微粒子としては、具体的には、例えば
メルク、炭酸カルシウム、シリカ、硫酸バリウム、クレ
ー カオリン、焼結タルクなどが挙げられる。これらは
シランカップリング剤などで表面処理して好適に用いる
こともできる。Specific examples of the zero-component inorganic fine particles include Merck, calcium carbonate, silica, barium sulfate, clay kaolin, and sintered talc. These can also be suitably used after surface treatment with a silane coupling agent or the like.
本発明の感光性組成物の第４の成分は、０のフッ素系界
面活性剤である。The fourth component of the photosensitive composition of the present invention is a 0 fluorine surfactant.
上記０成分のフッ素系界面活性剤としては、界面活性剤
の疎水性基の炭素原子に結合した水素原子が、一部又は
全部フッ素原子で置換されたものであり、下記のような
アニオン型、カチオン型、ノニオン型、両性型及び高分
子型のいずれも用いることができる。The above-mentioned 0-component fluorine-based surfactants are those in which the hydrogen atoms bonded to the carbon atoms of the hydrophobic group of the surfactant are partially or completely replaced with fluorine atoms, such as the following anionic type, Any of cationic type, nonionic type, amphoteric type and polymeric type can be used.
（１） アニオン型フッ素系界面活性剤親水性基とし
て一〇〇〇Ｍ、 −０３０３Ｍ、 −８ｏ３Ｍ。(1) Anionic fluorosurfactant: 1000M, -0303M, -8o3M as hydrophilic groups.
−ＯＰ （ＯＨ） ２ 等を含有するもので、例えば
、Ｒｆ Ｃ００Ｍ、 Ｒｆ ５ｏ２Ｎ（Ｒ’ ）２ＣＨ
２ＣＯＯＭ。-OP (OH) 2 etc., such as Rf C00M, Rf 5o2N(R')2CH
2 COOM.
Ｒｆ ＢＮＲ’ Ｃ２Ｈ，０８０３Ｍ、 Ｒｆ ８０３
Ｍ。Rf BNR' C2H, 0803M, Rf 803
M.
ＲｆＣＨ２０ＣｍＨ２ｍＳ０３Ｍ。RfCH20CmH2mS03M.
ＭＯ３Ｓ−ＣＨＣＯＯＣＨ２Ｒｆ。MO3S-CHCOOCH2Rf.
ＣＨ２Ｃ００ＣＨ２Ｒｆ Ｒｆ Ｂ ＮＣｍ Ｈ２ｍＣＰ （ＯＨ） ２Ｒ／ 等が挙げられる。CH2C00CH2Rf Rf B NCm H2mCP (OH) 2R/ etc.
（上式中、Ｒｆはアルキル基の水素原子の一部又は全部
をフッ素原子でおきかえたフッ化炭素基（炭素原子数２
〜２０）を表わし、Ｂはｃｏ又はＳＯ□を表わし、Ｒ′
は水素原子又は低級アルキル基を表わし、Ｍは水素原子
、アルカリ金属又はアルカリ土類金属を表わし、ｍは０
〜５の整数を表わす。）
カチオン型フッ素系界面活性剤
Ｒ’
ＲＩ
有するもの、例えば、
ＲＩ
ＲＬ／
等が挙げられる。(In the above formula, Rf is a fluorocarbon group (having 2 carbon atoms) in which some or all of the hydrogen atoms of an alkyl group are replaced with fluorine atoms.
~20), B represents co or SO□, and R'
represents a hydrogen atom or a lower alkyl group, M represents a hydrogen atom, an alkali metal or an alkaline earth metal, m is 0
Represents an integer between ~5. ) Those having a cationic fluorine-based surfactant R' RI , for example, RI RL/ and the like.
（上式中、Ｒ／／は水素原子又は低級アルキル基を表わ
し、Ｘは）・ロゲン酸根を表わし、ＨＸは酸を表わす。(In the above formula, R// represents a hydrogen atom or a lower alkyl group, X represents a) rogenoic acid group, and HX represents an acid.
Ｒｆ、Ｂ及びＲＩはそれぞれ上記（１）のアニオン型フ
ッ素系界面活性剤におけるＲｆ 、 Ｂ及びＲ′と同義
である。）
（３）両性型フッ素系界面活性剤
例えば、
Ｒｆ ＢＮＨ（Ｃ２Ｈ４）Ｎｅ（Ｒ’ ） ２ＣｍＨｚ
ｍＣＯＯｅＨＣＯＯｅ
２ｍ
Ｒｆ ＢＮＣｎ Ｈ２ｎ Ｎｅ（Ｒ’ ） ３ＲｆＢＮ
ＨＣｍＨ２ｒｒｌＮ（ＲＩ）２ＣｎＨ２ｎｏｓ０２等が
挙げられる。Rf, B and RI have the same meanings as Rf, B and R' in the anionic fluorosurfactant of (1) above, respectively. ) (3) Amphoteric fluorosurfactant, for example, Rf BNH(C2H4)Ne(R') 2CmHz
mCOOeHCOOe 2m Rf BNCn H2n Ne(R') 3RfBN
Examples include HCmH2rrlN(RI)2CnH2nos02.
（式中、ＲｆｌＢ及びＲ′はそれぞれアニオン型界面活
性剤におけるＲｆ 、 Ｂ及びＲ’と同義である。）（
４） ノニオン型フッ素系界面活性剤親水性基として
−ＯＨ，−８Ｈ，−ＣＨ２ＣＨ２０−等を含有するもの
で、例えば、Ｒｆ ＯＨ，Ｒｆ ＳＨ。(In the formula, RflB and R' are respectively synonymous with Rf, B and R' in the anionic surfactant.)
4) Nonionic fluorosurfactant containing -OH, -8H, -CH2CH20-, etc. as a hydrophilic group, for example, Rf OH, Rf SH.
Ｒｆ −Ａ−（Ｃ２Ｈ４０−）−ｎＲ等が挙げられる。Examples include Rf-A-(C2H40-)-nR.
（上式中、Ｒは置換基を有していてもよいアルキル基を
表わし、Ａは＋ＣＨ２＋ｍ５ｏ２ＮＲ’ −（−ＣＨ２
−）ｍＯ−、４ＣＲ２−）ｒＩＩＣ０ＮＲ５−、−３０
３−−ｃｏ２−、及び−５Ｏ２Ｎ（Ｒ６）ＣＲ２ＣＨ２
−からなる群よシ選ばれる基であり、ｎは０〜２ｏの整
数、ｍはθ〜５の整数を表わし Ｒ４、Ｒ５及びＲ６は
水素原子、炭素原子数１〜６のアルキル基又は＋ＣＨ２
ＣＨ２Ｏ←−Ｒ７を表わし、Ｒ４、Ｒ５及びＲ６は各々
同一のものも異なるものも含む。又は１〜２０の整数を
表わしＲ７は炭素原子数１〜６のアルキル基を表わす。(In the above formula, R represents an alkyl group that may have a substituent, and A is +CH2+m5o2NR' -(-CH2
-) mO-, 4CR2-) rIIC0NR5-, -30
3--co2-, and -5O2N(R6)CR2CH2
A group selected from the group consisting of -, where n represents an integer of 0 to 2o, m represents an integer of θ to 5, and R4, R5 and R6 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or +CH2
It represents CH2O←-R7, and R4, R5 and R6 each include the same or different ones. or an integer of 1 to 20, and R7 represents an alkyl group having 1 to 6 carbon atoms.
）
加えて、下記−数式（ＩＩ）
Ｒ−８４Ｒ８−ＣＨ＋。 ・山・・ （１
）Ｃ００Ｒ９−Ｈ
で示されるノニオン型フッ素系界面活性剤が挙げられる
。) In addition, the following formula (II) R-84R8-CH+.・Mountain... (1
) C00R9-H A nonionic fluorine-based surfactant can be mentioned.
（上式中、ｎは１〜２０の整数を表わす。Ｒ８はアルキ
レン基を表わす。Ｒ９は、アルキレンオキシ基又はその
１個以上の水素原子をフッ素原子に置きかえたフッ化ア
ルキレンオキシ基であって、くり返し単位で異なってい
てもよい。、さらに、Ｒは好ましくは炭素数１〜１０、
特に好ましくは炭素数４〜８のアルキル基であり、ｎは
好ましくは１〜１０の整数であυ、Ｒ８は好ましくは炭
素数１〜５のアルキレン基である。また、Ｒ９はアルキ
レンオキシ基又はフッ化アルキレ／オキシ基を表わすが
、アルキレンオキシ基単位はＯ〜３０の数、好まし、く
けＯ〜１８の数で、フッ化アルキレンオキシ基単位は１
〜３０の数、好ましくは２〜２０の数である。(In the above formula, n represents an integer from 1 to 20. R8 represents an alkylene group. R9 is an alkyleneoxy group or a fluorinated alkyleneoxy group in which one or more hydrogen atoms thereof are replaced with a fluorine atom; , may be different in repeat units.Furthermore, R preferably has 1 to 10 carbon atoms,
Particularly preferred is an alkyl group having 4 to 8 carbon atoms, n is preferably an integer of 1 to 10, and R8 is preferably an alkylene group having 1 to 5 carbon atoms. Further, R9 represents an alkyleneoxy group or a fluorinated alkylene/oxy group, and the alkyleneoxy group unit is a number of O to 30, preferably a number of O to 18, and the fluorinated alkyleneoxy group unit is 1
-30 numbers, preferably 2-20 numbers.
アルキレンオキシ基としては、エチレンオキシ基、イン
プロビレ／オキシ基が好適であシ、フッ化アルキレンオ
キシ基としては、フッ化エチレンオキシ基、フッ化イソ
プロピレンオキシ基が好適である。さらに、フッ化エチ
レンオキシ基としては、エチレンオキシ基の水素原子を
１〜７個、好ましくは１〜３個置換したものが挙げられ
、また、フッ化イソプロピレンオキシ基としては、イン
プロピレンオキシ基の水素原子を１〜７個、好ましくは
１〜４個置換したものが挙げられる。）
（５）高分子型フッ素系界面活性剤
例えば、４ＣＨ２−ＣＨ＋の構造単位を含む高分００Ｒ
ｆ
子化合物等が挙げられる。The alkyleneoxy group is preferably an ethyleneoxy group or an improvylene/oxy group, and the fluorinated alkyleneoxy group is preferably a fluorinated ethyleneoxy group or a fluorinated isopropyleneoxy group. Further, examples of the fluorinated ethyleneoxy group include those in which 1 to 7, preferably 1 to 3 hydrogen atoms are substituted for the ethyleneoxy group, and examples of the fluorinated isopropyleneoxy group include an inpropyleneoxy group. Examples include those in which 1 to 7 hydrogen atoms, preferably 1 to 4, are substituted. ) (5) Polymer-type fluorosurfactant, for example, polymer 00R containing the structural unit of 4CH2-CH+
Examples include f child compounds.
（上式中、Ｒｆは前記（１）のアニオン型フッ素系界面
活性剤におけると同義である。）
以上詳記し九〇成分のフッ素系界面活性剤の中では上記
（４）のノニオン型フッ素系界面活性剤が好ましく、該
（４）の中でも特に好ましいのは上記−数式Ｃｌ１）で
示されるノニオン型フッ素系界面活性剤である。(In the above formula, Rf has the same meaning as in the anionic fluorinated surfactant in (1) above.) Among the 90 component fluorinated surfactants detailed above, the nonionic fluorinated surfactant in (4) above Surfactants are preferred, and among these (4), particularly preferred are nonionic fluorosurfactants represented by the above-mentioned formula Cl1).
かかるＤ）成分のフッ素系界面活性剤の具体例としては
、例えば下記の化合物が挙げられる。Specific examples of the fluorosurfactant as component D) include the following compounds.
本発明の感光性組成物における（ト）、（Ｂ）、Ｉｃ’
）及び■の各成分の含有割合は次のとおりである。(g), (B), Ic' in the photosensitive composition of the present invention
) and () The content ratios of each component are as follows.
すなわち、（５）成分の重合性不飽和基を有する化合物
は全固型分に対して１０〜９５重量％、より好ましくは
２０〜８０重量％、（Ｂ）成分の光重合開始剤は０．０
１〜２０重量％、より好ましくは０．１〜１０重量係、
Ｃ）成分の無機微粒子は２〜８０重量係、よシ好ましく
は１０〜５０重量％、■）成分のフッ素系界面活性剤は
全固型分に対して０、 ＯＯＯ５〜１重量％、より好ま
しくは０．００１〜０．５重量％である。That is, the component (5), the compound having a polymerizable unsaturated group, is 10 to 95% by weight, more preferably 20 to 80% by weight, based on the total solid content, and the photopolymerization initiator, the component (B), is 0.5% by weight. 0
1 to 20% by weight, more preferably 0.1 to 10% by weight,
The inorganic fine particles as component C) are 2 to 80% by weight, preferably 10 to 50% by weight, and the fluorine surfactant as component (■) is 0 to 5 to 1% by weight, more preferably OOO5 to 1% by weight based on the total solid content. is 0.001 to 0.5% by weight.
なお、０成分のフッ素系界面活性剤は、特に無機微粒子
を含む感光性組成物に発現しやすい凹凸のある約０．７
１１Ｉの亀の甲状むらの発生を防止する効果がある。In addition, the 0-component fluorine-based surfactant has a roughness of approximately 0.7 cm, which is particularly likely to appear in photosensitive compositions containing inorganic fine particles.
It is effective in preventing the occurrence of 11I turtle thyroid irregularities.
更に、本発明の感光性組成物には、その他必要に応じ、
エポキシ環含有化合物、例えばグリシジルアクリレート
及び／又はグリシジルメタクリレート（共）重合体、ノ
ボラックエポキシ化合物、ビスフェノールＡ型エポキシ
化合物、グリシジルエーテル類などが好適に含有される
。Furthermore, the photosensitive composition of the present invention may contain other ingredients as necessary.
Epoxy ring-containing compounds such as glycidyl acrylate and/or glycidyl methacrylate (co)polymers, novolak epoxy compounds, bisphenol A type epoxy compounds, glycidyl ethers, etc. are preferably contained.
また、エポキシ硬化剤、熱重合禁止剤、着色剤、露光可
視画剤、難燃化剤、消泡剤、密着向上剤、紫外線吸収剤
、チクソトロピー付与剤などを配合してもよい。Further, an epoxy curing agent, a thermal polymerization inhibitor, a coloring agent, an exposed visible imager, a flame retardant, an antifoaming agent, an adhesion improver, an ultraviolet absorber, a thixotropy imparting agent, etc. may be added.
上記各成分を、必要ならば塗布溶剤に溶解あるいは分散
させて塗布液を調製する。A coating solution is prepared by dissolving or dispersing each of the above components in a coating solvent, if necessary.
塗布溶剤としては、適当な沸点を持ち組成物を溶解また
は分散し得るものならば使用可能であるが、例えば、メ
チルエチルケトン、メチルイソプロピルケトン、メチル
イソブチルケトン、メチルセロソルフ、エチルセロソル
ブ、プチルセｏ ７７ｔ、フ、シクロヘキサノン、セロ
ンルフアセテート、メチルセロソルブアセテート、ブチ
ルセロソルブアセテート、カルピトール、メチルカルピ
トール、ブチルカルピトール、カルピトールアセテ−１
−、メチルカルピトールアセテート、ブチルカルピトー
ルアセテート、キシレン、トルエン、クロピレングリコ
ールモノメチルエーテル、プロピレングリコールモノエ
チルエーテル、プロピレングリコールモノメチルエーテ
ルアセテート、プロピレングリコールモノエチルエーテ
ルアセテートなどが挙げられる。As the coating solvent, any solvent can be used as long as it has an appropriate boiling point and can dissolve or disperse the composition, such as methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, Ptylce O 77t, Cyclohexanone, selonulf acetate, methyl cellosolve acetate, butyl cellosolve acetate, calpitol, methyl calpitol, butyl calpitol, carpitol acetate-1
-, methylcarpitol acetate, butylcarpitol acetate, xylene, toluene, clopylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like.
本発明の感光性組成物を含有する感光層塗布液の塗布方
法としては、ロールコータ−カーテンコーター スクリ
ーン印刷法等の公知の方法が用いられる。As a method for applying the photosensitive layer coating solution containing the photosensitive composition of the present invention, known methods such as a roll coater-curtain coater screen printing method can be used.
このようにして、プリント配線板等に全面塗布された本
発明の感光性組成物は、その後、必要ならば溶剤を除去
し、像露光、現像を行うことにより半田の付着すべきで
ない部分をマスクする。この際の現像液は１，１．１−
）ＩＪジクロロタン又は弱アルカリ水などが用いられる
。The photosensitive composition of the present invention that has been applied to the entire surface of a printed wiring board, etc. is then subjected to imagewise exposure and development to mask areas to which solder should not adhere, after removing the solvent if necessary. do. The developer at this time was 1,1.1-
) IJ dichlorothane or weakly alkaline water is used.
本発明の組成物は、特にこれら現像液に対してきわめて
良好な現像性を示す。The composition of the present invention exhibits extremely good developability, especially with these developing solutions.
本発明組成物の他の応用例としては、電子部品や導線の
永久保護被覆、集積回路用の絶縁保護膜、その他恒久的
な保護コートや精密画像レジストとしても好適に用い得
る。また、種々のレジスト類や印刷板等にも応用するこ
とができる。Other applications of the composition of the present invention include permanent protective coatings for electronic components and conductive wires, insulating protective films for integrated circuits, other permanent protective coatings, and precision image resists. It can also be applied to various resists, printing plates, etc.
次に、本発明を実施例により更に具体的に説明するが、
本発明は、これらの実施例により限定されるものではな
い。Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.
実施例１
下記構造式（５）−１
％式％
で示される重量平均分子量１７万のポリマー６助とイン
シアヌレート系３官能アクリレートモノマー”アロニク
スＭ−３２５”（東亜合成化学工業■商品名）の重合性
単量体１０神との組合せ〔囚成分〕、ベンゾフェノン０
．３助及ヒミヒラーケトン０．１ｋｇ（（Ｂ）成分〕、
フッ素系界面活性剤で前記の例示化合物の（２）のｏ、
０２６ｋｇ〔０成分〕、アらかじめ７ランカツプリン
グ剤で表面処理した平均粒径１μｍのタルク微粉１０ｋ
ｑｃｆｌ成分〕、並びにフタロシアニングリーン０．２
ｋｙを、メチルセロソルブ３０ ｋｑに溶解又は分散
させて得られた２５℃における粘度４３０ｃｐｓの感光
液を、カーテンコーターを用いてスリット幅Ｑ、 ７
ｍ 、ヘッド高さｌＯＱｍ、塗布速度１００ ｍ ／
ｍで半田スルーホールプリント配線板上に塗布した。８
５℃、５分で乾燥後、上記と同様に裏面も塗布し、８５
℃、３０分乾燥した。べたつきとむらのない感光性塗膜
が得られた。乾燥後の基板平坦部の平均膜厚は７０μｍ
であった。超高圧水銀灯で６４０ｍＪ／−の光量で画像
露光後１，１．１−１−リクロロエタンを用いて２ ｋ
ｑ／ ｒｒｒのスプレー圧で１分間現像した。スルーホ
ール内の感光液は完全に溶解除去されており、解像性も
良好であった。水洗、乾燥後、高圧水銀灯８０Ｗ／ｆｆ
ｉの３本に１ｍ／ｍｉｎで通して後露光したのち、１３
０℃で１５分加熱した。Example 1 A polymer with a weight average molecular weight of 170,000 represented by the following structural formula (5)-1 % formula % and an incyanurate trifunctional acrylate monomer "Aronix M-325" (trade name of Toagosei Chemical Industry Co., Ltd.) Combination with 10 polymerizable monomers [capacity component], 0 benzophenone
．． 3suke and Himichler ketone 0.1kg (component (B)),
o of (2) of the above-mentioned exemplary compound as a fluorine-based surfactant;
026 kg [0 ingredients], 10 kg of fine talc powder with an average particle size of 1 μm that has been surface-treated with a 7-rank springing agent.
qcfl component] and phthalocyanine green 0.2
A photosensitive liquid having a viscosity of 430 cps at 25°C obtained by dissolving or dispersing ky in 30 kq of methyl cellosolve was coated with a curtain coater to form a slit width Q of 7.
m, head height lOQm, coating speed 100 m/
It was applied onto a solder through-hole printed wiring board using m. 8
After drying at 5℃ for 5 minutes, apply the same coating to the back side as above and apply 85
It was dried at ℃ for 30 minutes. A photosensitive coating film without stickiness and unevenness was obtained. The average film thickness on the flat part of the substrate after drying is 70 μm.
Met. After image exposure with an ultra-high-pressure mercury lamp at a light intensity of 640 mJ/-, the image was exposed to 2 k using 1,1.1-1-lichloroethane.
Developed for 1 minute at a spray pressure of q/rrr. The photosensitive liquid inside the through hole was completely dissolved and removed, and the resolution was also good. After washing and drying, high pressure mercury lamp 80W/ff
After post-exposure by passing through the 3 lines of i at 1 m/min, 13
Heated at 0°C for 15 minutes.
得られたプリント配線板上のソルダーマスクは、スジ状
むら、ピンホール、ユズ膚、濃淡むら、凹凸のある約０
．７１０１の亀の甲状むら等を全く発生することなく、
均一にかつ充分な厚さで回路を被覆していた。The obtained solder mask on the printed wiring board has streak-like unevenness, pinholes, yuzu skin, uneven shading, and unevenness.
．． No 7101 turtle thyroid unevenness occurs,
The circuit was coated uniformly and with sufficient thickness.
実施例２
無水マレイン酸とスチレンの２＝１の共重合体に２−ヒ
ドロキシエチルアクリレートを反応させたポリマー６ｋ
ｇとインシアヌレート系３官能アクリレートモノマーパ
アロニクスＭ−３１５″（東亜合成化学工業■製）７に
７、ペンタエリスリトールトリアクリレート３にり及び
メタクリロキシエチルフォスフニー） ０．０５ ｋｇ
のｉ合性ｓ量体とを組合せた（５）成分、ベンゾフェノ
ン０．３に９及びミヒラーケトン０．１ ｋｑのの）成
分、フッ素系界面活性剤の前記例示化合物の（４） ０
．０２６ ｋＬｉの０成分、平均粒径１μｍのタルク微
粉１０ｋｆのＣ）成分、並びにフタロシアニングリーン
０．２ ｋｇを、ブチルセロソルブ９ ｋｇに溶解又は
分散させてフォトフルダーインキを作った。スクリーン
印刷機を用い、配線板上に平均膜厚２５μｍで該インキ
の塗布を行った。次に、超高圧水銀灯で６４ｏｍＪ／−
の光量で画像露光後、１重量装炭酸ナトリウム水溶液を
用い３ ｋｇ ／ ｃｒＡのスプレー圧で１分間現像し
た。水洗、乾燥後、１３０′Ｃで６０分加熱した。Example 2 Polymer 6k made by reacting 2-hydroxyethyl acrylate with a 2=1 copolymer of maleic anhydride and styrene
g and incyanurate trifunctional acrylate monomer Parronix M-315'' (manufactured by Toagosei Kagaku Kogyo ■) 7 to 7, pentaerythritol triacrylate 3 and methacryloxyethylphosphny) 0.05 kg
Component (5) in combination with i-merging s-mer of 0.3 to 9 of benzophenone and 0.1 kq of Michler's ketone, component (4) of the above-mentioned exemplified compound of fluorosurfactant 0
．． A photofulder ink was prepared by dissolving or dispersing component 0 of 026 kLi, component C) of 10 kf of fine talc powder with an average particle size of 1 μm, and 0.2 kg of phthalocyanine green in 9 kg of butyl cellosolve. The ink was applied onto a wiring board using a screen printer to an average film thickness of 25 μm. Next, use an ultra-high pressure mercury lamp at 64 omJ/-
After imagewise exposure at a light intensity of , development was performed for 1 minute using a 1 weight portion of sodium carbonate aqueous solution at a spray pressure of 3 kg/crA. After washing with water and drying, it was heated at 130'C for 60 minutes.
得られたプリント配線板上のソルダーマスクは、スジ状
むら、ピンホール、ユズ膚、濃淡むら、凹凸のある約０
．７ ｍの亀の甲状むら等は全くみられず、均一にかつ
充分な厚さで回路を被覆していた。The obtained solder mask on the printed wiring board has streak-like unevenness, pinholes, yuzu skin, uneven shading, and unevenness.
．． No 7-meter tortoise shell irregularities were observed, and the circuit was coated uniformly and with sufficient thickness.
比較例１
実施例１の感光性組成物塗布液中のフッ素系界面活性剤
〔前記例示化合物の（２）〕を除外した以外は、実施例
１と同様にして、プリント配線板上にソルダーマスクを
付与させた。Comparative Example 1 A solder mask was applied on a printed wiring board in the same manner as in Example 1, except that the fluorine-based surfactant [(2) of the above-mentioned exemplified compounds] in the photosensitive composition coating solution of Example 1 was omitted. was granted.
得られたソルダーマスクは、凹凸のある約０、７■亀の
甲状むらが発生し、塗布性は不良で均一な感光層を得る
ことはできなかった。また、半田浴中に浸漬すると、む
らの部分のソルダーマスクが剥離したり、むらの部分の
ソルダーマスク上に半田が付着してしまった。The obtained solder mask had irregularities of about 0.7 mm, and the coating properties were poor, making it impossible to obtain a uniform photosensitive layer. Also, when immersed in a solder bath, the solder mask in the uneven parts peeled off, and the solder adhered to the solder mask in the uneven parts.
比較例２
実施例２の感光性組成物塗布液中のフッ素系界面活性剤
〔前記例示化合物の（４）〕を除外した以外は、実施例
２と同様にして、プリント配線板上にソルダーマスクを
付与させた。Comparative Example 2 A solder mask was applied on a printed wiring board in the same manner as in Example 2, except that the fluorine-based surfactant [(4) of the above-mentioned exemplified compounds] in the photosensitive composition coating solution of Example 2 was omitted. was granted.
得られたソルダーマスクは、凹凸のある約０、７１ｍの
亀の甲状むらが発生し、塗布性は不良で均一な感光層を
得ることはできなかった。The obtained solder mask had a tortoise-shaped unevenness of about 0.71 m with unevenness, and the coating properties were poor, making it impossible to obtain a uniform photosensitive layer.
以上の結果から明らかなように、本発明の感光性組成物
は、プリント配線板上等への塗布性に優れ、得られたプ
リント配線板上のソルダーマスクは、スジ状むら、ピン
ホール、ユズ膚、濃淡むらばかシでなく、従来の特に無
機微粒子を含有する感光性組成物には生じやすかった凹
凸のある約０．７１ｍの亀の甲状むら等をも全く発生す
ることなく、均一にかつ充分な厚さで回路を被覆するこ
とができ、その結果、従来の感度、回路被覆性、半田耐
熱性等の特性にみられた不安定性をも全く解消し得る、
というフォトソルダーレジストとして特に好適で工業的
価値ある顕著な効果を奏するものである。As is clear from the above results, the photosensitive composition of the present invention has excellent coating properties on printed wiring boards, etc., and the resulting solder mask on printed wiring boards has no streaky unevenness, pinholes, or yuzu. Evenly and sufficiently, there is no uneven skin, shading, or uneven tortoise-shaped unevenness of approximately 0.71 m, which is likely to occur with conventional photosensitive compositions containing inorganic fine particles. As a result, the instability seen in conventional characteristics such as sensitivity, circuit coverage, and soldering heat resistance can be completely eliminated.
It is particularly suitable as a photo solder resist and exhibits remarkable effects of industrial value.
Claims (1)
重合開始剤、（Ｃ）無機微粒子及び（Ｄ）フッ素系界面
活性剤よりなることを特徴とする感光性組成物。(1) A photosensitive composition comprising (A) a compound having a polymerizable unsaturated group, (B) a photopolymerization initiator, (C) inorganic fine particles, and (D) a fluorine-based surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17842488A JPH0228651A (en) | 1988-07-18 | 1988-07-18 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17842488A JPH0228651A (en) | 1988-07-18 | 1988-07-18 | Photosensitive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0228651A true JPH0228651A (en) | 1990-01-30 |
Family
ID=16048260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17842488A Pending JPH0228651A (en) | 1988-07-18 | 1988-07-18 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0228651A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0293458A (en) * | 1988-09-29 | 1990-04-04 | Konica Corp | Colored image forming material and transfer image forming method by using this material |
| JPH04363457A (en) * | 1991-06-11 | 1992-12-16 | Hokkaido Nouzai Kogyo Kk | Heat insulating tile, external heat insulating wall of building and construction method thereof |
| JP2011232709A (en) * | 2010-04-30 | 2011-11-17 | Taiyo Holdings Co Ltd | Curable resin composition |
-
1988
- 1988-07-18 JP JP17842488A patent/JPH0228651A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0293458A (en) * | 1988-09-29 | 1990-04-04 | Konica Corp | Colored image forming material and transfer image forming method by using this material |
| JPH04363457A (en) * | 1991-06-11 | 1992-12-16 | Hokkaido Nouzai Kogyo Kk | Heat insulating tile, external heat insulating wall of building and construction method thereof |
| JP2011232709A (en) * | 2010-04-30 | 2011-11-17 | Taiyo Holdings Co Ltd | Curable resin composition |
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