JPH04116181A - Cationic electrodeposition type negative type etching resist composition - Google Patents
Cationic electrodeposition type negative type etching resist compositionInfo
- Publication number
- JPH04116181A JPH04116181A JP23056790A JP23056790A JPH04116181A JP H04116181 A JPH04116181 A JP H04116181A JP 23056790 A JP23056790 A JP 23056790A JP 23056790 A JP23056790 A JP 23056790A JP H04116181 A JPH04116181 A JP H04116181A
- Authority
- JP
- Japan
- Prior art keywords
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- group
- reaction
- compd
- contg
- 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
- 238000005530 etching Methods 0.000 title claims abstract description 25
- 238000004070 electrodeposition Methods 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 19
- 125000002091 cationic group Chemical group 0.000 title claims description 16
- -1 methacryloyl group Chemical group 0.000 claims abstract description 23
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 21
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 12
- 239000003504 photosensitizing agent Substances 0.000 claims description 9
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 15
- 150000001412 amines Chemical class 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000010408 film Substances 0.000 description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 14
- 150000003335 secondary amines Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-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
- 239000004593 Epoxy Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OMRVSHQAOVGYNJ-UHFFFAOYSA-N bis[2-(2-prop-2-enoyloxyethoxy)ethyl] benzene-1,2-dicarboxylate Chemical compound C=CC(=O)OCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCOC(=O)C=C OMRVSHQAOVGYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- NWJXSVNLQJZDLV-UHFFFAOYSA-N formic acid;hydrogen peroxide Chemical compound OO.OC=O NWJXSVNLQJZDLV-UHFFFAOYSA-N 0.000 description 1
- ZTQSADJAYQOCDD-UHFFFAOYSA-N ginsenoside-Rd2 Natural products C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC1OCC(O)C(O)C1O ZTQSADJAYQOCDD-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 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 1
- 238000011165 process development Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は微細な配線パターンを有するプリント配線基板
等を作成するために適した高感度で、かつ高解像度を有
するカチオン電着型ネガ型エツチングレジスト組成物に
関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention is a cationic electrodeposition type negative etching method with high sensitivity and high resolution suitable for producing printed wiring boards etc. having fine wiring patterns. The present invention relates to a resist composition.
〈従来の技術〉
従来プリント配線基板製造用のエツチングレジストとし
ては、ドライフィルムが広く使用されている。しかしな
がら該ドライフィルムは、膜厚が大きいために解像度が
低く、配線パターンの微細化に限度があり、最近の電気
・電子機器等に用いられる配線基板において、素子の高
密度実装化のために強く要求される配線パターンの微細
化には、対処しきれなくなりつつある。<Prior Art> Dry films have been widely used as etching resists for manufacturing printed wiring boards. However, the dry film has a low resolution due to its large film thickness, and there is a limit to the miniaturization of wiring patterns. It is becoming impossible to cope with the required miniaturization of wiring patterns.
そこで、薄膜を均一に塗布することができるという特徴
を有する電着塗装法を利用したエツチングレジストによ
る微細配線パターン作成技術が開発されている。Therefore, a technique for creating a fine wiring pattern using an etching resist has been developed, which utilizes an electrodeposition coating method which has the characteristic of uniformly applying a thin film.
電着型エツチングレジストには、アニオン型とカチオン
型とがあるが、銅のエツチングにおいては酸性の溶液が
使用されるため、一般には硬化後の塗膜が耐酸性に優れ
るアニオン型が主に開発されている。There are two types of electrodeposited etching resists: anionic and cationic, but because acidic solutions are used in copper etching, the anionic type is generally developed because the cured coating has excellent acid resistance. has been done.
しかしながらアニオン電着型エツチングレジストは、電
着塗装時に被塗物を陽極として電圧を印加するので金属
の溶出が起こり、該溶出金属が電着により析出された樹
脂中のカルボン酸と反応してアルカリ性現像溶液に難溶
な塩を形成するために現像性が低下するという欠点があ
る。また印加する電圧を下げて金属の溶出を抑制すると
電着塗装法の特徴の一つであるつきまわり性が低下して
しまい、均一な薄膜が得られなくなる。However, with anionic electrodeposition type etching resists, metal is eluted because a voltage is applied using the object to be coated as an anode during electrodeposition, and the eluted metal reacts with the carboxylic acid in the resin deposited by electrodeposition, resulting in alkalinity. There is a drawback that developability is reduced due to the formation of salts that are poorly soluble in the developing solution. Furthermore, if the applied voltage is lowered to suppress metal elution, the throwing power, which is one of the characteristics of the electrodeposition coating method, will be reduced, making it impossible to obtain a uniform thin film.
一方、カチオン電着型エツチングレジストは、被塗物を
陰極として電圧を印加するので金属の溶出は起きないも
のの、硬化前のエツチングレジスト膜の粘着性が高く、
フォトマスクを密着させることができないため、露光を
行う際に解像度の著しい低下や塗膜の耐酸性の低下を招
き、更には塗膜の硬化が不充分になりやすい等の欠点が
ある。On the other hand, with cationic electrodeposition type etching resists, a voltage is applied using the object to be coated as a cathode, so metal elution does not occur, but the etching resist film is highly sticky before curing.
Since the photomask cannot be brought into close contact with the photomask, there are disadvantages such as a significant decrease in resolution and a decrease in the acid resistance of the coating film during exposure, and furthermore, the coating film tends to be insufficiently cured.
〈発明が解決しようとする課題〉
したがって本発明の目的は、高感度、高解像度を有し、
また基板上に薄膜を均一に塗布でき、配線パターンの微
細化が可能な電着型エツチングレジストを提供すること
にある。<Problem to be solved by the invention> Therefore, an object of the present invention is to have high sensitivity and high resolution,
Another object of the present invention is to provide an electrodeposition type etching resist that allows a thin film to be uniformly applied onto a substrate and allows miniaturization of wiring patterns.
く課題を解決するための手段〉
本発明によれば、（Ａ）二級アミンと、アクリル酸及び
／又はメタクリル酸とを付加したエポキシ化液状ポリブ
タジェンに、不飽和基含有イソシアナート化合物を反応
させて得られる樹脂１００重量部、（Ｂ）アクリロイル
基含有化合物及び／又はメタクリロイル基含有化合物Ｏ
〜５０重量部および（Ｃ）感光剤０．５〜２０重量部を
含有してなるカチオン電着型ネガ型エッチングレジス１
、組成物が提供される。According to the present invention, (A) an epoxidized liquid polybutadiene to which a secondary amine and acrylic acid and/or methacrylic acid have been added is reacted with an unsaturated group-containing isocyanate compound. (B) acryloyl group-containing compound and/or methacryloyl group-containing compound O
Cationic electrodeposition type negative etching resist 1 containing ~50 parts by weight and 0.5 to 20 parts by weight of (C) photosensitizer
, a composition is provided.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明のカチオン電着型ネガ型エツチングレジスト組成
物は、（Ａ）特定の樹脂（以下、成分（Ａ）と称す）、
（Ｂ）アクリロイル基含有化合物及び／又はメタクリロ
イル基含有化合物（以下、成分（Ｂ）と称す）および（
Ｃ）感光剤（以下、成分（Ｃ）と称す）を特定配合割合
で含有してなることを特徴とする。The cationic electrodeposition type negative etching resist composition of the present invention comprises (A) a specific resin (hereinafter referred to as component (A));
(B) Acryloyl group-containing compound and/or methacryloyl group-containing compound (hereinafter referred to as component (B)) and (
C) It is characterized by containing a photosensitizer (hereinafter referred to as component (C)) in a specific blending ratio.
本発明の成分（Ａ）は、二級アミンと、アクリル酸及び
／又はメタクリル酸とを付加したエポキシ化液状ポリブ
タジェンに、不飽和基含有イソシアナートを反応させて
得られる樹脂であって、好ましくは数平均分子量が、６
００〜１００００、特に好ましくは７００〜５０００の
樹脂である。Component (A) of the present invention is a resin obtained by reacting an unsaturated group-containing isocyanate with an epoxidized liquid polybutadiene to which a secondary amine and acrylic acid and/or methacrylic acid have been added, and is preferably a resin. Number average molecular weight is 6
00 to 10,000, particularly preferably 700 to 5,000.
本発明において、成分（Ａ）の原料成分であるエポキシ
化液状ポリブタジェンとしては、数平均分子量が好まし
くは５００〜５０００、特に好ましくは７００〜３００
０であって、ビニル結合を通常５０％以上含有する液状
ポリブタジェンを、公知の方法、例えば過酢酸若しくは
過酸化水素−ギ酸等を用いてエポキシ化することによっ
て得られる化合物を好ましく挙げることができ、また市
販のエポキシ化液状ポリブタジェンをそのまま用いるこ
ともできる。前記エポキシ化液状ポリブタジェンに含ま
れるオキシラン酸素量は、好ましくは３〜１２重量％、
特に５〜１０重量％であるのが好ましい。In the present invention, the epoxidized liquid polybutadiene, which is a raw material component of component (A), preferably has a number average molecular weight of 500 to 5000, particularly preferably 700 to 300.
Preferred examples include compounds obtained by epoxidizing a liquid polybutadiene containing 0 and usually containing 50% or more of vinyl bonds using a known method such as peracetic acid or hydrogen peroxide-formic acid. Moreover, commercially available epoxidized liquid polybutadiene can also be used as it is. The amount of oxirane oxygen contained in the epoxidized liquid polybutadiene is preferably 3 to 12% by weight,
In particular, it is preferably 5 to 10% by weight.
前記エポキシ化液状ポリブタジェンに付加する二級アミ
ンとしては、例えばジメチルアミン、ジエチルアミン、
ジブチルアミン等のジアルキルアミン類；メチルエタノ
ールアミン、ジェタノールアミン等のアルカノールアミ
ン類等を好ましく挙げることができる。前記二級アミン
の付加量は、そのアミン価がエポキシ化液状ポリブタジ
ェン１００ｇに対して、好ましくは５０〜３５０ＩＩＩ
ｒｎｏＱ、特に好ましくは８０〜２５０ｍｒａｏＱであ
る。二級アミンの付加量が５０ｍｍｏΩ未満の場合には
、水溶性や水分散性が不良となり、３５０ｍｍｏＱを超
えると硬化後のエツチング液に対する耐性が悪くなるの
で好ましくない。前記二級アミンをエポキシ化液状ポリ
ブタジェンに付加反応させるには、例えばヒドロキシル
基含有化合物を含む溶媒中において、好ましくは反応温
度１００〜２００℃。Examples of the secondary amine added to the epoxidized liquid polybutadiene include dimethylamine, diethylamine,
Preferable examples include dialkylamines such as dibutylamine; alkanolamines such as methylethanolamine and jetanolamine. The amount of the secondary amine added is preferably such that the amine value thereof is 50 to 350 III per 100 g of epoxidized liquid polybutadiene.
rnoQ, particularly preferably 80 to 250 mraoQ. If the amount of secondary amine added is less than 50 mmoQ, the water solubility and water dispersibility will be poor, and if it exceeds 350 mmoQ, the resistance to etching liquid after curing will be undesirable. In order to cause the addition reaction of the secondary amine to the epoxidized liquid polybutadiene, the reaction temperature is preferably 100 to 200°C in a solvent containing a hydroxyl group-containing compound, for example.
特に好ましくは１３０〜１７０℃にて、２〜１０時間反
応させることにより行なうことができる。Particularly preferably, the reaction can be carried out at 130 to 170°C for 2 to 10 hours.
前記ヒドロキシル基含有化合物としては、例えばエタノ
ール、イソプロピルアルコール、ブタノール、エチレン
グリコールモノエチルエーテル、エチレングリコールモ
ノブチルエーテル、エチレングリコールモノヘキシルエ
ーテル、エチレングリコールモノフェニルエーテル、プ
ロピレングリコールモノフェニルエーテル、メトキシブ
タノール、メチルエタノールアミン、ジェタノールアミ
ン等のアルカノールアミン類などを好ましく挙げること
ができ、前記ヒドロキシル基含有化合物と共に用いるこ
とができる溶媒としては、例えばトルエン、ジオキサン
、酢酸エトキシエチル、ジエチレングリコールジメチル
エーテルなどを好ましく挙げることができる。この際前
記ヒドロキシル基含有化合物と前記溶媒との混合割合は
、付加する二級アミンの種類、量及び反応温度等によっ
て任意に決定することができる。Examples of the hydroxyl group-containing compound include ethanol, isopropyl alcohol, butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methoxybutanol, and methyl ethanol. Preferred examples include alkanolamines such as amines and jetanolamine, and examples of solvents that can be used with the hydroxyl group-containing compound include toluene, dioxane, ethoxyethyl acetate, diethylene glycol dimethyl ether, and the like. . At this time, the mixing ratio of the hydroxyl group-containing compound and the solvent can be arbitrarily determined depending on the type and amount of the secondary amine to be added, the reaction temperature, etc.
本発明において、前記エポキシ化液状ポリブタジェンに
、アクリル酸及び／又はメタクリル酸（以下、（メタ）
アクリル酸と称す）を付加させる際の付加量は、特に限
定されるものではなく、例えば前記二級アミンを最初に
付加した場合には、二級アミンが付加されたエポキシ化
液状ポリブタジェン１００ｇに対して好ましくは５０〜
３００ｍｍｏ Ｑ、更に好ましくは５０〜２５０ｍｍｏ
ｎである。In the present invention, acrylic acid and/or methacrylic acid (hereinafter, (meth)) is added to the epoxidized liquid polybutadiene.
The amount of acrylic acid added is not particularly limited. For example, if the secondary amine is added first, the amount of acrylic acid added is not particularly limited. For example, if the secondary amine is added first, preferably from 50 to
300mmo Q, more preferably 50-250mmo
It is n.
前記（メタ）アクリル酸の付加量が５０ｍ１ＩｌｏＱ未
満の場合には、硬化後の架橋密度が小さく現像性が低下
し、３００ｍｍｏＱを超えると付加反応時にゲル化が生
しるため好ましくない。この際二級アミン及び（メタ）
アクリル酸の付加反応順序は特に限定されるものではな
い。前記（メタ）アクリル酸の付加反応を行なう際の反
応温度は、１００〜１８０℃とするのが好ましく、反応
時間は２〜１０時間とするのが好ましい。反応温度が１
００℃未満の場合には、反応が十分に進行せず、１８０
℃を超えるとゲル化が生じるために好ましくない。更に
該付加反応は、溶媒を用いて行なうことができる。該溶
媒としては、例えば前記ヒドロキシル基含有化合物、ト
ルエン、ジオキサン、ジエチレングリコールジメチルエ
ーテル、酢酸エトキシエチル等を好ましく挙げることが
でき、また二級アミンの付加反応において用いた溶媒を
そのまま用いることもできる。前記付加反応に際しては
、好ましくは例えばハイドロキノン、２，６−ジーｔ−
ブチル−４−メチルフェノール、を−ブチルカテコール
、ｐ−ベンゾキノン、トリフェニルホスフィン、フェノ
チアジン、Ｎ−ニトロフェニルアミン等の重合防止剤を
用いて行なうのが好ましい。該重合防止剤の配合割合は
、反応溶液全体に対して好ましくは、０．０１〜１重量
％の範囲である。更にまた反応に際して、より反応を速
やかに行う目的で三級アミン、三級ホスフィン等を添加
してもよい。If the amount of (meth)acrylic acid added is less than 50 m1IloQ, the crosslinking density after curing will be low and developability will deteriorate, and if it exceeds 300 mmoQ, gelation will occur during the addition reaction, which is not preferable. In this case, secondary amine and (meth)
The order of addition reaction of acrylic acid is not particularly limited. The reaction temperature during the addition reaction of (meth)acrylic acid is preferably 100 to 180°C, and the reaction time is preferably 2 to 10 hours. reaction temperature is 1
If the temperature is below 00°C, the reaction will not proceed sufficiently and the temperature will exceed 180°C.
If the temperature exceeds .degree. C., gelation will occur, which is not preferable. Furthermore, the addition reaction can be carried out using a solvent. Preferred examples of the solvent include the aforementioned hydroxyl group-containing compounds, toluene, dioxane, diethylene glycol dimethyl ether, ethoxyethyl acetate, and the like, and the solvent used in the addition reaction of the secondary amine can also be used as is. In the addition reaction, for example, hydroquinone, 2,6-di-t-
It is preferable to use a polymerization inhibitor such as butyl-4-methylphenol, -butylcatechol, p-benzoquinone, triphenylphosphine, phenothiazine, N-nitrophenylamine, or the like. The blending ratio of the polymerization inhibitor is preferably in the range of 0.01 to 1% by weight based on the entire reaction solution. Furthermore, during the reaction, tertiary amines, tertiary phosphine, etc. may be added for the purpose of speeding up the reaction.
本発明の成分（Ａ）において、前記エポキシ化液状ポリ
ブタジェンと反応させる不飽和基含有イソシアナート化
合物は、分子中にそれぞれ少なくとも１個のイソシアナ
ート基と不飽和基とを有する化合物であれば良く、具体
的には例えば、イソシアナートエチルメタクリレート、
イソシアナートエチルアクリレート又はジイソシアナー
ト化合物と不飽和モノアルコールとの反応物等を好まし
く挙げることができる。前記ジイソシアナート化合物と
不飽和モノアルコールとの反応物としては、２．４−ト
リレンジイソシアナート、２，４−トリレンジイソシア
ナートと２．６−トリレンジイソシアナートとの混合物
、パラフェニレンジイソシアナート、ジフェニルメタン
ジイソシアナート、１．５−ナフチレンジイソシアナー
ト、キシリレンジイソシアナート、水素化キシリレンジ
イソシアナート、ヘキサメチレンジイソシアナート、イ
ンホロンジイソシアナート及びこれらの混合物等からな
る群より選択されるジイソシアナート化合物と、２−ヒ
ドロキシエチル（メタ）アクリレート、２−ヒドロキシ
プロピル（メタ）アクリレート等又は（メタ）アクリル
酸等の不飽和カルボン酸及びアルキレンモノエポキサイ
ドの反応物等の不飽和モノアルコールとを反応させて得
られる化合物等を好ましく用いることができる。またこ
の際前記ジイソシアナート化合物と前記不飽和モノアル
コールとの仕込みモル比は１：１．１〜１．５とするの
が好ましい。前記不飽和モノアルコールの仕込みモル比
が１．１未満だとジイソシアナート化合物が多量残存し
、１．５を超えるとイソシアナート基が少なくなり、好
ましくない。In the component (A) of the present invention, the unsaturated group-containing isocyanate compound to be reacted with the epoxidized liquid polybutadiene may be a compound each having at least one isocyanate group and an unsaturated group in the molecule, Specifically, for example, isocyanatoethyl methacrylate,
Preferred examples include isocyanate ethyl acrylate or a reaction product of a diisocyanate compound and an unsaturated monoalcohol. The reaction product of the diisocyanate compound and unsaturated monoalcohol includes 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and paraphenylene diisocyanate. Isocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, mixtures thereof, etc. An unsaturated monomer such as a reaction product of a diisocyanate compound and an unsaturated carboxylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid, and an alkylene monoepoxide. Compounds obtained by reacting with alcohol can be preferably used. Further, at this time, it is preferable that the molar ratio of the diisocyanate compound and the unsaturated monoalcohol to be charged is 1:1.1 to 1.5. If the molar ratio of the unsaturated monoalcohol is less than 1.1, a large amount of diisocyanate compounds will remain, and if it exceeds 1.5, the number of isocyanate groups will decrease, which is not preferable.
前記ジイソシアナート化合物と不飽和モノアルコールと
の反応に際しては、無溶媒でも十分に反応は進行するが
、好ましくはジエチレングリコールジメチルエーテル、
酢酸エトキシエチル等の溶媒を用いることもできる。該
反応の反応温度は、好ましくは３０〜２００℃に加熱す
るだけで十分に進行する。この際３０℃未満では反応に
長時間を要し、２００’Ｃを超えるとゲル化が生じるの
で好ましくない。更に該反応を速やかに進行させる目的
で、三級アミンや錫系化合物を添加してもよい。In the reaction between the diisocyanate compound and the unsaturated monoalcohol, the reaction proceeds satisfactorily even without a solvent, but preferably diethylene glycol dimethyl ether,
Solvents such as ethoxyethyl acetate can also be used. The reaction temperature is preferably 30 to 200°C, and the reaction can proceed satisfactorily. In this case, if the temperature is lower than 30°C, the reaction will take a long time, and if the temperature exceeds 200°C, gelation will occur, which is not preferable. Furthermore, a tertiary amine or a tin-based compound may be added for the purpose of speeding up the reaction.
本発明に用いる成分（Ａ）を調製する際の前記二級アミ
ン及び（メタ）アクリル酸を付加したエポキシ化液状ポ
リブタジェン重合体あるいは共重合体と、不飽和基含有
イソシアナート化合物との仕込み比は該重合体あるいは
共重合体中のヒドロキシル基１当量に対して、不飽和基
含有イソシアナート化合物のイソシアナート基が、好ま
しくは１当量以下、特に好ましくは０．４〜１当量とな
るように仕込むのが好ましい。この際イソシアナート基
が１当量を超えると、生成物中にイソシアナート基が残
存するため好ましくない。またこの際の反応溶媒として
は、ジエチレングリコールジメチルエーテル、酢酸エト
キシエチル等を好ましく用いることができ、好ましくは
３０〜２００℃に加熱するだけで十分に反応させること
ができる。When preparing component (A) used in the present invention, the charging ratio of the epoxidized liquid polybutadiene polymer or copolymer added with the secondary amine and (meth)acrylic acid and the unsaturated group-containing isocyanate compound is The amount of isocyanate groups in the unsaturated group-containing isocyanate compound is preferably 1 equivalent or less, particularly preferably 0.4 to 1 equivalent, relative to 1 equivalent of hydroxyl groups in the polymer or copolymer. is preferable. In this case, if the amount of isocyanate groups exceeds 1 equivalent, the isocyanate groups will remain in the product, which is not preferable. Further, as the reaction solvent at this time, diethylene glycol dimethyl ether, ethoxyethyl acetate, etc. can be preferably used, and the reaction can be carried out sufficiently simply by heating preferably to 30 to 200°C.
この際３０℃未満の場合には反応に長時間を要し、２０
０℃を超えるとゲル化が生じるので好ましくない。更に
この反応を行う際においては、−周速やかに反応を進行
させる目的で、三級アミンや錫系化合物を添加してもよ
い。また、前記重合体あるいは共重合体を製造する際に
ヒドロキシル基含有化合物を使用した場合には、該ヒド
ロキシル基含有化合物を除去しておくのが好ましい。At this time, if the temperature is lower than 30°C, the reaction will take a long time, and
If the temperature exceeds 0°C, gelation will occur, which is not preferable. Furthermore, when carrying out this reaction, a tertiary amine or a tin-based compound may be added for the purpose of rapidly advancing the reaction. Further, when a hydroxyl group-containing compound is used in producing the polymer or copolymer, it is preferable to remove the hydroxyl group-containing compound.
本発明において成分（Ｂ）として用いられるアクリロイ
ル基含有化合物及び／又はメタクリロイル基含有化合物
は、電着析出塗膜の流動性を改善し、硬化塗膜の架橋密
度を高くするなどの目的で必要により添加される成分で
ある。前記成分（Ｂ）としては、分子中に（メタ）アク
リロイル基を含有する化合物であって、光及び熱によっ
て重合、硬化することのできる七ツマ−あるいはオリゴ
マー類であれば特に限定されるものではないが具体的に
は、例えばヒドロキシエチル（メタ）アクリレート、エ
チレングリコールジ（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、ペンタエリス
リトールトリ （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、ビス（５−アク
リロイルオキシ−３−オキサペンチル）フタレート、ト
リス（アクリロイルオキシエチル）インシアヌレート、
低分子量エポキシ化合物と（メタ）アクリル酸との反応
物などを好ましく挙げることができ、使用に際しては単
独若しくは混合物として用いることができる。この際オ
リゴマー類を用いる場合には、その数平均分子量が８０
〜３０００、特に１００〜１００ｏのものを用いるのが
好ましい。前記成分（Ｂ）の配合割合は成分（Ａ）１０
０重量部に対して０〜５０重量部の範囲であり、好まし
くは０〜３０重量部の範囲である。成分（Ｂ）の配合割
合が５０重量部を超えると安定な水分散が困難となり、
また電着析出塗膜に粘着性が出るので好ましくない。The acryloyl group-containing compound and/or methacryloyl group-containing compound used as component (B) in the present invention may be used as necessary for the purpose of improving the fluidity of the electrodeposited coating film and increasing the crosslinking density of the cured coating film. It is an added ingredient. The component (B) is not particularly limited as long as it is a compound containing a (meth)acryloyl group in the molecule and can be polymerized and cured by light and heat. However, specific examples include hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bis (5-acryloyloxy-3-oxapentyl) phthalate, tris(acryloyloxyethyl) in cyanurate,
Preferred examples include a reaction product of a low molecular weight epoxy compound and (meth)acrylic acid, which can be used alone or as a mixture. In this case, when oligomers are used, their number average molecular weight is 80
-3000, especially preferably 100-100o. The blending ratio of component (B) is component (A) 10
The amount is in the range of 0 to 50 parts by weight, preferably 0 to 30 parts by weight. If the blending ratio of component (B) exceeds 50 parts by weight, stable water dispersion becomes difficult;
Further, the electrodeposited coating film becomes sticky, which is not preferable.
本発明の成分（Ｃ）として使用される感光剤としては、
従来公知の光重合開始剤を用いればよく。As the photosensitizer used as component (C) of the present invention,
A conventionally known photopolymerization initiator may be used.
具体的には例えば、ベンゾイン、ベンゾフェノン、ベン
ゾインメチルエーテル、ベンゾインエチルエーテル、ベ
ンジル、ミヒラーケトン等を好ましく挙げることができ
る。前記成分（Ｃ）の配合割合は成分（Ａ）１００重量
部に対し０．５〜２０重量部、好ましくは１〜１０重量
部である。成分（Ｃ）の配合割合が０．５重量部未満の
場合には硬化性が不足し、また２０重量部を超えると硬
化塗膜の強度が低下し、経済的にも不経済であるので使
用できない。また必要によっては増感剤を用いることも
できる。Specifically, preferred examples include benzoin, benzophenone, benzoin methyl ether, benzoin ethyl ether, benzyl, and Michler's ketone. The blending ratio of component (C) is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (A). If the blending ratio of component (C) is less than 0.5 parts by weight, curability will be insufficient, and if it exceeds 20 parts by weight, the strength of the cured coating will decrease, making it uneconomical to use. Can not. A sensitizer may also be used if necessary.
本発明の組成物には、前記（Ａ）、（Ｂ）及び（Ｃ）成
分の他に、流動性や表面状態を改善・抑制するために溶
剤や顔料などの添加剤を添加してもよい。該溶剤として
は例えば、エチレングリコールモノエチルエーテル、エ
チレングリコールモノブチルエーテル、エチレングリコ
ールモノヘキシルエーテル、エチレングリコールモノフ
ェニルエーテル、プロピレングリコールモノフェニルエ
ーテル、メトキシブタノール、ジエチレングリコールジ
メチルエーテル、トリエチレングリコールジメチルエー
テル、ジアセトンアルコール、メチルエチルケトンなど
を好ましく挙げることができ、顔料としては、例えばケ
イ酸アルミニウム、タルク、酸化チタン、シリカ等の無
機顔料や着色を目的としたフタロシアニン系顔料などを
好ましく挙げることができる。また、添加剤の添加量は
、電着塗装条件、乾燥条件及び後工程の現像条件等によ
り任意に決定することができる。In addition to the components (A), (B), and (C), additives such as solvents and pigments may be added to the composition of the present invention in order to improve or suppress fluidity and surface condition. . Examples of the solvent include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methoxybutanol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diacetone alcohol, Preferred examples include methyl ethyl ketone, and examples of pigments include inorganic pigments such as aluminum silicate, talc, titanium oxide, and silica, and phthalocyanine pigments for coloring purposes. Further, the amount of the additive to be added can be arbitrarily determined depending on the electrodeposition coating conditions, drying conditions, post-process development conditions, and the like.
本発明のカチオン電着型ネガ型エツチングレジスト組成
物を使用する際には、電着に適するように、前記カチオ
ン電着型ネガ型エツチングレジスト組成物を水分散液と
して用いるのが好ましい。When using the cationic electrodeposition type negative etching resist composition of the present invention, it is preferable to use the cationic electrodeposition type negative etching resist composition as an aqueous dispersion so that it is suitable for electrodeposition.
前記水分散液を調製するには、成分（Ａ ）中のアミノ
基１当量に対して、好ましくは０．１〜１．０当量、特
に好ましくは０．２〜０．８当量のギ酸、酢酸、プロピ
オン酸およびこれらの混合物等からなる群より選択され
る有機酸等を添加し、組成物を中和した後、混合撹拌し
、分散する等して得ることができる。前記中和する際の
反応温度は特に限定されるものではなく、常温で十分に
反応は進行する。電着塗装および乾燥は公知方法により
行われる。また露光は紫外線を多量に発生できる装置で
あればよく、例えば、高圧水銀灯、超高圧水銀灯、メタ
ルハライドランプ等を光源に用いる。現像は酸性水溶液
を用いて行われ、使用する酸の種類や濃度は配線パター
ンの微細化度や現像時間・温度等によって適宜選定でき
る。To prepare the aqueous dispersion, preferably 0.1 to 1.0 equivalents, particularly preferably 0.2 to 0.8 equivalents of formic acid or acetic acid are added per equivalent of amino group in component (A). The composition can be obtained by adding an organic acid selected from the group consisting of , propionic acid, a mixture thereof, etc., neutralizing the composition, mixing and stirring, and dispersing. The reaction temperature during the neutralization is not particularly limited, and the reaction proceeds sufficiently at room temperature. Electrodeposition coating and drying are performed by known methods. Further, the exposure may be performed using any device that can generate a large amount of ultraviolet rays; for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or the like is used as a light source. Development is performed using an acidic aqueous solution, and the type and concentration of the acid used can be appropriately selected depending on the degree of fineness of the wiring pattern, development time, temperature, etc.
なお、本発明の組成物は必要によっては水分散液とせず
に上記の溶剤等に溶解してデイツプコート法、ロールコ
ート法、カーテンコート法、スクリーン印刷法等により
塗膜を形成し、露光・現像を行ってもよい。The composition of the present invention may not be made into an aqueous dispersion, but may be dissolved in the above-mentioned solvents to form a coating film by a dip coating method, a roll coating method, a curtain coating method, a screen printing method, etc., and then exposed to light and developed. You may do so.
〈発明の効果〉
本発明のカチオン電着型ネガ型エツチングレジスト組成
物は、高感度及び高解像度を有し、しかも電着塗装法を
用いているので基板上に均一な薄膜を塗布することがで
き、且つ露光前の塗膜に粘着性がないのでフォトマスク
を密着させることができる。従って、微細な配線パター
ンが要求されるプリント基板用エツチングレジストとし
て有用ある。<Effects of the Invention> The cationic electrodeposition type negative etching resist composition of the present invention has high sensitivity and high resolution, and since it uses an electrodeposition coating method, it is possible to coat a uniform thin film on a substrate. Moreover, since the coating film before exposure has no tackiness, it is possible to adhere the photomask closely. Therefore, it is useful as an etching resist for printed circuit boards that require fine wiring patterns.
〈実施例〉
以下に本発明を実施例によって具体的に説明するが、本
発明はこれらに限定されるものではない。<Examples> The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.
エポキシ化液状ポリブタジェン（日本石油化学（株）製
、商品名ｒＥ−”１８００−６．５Ｊ 、 数平均分子
量１８００、オキシラン酸素量６，５％）１０００ｇと
エチレングリコールモノブチルエーテル２６４ｇを２Ｑ
オートクレーブに仕込み、系内を窒素置換したのち、ジ
メチルアミン５７．２ｇを加え、１６０”Ｃで５時間反
応を行った。次に反応系を常圧にして未反応ジメチルア
ミンを留去し、ジメチルアミン付加樹脂溶液を得た。該
樹脂溶液のアミン価は９２．２ミリモル／１００ｇで固
形分濃度ば８０ｗｔ％であった。1000 g of epoxidized liquid polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name rE-"1800-6.5J, number average molecular weight 1800, oxirane oxygen content 6.5%) and 264 g of ethylene glycol monobutyl ether were added to 2Q
After charging the autoclave and purging the system with nitrogen, 57.2 g of dimethylamine was added and the reaction was carried out at 160"C for 5 hours.Then, the reaction system was brought to normal pressure, unreacted dimethylamine was distilled off, and dimethyl An amine-added resin solution was obtained.The amine value of the resin solution was 92.2 mmol/100 g, and the solid content concentration was 80 wt%.
次いで得られた樹脂溶液１０００ｇにアクリル酸１１５
．３ｇ、ハイドロキノン５．６ｇおよびトリフェニルホ
スフィン３．３ｇを添加し、１３５℃で３．５時間反応
させた後、減圧下にてエチレングリコールモノブチルエ
ーテルおよび未反応アクリル酸を留去し、アミンおよび
アクリル酸付加エポキシ化ポリブタジェン（以下（ａ−
１）と称す）を得た。Next, 115 g of acrylic acid was added to 1000 g of the obtained resin solution.
．． After adding 3g of hydroquinone, 5.6g of hydroquinone, and 3.3g of triphenylphosphine and reacting at 135°C for 3.5 hours, ethylene glycol monobutyl ether and unreacted acrylic acid were distilled off under reduced pressure. Acid-added epoxidized polybutadiene (hereinafter (a-
1) was obtained.
イソシアナート 八 の４
温度計、撹拌装置、冷却管および滴下漏斗の付いた加熱
および冷却可能な１０１００Ｏの丸底フラスコに２．４
−）−リレンジイソシアナート３４８．４ｇおよびジエ
チレングリコールジメチルエーテル２５８．８ｇを仕込
み、５０’Ｃに加熱後、２−ヒドロキシエチルアクリレ
ート２５５．４ｇを滴下漏斗から滴下した。この際１１
００ｐｐのバラベンゾキノンも添加した。２−ヒドロキ
シエチルアクリレートの滴下により発熱が見られるが、
必要に応じて冷却し５０℃に保った。２−ヒドロキシエ
チルアクリレートの滴下終了後、７０℃まで昇温し、同
温度で３時間反応させ、赤外線吸収スペクトル分析によ
りイソシアナート基の吸収強度が反応開始前のほぼ１／
２になったことを確認した後、冷却し不飽和イソシアナ
ート化合物（以下（ａ−２）と称す）を得た。Isocyanate 8 to 4 2.4 in a heatable and coolable 10100 O round bottom flask equipped with a thermometer, stirrer, condenser and addition funnel.
-)-348.4 g of lylene diisocyanate and 258.8 g of diethylene glycol dimethyl ether were charged, and after heating to 50'C, 255.4 g of 2-hydroxyethyl acrylate was added dropwise from the dropping funnel. At this time 11
00 pp of rosebenzoquinone was also added. Heat generation is observed when 2-hydroxyethyl acrylate is added dropwise, but
It was cooled and maintained at 50°C as necessary. After the dropwise addition of 2-hydroxyethyl acrylate was completed, the temperature was raised to 70°C, and the reaction was allowed to proceed at the same temperature for 3 hours. Infrared absorption spectrum analysis revealed that the absorption intensity of the isocyanate group was approximately 1/1 of that before the start of the reaction.
After confirming that it became 2, it was cooled to obtain an unsaturated isocyanate compound (hereinafter referred to as (a-2)).
Ａ−１のム
（ａ−１）５００ｇをジエチレングリコールジメチルエ
ーテル２１４．３ｇに溶解し、（ａ−２）５００ｇ （
（ａ−１）中のヒドロキシル基１当量に対してイソシア
ナート基００ｇ当量）を４０℃にて滴下し、さらに同温
度で３０分反応して、赤外線吸収スペクトル分析により
イソシアナート基が消失したことを確認し、（ａ−１）
に（ａ−２）を付加した化合物（以下成分（Ａ−１）と
称す）を得た。500 g of A-1 (a-1) was dissolved in 214.3 g of diethylene glycol dimethyl ether, and 500 g of (a-2) (
(00 g equivalent of isocyanate group per 1 equivalent of hydroxyl group in (a-1)) was added dropwise at 40°C, and further reacted for 30 minutes at the same temperature, and the isocyanate group disappeared by infrared absorption spectrum analysis. Check (a-1)
A compound (hereinafter referred to as component (A-1)) in which (a-2) was added to was obtained.
豆炭叢ｌ
アミンおよびアクリル エポキシ ボリブ克乏１受
θη色戊
エポキシ化液状ポリブタジェン（日本石油化学（株）製
、商品名ｒＥ−１０００−８Ｊ 、数平均分子量１００
０、オキシラン酸素量８％）１０００ｇとエチレングリ
コールモノブチルエーテル２８２ｇを２ρオートクレー
ブに仕込み、系内を窒素置換したのち、ジメチルアミン
１２７．０ｇを加え、１６０℃で５時間反応を行った。Soybean charcoal Amine and acrylic epoxy Bolibu-containing 1st grade θη color Epoxidized liquid polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name rE-1000-8J, number average molecular weight 100
1000 g of oxirane (8% oxygen content) and 282 g of ethylene glycol monobutyl ether were placed in a 2ρ autoclave, and after purging the system with nitrogen, 127.0 g of dimethylamine was added and the reaction was carried out at 160° C. for 5 hours.
次いで反応系を常圧にして未反応ジメチルアミンを留去
し、さらに減圧下にてエチレングリコールモノブチルエ
ーテルを留去してアミン付加樹脂を得た。該樹脂のアミ
ン価は２３０．０ミリモルフ１００ｇであった。Next, the reaction system was brought to normal pressure, unreacted dimethylamine was distilled off, and ethylene glycol monobutyl ether was further distilled off under reduced pressure to obtain an amine-added resin. The amine value of the resin was 230.0 mmolf 100 g.
次いで得られた樹脂５００ｇにアクリル酸５４．１ｇ、
ハイドロキノン２．７ｇ、トリフェニルホスフィン１．
７ｇおよびジエチレングリコールジメチルエーテル２３
７．５ｇを加え、１３５℃で３．５時間反応させ、アミ
ンおよびアクリル酸付加エポキシ化ポリブタジェン（以
下（ａ−３）と称す）を得た。Next, 54.1 g of acrylic acid was added to 500 g of the obtained resin,
Hydroquinone 2.7g, triphenylphosphine 1.
7g and diethylene glycol dimethyl ether 23
7.5 g was added and reacted at 135° C. for 3.5 hours to obtain amine and acrylic acid-added epoxidized polybutadiene (hereinafter referred to as (a-3)).
イソシアナート化ム の八
温度計、撹拌装置、冷却管および滴下漏斗の付いた加熱
および冷却可能な１０１００Ｏの丸底フラスコに２．４
−トリレンジイソシアナート３４８．４ｇおよびジエチ
レングリコールジメチルエーテル２７３．７ｇを仕込み
、５０℃に加熱後、２−ヒドロキシエチルアクリレート
２９０．３ｇを滴下漏斗から滴下した。この際１１００
ｐｐのバラベンゾキノンも添加した。２−ヒドロキシエ
チルアクリレートの滴下により発熱が見られるが、必要
に応じて冷却し５０℃に保った。２−ヒドロキシエチル
アクリレートの滴下終了後、７０℃まで昇温し、同温度
で３時間反応させた後、冷却し、不飽和イソシアナート
化合物（以下（ａ−４）と称す）を得た。2.4 in a heatable and coolable 10100 O round bottom flask equipped with a thermometer, stirrer, condenser and addition funnel.
348.4 g of -tolylene diisocyanate and 273.7 g of diethylene glycol dimethyl ether were charged, and after heating to 50°C, 290.3 g of 2-hydroxyethyl acrylate was added dropwise from the dropping funnel. At this time 1100
pp of rosebenzoquinone was also added. Although heat generation was observed due to the dropwise addition of 2-hydroxyethyl acrylate, the temperature was maintained at 50°C by cooling as necessary. After the completion of the dropwise addition of 2-hydroxyethyl acrylate, the temperature was raised to 70°C, and the mixture was reacted at the same temperature for 3 hours, and then cooled to obtain an unsaturated isocyanate compound (hereinafter referred to as (a-4)).
Ａ−２のム
（ａ−３）７５０ｇと（ａ−４）７２９．２ｇ（（ａ−
３）中のヒドロキシル基１当量に対してイソシアナート
基１当量）とを合成例１と同様にして反応を行い（ａ−
３）に（ａ−４）を付加した化合物（以下成分（Ａ−２
）と称す）を得た。Mu (a-3) 750g and (a-4) 729.2g ((a-
(1 equivalent of isocyanate group per equivalent of hydroxyl group in 3)) in the same manner as in Synthesis Example 1 (a-
A compound obtained by adding (a-4) to 3) (hereinafter referred to as component (A-2)
) was obtained.
皇戊■且
エポキシ化液状ポリブタジェン（日本石油化学（株）製
、商品名ｒＥ−１０００−８」）１０００ｇとエチレン
グリコールモノブチルエーテル２６４ｇを２Ｑオートク
レーブに仕込み、系内を窒素置換したのち、ジメチルア
ミン５７．２ｇを加え、１６０℃で６時間反応を行った
。次いで反応系を常圧にして未反応ジメチルアミンを留
去し、さらに減圧下にてエチレングリコールモノブチル
エーテルを留去してアミン付加樹脂を得た。該樹脂のア
ミン価は１１５ミリモルフ１００ｇであった。1,000 g of epoxidized liquid polybutadiene (manufactured by Japan Petrochemical Co., Ltd., trade name: rE-1000-8) and 264 g of ethylene glycol monobutyl ether were placed in a 2Q autoclave, and after purging the system with nitrogen, 57 g of dimethylamine was added. .2g was added and the reaction was carried out at 160°C for 6 hours. Next, the reaction system was brought to normal pressure, unreacted dimethylamine was distilled off, and ethylene glycol monobutyl ether was further distilled off under reduced pressure to obtain an amine-added resin. The amine value of the resin was 115 mmolf, 100 g.
次に、得られた樹脂５００ｇにアクリル酸１２６．１ｇ
、ハイドロキノン３．１ｇ、トリフェニルホスフィン１
．８ｇおよびジエチレングリコールジメチルエーテル２
７０．４ｇを加え、１３５℃で４時間反応させたところ
、著しい粘度上昇が見られ、アミンおよびアクリル酸付
加エポキシ化ポリブタジェン（以下成分（Ａ−３）と称
す）を得た。Next, 126.1 g of acrylic acid was added to 500 g of the obtained resin.
, hydroquinone 3.1g, triphenylphosphine 1
．． 8g and diethylene glycol dimethyl ether 2
When 70.4 g was added and reacted at 135° C. for 4 hours, a significant increase in viscosity was observed, and an epoxidized polybutadiene added with amine and acrylic acid (hereinafter referred to as component (A-3)) was obtained.
去」１」Ｌ
合成例１で得られた成分（Ａ−１）５００ｇに、感光剤
として商品名ｒＩｒｇａｃｕｒｅ ９０７Ｊチバガイ
ギ一社製（以下ｒＩｒｇａｃｕｒｅ９０７」と称す）２
５．２ｇおよび増感剤として商品名ｒＫＡＹＡＣＵＲＥ
ＤＥＴＸＪ日本化薬（株）製（以下、ｒＫＡＹＡＣ
ＵＲＥ ＤＥＴＸＪと称す）２．８ｇを加え、さらに
中和剤である酢酸１０．１ｇを加えて充分に撹拌し均一
化した後、脱イオン水１７９５ｇをゆっくりと加えなが
ら高速ミキサーで激しく混合し、水分散させて、固形分
濃度１５−ｔ％のカチオン電着型ネガ型エツチングレジ
スト水溶液を調製した。To 500 g of component (A-1) obtained in Synthesis Example 1, a photosensitizer with the trade name rIrgacure 907J manufactured by Ciba Geigi Co., Ltd. (hereinafter referred to as rIrgacure 907) 2 was added.
5.2g and the product name rKAYACURE as a sensitizer
DETXJ manufactured by Nippon Kayaku Co., Ltd. (rKAYAC
After adding 2.8 g of acetic acid (referred to as URE DETXJ) and further adding 10.1 g of acetic acid as a neutralizing agent and thoroughly stirring to homogenize, slowly add 1795 g of deionized water and mix vigorously with a high-speed mixer. A cationic electrodeposition type negative type etching resist aqueous solution having a solid content concentration of 15-t% was prepared by dispersing it.
失胤桝又
合成例２で得られた成分（Ａ−２）５００ｇに、感光剤
としてｒｌｒｇａｃｕｒｅ ９０７Ｊ２５．２ ｇお
よび増感剤としてｒＫＡＹＡＣＵＲＥＤＥＴＸＪ ２，
８ｇを加え、さらに中和剤である酢酸１１．３ｇを加え
て充分に撹拌し均一化した後、脱イオン水１７９４ｇを
ゆっくりと加えながら高速ミキサーで激しく混合し、水
分散させて、固形分濃度１５ｔｍｔ％のカチオン電着型
ネガ型エツチングレジスト水溶液を調製した。To 500 g of component (A-2) obtained in Synthesis Example 2, 25.2 g of rlrgacure 907J as a photosensitizer and rKAYACUREDETXJ 2 as a sensitizer were added.
After adding 8 g of acetic acid and 11.3 g of acetic acid as a neutralizing agent and thoroughly stirring to make it homogeneous, 1794 g of deionized water was slowly added and mixed vigorously with a high-speed mixer to disperse the water and determine the solid content concentration. A 15 tmt% cationic electrodeposition type negative etching resist aqueous solution was prepared.
失度五立
合成例２で得られた成分（Ａ−２）５００ｇ、成分（Ｂ
）として（商品名［アロニツクスＭ−３１５」東亜合成
化学（株）製）３５．０−ｇおよび感光剤としてｒｌｒ
ｇａｃｕｒｅ ９０７Ｊ２７．２ｇおよび増感剤とし
てｒＫＡＹＡＣＵＲＥＤＥＴＸＪ ３．Ｉｇを添加し、
さらに中和剤である酢酸１６．９ｇを加えて充分に撹拌
し均一化した後、脱イオン水１９８４ｇをゆっくりと加
えながら高速ミキサーで激しく混合し、水分散させて、
固形分濃度１５ｗｔ％のカチオン電着型ネガ型エツチン
グレジスト水溶液を調製した。500 g of component (A-2) obtained in Synthesis Example 2, component (B
) as (trade name [Aronix M-315] manufactured by Toagosei Kagaku Co., Ltd.) 35.0-g and rlr as a photosensitizer.
gacure 907J27.2g and rKAYACUREDETXJ as sensitizer 3. Add Ig,
Furthermore, after adding 16.9 g of acetic acid as a neutralizing agent and thoroughly stirring to homogenize, 1,984 g of deionized water was slowly added and mixed vigorously with a high-speed mixer to disperse the water.
A cationic electrodeposition type negative etching resist aqueous solution having a solid content concentration of 15 wt % was prepared.
坦敗鮭上
合成例１で得られた（ａ−１）５００ｇに感光剤として
ｒＩｒｇａｃｕｒｅ ９０７Ｊ ３６ｇおよび増感剤
としてｒＫＡＹＡｃＵＲＥ ＤＥＴＸＪ４、Ｏｇを加
え、さらに中和剤である酢酸２４．１ｇを加えて充分に
撹拌し均一化した後、脱イオン水２７６９ｇをゆっくり
と加えながら高速ミキサーで激しく混合し、水分散させ
て、固形分濃度１５ｔｎｔ％のカチオン電着型ネガ型エ
ツチングレジスト水溶液を調製した。Add 36 g of rIrgacure 907J as a photosensitizer and rKAYAcURE DETXJ4, Og as a sensitizer to 500 g of (a-1) obtained in Synthesis Example 1 on unfavorable salmon, and further add 24.1 g of acetic acid as a neutralizing agent. After stirring to homogenize, 2769 g of deionized water was slowly added and vigorously mixed using a high-speed mixer to disperse the mixture in water to prepare a cationic electrodeposition type negative etching resist aqueous solution having a solid content concentration of 15 tnt%.
比較例２
合成例３で得られた成分（Ａ−３）５００ｇに感光剤と
してｒＩｒｇａｃｕｒｅ ９０７Ｊ２５．２ ｇおよ
び増感剤としてｒＫＡＹＡＣＵＲＥＤＥＴＸＪ ２．８
ｇを加え、さらに中和剤である酢酸２１．３ｇを加えて
充分に撹拌し均一化した後、脱イオン水１７８４ｇをゆ
っくりと加えながら高速ミキサーで激しく混合し、水分
散させて、固形分濃度１５ｖｔ％のカチオン電着型ネガ
型エツチングレジスト水溶液を調製した。Comparative Example 2 25.2 g of rIrgacure 907J as a photosensitizer and 2.8 g of rKAYACUREDETXJ as a sensitizer were added to 500 g of component (A-3) obtained in Synthesis Example 3.
After adding 21.3 g of acetic acid as a neutralizing agent and thoroughly stirring to homogenize, 1784 g of deionized water was slowly added and mixed vigorously with a high-speed mixer to disperse the water and determine the solid content concentration. A 15 vt % cationic electrodeposition type negative etching resist aqueous solution was prepared.
Ｋ凱孤
実施例１，２．３および比較例１，２で調製したカチオ
ン電着型ネガ型エツチングレジスト水溶液を、それぞれ
２Ｑのステンレススチール製ビーカーに入れ、片面銅張
積層板を陰極に、ビーカーを陽極として電着塗装を行い
、均一な塗膜を作成した。８０℃で１０分間乾燥した後
、フォトマスクを密着させて高圧水銀ランプを有するＵ
Ｖ露光装置（（株）オーク製作所説、商品名ｒＪＬ−３
３００Ｊ）を使用して、表１に示す紫外線量を照射しフ
ォトレジストとしての性能を調べた。その結果を表１に
示す。この際の現像条件は全て同一とし、０．２５ｗｔ
％乳酸水溶液中にて１分間行った。また乾燥後の塗膜の
粘着性の有無は室温まで冷却後の塗面についてＪＩＳ
Ｋ ５４００の指触乾燥の判定に準拠して行った。The cationic electrodeposition type negative etching resist aqueous solutions prepared in Examples 1 and 2.3 and Comparative Examples 1 and 2 were placed in 2Q stainless steel beakers, and the single-sided copper-clad laminate was used as the cathode. Electrodeposition was performed using the material as an anode to create a uniform coating film. After drying at 80°C for 10 minutes, a photomask was attached and a high-pressure mercury lamp was used.
V exposure device (Oak Seisakusho Co., Ltd., product name rJL-3)
300J) and irradiated with the amount of ultraviolet rays shown in Table 1 to examine its performance as a photoresist. The results are shown in Table 1. The development conditions at this time were all the same, and 0.25wt
% lactic acid aqueous solution for 1 minute. In addition, the presence or absence of adhesion of the paint film after drying is determined by JIS on the painted surface after cooling to room temperature.
The test was conducted in accordance with the dryness to the touch test of K5400.
表１から明らかなように、二級アミンを付加したエポキ
シ化液状ポリブタジェンに、単にアクリル酸を付加した
だけの樹脂を成分（Ａ）として用いた場合には、電着塗
装・乾燥後の塗膜に粘着性があり、フォトマスクを密着
することができなかった（比較例１）。またアクリル酸
の付加量を増加させると付加時の粘度上昇が著しく合成
が困難となり、また粘着性は解消されるが、不飽和イソ
シアナート化合物を反応させていないため感度・解像度
ともに悪く実用的でなかった（比較例２）。As is clear from Table 1, when a resin obtained by simply adding acrylic acid to epoxidized liquid polybutadiene added with a secondary amine is used as component (A), the coating film after electrodeposition and drying is was sticky, and the photomask could not be adhered to it (Comparative Example 1). In addition, if the amount of acrylic acid added is increased, the viscosity increases significantly during addition, making synthesis difficult, and the stickiness can be resolved, but since the unsaturated isocyanate compound is not reacted, both sensitivity and resolution are poor, making it impractical. There was no (Comparative Example 2).
しかし、実施例１〜３のように不飽和イソシアナート化
合物を反応させた樹脂を用いた場合には、電着塗装・乾
燥後の塗膜に粘着性は全く見られず、しかも感度、解像
度ともに高いフォトレジストが得られ、更に（メタ）ア
クリロイル基を有する化合物を適当量添加しても粘着性
は見られず、さらに高感度、高解像度になることが判っ
た。However, when using a resin reacted with an unsaturated isocyanate compound as in Examples 1 to 3, no stickiness was observed in the coating film after electrodeposition and drying, and both sensitivity and resolution were low. It was found that a photoresist with high quality was obtained, and even when an appropriate amount of a compound having a (meth)acryloyl group was added, no tackiness was observed and further high sensitivity and resolution were obtained.
（以下余白ｈ＋’：、、（ ｌ１％Ｉン 手続補正書（自発） 平成 年３・９月５ 日(Below margin h+’:,,( l1%Iin Procedural amendment (voluntary) March and September 5, 2019
Claims (1)
酸とを付加したエポキシ化液状ポリブタジエンに、不飽
和基含有イソシアナート化合物を反応させて得られる樹
脂１００重量部、 （Ｂ）アクリロイル基含有化合物及び／又はメタクリロ
イル基含有化合物０〜５０重量部および（Ｃ）感光剤０
．５〜２０重量部 を含有してなるカチオン電着型ネガ型エッチングレジス
ト組成物。[Scope of Claims] (A) 100 parts by weight of a resin obtained by reacting an unsaturated group-containing isocyanate compound with an epoxidized liquid polybutadiene to which a secondary amine and acrylic acid and/or methacrylic acid have been added; B) 0 to 50 parts by weight of an acryloyl group-containing compound and/or a methacryloyl group-containing compound and (C) 0 photosensitizer
．． A cationic electrodeposition type negative etching resist composition containing 5 to 20 parts by weight.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23056790A JPH04116181A (en) | 1990-09-03 | 1990-09-03 | Cationic electrodeposition type negative type etching resist composition |
| US07/750,400 US5246816A (en) | 1990-09-03 | 1991-08-27 | Cationic electrodeposition negative type resist composition |
| EP91114753A EP0474163A1 (en) | 1990-09-03 | 1991-09-02 | Cationic electrodeposition negative type resist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23056790A JPH04116181A (en) | 1990-09-03 | 1990-09-03 | Cationic electrodeposition type negative type etching resist composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04116181A true JPH04116181A (en) | 1992-04-16 |
Family
ID=16909775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23056790A Pending JPH04116181A (en) | 1990-09-03 | 1990-09-03 | Cationic electrodeposition type negative type etching resist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04116181A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04251847A (en) * | 1990-08-02 | 1992-09-08 | Ppg Ind Inc | Composition of photoresist which can perform optical imaging and electrodeposition |
| JPH087440B2 (en) * | 1990-03-24 | 1996-01-29 | ビーエーエスエフ ラッケ ウント ファルベン アクチェンゲゼルシャフト | Water-developable, electrodepositable and photocurable negative type coating, method for producing printed circuit, and method for producing two-dimensional, two-dimensional and three-dimensional conductor plates |
| JP2006017843A (en) * | 2004-06-30 | 2006-01-19 | Hitachi Displays Ltd | Method for manufacturing display unit |
-
1990
- 1990-09-03 JP JP23056790A patent/JPH04116181A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH087440B2 (en) * | 1990-03-24 | 1996-01-29 | ビーエーエスエフ ラッケ ウント ファルベン アクチェンゲゼルシャフト | Water-developable, electrodepositable and photocurable negative type coating, method for producing printed circuit, and method for producing two-dimensional, two-dimensional and three-dimensional conductor plates |
| JPH04251847A (en) * | 1990-08-02 | 1992-09-08 | Ppg Ind Inc | Composition of photoresist which can perform optical imaging and electrodeposition |
| JP2006017843A (en) * | 2004-06-30 | 2006-01-19 | Hitachi Displays Ltd | Method for manufacturing display unit |
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