JP6432743B2 - Substrate manufacturing method using resin composition for plating resist - Google Patents
Substrate manufacturing method using resin composition for plating resist Download PDFInfo
- Publication number
- JP6432743B2 JP6432743B2 JP2015505420A JP2015505420A JP6432743B2 JP 6432743 B2 JP6432743 B2 JP 6432743B2 JP 2015505420 A JP2015505420 A JP 2015505420A JP 2015505420 A JP2015505420 A JP 2015505420A JP 6432743 B2 JP6432743 B2 JP 6432743B2
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- JP
- Japan
- Prior art keywords
- substrate
- acid
- meth
- acrylate
- polyol
- 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.)
- Expired - Fee Related
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- 239000000758 substrate Substances 0.000 title claims description 93
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 238000007747 plating Methods 0.000 title claims description 39
- 239000011342 resin composition Substances 0.000 title description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 115
- 150000003077 polyols Chemical class 0.000 claims description 88
- 229920005862 polyol Polymers 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 61
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 51
- 239000005062 Polybutadiene Substances 0.000 claims description 47
- 229920002857 polybutadiene Polymers 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000007772 electroless plating Methods 0.000 claims description 17
- 239000005056 polyisocyanate Substances 0.000 claims description 17
- 229920001228 polyisocyanate Polymers 0.000 claims description 17
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 229920001195 polyisoprene Polymers 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000000059 patterning Methods 0.000 claims description 5
- 238000006664 bond formation reaction Methods 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- -1 propionic acid Carboxylic acid esters Chemical class 0.000 description 33
- 239000002253 acid Substances 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 230000005855 radiation Effects 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229920005749 polyurethane resin Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- DNFUJUFGVPNZMP-UHFFFAOYSA-N 4-hydroxy-2-(2-hydroxyethyl)-2-methylbutanoic acid Chemical compound OCCC(C)(CCO)C(O)=O DNFUJUFGVPNZMP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
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- 239000008096 xylene Substances 0.000 description 4
- 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 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
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- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 3
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- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- KKSDGJDHHZEWEP-UHFFFAOYSA-N m-hydroxycinnamic acid Natural products OC(=O)C=CC1=CC=CC(O)=C1 KKSDGJDHHZEWEP-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 235000011090 malic acid Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- HDLRSIQOZFLEPK-UHFFFAOYSA-N naphthalene-1,2,5,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(=O)O)=CC=C21 HDLRSIQOZFLEPK-UHFFFAOYSA-N 0.000 description 1
- AKIDPNOWIHDLBQ-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarbonyl chloride Chemical compound C1=CC(C(Cl)=O)=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1C(Cl)=O AKIDPNOWIHDLBQ-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LQFIBCUGFNXYME-UHFFFAOYSA-N phosphono 5-chloropent-2-enoate Chemical compound C(CCl)C=CC(=O)OP(=O)(O)O LQFIBCUGFNXYME-UHFFFAOYSA-N 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 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
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002534 radiation-sensitizing agent Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 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 1
- KKSDGJDHHZEWEP-SNAWJCMRSA-N trans-3-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=CC(O)=C1 KKSDGJDHHZEWEP-SNAWJCMRSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J115/00—Adhesives based on rubber derivatives
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、基板を無電解めっき加工する際のレジスト膜の形成に好適な感光性樹脂組成物、及び該組成物を用いて形成された金属配線パターンを有する各種基板の製造方法に関する。 The present invention relates to a photosensitive resin composition suitable for forming a resist film when electroless plating a substrate, and a method for producing various substrates having a metal wiring pattern formed using the composition.
従来、プリント配線板などの金属配線パターンはフォトリソグラフィー法によって製造されている。フォトリソグラフィー法とは、感光性樹脂組成物を基板上に塗布し、パターン露光して該感光性樹脂組成物の露光部を重合硬化させ、未露光部を現像液で除去して基板上にレジストパターンを形成し、めっき処理を施して導体パターンを形成した後、該レジストパターンを該基板上から剥離除去することによって、基板上に導体パターンを形成する方法を言う。 Conventionally, a metal wiring pattern such as a printed wiring board is manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. This refers to a method of forming a conductor pattern on a substrate by forming a pattern and performing a plating process to form a conductor pattern and then peeling and removing the resist pattern from the substrate.
電子部品にはめっき技術が多く使用されている。めっき技術は、プリント配線板やセラミック基板などのように非導電性の材質に電気特性を付与できること、はんだ付け性のような接合に都合のよい機能(ボンディング性)を持たせることができ、安定した接触抵抗値を持たせることができるなど、新たな特性を付与できるからである。めっき用素材には多くの特性を持った様々な素材が開発されている。特に電子部品には耐食性が優れ、経時変化による接触抵抗値の変化が低く、かつボンディング性に優れる金めっき、また、金よりは酸化されやすいが、安価である銀めっきなどが用いられている。金めっき、銀めっきにはそれぞれ、シアン性浴(アルカリ性浴、中性浴、酸性浴)、非シアン性浴などがあり、被膜の要求特性に応じて、めっき浴が選択される。 Plating technology is often used for electronic components. Plating technology can impart electrical properties to non-conductive materials such as printed wiring boards and ceramic substrates, and can provide functions (bonding properties) convenient for joining, such as solderability, and is stable. This is because a new characteristic can be imparted, for example, the contact resistance value can be given. Various materials having many characteristics have been developed for plating materials. In particular, gold plating having excellent corrosion resistance, low change in contact resistance due to change with time and excellent bonding properties, and silver plating which is easier to oxidize than gold but is inexpensive are used for electronic parts. Each of the gold plating and silver plating includes a cyan bath (alkaline bath, neutral bath, acid bath), a non-cyan bath, and the like, and the plating bath is selected according to the required characteristics of the coating.
このような理由からレジストに用いられる感光性樹脂組成物は、強酸や強アルカリによる基板洗浄及び酸性〜アルカリ性のめっき浴に耐え、めっき浴の汚染への耐性に優れ、解像度、密着性に優れ、かつレジスト剥離性に優れていることが必要であり、これまでに様々な提案がなされている。例えば、ベンジル(メタ)アクリレート誘導体及びスチレン誘導体を主成分とするバインダーポリマーを用いた感光樹脂組成物(特許文献1)や、内部エポキシド基を有するポリブタジエン及びポリウレタン微粒子を含有する光硬化性・熱硬化性樹脂組成物(特許文献2)、チオール基を持った複素環化合物を保護基によって潜在化した化合物を含有する光硬化性・熱硬化性樹脂組成物(特許文献3)、などが提案されている。 For these reasons, the photosensitive resin composition used for resist resists substrate washing with strong acid or strong alkali and acid-alkaline plating bath, has excellent resistance to contamination of the plating bath, and has excellent resolution and adhesion. In addition, it is necessary to have excellent resist stripping properties, and various proposals have been made so far. For example, a photosensitive resin composition (Patent Document 1) using a binder polymer mainly composed of a benzyl (meth) acrylate derivative and a styrene derivative, a photo-curing / thermosetting containing polybutadiene having an internal epoxide group and polyurethane fine particles. Curable resin compositions (Patent Document 2), photocurable / thermosetting resin compositions (Patent Document 3) containing a compound in which a heterocyclic compound having a thiol group is latentized by a protecting group have been proposed. Yes.
近年、銀めっきより安価で導電性の高い被膜の作製方法として無電解ニッケルめっきが盛んに検討されている。そのなかで、フッ化水素酸(以下、フッ酸ともいう)を促進剤としてニッケルめっき溶液に加える方法(例えば、特許文献4及び5)や、基板洗浄に希釈フッ化水素酸を用いる方法(例えば、特許文献6)、さらには希釈フッ化水素酸と塩化パラジウム水溶液により基板を触媒化処理する方法(例えば、特許文献6及び7)などが提案されている。 In recent years, electroless nickel plating has been actively studied as a method for producing a coating film that is cheaper and more conductive than silver plating. Among them, a method of adding hydrofluoric acid (hereinafter also referred to as hydrofluoric acid) to the nickel plating solution as an accelerator (for example, Patent Documents 4 and 5), and a method of using diluted hydrofluoric acid for substrate cleaning (for example, Patent Document 6), and further, a method of catalyzing a substrate with diluted hydrofluoric acid and an aqueous palladium chloride solution (for example, Patent Documents 6 and 7) has been proposed.
ところが、酸のなかでもフッ酸は浸透力が高いため、フッ酸バリア性のある膜を作るのは難しい。そのため従来のめっき浴や洗浄工程では耐性のあったレジストであってもフッ酸が浸透してしまい、剥離や基板腐蝕といった問題が発生してしまう。また作業性の観点からも、耐酸性・耐アルカリ性及び剥離性をさらに向上させることが望まれている。 However, among acids, hydrofluoric acid has high penetrating power, so it is difficult to form a film having a hydrofluoric acid barrier property. For this reason, even if the resist is resistant to conventional plating baths and cleaning processes, hydrofluoric acid permeates, causing problems such as peeling and substrate corrosion. Further, from the viewpoint of workability, it is desired to further improve acid resistance / alkali resistance and peelability.
一般的な有機膜はフッ酸(HF)の浸透を防ぐことができず、下地基板が腐食して剥離する。また基板洗浄に用いる高濃度の酸及びアルカリ溶液では膨潤もしくは溶解して剥離してしまう。そこで、本発明の課題は、配線基板を無電解めっき加工する際のレジスト膜の形成に好適な樹脂組成物を用いた各種基板の製造方法を提供することである。 A general organic film cannot prevent permeation of hydrofluoric acid (HF), and the base substrate is corroded and peeled off. Further, in a high-concentration acid and alkali solution used for substrate cleaning, it swells or dissolves and peels off. Accordingly, an object of the present invention is to provide a method for producing various substrates using a resin composition suitable for forming a resist film when an electroless plating process is performed on a wiring substrate.
より詳しくは、本発明の課題は、例えばフッ酸を含む洗浄液及びめっき液に対して十分な耐性を有し、ガラス基板やSiO2又はSiN等の無機基板に対しても十分な密着性を有し、無電解めっき時のスカム及びフッティングを抑制して精度よく所望のパターン加工ができるレジスト膜を形成することができ、さらには加工後の剥離が容易な樹脂組成物を用いた各種基板の製造方法を提供することにある。More specifically, the problem of the present invention is that it has sufficient resistance to, for example, a cleaning solution and a plating solution containing hydrofluoric acid, and has sufficient adhesion to a glass substrate or an inorganic substrate such as SiO 2 or SiN. In addition, it is possible to form a resist film that can accurately perform a desired pattern processing by suppressing scum and footing during electroless plating, and further, various substrates using resin compositions that are easily peeled off after processing. It is to provide a manufacturing method.
本発明者らは上記課題を解決するために鋭意検討を行った。その結果、ポリブタジエンポリオールを原料として製造されるポリエステル樹脂及び/又はポリウレタン樹脂を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by using a polyester resin and / or a polyurethane resin produced from polybutadiene polyol as a raw material, and the present invention has been completed.
すなわち、本発明は、下記1〜15に関する。
1.(A)成分としてポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール及び水添ポリイソプレンポリオールから選ばれるポリオール(a1)と、多価カルボン酸、多価酸クロリド、及びポリイソシアネートからなる群から選択される架橋剤(a2)とを反応させて得られる樹脂を含む組成物を基板上に塗布してレジスト膜を形成する第1工程と、当該レジスト膜を形成した基板を無電解めっき加工してパターニングする第2工程とを含む無電解めっき加工により形成されたパターンを有する基板の製造方法であって、前記第2工程は、フッ酸を含む洗浄液を用いて前記基板を洗浄する工程と、フッ酸を含むめっき液を用いて前記無電解めっき加工する工程と、の少なくとも一方を含むことを特徴とする、基板の製造方法。
2.前記ポリオール(a1)と前記架橋剤(a2)との反応がエステル結合形成反応であることを特徴とする1に記載の基板の製造方法。
3.前記ポリオール(a1)と前記架橋剤(a2)との反応がウレタン結合形成反応であることを特徴とする1に記載の基板の製造方法。
4.前記ポリオール(a1)が、水添ポリブタジエンポリオールであることを特徴とする1〜3のいずれかに記載の基板の製造方法。
5.前記(A)成分の樹脂が、更に、(メタ)アクリレート基を有してなることを特徴とする1〜4のいずれかに記載の基板の製造方法。
6.前記(A)成分の樹脂が、更に、アルカリ可溶性基を有してなることを特徴とする1〜5のいずれかに記載の基板の製造方法。
7.前記組成物が、更に、(B)エチレン性不飽和単量体を含有してなることを特徴とする1〜6のいずれかに記載の基板の製造方法。
8.前記(B)エチレン性不飽和単量体が、炭素数6以上の脂肪族又は脂環族アルキルの(メタ)アクリレートであることを特徴とする7に記載の基板の製造方法。
9.前記組成物が、更に(C)光重合開始剤を含有してなることを特徴とする1〜8のいずれかに記載の基板の製造方法。
10.前記組成物を基板上に塗布する方法が、スピンコート法、スリットコート法、ロールコート法、スクリーン印刷法又はアプリケーター法であることを特徴とする1〜9のいずれかに記載の基板の製造方法。
11.前記基板がガラス基板であることを特徴とする1〜10のいずれかに記載の基板の製造方法。
12.前記基板が珪素を含む絶縁層で被覆された基板であることを特徴とする1〜10のいずれかに記載の基板の製造方法。
13.前記珪素を含む絶縁層がSiO2又はSiNで構成されていることを特徴とする12に記載の基板の製造方法。
That is, this invention relates to the following 1-15.
1. The component (A) is selected from the group consisting of a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol , a polyvalent carboxylic acid, a polyvalent acid chloride, and a polyisocyanate. A first step of forming a resist film by applying a composition containing a resin obtained by reacting with a crosslinking agent (a2) to be formed on the substrate, and patterning by electroless plating the substrate on which the resist film is formed a second step of a method of producing a substrate having a pattern formed by including electroless plating, the second step includes a step of washing the substrate with a cleaning liquid containing hydrofluoric acid, fluoride A step of performing electroless plating using a plating solution containing an acid, and The method of production.
2. 2. The method for producing a substrate according to 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is an ester bond forming reaction.
3. 2. The method for producing a substrate according to 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is a urethane bond forming reaction.
4). The said polyol (a1) is hydrogenated polybutadiene polyol, The manufacturing method of the board | substrate in any one of 1-3 characterized by the above-mentioned.
5. The method for producing a substrate according to any one of 1 to 4, wherein the resin of the component (A) further comprises a (meth) acrylate group.
6). The method for producing a substrate according to any one of 1 to 5, wherein the resin of the component (A) further has an alkali-soluble group.
7). The said composition contains the (B) ethylenically unsaturated monomer further, The manufacturing method of the board | substrate in any one of 1-6 characterized by the above-mentioned.
8). 8. The method for producing a substrate according to 7, wherein the (B) ethylenically unsaturated monomer is an aliphatic or alicyclic alkyl (meth) acrylate having 6 or more carbon atoms.
9. The method for producing a substrate according to any one of 1 to 8, wherein the composition further comprises (C) a photopolymerization initiator.
10. The method for producing a substrate according to any one of 1 to 9, wherein the method of applying the composition onto the substrate is a spin coating method, a slit coating method, a roll coating method, a screen printing method, or an applicator method. .
11. The substrate manufacturing method according to any one of 1 to 10, wherein the substrate is a glass substrate.
12 11. The method for manufacturing a substrate according to any one of 1 to 10, wherein the substrate is a substrate coated with an insulating layer containing silicon.
13. 13. The method for manufacturing a substrate according to 12, wherein the insulating layer containing silicon is made of SiO 2 or SiN .
ポリブタジエンポリオール(a1)と架橋剤(a2)とがエステル結合もしくはウレタン結合を形成しており、必要に応じて(メタ)アクリレート基及び/又はアルカリ可溶性基を含有している樹脂は優れたフッ酸バリア性を示し、高濃度の酸・アルカリでも腐食されない。さらに本樹脂は粘着剤として利用でき、残渣の原因となるシランカップリング剤を添加せずとも良好な密着性を発揮する。以上から本樹脂は剥離の容易な酸・アルカリ防止膜として非常に有望である。本発明における樹脂組成物を用いれば、例えばフッ酸を含む洗浄液やめっき液に対して十分な耐性を有し、さらにガラス基板やSiO2又はSiN等の無機基板に対して十分な密着性を有し、無電解めっき時のスカム及びフッティングを抑制して精度よく所望のパターン加工ができるレジスト膜を形成することができ、さらには容易に剥離し除去することができる。The polybutadiene polyol (a1) and the crosslinking agent (a2) form an ester bond or a urethane bond, and if necessary, a resin containing a (meth) acrylate group and / or an alkali-soluble group is an excellent hydrofluoric acid. Shows barrier properties, and does not corrode even with high concentrations of acid or alkali. Furthermore, the present resin can be used as an adhesive and exhibits good adhesion without adding a silane coupling agent that causes residue. From the above, this resin is very promising as an easily peelable acid / alkali prevention film. If the resin composition in the present invention is used, it has sufficient resistance to, for example, a cleaning solution or a plating solution containing hydrofluoric acid, and has sufficient adhesion to a glass substrate or an inorganic substrate such as SiO 2 or SiN. In addition, it is possible to form a resist film capable of accurately processing a desired pattern while suppressing scum and footing during electroless plating, and further, it can be easily peeled off and removed.
以下、本発明の樹脂組成物を用いて形成されたエッチングパターンを有する各種基板の製造方法について詳細に説明する。 Hereinafter, the manufacturing method of the various board | substrate which has an etching pattern formed using the resin composition of this invention is demonstrated in detail.
<樹脂組成物>
本発明の樹脂組成物は、(A)成分としてポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール及び水添ポリイソプレンポリオールから選ばれるポリオール(a1)と架橋剤(a2)とがエステル結合もしくはウレタン結合を形成しており、必要に応じて(メタ)アクリレート基及び/又はアルカリ可溶性基を含有している樹脂、及び、必要に応じて、少なくとも1個のエチレン性不飽和二重結合を有する化合物(B)及び/又は放射線ラジカル重合開始剤(C)を含有することを特徴とする。<Resin composition>
In the resin composition of the present invention, the polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol as the component (A) and the crosslinking agent (a2) are ester bonds or urethane bonds. A resin containing a (meth) acrylate group and / or an alkali-soluble group, if necessary, and, optionally, a compound having at least one ethylenically unsaturated double bond ( B) and / or a radiation radical polymerization initiator (C) is contained.
<(A)ポリブタジエン系樹脂>
本発明で用いられる(A)成分のポリブタジエン系樹脂(以下、樹脂(A)とも言う)は、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール及び水添ポリイソプレンポリオールから選ばれるポリオール(a1)と架橋剤(a2)との反応物であり、より具体的には架橋剤(a2)が多価カルボン酸(a2−1)及び/又は多価酸クロリド(a2−2)でありポリオール(a1)とエステル結合を形成してなるポリブタジエン系ポリエステル樹脂、及び、架橋剤(a2)がポリイソシアネート(a2−3)でありポリオール(a1)とウレタン結合を形成してなるポリブタジエン系ポリウレタン樹脂、のことを言う。また必要に応じてポリオール(a1)の一部分をハロゲン、イソシアネート基及び水酸基から選ばれる置換基を含有する(メタ)アクリレート(b)及び/又はカルボキシル基等のアルカリ可溶性基を含有するモノオール又はポリオール(c)と置き換えて、架橋剤(a2)と反応させてもよい。<(A) Polybutadiene resin>
The polybutadiene-based resin (hereinafter also referred to as resin (A)) used in the present invention is a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol. It is a reaction product with the crosslinking agent (a2), more specifically, the crosslinking agent (a2) is a polyvalent carboxylic acid (a2-1) and / or a polyvalent acid chloride (a2-2), and a polyol (a1). A polybutadiene-based polyester resin formed by forming an ester bond with a polybutadiene-based polyurethane resin formed by forming a urethane bond with a polyol (a1) in which the cross-linking agent (a2) is a polyisocyanate (a2-3). say. If necessary, a part of the polyol (a1) is a monool or polyol containing an alkali-soluble group such as (meth) acrylate (b) and / or a carboxyl group containing a substituent selected from halogen, an isocyanate group and a hydroxyl group. Instead of (c), it may be reacted with a crosslinking agent (a2).
該樹脂(A)を構成する各成分について以下に説明する。 Each component which comprises this resin (A) is demonstrated below.
<ポリオール(a1)>
本発明に用いるポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール及び水添ポリイソプレンポリオールから選ばれるポリオール(a1)としては、その分子内の不飽和結合を水添したものも含み、ポリブタジエン系ポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール等が挙げられる。
<Polyol (a1)>
Polybutadiene polyol used in the present invention, hydrogenated polybutadiene polyol, a polyisoprene polyol and a polyol selected from a hydrogenated polyisoprene polyol (a1), also include those hydrogenating unsaturated bonds in the molecule, Po Li butadiene Examples include polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol.
前記ポリブタジエンポリオールとしては、分子中に1,4−結合型、1,2−結合型又はそれらが混在したポリブタジエン構造及び2つの水酸基を有するものが好ましく、鎖状のポリブタジエン構造の両端にそれぞれ水酸基を有するものがより好ましい。 As the polybutadiene polyol, those having a 1,4-bond type, a 1,2-bond type or a polybutadiene structure in which they are mixed and two hydroxyl groups in the molecule are preferable, and hydroxyl groups are respectively formed at both ends of the chain polybutadiene structure. What has is more preferable.
これらのポリオールは、1種単独で又は2種以上を組み合わせて用いることができる。 These polyols can be used singly or in combination of two or more.
前記ポリブタジエンポリオールとしては、従来公知の一般的なものが挙げられ、例えば、日本曹達株式会社のNISSO PB(Gシリーズ)、出光石油化学株式会社のPoly−Pd等の両末端に水酸基を有する液状ポリブタジエン;日本曹達株式会社のNISSO PB(GIシリーズ)、三菱化学株式会社のポリテールH、ポリエーテルHA等の両末端に水酸基を有する水素添加ポリブタジエン;出光石油化学株式会社製のPoly−iP等の両末端に水酸基を有する液状C5系重合体;出光石油化学株式会社製のエポール、クラレ株式会社製のTH−1、TH−2、TH−3等の両末端に水酸基を有する水素添加ポリイソプレンなどのような市販されている、もしくは市販されていたものを用いることができるが、これに限定されるものではない。 Examples of the polybutadiene polyol include conventionally known general ones, such as liquid polybutadiene having hydroxyl groups at both ends, such as NISSO PB (G series) of Nippon Soda Co., Ltd., Poly-Pd of Idemitsu Petrochemical Co., Ltd. ; Nipponso Soda Co., Ltd. NISSO PB (GI series), Mitsubishi Chemical Co., Ltd. polytail H, hydrogenated polybutadiene having hydroxyl groups at both ends, such as Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd. A liquid C5 polymer having a hydroxyl group at the end; Epole manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene having hydroxyl groups at both ends, such as TH-1, TH-2, TH-3 manufactured by Kuraray Co., Ltd. Commercially available or commercially available products can be used, but are not limited thereto. Not.
前記ポリオールの中でも、特に水添ポリブタジエンポリオールがフッ酸へのバリア性や膜強度の点で好ましく用いられる。 Among the polyols, hydrogenated polybutadiene polyol is particularly preferably used in terms of barrier properties against hydrofluoric acid and film strength.
かかるポリオールは、例えば、分子量が300〜6,000、好ましくは500〜3,000のものが有用である。また、ヨウ素価は0〜50、好ましくは0〜20で、水酸基価は15〜400mgKOH/g、好ましくは30〜250mgKOH/gが適当である。 Such a polyol is useful, for example, having a molecular weight of 300 to 6,000, preferably 500 to 3,000. The iodine value is 0 to 50, preferably 0 to 20, and the hydroxyl value is 15 to 400 mgKOH / g, preferably 30 to 250 mgKOH / g.
<多価カルボン酸(a2−1)>
本発明に用いる多価カルボン酸(a2−1)としては、特に限定されることなく、例えば芳香族系、脂肪族系、脂環式系等の多価カルボン酸が挙げられ、例えば、フタル酸、3,4−ジメチルフタル酸、イソフタル酸、テレフタル酸、ピロメリット酸、トリメリット酸、1,4,5,8−ナフタレンテトラカルボン酸、3,3’,4,4’−ベンゾフェノンテトラカルボン酸等の芳香族多価カルボン酸;こはく酸、グルタル酸、アジピン酸、1,2,3,4−ブタンテトラカルボン酸、マレイン酸、フマル酸、イタコン酸等の脂肪族多価カルボン酸;ヘキサヒドロフタル酸、3,4−ジメチルテトラヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、1,2,4−シクロペンタントリカルボン酸、1,2,4−シクロヘキサントリカルボン酸、シクロペンタンテトラカルボン酸、1,2,4,5−シクロヘキサンテトラカルボン酸等の脂環式多価カルボン酸;等が挙げられる。<Polyvalent carboxylic acid (a2-1)>
The polyvalent carboxylic acid (a2-1) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polycarboxylic acids such as phthalic acid. 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Aromatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid and the like; hexahydro Phthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohe Suntory carboxylic acid, cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane alicyclic polycarboxylic acids such as tetracarboxylic acid; and the like.
前記多価カルボン酸の中でも、特に芳香族系又は脂環式系の多価カルボン酸がフッ酸へのバリア性や膜強度の点で好ましく用いられる。これらの多価カルボン酸は、1種単独で又は2種以上を組み合わせて用いることができる。 Among the polyvalent carboxylic acids, aromatic or alicyclic polyvalent carboxylic acids are particularly preferably used in terms of barrier properties to hydrofluoric acid and film strength. These polyvalent carboxylic acids can be used singly or in combination of two or more.
<多価酸クロリド(a2−2)>
本発明に用いる多価酸クロリド(a2−2)としては、特に限定されることなく、例えば芳香族系、脂肪族系、脂環式系等の多価酸クロリドが挙げられ、フタル酸ジクロリド、3,4−ジメチルフタル酸ジクロリド、イソフタル酸ジクロリド、テレフタル酸ジクロリド、ピロメリット酸ジクロリド、トリメリット酸ジクロリド、1,4,5,8−ナフタレンテトラカルボン酸テトラクロリド、3,3’,4,4’−ベンゾフェノンテトラカルボン酸テトラクロリド、等の芳香族多価酸クロリド;こはく酸ジクロリド、グルタル酸ジクロリド、アジピン酸ジクロリド、1,2,3,4−ブタンテトラカルボン酸テトラクロリド、マレイン酸ジクロリド、フマル酸ジクロリド、イタコン酸ジクロリド、等の脂肪族多価酸クロリド;ヘキサヒドロフタル酸ジクロリド、ヘキサヒドロテレフタル酸ジクロリド、シクロペンタンテトラカルボン酸、等の脂環式多価酸クロリド;等が挙げられる。<Polyacid chloride (a2-2)>
The polyvalent acid chloride (a2-2) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyvalent acid chlorides, such as phthalic dichloride, 3,4-dimethylphthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, pyromellitic acid dichloride, trimellitic acid dichloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride, 3,3 ', 4,4 '-Benzophenone tetracarboxylic acid tetrachloride, aromatic polyvalent acid chlorides; succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, 1,2,3,4-butanetetracarboxylic acid tetrachloride, maleic acid dichloride, fumarate Aliphatic polyvalent acid chlorides such as acid dichloride and itaconic acid dichloride; hexahydrophthal And the like; acid dichloride, hexahydroterephthalic acid dichloride, cyclopentane tetracarboxylic acid, alicyclic polyvalent acid chloride and the like.
前記多価酸クロリドの中でも、特に芳香族系又は脂環式系の多価酸クロリドがフッ酸へのバリア性や膜強度の点で好ましく用いられる。これらの多価酸クロリドは、1種単独で又は2種以上を組み合わせて用いることができる。 Among the polyvalent acid chlorides, aromatic or alicyclic polyvalent acid chlorides are particularly preferably used in terms of barrier properties to hydrofluoric acid and film strength. These polyvalent acid chlorides can be used singly or in combination of two or more.
<ポリイソシアネート(a2−3)>
本発明に用いるポリイソシアネート(a2−3)としては、特に限定されることなく、例えば芳香族系、脂肪族系、脂環式系等のポリイソシアネートが挙げられ、中でもトリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添化ジフェニルメタンジイソシアネート、変性ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、1,3−ビス(イソシアナトメチル)シクロヘキサン等のジイソシアネートあるいはこれらの3量体、ビューレット型ポリイソシアネート等が好適に用いられる。<Polyisocyanate (a2-3)>
The polyisocyanate (a2-3) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, Hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanato Diisocyanates such as methyl) cyclohexane or their trimers, burette type polyisocyanates, etc. are preferably used. .
該ポリイソシアネート(a2−3)の分子量は、水酸基との反応性の点から150〜700が好ましい。これらのポリイソシアネートは、1種単独で又は2種以上を組み合わせて用いることができる。 The molecular weight of the polyisocyanate (a2-3) is preferably 150 to 700 from the viewpoint of reactivity with a hydroxyl group. These polyisocyanates can be used singly or in combination of two or more.
本発明の樹脂(A)は、ポリブタジエンポリオール(a1)と架橋剤(a2)とがエステル結合もしくはウレタン結合を形成していることを特徴とする。これらは目的に応じて選択することができるが、膜強度や基板密着性の観点からはウレタン結合がより好ましい。その理由として、エステル結合と比べてウレタン結合はより水素結合が強いため、分子間や基板への親和性に優れることが挙げられる。 The resin (A) of the present invention is characterized in that the polybutadiene polyol (a1) and the crosslinking agent (a2) form an ester bond or a urethane bond. These can be selected according to the purpose, but urethane bonds are more preferable from the viewpoint of film strength and substrate adhesion. The reason is that the urethane bond has a stronger hydrogen bond than the ester bond, and thus has excellent affinity between molecules and the substrate.
<樹脂(A)の製造>
樹脂(A)は、ポリオール(a1)と、多価カルボン酸(a2−1)、多価酸クロリド(a2−2)又はポリイソシアネート(a2−3)を反応させることにより得られる。エステル結合を形成したい場合は、多価カルボン酸(a2−1)又は多価酸クロリド(a2−2)と反応させればよく、ウレタン結合を形成したい場合は、ポリイソシアネート(a2−3)を反応させればよい。<Manufacture of resin (A)>
Resin (A) is obtained by reacting polyol (a1) with polyvalent carboxylic acid (a2-1), polyvalent acid chloride (a2-2) or polyisocyanate (a2-3). When it is desired to form an ester bond, it may be reacted with a polyvalent carboxylic acid (a2-1) or a polyvalent acid chloride (a2-2). When a urethane bond is desired to be formed, polyisocyanate (a2-3) is added. What is necessary is just to make it react.
反応は、好ましくは溶媒中で行なわれる。溶媒としては、反応に不活性なものであれば特に限定はないが、例えば、ヘキサン、シクロヘキサン、ベンゼン、トルエン等の炭化水素類;四塩化炭素、クロロホルム、1,2−ジクロロエタン等のハロゲン系炭化水素類;ジエチルエーテル、ジイソプロピルエーテル、1,4−ジオキサン、テトラヒドロフラン等のエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;アセトニトリル、プロピオニトリル等のニトリル類;酢酸エチル、プロピオン酸エチル等のカルボン酸エステル類;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、1,3−ジメチル−2−イミダゾリジノン等の含窒素非プロトン性極性溶媒;ジメチルスルホキシド、スルホラン等の含硫黄非プロトン性極性溶媒が挙げられる。これらの溶媒は単独で用いても、これらのうちの2種類以上を混合して用いても良い。好ましくはトルエン、シクロヘキサノン等が挙げられる。 The reaction is preferably carried out in a solvent. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogen-based carbonization such as carbon tetrachloride, chloroform and 1,2-dichloroethane. Hydrogens; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; nitriles such as acetonitrile, propionitrile; ethyl acetate, propionic acid Carboxylic acid esters such as ethyl; nitrogen-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone Dimethyl sulfoxide, sulfur Sulfur-containing aprotic polar solvents such as Horan like. These solvents may be used alone, or two or more of these may be mixed and used. Preferably, toluene, cyclohexanone, etc. are mentioned.
溶媒の使用量(反応濃度)は特に限定されないが、ポリオール(a1)に対し、0.1〜100質量倍の溶媒を用いてもよい。好ましくは1〜10質量倍であり、さらに好ましくは2〜5質量倍である。 Although the usage-amount (reaction concentration) of a solvent is not specifically limited, You may use a 0.1-100 mass times solvent with respect to a polyol (a1). Preferably it is 1-10 mass times, More preferably, it is 2-5 mass times.
反応温度は特に限定されないが、反応がウレタン結合を形成するものである場合、30〜90℃、特には40〜80℃の範囲が好ましい。 Although reaction temperature is not specifically limited, When reaction forms a urethane bond, the range of 30-90 degreeC, especially 40-80 degreeC is preferable.
反応がエステル結合を形成するものである場合、30〜150℃、特には80〜150℃の範囲が好ましい。 When the reaction forms an ester bond, a range of 30 to 150 ° C, particularly 80 to 150 ° C is preferable.
反応時間は、通常、0.05〜200時間、好ましくは0.5〜100時間である。 The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
また、かかる反応においては、反応を促進する目的で触媒を用いることも好ましく、かかる触媒としては、例えば、ジブチル錫ジラウレート、トリメチル錫ヒドロキシド、テトラ−n−ブチル錫等の有機金属化合物、オクトエ酸亜鉛、オクトエ酸錫、ナフテン酸コバルト、塩化第1錫、塩化第2錫等の金属塩、ピリジン、トリエチルアミン、ベンジルジエチルアミン、1,4−ジアザビシクロ[2.2.2]オクタン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセン、1,5−ジアザビシクロ[4.3.0]−5−ノナン、N,N,N’,N’−テトラメチル−1,3−ブタンジアミン、N−エチルモルホリン等のアミン系触媒等が挙げられ、中でも、ウレタン結合を形成する場合はジブチル錫ジラウレート(以下、ジラウリン酸ジブチルすずとも言う)、が好ましく、エステル結合を形成する場合は、ピリジン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセンが好適である。 In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, and octoic acid. Metal salts such as zinc, tin octoate, cobalt naphthenate, stannous chloride, stannic chloride, pyridine, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N -Amine-based catalysts such as ethyl morpholine, etc., and in particular, when forming a urethane bond, dibutyltin dilaurate (hereinafter referred to as dilauric acid) Also referred to) is preferably a butyl tin, to form an ester bond, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene is preferred.
触媒を添加する場合の添加量は特に限定されないが、ポリオール(a1)の100質量部に対し、0.00001〜5質量部であり、好ましくは0.001〜0.1質量部である。 Although the addition amount in the case of adding a catalyst is not specifically limited, It is 0.00001-5 mass parts with respect to 100 mass parts of a polyol (a1), Preferably it is 0.001-0.1 mass part.
また本発明の樹脂(A)には放射線による硬化性を付与する目的で、(メタ)アクリレート基を導入してもよい。(メタ)アクリレート基の導入方法としては特に限定されることなく、2−クロロエチルアクリレート等のハロゲン化物、2−イソシアネートエチルアクリレート等のイソシアネート化合物、ヒドロキシエチルアクリレート等の水酸基含有化合物から選ばれる(メタ)アクリレート(b)を、ポリオール(a1)と、多価カルボン酸(a2−1)、多価酸クロリド(a2−2)又はポリイソシアネート(a2−3)との反応時に混在させることで、樹脂(A)に導入することができる。 Further, a (meth) acrylate group may be introduced into the resin (A) of the present invention for the purpose of imparting curability by radiation. The method for introducing the (meth) acrylate group is not particularly limited, and is selected from halides such as 2-chloroethyl acrylate, isocyanate compounds such as 2-isocyanatoethyl acrylate, and hydroxyl-containing compounds such as hydroxyethyl acrylate (meta ) The acrylate (b) is mixed with the polyol (a1) and the polyvalent carboxylic acid (a2-1), the polyvalent acid chloride (a2-2) or the polyisocyanate (a2-3) at the time of reaction. (A) can be introduced.
これらの(メタ)アクリレート化合物は、目的に応じていずれかを選択及び/又は混合して用いることができるが、原料の入手が容易なことから水酸基含有(メタ)アクリレート化合物がより好ましい。 Any one of these (meth) acrylate compounds can be selected and / or mixed depending on the purpose, but a hydroxyl group-containing (meth) acrylate compound is more preferable because of easy availability of raw materials.
ハロゲン基含有(メタ)アクリレートとしては、特に限定されることなく、例えば、2−クロロエチル(メタ)アクリレート、2−クロロプロピル(メタ)アクリレート、2−クロロブチル(メタ)アクリレート、2−クロロエチルアクリロイルホスフェート、4−クロロブチル(メタ)アクリレート、2−(メタ)アクリロイロキシエチル−2−クロロプロピルフタレート、2−クロロ−3−アクリロイロキシプロピル(メタ)アクリレート等が挙げられる。 The halogen group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-chloroethyl (meth) acrylate, 2-chloropropyl (meth) acrylate, 2-chlorobutyl (meth) acrylate, and 2-chloroethylacryloyl phosphate. 4-chlorobutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-chloropropyl phthalate, 2-chloro-3-acryloyloxypropyl (meth) acrylate, and the like.
イソシアネート基含有(メタ)アクリレートとしては、特に限定されることなく、例えば、2−イソシアネートエチル(メタ)アクリレート、2−イソシアネートプロピル(メタ)アクリレート、2−イソシアネートブチル(メタ)アクリレート、2−イソシアネートエチルアクリロイルホスフェート、4−イソシアネートブチル(メタ)アクリレート等が挙げられる。 The isocyanate group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-isocyanate ethyl (meth) acrylate, 2-isocyanate propyl (meth) acrylate, 2-isocyanate butyl (meth) acrylate, and 2-isocyanate ethyl. Examples include acryloyl phosphate and 4-isocyanatobutyl (meth) acrylate.
水酸基含有(メタ)アクリレートとしては、特に限定されることなく、例えば、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、2−ヒドロキシブチル(メタ)アクリレート、2−ヒドロキシエチルアクリロイルホスフェート、4−ヒドロキシブチル(メタ)アクリレート、2−(メタ)アクリロイロキシエチル−2−ヒドロキシプロピルフタレート、グリセリンジ(メタ)アクリレート、2−ヒドロキシ−3−アクリロイロキシプロピル(メタ)アクリレート、カプロラクトン変性2−ヒドロキシエチル(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ペンタ(メタ)アクリレート、カプロラクトン変性2−ヒドロキシエチル(メタ)アクリレート等が挙げられる。 The hydroxyl group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyethylacryloyl. Phosphate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone Modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate Over doors and the like.
これらの中でもアルキル基の炭素数が2〜20の水酸基含有(メタ)アクリレートが粘着性、耐候性の点で有用である。 Among these, a hydroxyl group-containing (meth) acrylate having an alkyl group having 2 to 20 carbon atoms is useful in terms of tackiness and weather resistance.
また樹脂(A)にはアルカリ水溶液による現像性及び/又は剥離性を付与する目的で、アルカリ可溶性基を導入してもよい。樹脂(A)にアルカリ可溶性基を導入する方法としては、アルカリ可溶性樹脂と混合して組成物とする方法、又は、アルカリ可溶性基を化学結合により樹脂中に導入する方法が挙げられるが、アルカリ水溶液に対する溶解性の観点からは、アルカリ可溶性基を化学結合により樹脂中に導入する方法がより好ましい。 In addition, an alkali-soluble group may be introduced into the resin (A) for the purpose of imparting developability and / or peelability with an aqueous alkali solution. Examples of the method for introducing an alkali-soluble group into the resin (A) include a method of mixing with an alkali-soluble resin to form a composition, or a method of introducing an alkali-soluble group into the resin by chemical bonding. From the viewpoint of solubility in the resin, a method of introducing an alkali-soluble group into the resin by chemical bonding is more preferable.
またアルカリ可溶性基としては、カルボキシル基等の酸性基、又は、カルボン酸のt−ブチルエステル基等の酸解離性基が挙げられ、目的に応じていずれかを選択及び/又は混合して用いることができる。 Examples of the alkali-soluble group include an acidic group such as a carboxyl group or an acid-dissociable group such as a t-butyl ester group of a carboxylic acid, and any one selected and / or mixed depending on the purpose is used. Can do.
本発明の樹脂(A)の製造の観点からは前記アルカリ可溶性基として、カルボキシル基等のアルカリ可溶性基を含有するモノオール又はポリオール(c)、を用いることが原料の入手が容易な点から好ましい。 From the viewpoint of production of the resin (A) of the present invention, it is preferable from the viewpoint of easy availability of raw materials that the monool or polyol (c) containing an alkali-soluble group such as a carboxyl group is used as the alkali-soluble group. .
例えば、アルカリ可溶性基を含有するモノオール又はポリオール(c)を、ポリオール(a1)と、多価カルボン酸(a2−1)、多価酸クロリド(a2−2)又はポリイソシアネート(a2−3)との反応時に混在させることで、樹脂(A)にアルカリ可溶性基を導入することができる。 For example, a monool or polyol (c) containing an alkali-soluble group, a polyol (a1), a polyvalent carboxylic acid (a2-1), a polyvalent acid chloride (a2-2) or a polyisocyanate (a2-3) By mixing in the reaction, an alkali-soluble group can be introduced into the resin (A).
カルボキシル基含有モノオール又はポリオール(c)としては、特に限定されることなく、カルボキシル基含有モノオールとして例えば、ヒドロキシ酢酸、ヒドロキシプロピオン酸、ヒドロキシブタン酸、12−ヒドロキシステアリン酸、ヒドロキシピバリン酸、15−ヒドロキシペンタデカン酸、16−ヒドロキシヘキサデカン酸、リンゴ酸、クエン酸等が挙げられ、カルボキシル基含有ポリオールとして例えば、2,2−ビス(ヒドロキシメチル)酪酸、酒石酸、2,4−ジヒドロキシ安息香酸、3,5−ジヒドロキシ安息香酸、2,2−ビス(ヒドロキシメチル)プロピオン酸、2,2−ビス(ヒドロキシエチル)プロピオン酸、2,2−ビス(ヒドロキシプロピル)プロピオン酸、ジヒドロキシメチル酢酸、ビス(4−ヒドロキシフェニル)酢酸、4,4−ビス(4−ヒドロキシフェニル)ペンタン酸、ホモゲンチジン酸等が挙げられる。 The carboxyl group-containing monool or polyol (c) is not particularly limited, and examples of the carboxyl group-containing monool include hydroxyacetic acid, hydroxypropionic acid, hydroxybutanoic acid, 12-hydroxystearic acid, hydroxypivalic acid, 15 -Hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, malic acid, citric acid and the like. Examples of the carboxyl group-containing polyol include 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4 -Hydroxyph Yl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, and homogentisic acid.
上記カルボキシル基含有モノオール又はポリオール(c)の中でも、特に12−ヒドロキシステアリン酸及び2,2−ビス(ヒドロキシエチル)プロピオン酸が粘着力の点で好ましい。 Among the carboxyl group-containing monool or polyol (c), 12-hydroxystearic acid and 2,2-bis (hydroxyethyl) propionic acid are particularly preferable in terms of adhesive strength.
尚、明細書中のカルボキシル基含有モノオール又はポリオール(c)の具体例として、「・・・酸」という一般的な慣用名で表現したが、これら具体例はいずれも、COOH基を1個以上有し、かつOH基を1個以上有する化合物である。 In addition, as a specific example of the carboxyl group-containing monool or polyol (c) in the specification, it is expressed by a general common name “... acid”, but each of these specific examples has one COOH group. A compound having at least one and having at least one OH group.
本発明の樹脂(A)に(メタ)アクリレート基及び/又はアルカリ可溶性基を導入する場合、(イ)ポリイソシアネート(a2−3)中に、ポリオール(a1)と、必要に応じてカルボキシル基含有モノオール又はポリオール(c)及び必要に応じて(メタ)アクリレート(b)を一括に仕込み反応させる方法、(ロ)ポリイソシアネート(a2−3)とポリオール(a1)と、必要に応じてカルボキシル基含有モノオール又はポリオール(c)を反応させた後、必要に応じて(メタ)アクリレート(b)を反応させる方法、(ハ)ポリイソシアネート(a2−3)と、必要に応じて(メタ)アクリレート(b)を反応させた後、必要に応じてカルボキシル基含有モノオール又はポリオール(c)を反応させる方法、が挙げられる。 When a (meth) acrylate group and / or an alkali-soluble group is introduced into the resin (A) of the present invention, (i) a polyisocyanate (a2-3) contains a polyol (a1) and, if necessary, a carboxyl group Monool or polyol (c) and, if necessary, (meth) acrylate (b) are charged and reacted together, (b) polyisocyanate (a2-3) and polyol (a1), and optionally carboxyl group A method of reacting (meth) acrylate (b) if necessary after reacting the contained monool or polyol (c), (c) polyisocyanate (a2-3), and (meth) acrylate if necessary After reacting (b), a method of reacting a carboxyl group-containing monol or polyol (c) as necessary is mentioned.
本発明の樹脂(A)に(メタ)アクリレート基及びアルカリ可溶性基を導入する場合、例えば、ポリオール(a1)とポリイソシアネート(a2−3)をk:k+1(モル比)(kは1以上の整数である)の反応モル比で反応させ、イソシアネート基含有化合物[a]を得た後、該イソシアネート基含有化合物[a]にカルボキシル基含有モノオール又はポリオール(c)を1:1の反応モル比で反応させ、更に得られた反応生成物に(メタ)アクリレート(b)を1:1〜1.10の反応モル比で反応させる方法、あるいは、該イソシアネート基含有化合物[a]に(メタ)アクリレート(b)を1:1の反応モル比で反応させ、更に得られた反応生成物にカルボキシル基含有モノオール又はポリオール(c)を1:1〜1.10の反応モル比で反応させる方法が好ましい。 When a (meth) acrylate group and an alkali-soluble group are introduced into the resin (A) of the present invention, for example, a polyol (a1) and a polyisocyanate (a2-3) are converted into k: k + 1 (molar ratio) (k is 1 or more). (Is an integer) to obtain an isocyanate group-containing compound [a], and then the carboxyl group-containing monool or polyol (c) is added to the isocyanate group-containing compound [a] in a 1: 1 reaction mole. The (meth) acrylate (b) is reacted at a reaction molar ratio of 1: 1 to 1.10 to the reaction product obtained, or the isocyanate group-containing compound [a] is subjected to (meta ) The acrylate (b) is reacted at a reaction molar ratio of 1: 1, and the resulting reaction product is further reacted with a carboxyl group-containing monool or polyol (c) at a reaction ratio of 1: 1 to 1.10. A method of reacting a ratio is preferred.
また、上記樹脂(A)の製造において、得られる樹脂(A)が高粘度となる場合は、必要に応じて反応缶にあらかじめ後述のエチレン性不飽和単量体(B)を仕込み、エチレン性不飽和単量体(B)中で各成分を反応させて樹脂(A)を製造することもできる。 Further, in the production of the resin (A), when the resulting resin (A) has a high viscosity, an ethylenically unsaturated monomer (B) described later is charged in a reaction can in advance as necessary, The resin (A) can also be produced by reacting each component in the unsaturated monomer (B).
かくして本発明で用いられる樹脂(A)が得られるが、本発明では樹脂(A)の重量平均分子量が5,000〜400,000であることが好ましく、更には10,000〜200,000であることが好ましい。かかる重量平均分子量が5,000未満では塗膜の強度が不足し、200,000を越えると溶解性及び塗工性が悪くなり好ましくない。 Thus, the resin (A) used in the present invention is obtained. In the present invention, the weight average molecular weight of the resin (A) is preferably 5,000 to 400,000, and more preferably 10,000 to 200,000. Preferably there is. When the weight average molecular weight is less than 5,000, the strength of the coating film is insufficient, and when it exceeds 200,000, the solubility and the coating property are deteriorated.
尚、上記の重量平均分子量とは、標準ポリスチレン分子量換算による重量平均分子量であり、高速液体クロマトグラフィー(昭和電工社製、「Shodex GPC system−11型」)に、カラム:Shodex GPC KF−806L(排除限界分子量:2×107、分離範囲:100〜2×107、理論段数:10,000段/本、充填剤材質:スチレン−ジビニルベンゼン共重合体、充填剤粒径:10μm)の3本直列を用いることにより測定される。In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (high-performance liquid chromatography (the Showa Denko company make, "Shodex GPC system-11 type | mold")). Exclusion limit molecular weight: 2 × 10 7 , separation range: 100 to 2 × 10 7 , theoretical plate number: 10,000 plate / book, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) 3 Measured by using this series.
また、樹脂(A)のガラス転移温度〔TMA(熱機械的分析)法により測定〕としては、0℃以上が好ましい。0℃より下だとレジスト表面にタック性がでてしまうので好ましくない。 The glass transition temperature of the resin (A) [measured by TMA (thermomechanical analysis) method] is preferably 0 ° C. or higher. When the temperature is lower than 0 ° C., tackiness is generated on the resist surface, which is not preferable.
更に、本発明では、樹脂(A)1分子中のエチレン性不飽和基数が1〜3個であることが好ましく、3個を越えると活性エネルギー線照射による硬化被膜の接着性が低下することとなり、またフッ酸バリア性も低下することとなるので好ましくない。 Furthermore, in this invention, it is preferable that the number of ethylenically unsaturated groups in 1 molecule of resin (A) is 1-3, and when it exceeds 3, the adhesiveness of the cured film by active energy ray irradiation will fall. Moreover, the hydrofluoric acid barrier property is also lowered, which is not preferable.
なおこのようにして製造された樹脂(A)は市販されているものを用いることも可能であり、市販品としては例えば、クラレ株式会社製のUC−203や、日本合成化学社製のUV−3610ID80、UV−3630ID80、などが挙げられる。 It is also possible to use a commercially available resin (A) produced in this manner. Examples of commercially available products include UC-203 manufactured by Kuraray Co., Ltd. and UV-manufactured by Nippon Synthetic Chemical Co., Ltd. 3610ID80, UV-3630ID80, etc. are mentioned.
<(B)エチレン性不飽和単量体>
本発明では、粘着特性及び塗工性の改善を目的として、更にエチレン性不飽和単量体(B)、すなわち、少なくとも1個のエチレン性不飽和二重結合を有する化合物を含有することができる。かかるエチレン性不飽和単量体(B)としては、特に限定されず、単官能(メタ)アクリレート、2官能(メタ)アクリレート、3官能以上の(メタ)アクリレート等が挙げられ、中でも接着性の点から単官能(メタ)アクリレートが有効であり、特には炭素数6以上の脂肪族又は脂環族アルキルの(メタ)アクリレートが好ましい。<(B) Ethylenically unsaturated monomer>
In the present invention, an ethylenically unsaturated monomer (B), that is, a compound having at least one ethylenically unsaturated double bond can be further contained for the purpose of improving adhesive properties and coatability. . The ethylenically unsaturated monomer (B) is not particularly limited, and examples thereof include monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher (meth) acrylates. From the standpoint, monofunctional (meth) acrylate is effective, and (meth) acrylate of aliphatic or alicyclic alkyl having 6 or more carbon atoms is particularly preferable.
炭素数6以上の脂肪族又は脂環族アルキルの(メタ)アクリレートとしては、例えばヘキシル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ラウリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、イソアミル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート等が挙げられ、中でもイソデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソステアリル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレートが好適に用いられる。 Examples of the aliphatic or alicyclic alkyl (meth) acrylate having 6 or more carbon atoms include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and isooctyl (meta). ) Acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate Etc., and among them isodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate is preferably used.
炭素数6以上の脂肪族又は脂環族アルキルの(メタ)アクリレート以外の単官能(メタ)アクリレートとしては、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、グリセリンモノ(メタ)アクリレート、グリシジル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、n−ブチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノールエチレンオキサイド変性(n=2)(メタ)アクリレート、ノニルフェノールプロピレンオキサイド変性(n=2.5)(メタ)アクリレート、2−(メタ)アクリロイルオキシエチルアシッドホスフェート、フルフリル(メタ)アクリレート、カルビトール(メタ)アクリレート、ベンジル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、アリル(メタ)アクリレート、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、2−ヒドロキシブチル(メタ)アクリレート、2−フェノキシ−2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリレート、3−クロロ−2−ヒドロキシプロピル(メタ)アクリレート等が挙げられる。 Examples of monofunctional (meth) acrylates other than (meth) acrylates of aliphatic or alicyclic alkyl having 6 or more carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycerin mono (Meth) acrylate, glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide Modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, Toxiethyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) Examples include acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate.
これらの中でも、水酸基を含有しない単官能(メタ)アクリレートが好ましく、更には、分子量が100〜300程度の該アクリレートが好ましい。 Among these, monofunctional (meth) acrylates that do not contain a hydroxyl group are preferable, and further, acrylates having a molecular weight of about 100 to 300 are preferable.
2官能(メタ)アクリレートとしては、例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、エチレンオキサイド変性ビスフェノールA型ジ(メタ)アクリレート、プロピレンオキサイド変性ビスフェノールA型ジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、エチレングリコールジグリシジルエーテルジ(メタ)アクリレート、ジエチレングリコールジグリシジルエーテルジ(メタ)アクリレート、フタル酸ジグリシジルエステルジ(メタ)アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ(メタ)アクリレート等が挙げられる。 Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified Bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pen Erythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) An acrylate etc. are mentioned.
3官能以上の(メタ)アクリレートとしては、例えば、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、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリ(メタ)アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ(メタ)アクリレート等が挙げられる。 Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Examples include hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, and glycerin polyglycidyl ether poly (meth) acrylate.
上記エチレン性不飽和単量体(B)は、単独で用いても又は2種以上併用して用いてもよい。 The ethylenically unsaturated monomer (B) may be used alone or in combination of two or more.
また本発明において、上記ウレタン(メタ)アクリレート系樹脂(A)とエチレン性不飽和単量体(B)の含有量については、(A):(B)が10:90〜95:5(質量比)であることが好ましく、更には50:50〜80:20(質量比)であることが好ましい。樹脂(A)の含有量が上記範囲未満では接着力が悪くなり、一方上記範囲を越えると塗工性が悪くなり、実用上問題が起こり好ましくない。 Moreover, in this invention, (A) :( B) is 10: 90-95: 5 (mass) about content of the said urethane (meth) acrylate type-resin (A) and an ethylenically unsaturated monomer (B). Ratio), more preferably 50:50 to 80:20 (mass ratio). When the content of the resin (A) is less than the above range, the adhesive strength is deteriorated. On the other hand, when the content exceeds the above range, the coating property is deteriorated, causing a problem in practical use.
<(C)放射線ラジカル重合開始剤(光重合開始剤)>
本発明で用いられる放射線ラジカル重合開始剤(C)としては、例えば、ジアセチルなどのα−ジケトン類;ベンゾインなどのアシロイン類;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのアシロインエーテル類;チオキサントン、2,4−ジエチルチオキサントン、チオキサントン−4−スルホン酸、ベンゾフェノン、4,4’−ビス(ジメチルアミノ)ベンゾフェノン、4,4’−ビス(ジエチルアミノ)ベンゾフェノンなどのベンゾフェノン類;アセトフェノン、p−ジメチルアミノアセトフェノン、α,α−ジメトキシ−α−アセトキシアセトフェノン、α,α−ジメトキシ−α−フェニルアセトフェノン、p−メトキシアセトフェノン、1−[2−メチル−4−メチルチオフェニル]−2−モルフォリノ−1−プロパノン、α,α−ジメトキシ−α−モルホリノ−メチルチオフェニルアセトフェノン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタン−1−オンなどのアセトフェノン類;アントラキノン、1,4−ナフトキノンなどのキノン類;フェナシルクロライド、トリブロモメチルフェニルスルホン、トリス(トリクロロメチル)−s−トリアジンなどのハロゲン化合物;[1,2’−ビスイミダゾール]−3,3’,4,4’−テトラフェニル、[1,2’−ビスイミダゾール]−1,2’−ジクロロフェニル−3,3’,4,4’−テトラフェニルなどのビスイミダゾール類、ジ−tert−ブチルパーオキサイドなどの過酸化物;2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類などが挙げられる。<(C) Radiation radical polymerization initiator (photopolymerization initiator)>
Examples of the radiation radical polymerization initiator (C) used in the present invention include α-diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethyl Aminoacetophenone, α, α-dimethoxy-α-acetoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4-methylthiophenyl] -2 Acetophenones such as morpholino-1-propanone, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; [1,2'-bisimidazole] -3,3 ' , 4,4′-tetraphenyl, [1,2′-bisimidazole] -1,2′-dichlorophenyl-3,3 ′, 4,4′-tetraphenyl, and the like, di-tert-butylper Peroxides such as oxides; 2,4,6-trimethylbenzoyldiphenylphosphine oxy And acylphosphine oxides such as side.
市販品としては、イルガキュア184、651、500、907、CGI369、CG24−61、ルシリンLR8728、ルシリンTPO、ダロキュア1116、1173(以上、BASF(株)製)、ユベクリルP36(UCB(株)製)などの商品名で市販されているものを挙げることができる。 Commercially available products include Irgacure 184, 651, 500, 907, CGI 369, CG 24-61, Lucirin LR8728, Lucilin TPO, Darocur 1116, 1173 (above, manufactured by BASF Corp.), Ubekrill P36 (manufactured by UCB Corp.), etc. The commercial name can be mentioned.
上記の中では、1−[2−メチル−4−メチルチオフェニル]−2−モルフォリノ−1−プロパノン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタン−1−オン、α,α−ジメトキシ−α−フェニルアセトフェノンなどのアセトフェノン類、フェナシルクロライド、トリブロモメチルフェニルスルホン、2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキサイド、1,2’−ビスイミダゾール類と4,4’−ジエチルアミノベンゾフェノンとメルカプトベンゾチアゾールとの併用、ルシリンTPO(商品名)、イルガキュア651(商品名)、イルガキュア369(商品名)が好ましい。 Among the above, 1- [2-methyl-4-methylthiophenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Acetophenones such as α, α-dimethoxy-α-phenylacetophenone, phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2′-bisimidazoles and 4, A combination of 4′-diethylaminobenzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irgacure 651 (trade name), and Irgacure 369 (trade name) are preferred.
上記放射線ラジカル重合開始剤(C)は、1種単独で用いても2種以上を組み合わせて用いてもよい。上記放射線ラジカル重合開始剤(C)は、上記樹脂(A)100質量部に対して、好ましくは0.1〜50質量部、より好ましくは1〜30質量部、特に好ましくは2〜30質量部の量で用いることができる。放射線ラジカル重合開始剤(C)の使用量が前記範囲より少ないと、酸素によるラジカルの失活の影響(感度の低下)を受けやすく、前記範囲よりも多いと、相溶性が悪くなったり、保存安定性が低下したりする傾向がある。 The radiation radical polymerization initiator (C) may be used alone or in combination of two or more. The radiation radical polymerization initiator (C) is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass with respect to 100 parts by mass of the resin (A). Can be used. If the amount of the radiation radical polymerization initiator (C) used is less than the above range, it is easily affected by radical deactivation (sensitivity reduction) due to oxygen, and if it is more than the above range, the compatibility may be deteriorated or stored. The stability tends to decrease.
本発明の組成物では、必要に応じてメルカプトベンゾチオアゾール、メルカプトベンゾオキサゾールのような水素供与性を有する化合物や、放射線増感剤を上記放射線ラジカル重合開始剤(C)と併用することもできる。 In the composition of the present invention, if necessary, a compound having a hydrogen donating property such as mercaptobenzothioazole or mercaptobenzoxazole, or a radiosensitizer can be used in combination with the radiation radical polymerization initiator (C). .
<他の成分>
本発明の樹脂組成物は、上述した樹脂(A)、及び、必要に応じて、少なくとも1個のエチレン性不飽和二重結合を有する化合物(B)及び/又は放射線ラジカル重合開始剤(C)の他に、必要に応じて、界面活性剤(D)、熱重合禁止剤(E)、酸無水物(F)等の各種添加剤や溶剤などの他の成分を含有してもよい。<Other ingredients>
The resin composition of the present invention comprises the above-described resin (A) and, if necessary, a compound (B) having at least one ethylenically unsaturated double bond and / or a radiation radical polymerization initiator (C). In addition, other components such as surfactants (D), thermal polymerization inhibitors (E), acid anhydrides (F), and other additives and solvents may be contained as necessary.
<(D)界面活性剤>
本発明の樹脂組成物には、塗布性、消泡性、レベリング性などを向上させる目的で界面活性剤(D)を配合することもできる。<(D) Surfactant>
In the resin composition of the present invention, a surfactant (D) can be blended for the purpose of improving applicability, antifoaming property, leveling property and the like.
このような界面活性剤(D)としては、例えば、BM−1000、BM−1100(以上、BM ケミー社製)、メガファックF142D、同F172、同F173、同F183(以上、DIC(株)製)、フロラードFC−135、同FC−170C、同FC−430、同FC−431(以上、住友スリーエム(株)製)、サーフロンS−112、同S−113、同S−131、同S−141、同S−145(以上、旭硝子(株)製)、SH−28PA、同−190、同−193、SZ−6032、SF−8428(以上、東レダウコーニングシリコーン(株)製)などの商品名で市販されているフッ素系界面活性剤を使用することができる。 Examples of such a surfactant (D) include BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F173 (above, manufactured by DIC Corporation). ), FLORARD FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S- 141, S-145 (made by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, made by Toray Dow Corning Silicone) Fluorosurfactants marketed by name can be used.
上記界面活性剤(D)の配合量は、上記樹脂(A)100質量部に対して好ましくは5質量部以下である。 The compounding amount of the surfactant (D) is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (A).
<(E)熱重合禁止剤>
本発明の樹脂組成物には、熱重合禁止剤(E)を添加することができる。このような熱重合禁止剤(E)としては、例えば、ピロガロール、ベンゾキノン、ヒドロキノン、メチレンブルー、tert−ブチルカテコール、モノベンジルエーテル、メチルヒドロキノン、アミルキノン、アミロキシヒドロキノン、n−ブチルフェノール、フェノール、ヒドロキノンモノプロピルエーテル、4,4’−(1−メチルエチリデン)ビス(2−メチルフェノール)、4,4’−(1−メチルエチリデン)ビス(2,6−ジメチルフェノール)、4,4’−[1−〔4−(1−(4−ヒドロキシフェニル)−1−メチルエチル)フェニル〕エチリデン]ビスフェノール、4,4’,4’’−エチリデントリス(2−メチルフェノール)、4,4’,4’’−エチリデントリスフェノール、1,1,3−トリス(2,5−ジメチル−4−ヒドロキシフェニル)−3−フェニルプロパンなどを挙げることができる。<(E) Thermal polymerization inhibitor>
A thermal polymerization inhibitor (E) can be added to the resin composition of the present invention. Examples of such thermal polymerization inhibitors (E) include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl. Ether, 4,4 ′-(1-methylethylidene) bis (2-methylphenol), 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 ′-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidene tris (2-methylphenol), 4,4 ′, 4 ″ Ethylidene trisphenol, 1,1,3-tris (2,5-dimethyl-4-hydride Kishifeniru) -3-phenyl-propane and the like.
上記熱重合禁止剤(E)の使用量は、樹脂(A)100質量部に対して好ましくは5質量部以下である。 The amount of the thermal polymerization inhibitor (E) used is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (A).
<(F)酸又は酸無水物>
本発明の樹脂組成物には、アルカリ現像液に対する溶解性の微調整を行うために、例えば、酢酸、プロピオン酸、n−酪酸、iso−酪酸、n−吉草酸、iso−吉草酸、安息香酸、けい皮酸などのモノカルボン酸;乳酸、2−ヒドロキシ酪酸、3−ヒドロキシ酪酸、サリチル酸、m−ヒドロキシ安息香酸、p−ヒドロキシ安息香酸、2−ヒドロキシけい皮酸、3−ヒドロキシけい皮酸、4−ヒドロキシけい皮酸、5−ヒドロキシイソフタル酸、シリンギン酸などのヒドロキシモノカルボン酸;シュウ酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、イタコン酸、ヘキサヒドロフタル酸、フタル酸、イソフタル酸、テレフタル酸、1,2−シクロヘキサンジカルボン酸、1,2,4−シクロヘキサントリカルボン酸、トリメリット酸、ピロメリット酸、シクロペンタンテトラカルボン酸、ブタンテトラカルボン酸、1,2,5,8−ナフタレンテトラカルボン酸などの多価カルボン酸;無水イタコン酸、無水コハク酸、無水シトラコン酸、無水ドデセニルコハク酸、無水トリカルバニル酸、無水マレイン酸、無水ヘキサヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水ハイミック酸、1,2,3,4−ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水フタル酸、無水ピロメリット酸、無水トリメリット酸、無水ベンゾフェノンテトラカルボン酸、エチレングリコールビス無水トリメリテート、グリセリントリス無水トリメリテートなどの酸又は酸無水物(F)を添加してもよい。<(F) Acid or acid anhydride>
In the resin composition of the present invention, for example, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid are used for fine adjustment of solubility in an alkali developer. Monocarboxylic acids such as cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, Hydroxymonocarboxylic acids such as 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid Terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, Polycarboxylic acids such as lomellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, anhydrous Tricarbanilic acid, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride Acids or acid anhydrides (F) such as acid, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, glycerin tris anhydrous trimellitate may be added.
<溶剤>
溶剤としては、樹脂(A)及び各成分を均一に溶解させることができ、また各成分と反応しないものが用いられる。このような溶剤としては、上記ウレタン(メタ)アクリレート系樹脂(A)を製造する際に用いられる重合溶剤と同様の溶剤を用いることができ、さらに、N−メチルホルムアミド、N,N−ジメチルホルムアミド、N−メチルホルムアニリド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、1−オクタノール、1−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテートなどの高沸点溶媒を添加することもできる。<Solvent>
As the solvent, those that can uniformly dissolve the resin (A) and each component and that do not react with each component are used. As such a solvent, the same solvent as the polymerization solvent used when producing the urethane (meth) acrylate resin (A) can be used, and N-methylformamide, N, N-dimethylformamide can be used. N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, High-boiling solvents such as 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.
これらの中では、溶解性、各成分との反応性及び塗膜形成の容易性から、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテルなどの多価アルコールのアルキルエーテル類;エチレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどの多価アルコールのアルキルエーテルアセテート類;3−エトキシプロピオン酸エチル、3−メトキシプロピオン酸メチル、2−ヒドロキシプロピオン酸エチル、乳酸エチルなどのエステル類;ジアセトンアルコールなどのケトン類が好適である。上記溶剤の使用量は、用途や塗布方法などに応じて適宜決めることができる。 Among them, polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether; ethylene glycol ethyl ether acetate, propylene glycol due to solubility, reactivity with each component and ease of film formation Alkyl ether acetates of polyhydric alcohols such as monomethyl ether acetate; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 2-hydroxypropionate and ethyl lactate; ketones such as diacetone alcohol Is preferred. The amount of the solvent used can be determined as appropriate according to the application and application method.
<樹脂組成物の調製>
本発明の樹脂組成物を調製するには、上記樹脂(A)、必要に応じて(B)及び/又は(C)、ならびに必要に応じて上記成分(D)やその他の成分を公知の方法で混合して攪拌する。例えば、攪拌羽根を有するSUS製調製タンクに各原料を必要量投入し、室温下において均一になるまで攪拌する。また必要に応じて、さらにメッシュ、メンブレンフィルターなどを用いて得られた組成物をろ過してもよい。<Preparation of resin composition>
In order to prepare the resin composition of the present invention, the above-mentioned resin (A), if necessary (B) and / or (C), and if necessary, the above-mentioned component (D) and other components are known methods. Mix with stirring. For example, a necessary amount of each raw material is put into a SUS preparation tank having stirring blades, and stirred at room temperature until uniform. Moreover, you may filter the composition obtained using the mesh, the membrane filter, etc. further as needed.
<導体パターンを有する各種基板の製造方法>
本発明の導体パターンを有する各種基板の製造方法は、上述した本発明の樹脂組成物を、ガラス基板又はSiO2膜もしくはSiN膜等の絶縁膜で被覆された基板等に塗布してレジスト膜を形成する工程と、無電解めっき加工してパターニングする工程とを含む。以下、本発明の導体パターンを有する各種基板の製造方法について、工程ごとに詳しく説明する。<Manufacturing method of various substrates having conductor patterns>
In the method for producing various substrates having a conductor pattern of the present invention, the above-described resin composition of the present invention is applied to a glass substrate or a substrate coated with an insulating film such as a SiO 2 film or a SiN film, and a resist film is applied. And forming and patterning by electroless plating. Hereafter, the manufacturing method of the various board | substrate which has a conductor pattern of this invention is demonstrated in detail for every process.
(1)レジスト膜の形成
本発明の樹脂組成物をガラス基板又はSiO2膜もしくはSiN膜等の絶縁膜で被覆された基板に塗布し、加熱により溶媒を除去することにより所望のレジスト膜を形成することができる。(1) Formation of resist film The resin composition of the present invention is applied to a glass substrate or a substrate covered with an insulating film such as a SiO 2 film or SiN film, and the solvent is removed by heating to form a desired resist film. can do.
基板への塗布方法としては、スピンコート法、スリットコート法、ロールコート法、スクリーン印刷法、アプリケーター法などが適用できる。 As a coating method on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be applied.
本発明の樹脂組成物の塗膜の乾燥条件は、組成物中の各成分の種類、配合割合、塗膜の厚さなどによって異なるが、通常は40〜160℃、好ましくは60〜120℃で、3〜15分程度である。乾燥時間が短すぎると、現像時の密着状態が悪くなり、また、長すぎると熱かぶりによる解像度の低下を招くことがある。 The drying condition of the coating film of the resin composition of the present invention varies depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, etc., but is usually 40 to 160 ° C., preferably 60 to 120 ° C. 3 to 15 minutes. If the drying time is too short, the adhesion state at the time of development deteriorates, and if it is too long, the resolution may be lowered due to heat fogging.
(2)放射線照射
得られた塗膜に所望のパターンを有するフォトマスクを介し、例えば波長が300〜500nmの紫外線又は可視光線などの放射線を照射することにより、露光部を硬化させることができる。(2) Irradiation The exposed portion can be cured by irradiating the obtained coating film with radiation such as ultraviolet rays or visible rays having a wavelength of 300 to 500 nm through a photomask having a desired pattern.
ここで放射線とは、紫外線、可視光線、遠紫外線、X線、電子線などを意味し、光源として、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、アルゴンガスレーザーなどを用いることができる。 Here, the radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like, and a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used as a light source.
放射線照射量は、組成物中の各成分の種類、配合量、塗膜の厚さなどによって異なるが、例えば高圧水銀灯使用の場合、100〜1500mJ/cm2の範囲である。The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the thickness of the coating film, etc., but is, for example, in the range of 100 to 1500 mJ / cm 2 when using a high-pressure mercury lamp.
(3)現像
放射線照射後の現像方法としては、アルカリ性水溶液又は有機溶媒を現像液として用いて、不要な非露光部を溶解、除去し、露光部のみを残存させ、所望のパターンの硬化膜を得る。アルカリ性の現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水、エチルアミン、n−プロピルアミン、ジエチルアミン、ジ−n−プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセン、1,5−ジアザビシクロ[4.3.0]−5−ノナンなどのアルカリ類の水溶液を使用することができる。(3) Development As a development method after radiation irradiation, an alkaline aqueous solution or an organic solvent is used as a developer to dissolve and remove unnecessary non-exposed portions, leaving only the exposed portions, and forming a cured film with a desired pattern. obtain. Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. 3.0] An aqueous solution of an alkali such as 5-nonane can be used.
また、上記アルカリ類の水溶液にメタノール、エタノールなどの水溶性有機溶媒や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。 Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
有機溶媒の現像液は樹脂(A)を良好に溶解するものなら特に制限は受けず、例えば、トルエン、キシレンなどの芳香族系化合物、n−ヘキサン、シクロヘキサン、イソパラフィンなどの脂肪族系化合物、テトラヒドロフランなどのエーテル系化合物、メチルエチルケトン、シクロヘキサノンなどのケトン系化合物、酢酸エステルなどのエステル系化合物、1,1,1−トリクロロエタンなどのハロゲン系化合物、などを使用することができる。また現像速度を調整する目的で上記現像液にエタノール、イソプロパノール等の樹脂(A)を溶解しない溶媒を適当量添加して使用することもできる。 The organic solvent developer is not particularly limited as long as it can dissolve the resin (A) satisfactorily. For example, aromatic compounds such as toluene and xylene, aliphatic compounds such as n-hexane, cyclohexane and isoparaffin, tetrahydrofuran And ether compounds such as methyl ethyl ketone and cyclohexanone, ester compounds such as acetate, halogen compounds such as 1,1,1-trichloroethane, and the like. For the purpose of adjusting the developing speed, an appropriate amount of a solvent that does not dissolve the resin (A) such as ethanol or isopropanol can be added to the developer and used.
現像時間は、組成物中の各成分の種類、配合割合、塗膜の厚さなどによって異なるが、通常30〜1000秒間であり、また現像の方法はディッピング法、パドル法、スプレー法、シャワー現像法などのいずれでもよい。現像後は、流水洗浄を30〜90秒間行い、スピンドライやエアーガンなどを用いて風乾させたり、ホットプレート、オーブンなど加熱下で乾燥させたりする。 The development time varies depending on the type of each component in the composition, the mixing ratio, the thickness of the coating film, etc., but is usually 30 to 1000 seconds, and the development method is a dipping method, paddle method, spray method, shower development. Any of the methods may be used. After the development, washing with running water is performed for 30 to 90 seconds, and air drying is performed using a spin dry, an air gun, or the like, or drying is performed under heating such as a hot plate or an oven.
(4)後処理
本発明の樹脂組成物から得られる塗膜は、前記の放射線照射のみでも、十分に硬化させることができるが、追加の放射線照射(以下「後露光」という)や加熱によってさらに硬化させることができる。(4) Post-treatment Although the coating film obtained from the resin composition of the present invention can be sufficiently cured only by the above-mentioned radiation irradiation, it can be further cured by additional radiation irradiation (hereinafter referred to as “post-exposure”) or heating. It can be cured.
後露光としては、上記放射線照射方法と同様の方法で行うことができ、放射線照射量は特に限定されるものではないが、高圧水銀灯使用の場合100〜2000mJ/cm2の範囲が好ましい。また、加熱する際の方法は、ホットプレート、オーブンなどの加熱装置を用いて、所定の温度、例えば60〜150℃で、所定の時間、例えばホットプレート上なら5〜30分間、オーブン中では5〜60分間加熱処理をすればよい。この後処理によって、さらに良好な特性を有する所望のパターンの硬化膜を得ることができる。The post-exposure can be performed by the same method as the above-mentioned radiation irradiation method, and the radiation irradiation amount is not particularly limited, but is preferably in the range of 100 to 2000 mJ / cm 2 when using a high-pressure mercury lamp. The heating method is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 60 to 150 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, or 5 in the oven. What is necessary is just to heat-process for ~ 60 minutes. By this post-treatment, a cured film having a desired pattern having even better characteristics can be obtained.
(5)無電解めっき加工
上記のようにして硬化膜のパターンが形成された各種基板を無電解めっきする方法としては、公知の方法が採用される。すなわち、必要に応じて、脱脂、エッチング、洗浄等の前処理や予備めっきで表面を清浄し、あるいは活性化後、めっき浴中で無電解めっきする。無電解めっきしたときは、その後、必要に応じて電気めっきしてもよい。(5) Electroless Plating Processing As a method for electroless plating the various substrates on which the cured film pattern is formed as described above, a known method is employed. That is, if necessary, the surface is cleaned by pretreatment such as degreasing, etching, washing, or preliminary plating, or after activation, electroless plating is performed in a plating bath. When electroless plating is performed, electroplating may then be performed as necessary.
例えば、銀めっきには、シアン化銀めっき浴、銅めっきには、シアン化銅めっき浴、硫酸銅浴、ピロリン酸銅浴、無電解銅めっき浴、ニッケルめっきには、酸性ニッケル浴、無電解ニッケルめっき浴、金めっきには、酸性又はアルカリ性金めっき浴、中性浴、シアン浴を適用することができる。これらのめっき浴には、めっきされる銀、銅、ニッケル、金などの金属成分のほか、シアン、ピロリン酸などの無機錯化剤、ギ酸、酢酸、クエン酸などの有機錯化剤、化学めっきで使用されるコハク酸、グルコン酸、トリエタノールアミンなどの錯化剤、ギ酸、ほう酸、アンモニアなどの緩衝剤、硫酸、塩酸、塩化物、炭酸塩などの電導度塩や、触媒、補助成分としてpH調整剤、酸化剤、還元剤、イオン封鎖剤、沈殿防止剤、光沢剤、物性調整剤などが添加されていてもよい。 For example, for silver plating, silver cyanide plating bath, for copper plating, copper cyanide plating bath, copper sulfate bath, copper pyrophosphate bath, electroless copper plating bath, for nickel plating, acidic nickel bath, electroless An acid or alkaline gold plating bath, neutral bath, and cyan bath can be applied to the nickel plating bath and gold plating. These plating baths include metal components such as silver, copper, nickel and gold to be plated, inorganic complexing agents such as cyan and pyrophosphoric acid, organic complexing agents such as formic acid, acetic acid and citric acid, and chemical plating. As a complexing agent such as succinic acid, gluconic acid and triethanolamine, buffering agents such as formic acid, boric acid and ammonia, conductive salts such as sulfuric acid, hydrochloric acid, chloride and carbonate, catalysts, and auxiliary components A pH adjuster, an oxidizing agent, a reducing agent, an ion sequestering agent, a suspending agent, a brightening agent, a physical property adjusting agent and the like may be added.
(6)剥離処理
エッチング後、レジスト膜を基板から剥離する。ここで使用される剥離液は、水酸化ナトリウム、水酸化カリウム等の無機アルカリ成分や、トリメタノールアミン、トリエタノールアミン、ジメチルアニリン等の第3級アミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の第4級アンモニウムの有機アルカリ成分を、水、ジメチルスルホキシド、N−メチルピロリドン単独又はこれらの混合溶液に溶解したものが挙げられる。またトルエン、キシレンなどの脂肪族系溶媒を剥離液として使用することで、レジスト膜を膨潤させて剥離することもできる。(6) Stripping treatment After etching, the resist film is stripped from the substrate. The stripping solution used here includes inorganic alkali components such as sodium hydroxide and potassium hydroxide, tertiary amines such as trimethanolamine, triethanolamine and dimethylaniline, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. And those obtained by dissolving an organic alkali component of quaternary ammonium such as water, dimethyl sulfoxide, N-methylpyrrolidone alone or a mixed solution thereof. Further, by using an aliphatic solvent such as toluene or xylene as a stripping solution, the resist film can be swollen and stripped.
これらの剥離液を使用し、スプレー法、シャワー法及びパドル法等の方法で剥離することも可能である。具体的には、ジメチルスルホキシドに2質量%のテトラメチルアンモニウムヒドロキシドを溶解した剥離液を30〜80℃に加温し、上記基板を5〜30分間浸漬し、攪拌することでレジスト膜を剥離することができる。 Using these stripping solutions, stripping can be performed by a method such as a spray method, a shower method, or a paddle method. Specifically, the resist film is removed by heating a stripping solution in which 2% by mass of tetramethylammonium hydroxide is dissolved in dimethyl sulfoxide to 30 to 80 ° C., immersing the substrate for 5 to 30 minutes, and stirring. can do.
さらには、加温したアルコールに浸漬して超音波処理により膨潤剥離する方法や、手動でピーリングにより物理的に剥離することも可能である。 Furthermore, it is also possible to swell and peel by ultrasonic treatment after immersing in warm alcohol, or physically peel by peeling manually.
以下、実施例に基づいて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
[合成例1]
・ポリブタジエン系ポリウレタン樹脂[A−1]
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた4つ口フラスコに、両末端水酸基水素化ポリブタジエン(日本曹達社製GI−3000)100g、ジイソシアン酸イソホロン7g、シクロヘキサノン(溶媒)200g、ジラウリン酸ジブチルすず(触媒)0.002gを仕込み、70℃で一晩反応させて水添ポリブタジエン系ポリウレタン樹脂[A−1]〔重量平均分子量79,000〕を樹脂溶液として得た。[Synthesis Example 1]
・ Polybutadiene polyurethane resin [A-1]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of both ends hydroxylated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 7 g of isophorone diisocyanate, 200 g of cyclohexanone (solvent) 0.002 g of dibutyltin dilaurate (catalyst) was charged and reacted at 70 ° C. overnight to obtain a hydrogenated polybutadiene polyurethane resin [A-1] [weight average molecular weight 79,000] as a resin solution.
[合成例2]〜[合成例5]
各化合物の量を表1に記載の組成に変更した以外は合成例1と同様にして、樹脂[A−2]〜[A−5]をそれぞれ合成した。[Synthesis Example 2] to [Synthesis Example 5]
Resins [A-2] to [A-5] were synthesized in the same manner as in Synthesis Example 1 except that the amount of each compound was changed to the composition shown in Table 1.
[合成例6]
・アルカリ可溶性基導入ポリブタジエン系ポリウレタン樹脂[A−6]
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた4つ口フラスコに、両末端水酸基水素化ポリブタジエン(日本曹達社製GI−3000)100g、2,2−ビス(ヒドロキシエチル)プロピオン酸2.7g、ジイソシアン酸イソホロン18.4g、シクロヘキサノン(溶媒)200g、ジラウリン酸ジブチルすず(触媒)0.005gを仕込み、70℃で3時間反応させて水添ポリブタジエン系ポリウレタン樹脂[A−6]〔重量平均分子量19,000〕を樹脂溶液として得た。[Synthesis Example 6]
・ Alkali-soluble group-introduced polybutadiene polyurethane resin [A-6]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of hydroxylated hydrogenated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 2,2-bis (hydroxyethyl) propionic acid 2.7 g, isophorone diisocyanate 18.4 g, cyclohexanone (solvent) 200 g, dibutyltin dilaurate (catalyst) 0.005 g were charged and reacted at 70 ° C. for 3 hours to give a hydrogenated polybutadiene polyurethane resin [A-6] [ Weight average molecular weight 19,000] was obtained as a resin solution.
[合成例7]
・ポリブタジエン系ポリエステル樹脂[A−7]
温度計、撹拌子、ディーン・スターク装置、水冷コンデンサーを備えたフラスコに、両末端水酸基水素化ポリブタジエン(日本曹達社製GI−3000)100g、テレフタロイルクロリド5.9g、トルエン(溶媒)200g、ピリジン(触媒)6.9gを仕込み、130℃で一晩反応させてポリブタジエン系ポリエステル樹脂[A−7]〔重量平均分子量49,000〕を得た。[Synthesis Example 7]
・ Polybutadiene polyester resin [A-7]
In a flask equipped with a thermometer, a stirrer, a Dean-Stark device, and a water-cooled condenser, 100 g of both-end hydroxylated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 5.9 g of terephthaloyl chloride, 200 g of toluene (solvent), 6.9 g of pyridine (catalyst) was charged and reacted at 130 ° C. overnight to obtain a polybutadiene-based polyester resin [A-7] [weight average molecular weight 49,000].
[合成例8]
・(メタ)アクリレート基導入ポリブタジエン系ポリウレタン樹脂[A−8]
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた4つ口フラスコに、両末端水酸基水素化ポリブタジエン(日本曹達社製GI−3000)100g、ジイソシアン酸イソホロン13.8g、シクロヘキサノン(溶媒)200g、ジラウリン酸ジブチルすず(触媒)0.005gを仕込み、70℃で3時間反応させた後、さらにジイソシアン酸イソホロン3.4g、アクリル酸2−ヒドロキシエチル3.6gを加えて70℃で3時間反応させて(メタ)アクリレート基導入ポリブタジエン系ポリウレタン樹脂[A−8]〔重量平均分子量17,000〕を樹脂溶液として得た。以下、樹脂[A−1]〜樹脂[A−8]の組成を表1に示す。[Synthesis Example 8]
・ (Meth) acrylate group-introduced polybutadiene polyurethane resin [A-8]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of hydroxylated hydrogenated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 13.8 g of isophorone diisocyanate, cyclohexanone (solvent) 200 g and 0.005 g of dibutyltin dilaurate (catalyst) were added and reacted at 70 ° C. for 3 hours. Then, 3.4 g of isophorone diisocyanate and 3.6 g of 2-hydroxyethyl acrylate were added and the mixture was stirred at 70 ° C. for 3 hours. By reacting, a (meth) acrylate group-introduced polybutadiene polyurethane resin [A-8] [weight average molecular weight 17,000] was obtained as a resin solution. The compositions of Resin [A-1] to Resin [A-8] are shown in Table 1.
a−1−1:両末端水酸基水素化ポリブタジエン GI−3000 (日本曹達社製)
a−1−2:両末端水酸基水素化ポリブタジエン GI−1000 (日本曹達社製)
a−1−3:水酸基末端液状ポリブタジエン R−45HT (出光興産社製)
a−2−1:ジイソシアン酸イソホロン (東京化成工業社製)
a−2−2:ヘキサメチレンジイソシアナート (東京化成工業社製)
a−2−3:4,4’−ジイソシアン酸メチレンジフェニル (東京化成工業社製)
a−2−4:テレフタロイルクロリド (東京化成工業社製)
b−1:アクリル酸2−ヒドロキシエチル (東京化成工業社製)
c−1:2,2−ビス(ヒドロキシエチル)プロピオン酸a-1-1: Both end hydroxyl group-hydrogenated polybutadiene GI-3000 (manufactured by Nippon Soda Co., Ltd.)
a-1-2: hydroxylated hydrogenated polybutadiene at both ends GI-1000 (manufactured by Nippon Soda Co., Ltd.)
a-1-3: Hydroxyl-terminated liquid polybutadiene R-45HT (manufactured by Idemitsu Kosan Co., Ltd.)
a-2-1: Isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-2: Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-3: Methylenediphenyl 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-4: terephthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
b-1: 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
c-1: 2,2-bis (hydroxyethyl) propionic acid
<実用特性の評価>
(1)レジスト付き基板の作製
表2に記載の実施例1〜実施例7及び比較例1では、熱酸化膜(SiO2膜厚:300nm)を有するシリコン基板上にスピンコーターを用いて上述の樹脂溶液を塗布した後、ホットプレートにて120℃で10分間ベークして膜厚40μmの塗膜(レジスト)を形成した。比較例2〜比較例3では樹脂液に触媒としてp−トルエンスルホン酸4質量%を配合したのち、ベーク条件を220℃で5分間とした以外は実施例1と同様にして膜厚40μmの塗膜(レジスト)を形成した。実施例8〜実施例10では樹脂溶液もしくは樹脂液にエチレン性不飽和単量体(B)(樹脂(A)100質量部に対して127質量部)と光重合開始剤(C)(樹脂(A)及び(B)成分の合計100質量部に対して3質量部)を混合した後、実施例1と同様にして膜厚40μmの塗膜を形成し、さらに高圧水銀灯を用いて2Jの紫外線に露光させることで塗膜(レジスト)を硬化させた。レジストの表面タック性を指で触って確認し、タック性が認められた場合は「あり」、認められない場合は「なし」とした。<Evaluation of practical properties>
(1) Production of Substrate with Resist In Examples 1 to 7 and Comparative Example 1 described in Table 2, the above-described process was performed using a spin coater on a silicon substrate having a thermal oxide film (SiO 2 film thickness: 300 nm). After the resin solution was applied, it was baked on a hot plate at 120 ° C. for 10 minutes to form a coating film (resist) having a thickness of 40 μm. In Comparative Examples 2 to 3, the resin solution was blended with 4% by mass of p-toluenesulfonic acid as a catalyst, and then coated in a film thickness of 40 μm in the same manner as in Example 1 except that the baking conditions were changed to 220 ° C. for 5 minutes. A film (resist) was formed. In Examples 8 to 10, an ethylenically unsaturated monomer (B) (127 parts by mass with respect to 100 parts by mass of the resin (A)) and a photopolymerization initiator (C) (resin ( A) and (B) 3 parts by mass with respect to the total of 100 parts by mass of the component (B), a coating film having a film thickness of 40 μm was formed in the same manner as in Example 1, and 2J ultraviolet rays were used using a high-pressure mercury lamp. The coating film (resist) was hardened by exposing to. The surface tackiness of the resist was confirmed by touching with a finger. When tackiness was recognized, “Yes” was indicated, and when it was not recognized, “No” was indicated.
(2)洗浄液(フッ酸溶液)耐性
上述の方法により作製したレジスト付き基板を25℃のフッ化水素酸20%水溶液に1時間浸漬後、レジストを物理的に剥離し、レジストに覆われていた部分の熱酸化膜の膜厚をエリプソメーター(J.A.Woollam社製M−2000)を用いて測定した。熱酸化膜の膜厚が290nm以上の場合を「◎」、200nm以上の場合を「○」、200nm未満の場合を「×」とした。(2) Resistance to cleaning liquid (hydrofluoric acid solution) The resist-coated substrate prepared by the above method was immersed in a 20% aqueous hydrofluoric acid solution at 25 ° C. for 1 hour, and then the resist was physically peeled off and covered with the resist. The thickness of the portion of the thermal oxide film was measured using an ellipsometer (JA Woollam M-2000). The case where the thickness of the thermal oxide film was 290 nm or more was “◎”, the case where it was 200 nm or more was “◯”, and the case where it was less than 200 nm was “×”.
(3)洗浄液(酸・アルカリ)耐性
フッ酸溶液耐性と同様にして表3に記載の酸性水溶液もしくはアルカリ性水溶液に1時間浸漬した後、水洗して乾燥させた。レジストに膨潤・溶解・剥離などの変質が認められた場合は「×」、認められない場合は「○」とした。(3) Washing liquid (acid / alkali) resistance In the same manner as the hydrofluoric acid solution resistance, the film was immersed in an acidic aqueous solution or alkaline aqueous solution described in Table 3 for 1 hour, then washed with water and dried. When the resist was observed to be altered such as swelling / dissolution / peeling, “x” was assigned.
(4)パターニング性
シリコン基板上にスピンコーターを用いて実施例9に用いた樹脂組成物を塗布した後、ホットプレートにて120℃で10分間ベークし、さらにマスクアライナ(ズース マイクロテック社製MA−6)を用いて2Jの紫外線に露光させることでパターン硬化させた。さらに120℃で10分間ベークした後、メチルイソブチルケトン60質量部とイソプロパノール40質量部を混合した溶媒により未露光部を除去することで高さ約70μm、幅約40μmのライン状レジストパターンを有する基板を作製した。作製した基板をへき開により切断して4cm角の大きさにし、レジストパターンの形状を走査型電子顕微鏡を用いて観察した。顕微鏡画像を図1に示す。(4) Patterning property After applying the resin composition used in Example 9 on a silicon substrate using a spin coater, the resultant was baked on a hot plate at 120 ° C. for 10 minutes, and then a mask aligner (MA manufactured by SUSS MICROTECH). The pattern was cured by exposing to 2J ultraviolet rays using -6). Further, after baking at 120 ° C. for 10 minutes, a substrate having a linear resist pattern having a height of about 70 μm and a width of about 40 μm is obtained by removing unexposed portions with a solvent in which 60 parts by mass of methyl isobutyl ketone and 40 parts by mass of isopropanol are mixed. Was made. The produced substrate was cut by cleavage to a size of 4 cm square, and the shape of the resist pattern was observed using a scanning electron microscope. A microscopic image is shown in FIG.
(5)無電解めっき液耐性
上記の(4)パターニング性の欄で作製したライン状レジストパターンを有するシリコン基板にメルテックス社の無電解ニッケルめっき試作用キット(メルプレート G・Si プロセスキット)を用いて、同キットの標準工程に従って脱脂、エッチング、コンディショニング、触媒付与、無電解ニッケルめっき、の一連の処理を行った。無電解めっき処理後の基板は水洗後、レジストをピーリングにより剥離し、ニッケルめっき被膜パターンの形状を光学顕微鏡を用いて観察した。顕微鏡画像を図2に示す。(5) Electroless plating solution resistance Electrolytic nickel plating prototype kit (Melplate G / Si process kit) manufactured by Meltex on a silicon substrate having a line resist pattern prepared in the above (4) Patterning section. A series of treatments of degreasing, etching, conditioning, catalyst application, and electroless nickel plating were performed according to the standard steps of the kit. The substrate after the electroless plating treatment was washed with water, the resist was peeled off by peeling, and the shape of the nickel plating film pattern was observed using an optical microscope. A microscopic image is shown in FIG.
UC−203:クラレ社製 メタクロイル変性液状イソプレンゴム
V−4221:DIC社製 ポリエステル系ポリウレタン
G−3000:日本曹達社製 両末端水酸基ポリブタジエン
R−45HT:出光興産社製 水酸基末端液状ポリブタジエン
B−1:イソデシルアクリレート (サートマー社製)
C−1:Irgacure(イルガキュア) 907 (BASF社製)UC-203: Kuraray-made methacryloyl-modified liquid isoprene rubber V-4221: DIC Corporation polyester polyurethane G-3000: Nippon Soda Co., Ltd. both-end hydroxyl group polybutadiene R-45HT: Idemitsu Kosan group hydroxyl-terminated liquid polybutadiene
B-1: Isodecyl acrylate (manufactured by Sartomer)
C-1: Irgacure (Irgacure) 907 (manufactured by BASF)
表2から次のことが言える。本発明の樹脂はシランカップリング剤を含まずとも基板密着性が良好なためエッチング後も基板に密着しており、またフッ酸のバリア性にも優れている。一方でポリブタジエン系ではないポリウレタン樹脂(比較例1)は密着性は良好なものの、フッ酸バリア性が得られない。またポリブタジエン系であってもウレタン結合やエステル結合などにより形成される水素結合がない場合はフッ酸バリア性が得られない(比較例2,3)。本発明の樹脂は軟質であるため、ベーク後も膜表面にタック性が残る場合があるが、水素結合の量によりタック性は制御することができる。すなわちウレタン結合やカルボン酸基などの水素結合を形成する部位の量を多くすると、膜が硬質になり表面タック性をなくすことができる。一方で水素結合が弱い、もしくは水素結合の量が少ない場合、フッ酸バリア性は若干ではあるが低下する(実施例7,実施例9,実施例10)。 From Table 2, the following can be said. Since the resin of the present invention does not contain a silane coupling agent and has good substrate adhesion, it adheres to the substrate even after etching, and also has excellent hydrofluoric acid barrier properties. On the other hand, polyurethane resin that is not polybutadiene (Comparative Example 1) has good adhesion, but does not have hydrofluoric acid barrier properties. Moreover, even if it is a polybutadiene type, when there is no hydrogen bond formed by a urethane bond or an ester bond, a hydrofluoric acid barrier property cannot be obtained (Comparative Examples 2 and 3). Since the resin of the present invention is soft, tackiness may remain on the film surface after baking, but the tackiness can be controlled by the amount of hydrogen bonds. That is, if the amount of the sites forming hydrogen bonds such as urethane bonds and carboxylic acid groups is increased, the film becomes hard and surface tackiness can be eliminated. On the other hand, when the hydrogen bond is weak or the amount of hydrogen bond is small, the hydrofluoric acid barrier property is slightly reduced (Example 7, Example 9, and Example 10).
また表3に示すように、本発明のレジストは高濃度の酸性水溶液もしくはアルカリ性水溶液中でも変質することなく良好な耐性を示す。特に、濃度70%の濃硝酸中では一般的な樹脂レジストは溶解してしまうが、本発明のレジストは変質することなく良好な基板密着性を維持した。なお粘度を低下させる目的でエチレン性不飽和単量体(B)を含有させたレジスト(実施例9)は硝酸耐性が低下し、一時間の浸漬後ではレジストが基板から剥離したが、30分間の浸漬後では剥離などの変質は見られなかった。 Further, as shown in Table 3, the resist of the present invention exhibits good resistance without being deteriorated even in a high concentration acidic aqueous solution or alkaline aqueous solution. In particular, a general resin resist is dissolved in concentrated nitric acid having a concentration of 70%, but the resist of the present invention maintains good substrate adhesion without being altered. Note that the resist containing the ethylenically unsaturated monomer (B) for the purpose of reducing the viscosity (Example 9) has reduced nitric acid resistance, and the resist peeled off from the substrate after immersion for one hour, but for 30 minutes. After immersion, no alteration such as peeling was observed.
また本発明の樹脂は、保護適切な溶媒の選択により現像・剥離が可能である。パターンUV露光及び現像処理により図1に示すように高アスペクトの良好なパターンが得られている。またエッチングプロセス後はキシレンやトルエンなどの有機溶媒で膨潤させることで残渣なく容易に剥離することができる。実際、図1に示すパターンをキシレンに浸漬すると約5秒でレジストが膨潤・剥離した。なお本発明においてアルカリ可溶性基を導入したレジスト(実施例6)はアルカリ性水溶液により剥離することも可能である。また図2に示すように本発明のレジストに覆われていた基板領域はニッケルめっき被膜が形成されておらず、スカムやフィッティングといっためっき液の浸透による被膜パターン汚染はほとんど確認されなかった。 Further, the resin of the present invention can be developed and peeled off by selecting a suitable solvent for protection. As shown in FIG. 1, a good pattern with a high aspect is obtained by pattern UV exposure and development processing. Further, after the etching process, it can be easily peeled without residue by swelling with an organic solvent such as xylene or toluene. Actually, when the pattern shown in FIG. 1 was immersed in xylene, the resist swelled and peeled off in about 5 seconds. In the present invention, the resist into which an alkali-soluble group has been introduced (Example 6) can be stripped with an alkaline aqueous solution. Further, as shown in FIG. 2, the nickel plating film was not formed in the substrate region covered with the resist of the present invention, and almost no coating pattern contamination due to the penetration of the plating solution such as scum and fitting was confirmed.
1…ガラス基板、2…ニッケル被膜 1 ... Glass substrate, 2 ... Nickel coating
Claims (13)
前記第2工程は、フッ酸を含む洗浄液を用いて前記基板を洗浄する工程と、フッ酸を含むめっき液を用いて前記無電解めっき加工する工程と、の少なくとも一方を含むことを特徴とする、基板の製造方法。 The component (A) is selected from the group consisting of a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol , a polyvalent carboxylic acid, a polyvalent acid chloride, and a polyisocyanate. A first step of forming a resist film by applying a composition containing a resin obtained by reacting with a crosslinking agent (a2) to be formed on the substrate, and patterning by electroless plating the substrate on which the resist film is formed a second step of a method of producing a substrate having a pattern formed by including electroless plating,
The second step includes at least one of a step of cleaning the substrate using a cleaning solution containing hydrofluoric acid and a step of performing the electroless plating using a plating solution containing hydrofluoric acid. A method for manufacturing a substrate.
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