JP7462573B2 - Etching resist composition and processed substrate obtained using the same - Google Patents
Etching resist composition and processed substrate obtained using the same Download PDFInfo
- Publication number
- JP7462573B2 JP7462573B2 JP2020561556A JP2020561556A JP7462573B2 JP 7462573 B2 JP7462573 B2 JP 7462573B2 JP 2020561556 A JP2020561556 A JP 2020561556A JP 2020561556 A JP2020561556 A JP 2020561556A JP 7462573 B2 JP7462573 B2 JP 7462573B2
- Authority
- JP
- Japan
- Prior art keywords
- resist composition
- etching
- carboxyl group
- meth
- containing resin
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 118
- 238000005530 etching Methods 0.000 title claims description 102
- 239000000758 substrate Substances 0.000 title claims description 84
- 229920005989 resin Polymers 0.000 claims description 66
- 239000011347 resin Substances 0.000 claims description 66
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 60
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 52
- -1 thiol compound Chemical class 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 23
- 229910052623 talc Inorganic materials 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000000454 talc Substances 0.000 claims description 19
- 150000008065 acid anhydrides Chemical class 0.000 claims description 17
- 150000007519 polyprotic acids Polymers 0.000 claims description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- NKMOLEYVYVWWJC-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCN1C(=O)N(CCOC(=O)CC(C)S)C(=O)N(CCOC(=O)CC(C)S)C1=O NKMOLEYVYVWWJC-UHFFFAOYSA-N 0.000 claims description 5
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 31
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 27
- 238000011161 development Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 230000035515 penetration Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 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 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000003698 laser cutting Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- SHJIJMBTDZCOFE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCO SHJIJMBTDZCOFE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 description 1
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920005731 JONCRYL® 67 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000038 blue colorant Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical class OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 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
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- YFDSDPIBEUFTMI-UHFFFAOYSA-N tribromoethanol Chemical compound OCC(Br)(Br)Br YFDSDPIBEUFTMI-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
-
- 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
- G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、フッ酸耐性に優れるエッチングレジスト組成物に関する。 The present invention relates to an etching resist composition having excellent resistance to hydrofluoric acid.
携帯電話機や、携帯情報端末、カーナビゲーションシステムを始め、様々な電子機器の操作部に採用されているタッチパネル型入力装置（以下、単に「タッチパネル」ともいう）や、光学材料、計測器等には、一般に、ガラス基板が用いられている。このようなガラス基板は、従来は機械加工又はレーザーカッティングにより切り出しにより製造されていた。 Glass substrates are generally used in touch panel input devices (hereinafter simply referred to as "touch panels") that are used in the operating sections of various electronic devices, including mobile phones, personal digital assistants, and car navigation systems, as well as in optical materials, measuring instruments, etc. Such glass substrates have traditionally been manufactured by cutting out the substrate using machining or laser cutting.
しかしながら、機械加工又はレーザーカッティング技術によると、特に強化ガラスのカッティングおよび穿孔加工の際に、ガラス端面や孔穴にバリや亀裂が生ずることがある。さらに、タッチパネル等の軽薄短小化に伴い、繊細な加工が可能なエッチング加工が求められるようになりつつある。 However, mechanical processing or laser cutting techniques can result in burrs and cracks on the glass edges and holes, especially when cutting and drilling tempered glass. Furthermore, as touch panels and other devices become lighter, thinner, shorter, and smaller, there is a growing demand for etching, which allows for delicate processing.
ガラスエッチングが可能なレジスト組成物としては、これまでに多くの提案がなされているが、その一例として、ガラス基板との密着性向上のためにシランカップリング剤を含むレジスト組成物が提案されている（特許文献１参照）。 Many resist compositions capable of glass etching have been proposed, one example of which is a resist composition containing a silane coupling agent to improve adhesion to glass substrates (see Patent Document 1).
しかしながら、特許文献１のレジスト組成物は、レジスト組成物とガラス基板の密着性が未だ不十分であり、フッ酸耐性および剥離性においても完全に満足とは言えない。
また、近年、ガラス以外の基材として、シリコンウェハ、チタンや金属酸化物等を含む基材の加工にフッ酸が使われているが、これらの基材に対しても密着性、フッ酸耐性および剥離性に優れるレジスト組成物については未だ報告されていない。
However, the resist composition of Patent Document 1 still has insufficient adhesion between the resist composition and a glass substrate, and the hydrofluoric acid resistance and strippability are also not completely satisfactory.
Furthermore, in recent years, hydrofluoric acid has been used to process substrates other than glass, such as silicon wafers, and substrates containing titanium and metal oxides. However, no resist compositions that exhibit excellent adhesion, hydrofluoric acid resistance, and strippability for these substrates have yet to be reported.
しかるに、本発明の目的は、レジスト組成物のガラスの他、シリコンウェハ、チタン、金属酸化物等の基材に対する密着性に優れ、フッ酸を含むエッチング液に対する耐性が十分であり、エッチング後の剥離性も向上したレジスト組成物を提供することにある。
また、本発明は上記のレジスト組成物を用いて、基材をエッチング加工することにより得られた基材加工品を得ることを目的とする。
Therefore, an object of the present invention is to provide a resist composition that has excellent adhesion to substrates such as glass, silicon wafers, titanium, and metal oxides, has sufficient resistance to an etching solution containing hydrofluoric acid, and has improved removability after etching.
Another object of the present invention is to obtain a processed substrate product by etching a substrate using the above resist composition.
本発明者らは、鋭意研究の結果、本発明の上記目的が、
フッ化水素酸単独若しくはフッ化水素酸を含むエッチング液を用いたエッチング加工から基板を保護するレジスト膜の形成に用いられるエッチングレジスト組成物であって、
（Ａ）カルボキシル基含有樹脂、
（Ｂ）多官能（メタ）アクリレートモノマー、
（Ｃ）多官能チオール化合物、
（Ｄ）光重合開始剤、および
（Ｅ）前記（Ａ）カルボキシル基含有樹脂１００質量部に対して２０～１００質量部のタルクを含み、
前記（Ｃ）多官能チオール化合物は、ペンタエリスリトールテトラキス（３-メルカプトブチレート)、および１，３，５-トリス（３-メルカプトブチリルオキシエチル）-１,３,５-トリアジン-２,４,６（１Ｈ，３Ｈ，５Ｈ）-トリオンのいずれか少なくとも一つであり、
前記（Ｃ）多官能チオール化合物を前記（Ａ）カルボキシル基含有樹脂１００質量部に対して１～１０質量部含むことを特徴とする、エッチングレジスト組成物により達成されることを見出した。
As a result of intensive research, the present inventors have found that the above object of the present invention is achieved by:
An etching resist composition for use in forming a resist film that protects a substrate from etching using hydrofluoric acid alone or an etching solution containing hydrofluoric acid,
(A) a carboxyl group-containing resin,
(B) a polyfunctional (meth)acrylate monomer,
(C) a polyfunctional thiol compound,
(D) a photopolymerization initiator; and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the (A) carboxyl group-containing resin,
The polyfunctional thiol compound (C) is at least one of pentaerythritol tetrakis(3-mercaptobutyrate) and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione,
It has been found that this object can be achieved by an etching resist composition comprising the polyfunctional thiol compound (C) in an amount of 1 to 10 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A).
本発明のエッチングレジスト組成物は、（Ｃ）多官能チオール化合物が、一分子あたり２～６個のチオール基を含む化合物であることが好ましい。
また、本発明のエッチングレジスト組成物は、（Ａ）カルボキシル基含有樹脂として、熱硬化性基を有する化合物を含むことが好ましい。
さらに、本発明のエッチングレジスト組成物は、（Ａ）カルボキシル基含有樹脂として、多塩基酸無水物とヒドロキシアルキル（メタ）アクリレート単量体のハーフエステルを含むことが好ましい。
In the etching resist composition of the present invention, the polyfunctional thiol compound (C) is preferably a compound containing 2 to 6 thiol groups per molecule.
Furthermore, the etching resist composition of the present invention preferably contains, as the (A) carboxyl group-containing resin, a compound having a thermosetting group.
Furthermore, the etching resist composition of the present invention preferably contains, as the (A) carboxyl group-containing resin, a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer.
また、本発明のエッチングレジスト組成物は、シランカップリング剤を含まないことが好ましい。 In addition, the etching resist composition of the present invention preferably does not contain a silane coupling agent.
さらに、上記目的は、本発明のエッチングレジスト組成物を用いてエッチング加工された基材加工品により達成される。 Furthermore, the above object can be achieved by a processed substrate which is etched using the etching resist composition of the present invention.
本発明のエッチングレジスト組成物は、
（Ａ）カルボキシル基含有樹脂、
（Ｂ）多官能（メタ）アクリレートモノマー、
（Ｃ）多官能チオール化合物、
（Ｄ）光重合開始剤、および
（Ｅ）前記（Ａ）カルボキシル基含有樹脂１００質量部に対して２０～１００質量部のタルクを含むことにより、ガラス基板や、ガラス以外の基材として、シリコンウェハ、チタンや金属酸化物等を含む基材に対する密着性に優れ、フッ酸を含むエッチング液に対する耐性が十分であり、エッチング後の剥離性も向上し、かつ優れた解像性を有する。
The etching resist composition of the present invention comprises
(A) a carboxyl group-containing resin,
(B) a polyfunctional (meth)acrylate monomer,
(C) a polyfunctional thiol compound,
By containing (D) a photopolymerization initiator and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the (A) carboxyl group-containing resin, the composition has excellent adhesion to glass substrates and substrates other than glass, such as silicon wafers, titanium, metal oxides, and the like, sufficient resistance to an etching solution containing hydrofluoric acid, improved releasability after etching, and excellent resolution.
以下、本発明の実施の形態を、詳細に説明する。 The following describes in detail the embodiments of the present invention.
本発明のフッ酸耐性を有するエッチングレジスト組成物（以下、レジスト組成物ともいう）は、基板をエッチング加工から保護するための組成物であり、（Ａ）カルボキシル基含有樹脂、(Ｂ）多官能（メタ）アクリレートモノマー、（Ｃ）多官能チオール化合物（Ｄ）光重合開始剤、および（Ｅ）前記（Ａ）カルボキシル基含有樹脂１００質量部に対して２０～１００質量部のタルクを含有する。本発明のレジスト組成物をアルカリ現像型レジスト組成物として用いる場合、この組成物をガラス基板上に塗布して塗膜を形成する塗布工程、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て選択的に活性エネルギー線により露光し塗膜を硬化する露光工程、未露光部を希アルカリ水溶液（例えば０．３～３質量％炭酸ナトリウム水溶液）により現像して硬化物のパターンを形成する現像工程によりレジストを形成する。また、本発明のレジスト組成物を紫外線硬化型レジスト組成物として用いる場合、本発明のレジスト組成物をスクリーン印刷等でガラス基板上に所望のパターンに印刷して、ＵＶ光（紫外線）を照射することにより硬化してレジストを形成する。 The etching resist composition having hydrofluoric acid resistance (hereinafter, also referred to as resist composition) of the present invention is a composition for protecting a substrate from etching processing, and contains (A) a carboxyl group-containing resin, (B) a polyfunctional (meth)acrylate monomer, (C) a polyfunctional thiol compound, (D) a photopolymerization initiator, and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the carboxyl group-containing resin (A). When the resist composition of the present invention is used as an alkali development type resist composition, a resist is formed by a coating step of coating the composition on a glass substrate to form a coating film, an exposure step of selectively exposing the resulting coating film to active energy rays through a photomask having a desired pattern to harden the coating film, and a development step of developing the unexposed part with a dilute alkali aqueous solution (for example, a 0.3 to 3 mass % sodium carbonate aqueous solution) to form a pattern of the hardened product. When the resist composition of the present invention is used as an ultraviolet ray curing type resist composition, the resist composition of the present invention is printed in a desired pattern on a glass substrate by screen printing or the like, and hardened by irradiating UV light (ultraviolet rays) to form a resist.
すなわち、本発明のエッチングレジスト組成物は、所定の基板（処理対象）、例えば、特にソーダガラス（ソーダライムガラス）、クリスタルガラス、硼珪酸ガラス等のガラスに対し、所定のパターン状に形成される。この所定のパターン状に形成されたレジストは、エッチング処理の際の基板の保護膜（レジスト）となる。 That is, the etching resist composition of the present invention is formed into a predetermined pattern on a predetermined substrate (processing target), for example, particularly, glass such as soda glass (soda lime glass), crystal glass, borosilicate glass, etc. The resist formed into this predetermined pattern serves as a protective film (resist) for the substrate during etching processing.
本発明のエッチングレジスト組成物は、基材に対する密着性が高く、優れた耐薬品性を有するため、フッ酸や硝酸、硫酸、塩酸等の強酸を含むエッチング液に対する耐性が十分であるためにエッチング工程でも密着性が維持される。本発明では、このことにも起因して、レジストのパターンに忠実な、高い精度で基材のエッチング加工が行われるため、本発明のエッチングレジスト組成物を用いて得られた基材は解像度においても優れている。したがって、ガラス基板は、精度よくエッチング加工され、バリや割れを生ずる可能性が極めて低く抑制される。さらに、エッチング完了後に、エッチングレジスト組成物を基材から剥離する際の剥離性も極めて良好である。 The etching resist composition of the present invention has high adhesion to the substrate and excellent chemical resistance, and therefore has sufficient resistance to etching solutions containing strong acids such as hydrofluoric acid, nitric acid, sulfuric acid, and hydrochloric acid, so that adhesion is maintained even during the etching process. In the present invention, due to this, the substrate is etched with high accuracy faithful to the resist pattern, so that the substrate obtained using the etching resist composition of the present invention has excellent resolution. Therefore, the glass substrate is etched with high accuracy, and the possibility of burrs and cracks is extremely low. Furthermore, the peelability when peeling the etching resist composition from the substrate after etching is completed is also extremely good.
以下、本発明のエッチングレジスト組成物の成分を説明する。 The components of the etching resist composition of the present invention will be described below.
［（Ａ）カルボキシル基含有樹脂］
本発明のエッチングレジスト組成物が含有する（Ａ）カルボキシル基含有樹脂としては、カルボキシル基を有する樹脂、具体的にはそれ自体がエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂およびエチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能である。このうち、特に、分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂が、アルカリ現像を行う感光性の組成物として、更にはエッチング耐性、感度、解像性の面からより好ましい。そして、その不飽和二重結合は、アクリル酸もしくはメタアクリル酸、または、それらの誘導体由来のものが好ましい。
[(A) Carboxyl group-containing resin]
The (A) carboxyl group-containing resin contained in the etching resist composition of the present invention can be any resin having a carboxyl group, specifically, a carboxyl group-containing photosensitive resin that has an ethylenically unsaturated double bond itself, and a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond.Among these, a carboxyl group-containing photosensitive resin that has an ethylenically unsaturated double bond in the molecule is particularly preferred as a photosensitive composition that undergoes alkaline development, and furthermore from the viewpoints of etching resistance, sensitivity, and resolution.The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid, or a derivative thereof.
（Ａ）カルボキシル基含有樹脂の具体例としては、以下に列挙するような化合物（オリゴマーおよびポリマーのいずれでもよい）が好ましい。 (A) Specific examples of the carboxyl group-containing resin are preferably the compounds (which may be either oligomers or polymers) listed below.
（１）（メタ）アクリル酸等の不飽和カルボン酸と、スチレン、α－メチルスチレン、低級アルキル（メタ）アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
（２）脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸等のカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールＡ系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物および必要に応じて１つのアルコール性ヒドロキシル基を有する化合物との重付加反応によるカルボキシル基含有ウレタン樹脂。 (2) Carboxylic group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and compounds having one alcoholic hydroxyl group as required.
（３）ジイソシアネートと、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の２官能エポキシ樹脂の（メタ）アクリレート若しくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有感光性ウレタン樹脂。 (3) Carboxyl group-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with (meth)acrylates of bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modifications, carboxyl group-containing dialcohol compounds, and diol compounds.
（４）前記（２）または（３）の樹脂の合成中に、ヒドロキシアルキル（メタ）アクリレート等の分子中に１つの水酸基と１つ以上の（メタ）アクリロイル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (4) A photosensitive urethane resin containing a carboxyl group, which is terminated with (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (3).
（５）前記（２）または（３）の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物等、分子中に１つのイソシアネート基と１つ以上の（メタ）アクリロイル基を有する化合物を加え末端（メタ）アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (5) A carboxyl group-containing photosensitive urethane resin that is (meth)acrylated at the end by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3).
（６）２官能またはそれ以上の多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、側鎖に存在する水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。ここで、エポキシ樹脂が固形であることが好ましい。 (6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or more polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain. Here, it is preferable that the epoxy resin is solid.
（７）２官能エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、生じた水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (7) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional epoxy resin have been further epoxidized with epichlorohydrin with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
（８）２官能オキセタン樹脂にアジピン酸、フタル酸、ヘキサヒドロフタル酸等のジカルボン酸を反応させ、生じた１級の水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の２塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。 (8) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.
（９）ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ノボラック型フェノール樹脂、ポリ－ｐ－ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物等の１分子中に複数のフェノール性水酸基を有する化合物と、エチレンオキシド、プロピレンオキシド等のアルキレンオキシドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (9) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, such as bisphenol A, bisphenol F, bisphenol S, novolac-type phenolic resin, poly-p-hydroxystyrene, condensation products of naphthol and aldehydes, or condensation products of dihydroxynaphthalene and aldehydes, with an alkylene oxide, such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
（１０）１分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネート等の環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (10) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
（１１）１分子中に複数のエポキシ基を有するエポキシ化合物に、ｐ－ヒドロキシフェネチルアルコール等の１分子中に少なくとも１個のアルコール性水酸基と１個のフェノール性水酸基を有する化合物と、（メタ）アクリル酸等の不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (11) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.
（１２）上記（１）～（１１）の樹脂に、さらにグリシジル（メタ）アクリレート、α－メチルグリシジル（メタ）アクリレート等の１分子中に１つのエポキシ基と１つ以上の（メタ）アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。 (12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule, such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc., to the resins (1) to (11) above.
上記（１）～（１２）として例示した（Ａ）カルボキシル基含有樹脂のうち、特に上記（７）が好ましく、更にビスフェノール型構造（ビスフェノールＡ、ビスフェノールＦ等）を含む場合には特に好ましく用いられる。
なお、本発明のレジスト組成物を用いて、基材のエッチングを行う際には、後述のように種々のエッチング液を用いることができるが、フッ酸をエッチング液として用いる場合には、上記の（２）～（５）以外の（Ａ）カルボキシル基含有樹脂を用いることが好ましい。
Among the carboxyl group-containing resins (A) exemplified as (1) to (12) above, the above (7) is particularly preferred, and those which further contain a bisphenol structure (bisphenol A, bisphenol F, etc.) are particularly preferred.
When etching a substrate using the resist composition of the present invention, various etching solutions can be used as described below. When hydrofluoric acid is used as the etching solution, it is preferable to use a carboxyl group-containing resin (A) other than the above-mentioned (2) to (5).
本発明のエッチングレジスト組成物において、（Ａ）カルボキシル基含有樹脂は、現像性、感度、解像性をより良好とする役割を果たす。また、（Ａ）カルボキシル基含有樹脂は、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、これを用いることによりアルカリ水溶液による現像が可能になる。 In the etching resist composition of the present invention, the carboxyl group-containing resin (A) plays a role in improving developability, sensitivity, and resolution. In addition, since the carboxyl group-containing resin (A) has many carboxyl groups in the side chains of the backbone polymer, the use of this resin makes it possible to carry out development with an alkaline aqueous solution.
上記（Ａ）カルボキシル基含有樹脂の酸価は、２０～２００ｍｇＫＯＨ／ｇの範囲が好ましく、より好ましくは４０～１５０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有樹脂の酸価が２０ｍｇＫＯＨ／ｇ以上の場合、塗膜の密着性が良好となり、アルカリ現像性が良好となる。一方、酸価が２００ｍｇＫＯＨ／ｇ以下の場合には、現像液による露光部の溶解を良好に抑制できるために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離したりすることを抑制して、良好にパターン状のレジストを描画することができる。 The acid value of the carboxyl group-containing resin (A) is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20 mgKOH/g or more, the adhesion of the coating film is good and the alkaline developability is good. On the other hand, when the acid value is 200 mgKOH/g or less, dissolution of the exposed area by the developer can be effectively suppressed, so that the lines are prevented from becoming thinner than necessary, and in some cases, the exposed and unexposed areas are prevented from being dissolved and peeled off by the developer without distinction, and a patterned resist can be successfully drawn.
また、（Ａ）カルボキシル基含有樹脂の重量平均分子量は、樹脂骨格により異なるが、２，０００～１５０，０００、さらには５，０００～１００，０００の範囲が好ましい。重量平均分子量が２，０００以上の場合、タックフリー性能が良好であり、露光後の塗膜の耐湿性が良好で、現像時に膜減りを抑制し、解像度の低下を抑制できる。一方、重量平均分子量が１５０，０００以下の場合、現像性が良好で、貯蔵安定性にも優れる。 The weight-average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, and more preferably 5,000 to 100,000. When the weight-average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, and film loss during development is suppressed, thereby suppressing a decrease in resolution. On the other hand, when the weight-average molecular weight is 150,000 or less, the developability is good and storage stability is also excellent.
（Ａ）カルボキシル基含有樹脂は、１種を単独でまたは２種以上を組み合わせて用いてよい。本発明のエッチングレジスト組成物が２種以上のカルボキシル基含有樹脂を含有する場合、例えば、上述したカルボキシル基含有感光性樹脂を１種類以上含有することが好ましい。 (A) The carboxyl group-containing resin may be used alone or in combination of two or more. When the etching resist composition of the present invention contains two or more types of carboxyl group-containing resins, it is preferable that the composition contains, for example, one or more of the above-mentioned carboxyl group-containing photosensitive resins.
本発明の（Ａ）カルボキシル基含有樹脂が、熱硬化性基（エポキシ基、アミン基等）を含む場合、エッチング用レジスト組成物のエッチング耐性が向上するため、好ましい。その場合は、シランカップリング剤を配合すると、現像性の劣化と剥離性の劣化（すなわち現像や剥離が遅くなる、剥離できなくなる）等の不具合が生ずることがある。したがって、（Ａ）カルボキシル基含有樹脂が熱硬化性基を含む場合にはシランカップリング剤を含まないことが好ましい。 When the (A) carboxyl group-containing resin of the present invention contains a thermosetting group (epoxy group, amine group, etc.), the etching resistance of the etching resist composition is improved, which is preferable. In that case, adding a silane coupling agent may cause problems such as deterioration in developability and peelability (i.e., slow development and peeling, or inability to peel). Therefore, when the (A) carboxyl group-containing resin contains a thermosetting group, it is preferable not to include a silane coupling agent.
（Ａ）カルボキシル基含有樹脂の配合量は、レジスト組成物総質量のうち３５質量％～６５質量％、好ましくは４０質量％～６０質量％の範囲である。（Ａ）カルボキシル基含有樹脂の配合量がレジスト組成物中、上記の割合にあるとき、ガラス等の基板に対する密着性が良好に得られ、ガラスエッチングの解像性が良好となる。さらに、（Ａ）カルボキシル基含有樹脂の配合量が上記範囲を下回る場合には、レジスト組成物を乾燥して得られるレジスト強度が十分に得られず、配合量が上記範囲を超過する場合には、組成物の粘度が上がり、塗布性、製膜性が低下することがある。 The amount of the carboxyl group-containing resin (A) is in the range of 35% to 65% by weight, preferably 40% to 60% by weight, of the total weight of the resist composition. When the amount of the carboxyl group-containing resin (A) in the resist composition is in the above ratio, good adhesion to substrates such as glass is obtained, and the resolution of glass etching is good. Furthermore, if the amount of the carboxyl group-containing resin (A) is below the above range, the resist strength obtained by drying the resist composition is insufficient, and if the amount exceeds the above range, the viscosity of the composition increases, and the coatability and film-forming properties may be reduced.
（多塩基酸無水物とヒドロキシアルキル（メタ）アクリレート単量体のハーフエステル）
本発明のエッチングレジスト組成物を紫外線硬化型レジスト組成物として用いる場合、（Ａ）カルボキシル基含有樹脂として、多塩基酸無水物とヒドロキシアルキル（メタ）アクリレート単量体のハーフエステル(以下、単にハーフエステルともいう）を含有することが好ましい。ハーフエステルは、ガラス、金属など多くの基材との密着に優れ、アルカリ水溶液への溶解性も容易である。
(Half ester of polybasic acid anhydride and hydroxyalkyl (meth)acrylate monomer)
When the etching resist composition of the present invention is used as an ultraviolet-curable resist composition, it is preferable that the carboxyl group-containing resin (A) contains a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer (hereinafter, simply referred to as half ester). Half esters have excellent adhesion to many substrates such as glass and metal, and are easily soluble in an alkaline aqueous solution.
多塩基酸無水物とヒドロキシアルキル（メタ）アクリレート単量体のハーフエステルとしては、レジスト用組成物に用いることができる慣用公知のものを用いればよい。ここでハーフエステルは、多塩基酸無水物１モルに対し(メタ)アクリレート単量体１モルとで合成するのが典型的であるが、(メタ)アクリレート単量体を過剰に用いてもよい。多塩基酸無水物としては、例えば、無水フタル酸、無水テトラヒドロフタル酸、３－メチル無水テトラヒドロフタル酸、４－メチル無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、３－メチル無水ヘキサヒドロフタル酸、４－メチル無水ヘキサヒドロフタル酸、無水マレイン酸、無水コハク酸、無水ドデセシルコハク酸、無水ハイミック酸、無水トリメリット酸、無水ピロメリット酸等が挙げられる。また、ヒドロキシアルキル（メタ）アクリレート単量体としては、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、１，４－ブタンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、ジエチレングリコールモノ（メチル）アクリレート等が挙げられる。前記ハーフエステルは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 As the half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer, any conventionally known compound that can be used in a resist composition may be used. Here, the half ester is typically synthesized from 1 mole of a polybasic acid anhydride and 1 mole of a (meth)acrylate monomer, but the (meth)acrylate monomer may be used in excess. Examples of polybasic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, maleic anhydride, succinic anhydride, dodecylsuccinic anhydride, himic anhydride, trimellitic anhydride, and pyromellitic anhydride. Examples of hydroxyalkyl (meth)acrylate monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, diethylene glycol mono(methyl)acrylate, etc. The half esters may be used alone or in combination of two or more.
前記ハーフエステルは、多塩基酸無水物とヒドロキシアルキル（メタ）アクリレート単量体とを通常のエステル化反応させた構造を有するハーフエステルであればよく、例えば、多塩基酸無水物に代えて多塩基酸を用いて得られたハーフエステルであってもよい。 The half ester may be any half ester having a structure obtained by a normal esterification reaction between a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer, and may be, for example, a half ester obtained by using a polybasic acid instead of a polybasic acid anhydride.
（Ａ）カルボキシル基含有樹脂として、前記ハーフエステルを用いる場合、その粘度は、２５℃で、２，０００～１０，０００ｍＰａ・ｓ、好ましくは、３，０００～７，０００ｍＰａ・ｓの範囲である。 (A) When the half ester is used as the carboxyl group-containing resin, its viscosity at 25°C is in the range of 2,000 to 10,000 mPa·s, preferably 3,000 to 7,000 mPa·s.
前記ハーフエステルの配合量は、本発明のエッチングレジスト組成物総質量中に、１０～６０質量％、より好ましくは１５～５０質量％の範囲である。１０質量％以上の場合は、硬化性が良好であり、塗膜へのめっき液の染み込みが抑制される。６０質量％以下の場合、剥離時の溶解性により優れ、又硬化塗膜のべた付きが抑制され、作業性が良好となる。前記ハーフエステルと、その他のカルボキシル基含有樹脂を併用する場合、その比率は、前記ハーフエステル：その他のカルボキシル基含有樹脂が、９：1～１：９、好ましくは、７：３～３：７であり、併用することで塗膜の平滑性が向上する。 The amount of the half ester is in the range of 10 to 60% by mass, more preferably 15 to 50% by mass, based on the total mass of the etching resist composition of the present invention. When the amount is 10% by mass or more, the curability is good and the penetration of the plating solution into the coating film is suppressed. When the amount is 60% by mass or less, the solubility during stripping is excellent, and the stickiness of the cured coating film is suppressed, resulting in good workability. When the half ester is used in combination with another carboxyl group-containing resin, the ratio of the half ester to the other carboxyl group-containing resin is 9:1 to 1:9, preferably 7:3 to 3:7, and the combination improves the smoothness of the coating film.
［（Ｂ）多官能（メタ）アクリレートモノマー］
本発明のレジスト組成物は、（Ｂ）多官能（メタ）アクリレート（（メタ）アクリロイル基を２個以上有する（メタ）アクリレートモノマー）を含む。なお、本明細書及び特許請求の範囲において、「（メタ）アクリレート」とは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語で、他の類似の表現についても同様である。多官能（メタ）アクリレート化合物は、活性エネルギー線照射、特に紫外線照射により光硬化して、樹脂成分を、アルカリ水溶液に不溶化し、または、不溶化を助けるものである。このような化合物としては、慣用公知のポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが使用できる。多官能（メタ）アクリレートモノマーを用いる理由は、（メタ）アクリロイル官能基の数が１つの場合よりも、光反応性が向上して解像性が優れるためである。
[(B) Polyfunctional (meth)acrylate monomer]
The resist composition of the present invention contains (B) a polyfunctional (meth)acrylate (a (meth)acrylate monomer having two or more (meth)acryloyl groups). In the present specification and claims, the term "(meth)acrylate" is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions. The polyfunctional (meth)acrylate compound is photocured by irradiation with active energy rays, particularly ultraviolet rays, to insolubilize or assist insolubilization of a resin component in an alkaline aqueous solution. As such a compound, commonly known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth)acrylate, etc. can be used. The reason for using a polyfunctional (meth)acrylate monomer is that the photoreactivity is improved and the resolution is superior to that of a compound having one (meth)acryloyl functional group.
多官能（メタ）アクリレートモノマーの例としては、慣用公知のポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが挙げられる。具体的には、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類；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、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス－ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物などの、多価アクリレート類；ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類；ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類及びメラミンアクリレート、及び前記アクリレートに対応する各メタアクリレート類の１種、又は複数以上を組み合わせて用いることができる。 Examples of polyfunctional (meth)acrylate monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, etc. Specific examples include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts of these; bisphenol A diacrylate, and ethylene oxide adducts of these phenols. Polyhydric acrylates such as propylene oxide adducts or propylene oxide adducts; polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; acrylates and melamine acrylates obtained by directly acrilating polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, or by urethane acrilation via diisocyanates, and methacrylates corresponding to the above acrylates, can be used alone or in combination of two or more.
本発明では、ポリエステルポリオール、好ましくはポリエステルポリオールに対して（メタ）アクリル酸を反応させた、多官能、好ましくは２官能以上３官能未満の（メタ）アクリレートが好ましく用いられる。ここで３官能未満とは、アクリロイル基とメタアクリロイル基の合計量が一分子あたり平均で３官能未満であることを言う。また、（Ｂ）多官能（メタ）アクリレートモノマーの分子量は、２００～５，０００の範囲、好ましくは４００～３，０００の範囲である。 In the present invention, a polyfunctional (preferably difunctional or more but less than trifunctional) (meth)acrylate is preferably used, which is prepared by reacting a polyester polyol, preferably a polyester polyol, with (meth)acrylic acid. Here, "less than trifunctional" means that the total amount of acryloyl groups and methacryloyl groups is less than trifunctional on average per molecule. The molecular weight of the (B) polyfunctional (meth)acrylate monomer is in the range of 200 to 5,000, preferably 400 to 3,000.
本発明では、上記多官能（メタ）アクリレートモノマーの他に、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類；Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類；フェノキシアクリレートを含む単官能アクリレートを、例えばエッチング組成物の粘度調節等の目的で使用することができる。
また、上記多官能（メタ）アクリレートモノマーに、本発明の目的を損なわない範囲で、単官能又は多官能（メタ）アクリレートオリゴマーを添加することもできる。
In the present invention, in addition to the above-mentioned polyfunctional (meth)acrylate monomers, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; and monofunctional acrylates including phenoxy acrylate can be used for the purpose of, for example, adjusting the viscosity of the etching composition.
Furthermore, a monofunctional or polyfunctional (meth)acrylate oligomer can be added to the above polyfunctional (meth)acrylate monomer within the scope of not impairing the object of the present invention.
（Ｂ）多官能（メタ）アクリレートモノマーの配合量は、（Ａ）カルボキシル基含有樹脂１００質量部に対して、１０～６０質量部、好ましくは２０～４０質量部の割合が適当である。配合量を、１０質量部以上とすることにより、光硬化性が確実化し、活性エネルギー線照射後のアルカリ現像により、導電パターンのラインの形成が良好とされる。一方、６００質量部以下とすることにより、アルカリ水溶液に対する溶解性が確保され、強靭な導電パターン膜が得られる。 The amount of (B) polyfunctional (meth)acrylate monomer is preferably 10 to 60 parts by weight, and more preferably 20 to 40 parts by weight, per 100 parts by weight of (A) carboxyl group-containing resin. By making the amount 10 parts by weight or more, the photocurability is ensured, and the formation of conductive pattern lines is improved by alkaline development after irradiation with active energy rays. On the other hand, by making the amount 600 parts by weight or less, solubility in an alkaline aqueous solution is ensured, and a tough conductive pattern film is obtained.
［（Ｃ）多官能チオール化合物］
本発明のレジスト組成物は、（Ｃ）多官能チオール化合物を含む。（Ｃ）多官能チオール化合物が、一分子あたり２～６個のチオール基（メルカプト基ともいう）を含む化合物であると好ましい。
[(C) Polyfunctional thiol compound]
The resist composition of the present invention contains (C) a polyfunctional thiol compound. (C) The polyfunctional thiol compound is preferably a compound containing 2 to 6 thiol groups (also called mercapto groups) per molecule.
さらに、（Ｃ）多官能チオール化合物は、チオール基（－ＳＨ）と、カルボン酸エステル基（－ＲＣＯＯ－（ＲはＣ１－Ｃ４アルキル）と、をそれぞれ１個以上含む化合物であることが好ましく、メルカプトプロピオニルオキシ基、例えば
具体例としては、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリトリトールテトラ(３-メルカプトプロピネナート)、ジペンタエリトリトールヘキサキス（３‐メルカプトプロピオナート）等のメルカプトプロピオニルオキシ基を含有する化合物、１，４-ビス(３-メルカプトブチリルオキシ)ブタン、ペンタエリスリトールテトラキス（３-メルカプトブチレート)、１，３，５-トリス（３-メルカプトブチリルオキシエチル）-１,３,５-トリアジン-２,４,６（１Ｈ，３Ｈ，５Ｈ）-トリオン等のメルカプトブチリルオキシ基を有する化合物が挙げられる。
上記化合物の市販品の例には、カレンズＭＴ（登録商標）ＰＥ１、カレンズＭＴ（登録商標）ＢＤ１、カレンズＭＴ（登録商標）ＮＲ１（昭和電工株式会社製）が存在する。
（Ｃ）多官能チオール化合物は、フッ酸耐性に優れるだけでなく、密着性、剥離性等の他の特性にも優れる点で、上記の中でも、３官能以上のカレンズＭＴ（登録商標）ＰＥ１、カレンズＭＴ（登録商標）ＮＲ１が好ましい。
Specific examples include compounds containing a mercaptopropionyloxy group, such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropinenate), and dipentaerythritol hexakis(3-mercaptopropionate), and compounds having a mercaptobutyryloxy group, such as 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
Examples of commercially available products of the above compound include Karenz MT (registered trademark) PE1, Karenz MT (registered trademark) BD1, and Karenz MT (registered trademark) NR1 (manufactured by Showa Denko KK).
(C) The polyfunctional thiol compound is not only excellent in hydrofluoric acid resistance but also excellent in other properties such as adhesion and peelability, and among the above, Karenz MT (registered trademark) PE1 and Karenz MT (registered trademark) NR1, which are tri- or higher functional, are preferred.
（Ｃ）多官能チオール化合物の配合量は、（Ａ）カルボキシル基含有樹脂１００質量部に対して、１～１０質量部、好ましくは２～５質量部の割合が適当である。
（Ｃ）多官能チオール化合物を含む本発明のガラスエッチング組成物はガラス基板に対する密着性と、剥離性の双方に優れたものとされ、ガラスエッチングの際のフッ酸耐性が向上する。この結果、ガラス基板を優れた解像度でエッチングすることが可能となる。
The amount of the polyfunctional thiol compound (C) to be mixed is suitably 1 to 10 parts by mass, preferably 2 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A).
The glass etching composition of the present invention containing the polyfunctional thiol compound (C) has excellent adhesion to glass substrates and excellent peelability, and improves resistance to hydrofluoric acid during glass etching. As a result, the glass substrate can be etched with excellent resolution.
［（Ｄ）光重合開始剤］
（Ｄ）光重合開始剤としては、エネルギー線の照射により、（メタ）アクリレートを重合させることが可能なものであれば、特に制限はない。
[(D) Photopolymerization initiator]
There are no particular limitations on the photopolymerization initiator (D) as long as it is capable of polymerizing a (meth)acrylate by irradiation with energy rays.
（Ｄ）光重合開始剤は、光、レーザー、電子線等によりラジカルを発生し、ラジカル重合反応を開始する化合物であれば全て用いることができる。当該（Ｄ）光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン等のアセトフェノン類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、Ｎ，Ｎ－ジメチルアミノアセトフェノン等のアミノアセトフェノン類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン類；２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；２，４，５－トリアリールイミダゾール二量体；リボフラビンテトラブチレート；２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール等のチオール化合物；２，４，６－トリス－ｓ－トリアジン、２，２，２－トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物；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等のベンゾフェノン類またはキサントン類；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フォスフィンオキサイド類；α-ヒドロキシアルキルフェノン等のアルキルフェノン類が挙げられる。 (D) The photopolymerization initiator can be any compound that generates radicals when exposed to light, laser, electron beam, etc., and initiates a radical polymerization reaction. Examples of the photopolymerization initiator (D) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; aminoacetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and N,N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthones such as thioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, and tribromomethylphenylsulfone; benzophenones or xanthones such as benzophenone and 4,4'-bisdiethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and alkylphenones such as α-hydroxyalkylphenone.
（Ｄ）光重合開始剤は、単独でまたは複数種を混合して使用することができる。また更に、これらに加え、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル、ペンチル－４－ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類などの光開始助剤を使用することができる。また、可視光領域に吸収のあるＣＧＩ－７８４等（ＢＡＳＦジャパン社製）のチタノセン化合物等も、光反応を促進するために（Ｄ）光重合開始剤に添加することもできる。尚、（Ｄ）光重合開始剤に添加する成分はこれらに限られるものではなく、紫外光もしくは可視光領域で光を吸収し、（メタ）アクリロイル基等の不飽和基をラジカル重合させるものであれば、単独であるいは複数併用して使用できる。 The photopolymerization initiator (D) can be used alone or in combination. In addition to these, photoinitiator assistants such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and other tertiary amines can be used. Titanocene compounds such as CGI-784 (manufactured by BASF Japan) that absorb in the visible light region can also be added to the photopolymerization initiator (D) to promote photoreaction. Note that the components added to the photopolymerization initiator (D) are not limited to these, and any components that absorb light in the ultraviolet or visible light region and radically polymerize unsaturated groups such as (meth)acryloyl groups can be used alone or in combination.
光重合開始剤で市販されているものの製品名としては、例えば、Ｏｍｎｉｒａｄ９０
７、Ｏｍｎｉｒａｄ１２７、Ｏｍｎｉｒａｄ３６９（いずれもＩＧＭ Ｒｅｓｉｎｓ社製）等のアルキルフェノン系、Ｏｍｎｉｒａｄ ＴＰＯ Ｈ（ＩＧＭ Ｒｅｓｉｎｓ社製）等のフォスフィンオキサイド系が挙げられる。（Ｄ）光重合開始剤は、特に限定されず、上記いずれを用いてもよいが、アルキルフェノン系を用いることが好ましい。
本発明のレジスト組成物を紫外線硬化型レジスト組成物として用いる場合、（Ｄ）光重合開始剤は、ベンジルケタール系、例えば、Ｏｍｎｉｒａｄ６５１（ＩＧＭ Ｒｅｓｉｎｓ社製）を用いることが好ましい。
Examples of commercially available photopolymerization initiators include Omnirad 90.
Examples of the photopolymerization initiator include alkylphenone-based initiators such as Omnirad 7, Omnirad 127, and Omnirad 369 (all manufactured by IGM Resins), and phosphine oxide-based initiators such as Omnirad TPO H (manufactured by IGM Resins). The photopolymerization initiator (D) is not particularly limited, and any of the above may be used, but it is preferable to use an alkylphenone-based initiator.
When the resist composition of the present invention is used as an ultraviolet-curable resist composition, it is preferable to use a benzyl ketal type photopolymerization initiator such as Omnirad 651 (manufactured by IGM Resins) as the (D) photopolymerization initiator.
（Ｄ）光重合開始剤の配合量は、レジスト組成物中の（Ａ）カルボキシル基含有樹脂１００質量部に対して０．５～３５質量部、より好ましくは０．５～２０質量部、さらに好ましくは１～１０質量部である。
光重合開始剤の配合量が０．５質量部以上とすることにより、光硬化性が十分とされるため、レジスト組成物の基板に対する密着性が向上する。一方、３５質量部以下とすることによりレジスト組成物表面での光吸収が過度に激しくなる傾向を抑制し、深部硬化性を確保することができる。
The blend amount of the photopolymerization initiator (D) is preferably 0.5 to 35 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 10 parts by weight, per 100 parts by weight of the carboxyl group-containing resin (A) in the resist composition.
By setting the amount of the photopolymerization initiator to 0.5 parts by mass or more, sufficient photocurability is achieved, improving the adhesion of the resist composition to the substrate, while by setting the amount to 35 parts by mass or less, the tendency for excessive light absorption at the surface of the resist composition to become intense is suppressed, ensuring deep curability.
［（Ｅ）タルク］
本発明のエッチングレジスト組成物は、無機フィラーとして（Ｅ）タルクを含む。使用する（Ｅ）タルクの種類に特に制限はなく、市販品としてはＬＭＳ－１００、ＬＭＳ－２００、ＬＭＳ－３００、ＬＭＳ－３５００、ＬＭＳ－４００、ＬＭＰ－１００、ＰＫＰ－５３、ＰＫＰ－８０、ＰＫＰ－８１、ミクロエースＫ－１（富士タルク工業株式会社製）；Ｐ－２、Ｐ－３、Ｐ－４、Ｐ－６、Ｐ－８、ＳＧ－９５等の微粉タルク（ＢＥＴ法による比表面積７．５～１５．０ｍ２/g）、ナノエースＤ－６００、ナノエースＤ－８００、ナノエースＤ－１０００等の板体形状の微粉タルク（ＢＥＴ法による比表面積１８～２４ｍ２/g）、ＳＧ－２０００、ＳＧ－２００、ＳＧ－２００Ｎ１５等の超微粉タルク（ＢＥＴ法による比表面積３０～４０ｍ２/g）、（いずれも日本タルク株式会社製）を使用することができる。本発明では超微粉タルクを用いることが好ましい。
[(E) Talc]
The etching resist composition of the present invention contains (E) talc as an inorganic filler. There is no particular limitation on the type of (E) talc used, and examples of commercially available products include LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81, and Microace K-1 (manufactured by Fuji Talc Industries Co., Ltd.); fine powder talc such as P-2, P-3, P-4, P-6, P-8, and SG-95 (specific surface area measured by the BET method); Examples of talc that can be used include fine talc particles in the form of a plate (specific surface area by BET method: 18 to 24 m2/g), Nanoace D-600, Nanoace D-800, Nanoace D-1000, etc., and ultrafine talc particles (specific surface area by BET method: 30 to 40 m2/g), such as SG-2000, SG-200, SG-200N15, etc. (all manufactured by Nippon Talc Co., Ltd.). In the present invention, it is preferable to use ultrafine talc particles.
レジスト組成物による解像性を向上させるために、（Ｅ）タルクの平均粒径（光散乱法により測定）６μｍ以下、特に３μｍ以下とすることが好ましく、凝集防止の観点からは０．１μｍ以上とすることが好ましい。（Ｅ）タルクは単独あるいは複数組み合わせて使用することができる。 In order to improve the resolution of the resist composition, the average particle size of the talc (E) (measured by light scattering) is preferably 6 μm or less, particularly 3 μm or less, and from the viewpoint of preventing aggregation, it is preferably 0.1 μm or more. (E) Talc can be used alone or in combination.
本発明では、上記（Ｅ）タルクを（Ａ）カルボキシル基含有樹脂１００質量部に対して２０～１００質量部の上記配合量にて用いることにより、レジスト組成物が膜形状でガラス基板上に保持可能となり、レジスト組成物のガラスに対する密着性、フッ酸耐性が得られる。 In the present invention, by using the above-mentioned (E) talc in the above-mentioned amount of 20 to 100 parts by mass per 100 parts by mass of the (A) carboxyl group-containing resin, the resist composition can be held in a film form on the glass substrate, and the resist composition can obtain adhesion to glass and resistance to hydrofluoric acid.
［その他の成分］
この他、本発明のレジスト組成物には、必要に応じて、増粘剤、流動性改質剤、表面張力調整剤、密着性付与剤、界面活性剤、着色剤、紫外線吸収剤、シリコーン系、フッ素系、高分子系等の消泡剤およびレベリング剤、マット剤、膜物性を調整するためのポリエステル系樹脂、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類の少なくとも１種を、さらに配合することができる。上記成分は、各成分（Ａ）～（Ｅ）の性能を損なわず、添加による所望の効果が得られる範囲で、適宜使用量を調節して使用される。
尚、エポキシ樹脂やエラストマーは、形成したレジストの剥離が困難なことから、配合しないことが好ましい。
[Other ingredients]
In addition, the resist composition of the present invention may further contain, as necessary, at least one of a thickener, a flowability modifier, a surface tension regulator, an adhesion imparting agent, a surfactant, a colorant, an ultraviolet absorber, a silicone-based, fluorine-based, or polymer-based defoaming agent and a leveling agent, a matting agent, a polyester resin, a vinyl resin, an acrylic resin, a rubber resin, and a wax for adjusting the film properties. The above components are used by appropriately adjusting the amount used within a range in which the performance of each of the components (A) to (E) is not impaired and the desired effect is obtained by adding them.
It is preferable not to include epoxy resins or elastomers since the formed resist is difficult to remove.
使用可能な消泡剤の例としては、シリコーン系消泡剤、フッ素系消泡剤、アクリル系消泡剤が挙げられる。シリコーン系の消泡剤としてはビックケミー・ジャパン株式会社製のＢＹＫ（登録商標）－０６３、－０６５、－０６６Ｎ、－０８１、－１４１、－３２３、および信越化学株式会社製のＫＳ－６６、ＫＳ－６９、Ｘ－５０－１１０５Ｇ等、フッ素系消泡剤としてはＤＩＣ株式会社製のメガファックＲＳ、Ｆ－５５４、Ｆ－５５７等、アクリル系消泡剤としては楠本化成株式会社製のディスパロンＯＸ－８８０ＥＦ、ＯＸ－７０などが挙げられる。 Examples of usable defoamers include silicone-based defoamers, fluorine-based defoamers, and acrylic-based defoamers. Examples of silicone-based defoamers include BYK (registered trademark)-063, -065, -066N, -081, -141, and -323 manufactured by BYK Japan Co., Ltd., and KS-66, KS-69, and X-50-1105G manufactured by Shin-Etsu Chemical Co., Ltd. Examples of fluorine-based defoamers include Megafac RS, F-554, and F-557 manufactured by DIC Corporation, and examples of acrylic defoamers include Disparlon OX-880EF and OX-70 manufactured by Kusumoto Chemical Co., Ltd.
着色剤としては、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックを、増粘剤としては、ベントナイト、微紛シリカを含む公知慣用の増粘剤を挙げることができる。 Colorants include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, and thickeners include well-known and commonly used thickeners including bentonite and finely powdered silica.
上記添加剤のなかでも特に消泡剤及び／又はレベリング剤を配合することにより、表面平滑性の劣化を防止し、ボイドやピンホールによる層間絶縁性の劣化も防止することができる。 Among the above additives, the incorporation of an antifoaming agent and/or a leveling agent in particular can prevent deterioration of surface smoothness and also prevent deterioration of interlayer insulation due to voids and pinholes.
本発明のレジスト組成物の２５℃における粘度は、１から１，５００ｄＰａ・ｓの範囲、特に１０から１，０００ｄＰａ・ｓの範囲にあると好ましい。エッチングレジスト組成物の粘度が１ｄＰａ・ｓ以上であると、レジスト組成物が加熱乾燥により、エッチングレジストとして基板を良好に保護可能な膜厚で塗膜になる。一方、エッチングレジスト組成物の粘度が１，５００ｄＰａ・ｓ以下であると、組成物が扱いやすく、スクリーン印刷等による印刷に好適であり、エッチング後のレジスト剥離処理も簡単かつ経済的に行われる。 The viscosity of the resist composition of the present invention at 25°C is preferably in the range of 1 to 1,500 dPa·s, particularly in the range of 10 to 1,000 dPa·s. When the viscosity of the etching resist composition is 1 dPa·s or more, the resist composition is heated and dried to form a coating film with a thickness that can effectively protect the substrate as an etching resist. On the other hand, when the viscosity of the etching resist composition is 1,500 dPa·s or less, the composition is easy to handle and suitable for printing by screen printing, etc., and the resist stripping process after etching can be performed simply and economically.
なお、本発明のエッチングレジスト組成物は、主にアルカリ現像型レジスト組成物、紫外線硬化型レジスト組成物に好適に用いられる。 The etching resist composition of the present invention is preferably used mainly as an alkali development type resist composition or an ultraviolet ray curing type resist composition.
＜本発明のガラス基板の製造方法＞
次に、上述のエッチングレジスト組成物（レジスト組成物ともいう）をアルカリ現像型レジスト組成物として用いた本発明のガラス基板の製造方法について、各工程ごとにさらに詳しく説明する。
<Method of Manufacturing Glass Substrate of the Present Invention>
Next, each step of the method for producing a glass substrate of the present invention, in which the above-mentioned etching resist composition (also referred to as a resist composition) is used as an alkali development type resist composition, will be described in more detail.
[（１）塗膜形成工程]
上述した本発明のレジスト組成物をアルカリ現像型レジスト組成物として使用する場合、本発明のレジスト組成物の溶液をガラス基板上に塗布し、加熱により溶媒を除去することによって所望の塗膜を形成することができる。ガラス基板上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、アプリケーター法が適用可能であり、その際の塗布方式としては、従来より知られる２コート１ベークなどのウエットオンウエット塗装や、２コート２ベークなどのドライオンウエット塗装が可能である。なお、本発明のレジスト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６０～１６０℃、好ましくは８０～１５０℃で、３～１５分間程度である。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。また、レジスト組成物は一回（１層）の塗布を複数回に分けて行うこともできる。
[(1) Coating film formation process]
When the resist composition of the present invention is used as an alkali development type resist composition, a solution of the resist composition of the present invention is applied onto a glass substrate, and the solvent is removed by heating to form a desired coating film. As a coating method onto a glass substrate, spin coating, slit coating, roll coating, screen printing, and applicator methods can be applied, and as a coating method, a conventionally known wet-on-wet coating such as 2 coat 1 bake, or a dry-on-wet coating such as 2 coat 2 bake, can be used. The drying conditions of the coating film of the resist composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, and the like, but are usually 60 to 160°C, preferably 80 to 150°C, for about 3 to 15 minutes. If the drying time is too short, the adhesion state during development will be poor, and if it is too long, it may cause a decrease in resolution due to heat fog. In addition, the resist composition can be applied in multiple times instead of one time (one layer).
上述のように、基板上にパターン状に施与される未硬化のレジスト組成物の膜厚は、エッチング液の性状に応じて、３～７０μｍ、特に３０～６０μｍの範囲で適宜調整されると好ましい。この範囲の膜厚を有するレジスト組成物は、エッチング液に対して十分な耐性を有するため、エッチング処理における基板の保護の観点から有効である。ただし、本発明のレジスト組成物は、乾燥温度および乾燥時間の要求を満たせば、７０μｍを超過する膜厚としてもよい。上記膜厚は、一般的な印刷条件により得られるものである。 As described above, the film thickness of the uncured resist composition applied in a pattern onto the substrate is preferably adjusted appropriately within the range of 3 to 70 μm, particularly 30 to 60 μm, depending on the properties of the etching solution. A resist composition having a film thickness within this range is effective from the viewpoint of protecting the substrate during etching processing, since it has sufficient resistance to the etching solution. However, the resist composition of the present invention may have a film thickness exceeding 70 μm, provided that the drying temperature and drying time requirements are met. The above film thickness is obtained under general printing conditions.
[（２）露光工程]
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、又はダイレクト露光機を用い、例えば波長が３００～５００ｎｍの紫外線または可視光線などの放射線を照射して、露光部を硬化させることができる。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。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、１００～１，５００ｍＪ／ｃｍ２の範囲である。
(2) Exposure process
The resulting coating film can be irradiated with radiation such as ultraviolet light or visible light having a wavelength of 300 to 500 nm through a photomask having a desired pattern or using a direct exposure machine to cure the exposed areas. Here, radiation means ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc., and low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc. can be used as light sources. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but is in the range of 100 to 1,500 mJ/ cm2 when a high-pressure mercury lamp is used, for example.
[（３）現像工程]
放射線照射後の現像方法としては、アルカリ性水溶液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。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 process
As a development method after irradiation with radiation, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary non-exposed areas, leaving only exposed areas to obtain a cured film with a desired pattern. As the developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, or 1,5-diazabicyclo[4.3.0]-5-nonane can be used.
この他、本発明のレジスト組成物は、スクリーン印刷法、グラビア法、グラビアオフセット法などの印刷方法により直接イメージ状に印刷することにより、現像工程を省略して用いることも可能である。 In addition, the resist composition of the present invention can be used without the development step by directly printing an image using a printing method such as screen printing, gravure printing, or gravure offset printing.
[（４）エッチング工程]
上記に準じた手順により所望のパターン状に光硬化したレジストで被覆された基板は、次いでエッチング液によりエッチング処理に付される。エッチング処理により、レジストに被覆されていない基板部分（レジストのパターン以外の部分）がエッチングされる。これにより所定パターンのガラス成型品を得ることができる。
なお、本発明のレジスト組成物を紫外線硬化型レジスト組成物として用いる場合、本発明のレジスト組成物をスクリーン印刷等でガラス基板上に膜厚１５~８０μｍ、好ましくは、２０~５０μｍで所望のパターンに印刷し、ＵＶ光（紫外線）を５００~２，０００ｍＪ／ｃｍ２、好ましくは、１，０００~１，５００ｍＪ／ｃｍ２照射することにより硬化してレジストを形成後、上記エッチング工程により、レジストに被覆されていない基板部分（レジストのパターン以外の部分）がエッチングされる。
(4) Etching process
The substrate coated with the resist photocured in the desired pattern by the procedure similar to that described above is then subjected to an etching process using an etching solution. The substrate portions not coated with the resist (portions other than the resist pattern) are etched by the etching process. This allows a glass molded product of the desired pattern to be obtained.
When the resist composition of the present invention is used as an ultraviolet-curable resist composition, the resist composition of the present invention is printed in a desired pattern on a glass substrate by screen printing or the like to a film thickness of 15 to 80 μm, preferably 20 to 50 μm, and then cured by irradiating with UV light (ultraviolet rays) at 500 to 2,000 mJ/cm 2 , preferably 1,000 to 1,500 mJ/cm 2 to form a resist. Thereafter, the portions of the substrate not covered with the resist (portions other than the resist pattern) are etched by the above-mentioned etching step.
エッチング液としては、フッ化水素酸単独若しくはフッ化水素酸を含むエッチング液（例えば、フッ化水素酸と、鉱酸（硝酸、リン酸等）との混合物が挙げられる。 The etching solution may be hydrofluoric acid alone or an etching solution containing hydrofluoric acid (e.g., a mixture of hydrofluoric acid and a mineral acid (such as nitric acid or phosphoric acid)).
本発明のレジスト組成物から得られるレジスト膜は、エッチング液に対して優れた耐性を有することから、エッチング処理中に基板からの剥離が生じずに、基板を高精度でエッチング処理することができる。 The resist film obtained from the resist composition of the present invention has excellent resistance to etching solutions, so that the substrate can be etched with high precision without peeling off from the substrate during the etching process.
なお、本発明のレジスト組成物は、上記工程により、基板に良好に密着したレジストを構成し、基板をエッチング液から良好に保護する。更には高精度のエッチングを可能とし、エッチング完了後にはケトン類、エステル類、芳香族炭化水素類、石油系溶剤類等の溶剤を用いて短時間で容易に除去可能である。エッチングレジスト除去用には、特に、溶解性の観点と経済性の観点より石油系溶剤を用いることが好ましい。 The resist composition of the present invention forms a resist that adheres well to the substrate through the above process, and effectively protects the substrate from the etching solution. Furthermore, it enables highly accurate etching, and after etching is completed, it can be easily removed in a short time using a solvent such as ketones, esters, aromatic hydrocarbons, or petroleum-based solvents. For removing the etching resist, it is particularly preferable to use a petroleum-based solvent from the standpoint of solubility and economy.
なお、本発明のレジスト組成物は、フッ化水素酸系エッチング液だけではなく、強酸系の各種エッチング液によるエッチングにおいても非常に優れた耐性と基板に対する優れた密着性を有する。 The resist composition of the present invention has excellent resistance to etching not only with hydrofluoric acid-based etching solutions, but also with various strong acid-based etching solutions, and has excellent adhesion to substrates.
以下、実施例を示して本発明について具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、以下において特に断りのない限り、「部」は質量部を意味するものとする。 The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" refers to parts by mass unless otherwise specified.
［実施例１～５及び比較例１～６］
Ｉ－Ｉ．アルカリ現像型レジスト組成物の作製
表１に示す成分をそれぞれ記載した割合（単位：部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで分散および混練して、実施例１～５(本発明の組成物)、および比較例１～６(比較組成物)の各アルカリ現像型レジスト組成物を得た。
[Examples 1 to 5 and Comparative Examples 1 to 6]
I-I. Preparation of Alkaline Development Type Resist Compositions The components shown in Table 1 were blended in the ratios (units: parts) shown, premixed in a stirrer, and then dispersed and kneaded in a three-roll mill to obtain alkali development type resist compositions of Examples 1 to 5 (compositions of the present invention) and Comparative Examples 1 to 6 (comparative compositions).
Ｉ－ＩＩ．評価基板１：エッチングレジストの製造
膜厚１．８ｍｍのソーダライムガラスをあらかじめアルコールで洗浄し、表面を乾燥させた。これに対し、実施例１から５、および比較例１から６の各アルカリ現像型レジスト組成物を、それぞれ８０メッシュのポリエステル版に所定の感光性乳剤を膜厚８０μｍで付したスクリーン印刷版を用いて、膜厚８０μｍに全面印刷した。このように塗布されたアルカリ現像型レジスト組成物を、熱風循環式乾燥機（ヤマト科学社製ＤＦ－６１０）により、乾燥温度１００℃にて３０分加熱して、溶剤を蒸発、乾燥させて膜厚５０μmのエッチングレジスト（評価基板１）を得た。
I-II. Evaluation substrate 1: preparation of etching resist A soda lime glass with a thickness of 1.8 mm was washed with alcohol in advance, and the surface was dried. On this, each of the alkali development type resist compositions of Examples 1 to 5 and Comparative Examples 1 to 6 was printed on the entire surface to a thickness of 80 μm using a screen printing plate in which a predetermined photosensitive emulsion was applied to a thickness of 80 μm on an 80 mesh polyester plate. The alkali development type resist composition thus applied was heated at a drying temperature of 100° C. for 30 minutes using a hot air circulation dryer (DF-610 manufactured by Yamato Scientific Co., Ltd.) to evaporate the solvent and dry, thereby obtaining an etching resist (evaluation substrate 1) with a thickness of 50 μm.
Ｉ－ＩＩＩ．密着性
ガラス密着性試験上記評価基板１に対し、ＪＩＳ Ｋ ５６００－５－６に準拠し、クロスカットテープピールリング試験を実施した。すなわち、評価基板１のエッチングレジストに、１ｍｍの間隔で縦横に交差する切込みを入れて、この切込みにより多数の碁盤目（格子）を作成し、そのうちの１００個の碁盤目に対してＪＩＳ Ｋ ５６００－５－６に記載の方法によりテープを付着して、これを引き剥し、ガラス基板からの剥がれ・欠けを生じた格子の数を、以下のように、観察・評価した。評価結果を表１に示す。
◎ １００すべての格子に剥がれ・欠けのいずれも生じない
〇１００すべての格子に剥がれはないが、１０個未満の格子の端が欠けた
△ ９０個未満の格子に部分的又は完全な剥がれが観察された
× ９０個以上の格子に部分的又は完全な剥がれが観察された
I-III. Adhesion Glass Adhesion Test A cross-cut tape peel ring test was carried out on the above-mentioned evaluation substrate 1 in accordance with JIS K 5600-5-6. That is, in the etching resist of the evaluation substrate 1, vertical and horizontal cuts were made at intervals of 1 mm, and a large number of grids (lattices) were created by these cuts, and tape was attached to 100 of these grids by the method described in JIS K 5600-5-6, and the tape was peeled off, and the number of grids that peeled off or chipped from the glass substrate was observed and evaluated as follows. The evaluation results are shown in Table 1.
◎ None of the 100 lattices showed peeling or chipping. 〇 None of the 100 lattices showed peeling, but the edges of less than 10 lattices were chipped. △ Partial or complete peeling was observed in less than 90 lattices. × Partial or complete peeling was observed in 90 or more lattices.
Ｉ－ＩＶ．評価基板２：エッチングレジスト(硬化膜）の作製
フッ酸耐性試験評価基板１に対し、一定のパターンを有するフォトマスク載置し、波長３００～４５０ｎｍの紫外線を３００ｍＪ／ｃｍ２照射して、露光部を硬化させることにより評価基板２を製造した。
I-IV. Preparation of Evaluation Substrate 2: Etching Resist (Cured Film) A photomask having a certain pattern was placed on evaluation substrate 1 for hydrofluoric acid resistance test, and ultraviolet rays having a wavelength of 300 to 450 nm were irradiated at 300 mJ/cm2 to cure the exposed portion, thereby producing evaluation substrate 2.
１０容量％のフッ化水素酸に各実施例および比較例の評価基板２を浸漬することにより、深さ１００μｍのエッチングを行った。その後、評価基板２について、ガラス基板のエッチングレジストにより被覆された直下の部分（エッチングから保護すべき部分）がエッチング液の染み込みにより水平方向にエッチングを受けている程度（染み込み程度）を、以下の基準により観察した。評価結果を表１に示す。
◎ 染み込み１００μｍ
○ 染み込み１００μｍ超、１５０μｍ未満
△ 染み込み１５０μｍ以上、２５０μｍ未満
× 染み込み２５０μｍ以上、５００μｍ以下
The evaluation substrates 2 of the examples and comparative examples were immersed in 10% by volume hydrofluoric acid to perform etching to a depth of 100 μm. Thereafter, the evaluation substrates 2 were observed for the degree to which the portion of the glass substrate directly below the etching resist (the portion to be protected from etching) had been etched horizontally due to penetration of the etching solution (degree of penetration) according to the following criteria. The evaluation results are shown in Table 1.
◎ Penetration 100μm
○ Penetration over 100 μm, less than 150 μm △ Penetration 150 μm or more, less than 250 μm × Penetration 250 μm or more, less than 500 μm
Ｉ－Ｖ．剥離性
各評価基板２を、ビーカー中の３質量％の水酸化ナトリウム水溶液（５０℃）に浸漬した。時間経過に伴う、レジストの状態を、以下の評価基準により、目視観察した。評価結果を表１に示す。
◎ ５分以内に完全に剥離した
〇５分超過、３０分以内に剥離した
△ ３０分以内には剥離せず、その後スプレー処理、超音波処理、または温度７０℃以上の水酸化ナトリウム水溶液に１８０分浸漬することにより剥離した
× １０時間以上の浸漬により剥離した
IV. Peelability Each evaluation substrate 2 was immersed in a 3% by weight aqueous solution of sodium hydroxide (50° C.) in a beaker. The state of the resist over time was visually observed according to the following evaluation criteria. The evaluation results are shown in Table 1.
◎ Peeled off completely within 5 minutes. 〇 Peeled off within 30 minutes, but more than 5 minutes. △ Did not peel off within 30 minutes, but peeled off after spray treatment, ultrasonic treatment, or immersion in a sodium hydroxide solution at a temperature of 70°C or higher for 180 minutes. × Peeled off after immersion for 10 hours or more.
Ｉ－ＶI．解像性試験
上記フッ酸耐性試験後の各評価基板２のエッチングの状態をＳＥＭ（走査型電子顕微鏡）により観察し、以下の基準にて評価した。結果を表１に記載する。
◎ アンダーカットは発生せず、エッチング後のガラス基板の端面が滑らかで、パターンどおりのエッチングがされた
〇アンダーカットは無いが、エッチング後のガラス基板の端面がギザ付いていた
△ ハレーションが激しく、アンダーカットが観察された
× ハレーション、アンダーカットが観察され、さらにエッチング箇所の底面に残渣が生じていた
The etching state of each evaluation substrate 2 after the hydrofluoric acid resistance test was observed by SEM (scanning electron microscope) and evaluated according to the following criteria. The results are shown in Table 1.
◎ No undercut occurred, the edge of the glass substrate after etching was smooth, and etching was performed according to the pattern. 〇 No undercut, but the edge of the glass substrate after etching was jagged. △ Severe halation and undercut were observed. × Halation and undercut were observed, and furthermore residue was generated on the bottom of the etched area.
＊１ Ｋａｙａｒａｄ ＺＦＲ-１４０１Ｈ、日本化薬株式会社製、カルボキシル基含有樹脂(酸変性多官能ビスフェノールＦ型エポキシアクリレート、官能基数平均５、固形分換算酸価１００ｍｇ・ＫＯＨ／ｇ）、上記（７）のカルボキシル基含有樹脂に該当
＊２ ＤＰＨＡ、日本化薬株式会社製、ジペンタエリスリトールヘキサアクリレート、
＊３ カレンズＭＴ（登録商標）ＰＥ１、昭和電工株式会社製、４官能チオール化合物
（ペンタエリスリトール テトラキス（３‐メルカプトブチレート）
＊４ カレンズＭＴ（登録商標）ＢＤ１、昭和電工株式会社製、２官能チオール化合物（１，４-ビス（３-メルカプトブチリルオキシ）ブタン)
＊５ カレンズＭＴ（登録商標）ＮＲ１、昭和電工株式会社製、３官能チオール化合物
（１，３，５-トリス（３-メルカプトブチリルオキシエチル）-１,３,５-トリアジン-２,４,６（１Ｈ，３Ｈ，５Ｈ）-トリオン)
＊６ ＫＢＭ－５０３ メタクリル基シランカップリング剤、信越化学工業株式会社製
＊７ ＫＢＭ－４０３ エポキシ基シランカップリング剤、信越化学工業株式会社製
＊８ ＫＢＭ－６０３ アミノ基シランカップリング剤、信越化学工業株式会社製
＊９ Ｏｍｎｉｒａｄ ３６９、ＩＧＭ Ｒｅｓｉｎｓ社製、α-アミノアルキルフェノン系光重合開始剤
＊１０ ＳＧ－２０００、日本タルク株式会社製、超微粉タルク
＊１１ ＢＡＲＩＡＣＥ（登録商標）Ｂ－３０、堺化学工業株式会社製、硫酸バリウム
＊１２ ＫＳ－６６、ジメチルポリシロキサン、信越化学工業株式会社製、オイルコンパウンド型消泡剤
＊１３ ファストゲングリーンＳ、ＤＩＣ株式会社製、フタロシアニングリーン顔料
*1 Kayarad ZFR-1401H, manufactured by Nippon Kayaku Co., Ltd., carboxyl group-containing resin (acid-modified multifunctional bisphenol F type epoxy acrylate, average number of functional groups: 5, acid value converted to solid content: 100 mg KOH/g), corresponds to the carboxyl group-containing resin in (7) above. *2 DPHA, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate,
*3 Karenz MT (registered trademark) PE1, manufactured by Showa Denko K.K., tetrafunctional thiol compound (pentaerythritol tetrakis (3-mercaptobutyrate)
*4 Karenz MT (registered trademark) BD1, manufactured by Showa Denko K.K., bifunctional thiol compound (1,4-bis (3-mercaptobutyryloxy) butane)
*5 Karenz MT (registered trademark) NR1, manufactured by Showa Denko K.K., trifunctional thiol compound (1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione)
* 6 KBM-503 Methacrylic silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. * 7 KBM-403 Epoxy silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. * 8 KBM-603 Amino silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. * 9 Omnirad 369, manufactured by IGM Resins, α-aminoalkylphenone photopolymerization initiator * 10 SG-2000, manufactured by Nippon Talc Co., Ltd., ultrafine powder talc * 11 BARIACE (registered trademark) B-30, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate * 12 KS-66, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., oil compound type defoamer * 13 Fastgen Green S, manufactured by DIC Corporation, phthalocyanine green pigment
実施例の結果より、本発明のアルカリ現像型レジスト組成物は、ガラス密着性、エッチング液に対する耐性、剥離性、解像性の全てにおいて優れていることがわかる。このレジスト組成物を用いることにより得られるガラス等の基材の加工品も精度の良いエッチングが施されたものとされる。 The results of the examples show that the alkali development type resist composition of the present invention is excellent in all respects: glass adhesion, resistance to etching solutions, strippability, and resolution. By using this resist composition, processed products made of substrates such as glass can also be said to have been etched with high precision.
さらに、紫外線硬化型レジスト組成物の実施例および比較例を示して本発明について具体的に説明するが、本発明は下記実施例に限定されるものではない。
［実施例７～１０及び比較例７～８］
Furthermore, the present invention will be specifically explained by showing examples and comparative examples of the ultraviolet-curable resist composition, but the present invention is not limited to the following examples.
[Examples 7 to 10 and Comparative Examples 7 to 8]
ＩＩ－Ｉ． 紫外線硬化型レジスト組成物の作製
表２に示す成分をそれぞれ記載した割合（単位：部）にて配合し、撹拌により混合した。その後３本ロールで２回練り、実施例６～１０(本発明の組成物)、および比較例７～８(比較組成物)の各紫外線硬化型レジスト組成物を得た。
II-I. Preparation of UV-curable resist composition The components shown in Table 2 were mixed in the ratios (unit: parts) shown and mixed by stirring. Then, the mixture was kneaded twice with a three-roll mill to obtain UV-curable resist compositions of Examples 6 to 10 (compositions of the present invention) and Comparative Examples 7 to 8 (comparative compositions).
ＩＩ－ＩＩ． 評価基板３：エッチングレジスト(硬化膜）の作製
酸処理後バフ研磨した銅張積層板の上に、実施例６～１０、比較例７～８の各紫外線硬化型レジスト組成物を２００メッシュのポリエステル製のバイアススクリーンを用いて印刷した。その時の塗膜厚みは、２５μｍであった。メタルハライドランプを光源とするＵＶ照射機を使用して、１０００ｍＪ/ｃｍ２の光量で塗膜を硬化させ、評価基板３を作製した。
II-II. Evaluation substrate 3: Preparation of etching resist (cured film) Each of the ultraviolet-curable resist compositions of Examples 6 to 10 and Comparative Examples 7 to 8 was printed on a copper-clad laminate that had been buffed after acid treatment using a 200-mesh polyester bias screen. The coating thickness was 25 μm. Using a UV irradiator with a metal halide lamp as a light source, the coating was cured with a light amount of 1000 mJ/ cm2 to prepare evaluation substrate 3.
ＩＩ－ＩＩＩ． 指触乾燥性
評価基板３を室温まで冷却し、塗膜どうしを張り合わせ、１ｋｇの荷重をかけ、６時間放置後の張り付き度合いを確認した。評価結果を表２に示す。
評価方法：
〇：引き離しても、塗膜に異常がなかった
△：引き離し時に、塗膜に後が付いた
×：引き離し時に、塗膜が剥がれた
II-III. Dryness to Touch Evaluation substrate 3 was cooled to room temperature, the coating films were attached to each other, a load of 1 kg was applied, and the degree of adhesion after leaving for 6 hours was confirmed. The evaluation results are shown in Table 2.
Evaluation method:
◯: No abnormality in the coating film when pulled apart △: Traces were left on the coating film when pulled apart ×: The coating film peeled off when pulled apart
ＩＩ－ＩＶ． 印刷性
上記各評価基板３の解像線幅１００μｍの箇所のにじみ幅を測定した。評価結果を表２に示す。
◎：３０％未満
〇：にじみ幅が３０～５０％
×：にじみ幅が５０％超
II-IV. Printability The bleeding width was measured at a location where the resolution line width was 100 μm on each of the evaluation substrates 3. The evaluation results are shown in Table 2.
◎: Less than 30% ◯: Bleeding width is 30-50%
×: Bleeding width exceeds 50%
ＩＩ－Ｖ. ガラス密着性
上記各評価基板３に対し、ＪＩＳ Ｋ ５６００－５－６に準拠し、クロスカットテープピールリング試験を実施した。すなわち、評価基板１のエッチングレジストに、１ｍｍの間隔で縦横に交差する切込みを入れて、この切込みにより多数の碁盤目（格子）を作成し、そのうちの１００個の碁盤目に対してＪＩＳ Ｋ ５６００－５－６に記載の方法によりテープを付着して、これを引き剥し、ガラス基板からの剥がれ・欠けを生じた格子の数を、以下のように、観察・評価した。評価結果を表２に示す。
◎ １００すべての格子に剥がれ・欠けのいずれも生じない
〇１００すべての格子に剥がれはないが、１０個未満の格子の端が欠けた
△ ９０個未満の格子に部分的又は完全な剥がれが観察された
× ９０個以上の格子に部分的又は完全な剥がれが観察された
II-V. Glass Adhesion A cross-cut tape peel ring test was carried out on each of the evaluation substrates 3 in accordance with JIS K 5600-5-6. That is, in the etching resist of the evaluation substrate 1, vertical and horizontal cuts were made at intervals of 1 mm to create a large number of grids (lattices), and tape was attached to 100 of these grids by the method described in JIS K 5600-5-6, which was then peeled off, and the number of grids that peeled off or were chipped from the glass substrate was observed and evaluated as follows. The evaluation results are shown in Table 2.
◎ None of the 100 lattices showed peeling or chipping. 〇 None of the 100 lattices showed peeling, but the edges of less than 10 lattices were chipped. △ Partial or complete peeling was observed in less than 90 lattices. × Partial or complete peeling was observed in 90 or more lattices.
ＩＩ－ＶＩ. フッ酸耐性
１０容量％のフッ化水素酸に各実施例および比較例の評価基板３を浸漬することにより、深さ５０μｍのエッチングを行った。その後、各評価基板３について、ガラス基板のエッチングレジストにより被覆された直下の部分（エッチングから保護すべき部分）がエッチング液の染み込みにより水平方向にエッチングを受けている程度（染み込み程度）を、以下の基準により観察した。評価結果を表２に示す。
◎ 染み込み５０μｍ
○ 染み込み５０μｍ超、１００μｍ未満
△ 染み込み１００μｍ以上、２５０μｍ未満
× 染み込み２５０μｍ以上、５００μｍ以下
II-VI. Hydrofluoric Acid Resistance The evaluation substrates 3 of the examples and comparative examples were immersed in 10% by volume of hydrofluoric acid, and etched to a depth of 50 μm. After that, for each evaluation substrate 3, the extent to which the portion of the glass substrate directly below the etching resist (the portion to be protected from etching) was etched horizontally due to penetration of the etching solution (degree of penetration) was observed according to the following criteria. The evaluation results are shown in Table 2.
◎ Penetration 50μm
○ Penetration over 50 μm, less than 100 μm △ Penetration 100 μm or more, less than 250 μm × Penetration 250 μm or more, 500 μm or less
ＩＩ－ＶＩＩ. 剥離性
各評価基板３を、ビーカー中の３質量％の水酸化ナトリウム水溶液（５０℃）に浸漬した。時間経過に伴う、レジストの状態を、以下の評価基準により、目視観察した。評価結果を表２に示す。
〇 １分以内に剥離した
× １分以内には剥離しなかった
Each evaluation substrate 3 was immersed in a 3% by weight aqueous solution of sodium hydroxide (50° C.) in a beaker. The state of the resist over time was visually observed according to the following evaluation criteria. The evaluation results are shown in Table 2.
○ Peeled off within 1 minute × Did not peel off within 1 minute
＊１：ハーフエステル、多塩基酸無水物のヒドロキシアルキル（メタ）アクリレートとのハーフエステル（共栄社化学社製ＨＯＡ－ＭＰＬ）
＊２：ジョンクリル６７、スチレン－アクリル酸共重合樹脂（ＢＡＳＦ社製、重量平均分子量＝１２，５００、酸価＝２１３ｍｇＫＯＨ／ｇ）
＊３：アロニックスＭ－３５０、東亜合成社製、光反応性モノマー、トリメチロールプロパンＥＯ変成トリアクリレート
＊４：ライトエステルＨＯ－２５０、共栄社化学社製、光反応性モノマー、２－ヒドロキシエチルメタクリレート
＊５：３ カレンズＭＴ（登録商標）ＰＥ１、昭和電工株式会社製、４官能チオール化合物（ペンタエリスリトール テトラキス（３‐メルカプトブチレート）
＊６：カレンズＭＴ（登録商標）ＢＤ１、昭和電工株式会社製、２官能チオール化合物（１，４-ビス（３-メルカプトブチリルオキシ）ブタン)
＊７： カレンズＭＴ（登録商標）ＮＲ１、昭和電工株式会社製、３官能チオール化合物（１，３，５-トリス（３-メルカプトブチリルオキシエチル）-１,３,５-トリアジン-２,４,６（１Ｈ，３Ｈ，５Ｈ）-トリオン)
＊８：ＫＳ－６６、ジメチルポリシロキサン、信越化学工業社製
＊９：フタロシアニンブルー、青色着色剤
＊１０：Ｏｍｎｉｒａｄ６５１、ＩＧＭ社製、ベンジルケタール系光重合開始剤
＊１１：アエロジル＃２００、揺変剤、日本アエロジル社製、微粉末シリカ
＊１２：ミクロエースＫ－１、タルク、富士タルク工業社製
*1: Half ester, half ester of polybasic acid anhydride with hydroxyalkyl (meth)acrylate (HOA-MPL manufactured by Kyoeisha Chemical Co., Ltd.)
*2: Joncryl 67, styrene-acrylic acid copolymer resin (manufactured by BASF, weight average molecular weight = 12,500, acid value = 213 mg KOH / g)
*3: Aronix M-350, manufactured by Toagosei Co., Ltd., photoreactive monomer, trimethylolpropane EO modified triacrylate
* 4: Light Ester HO-250, Kyoeisha Chemical Co., Ltd., photoreactive monomer, 2-hydroxyethyl methacrylate * 5: 3 Karenz MT (registered trademark) PE1, Showa Denko K.K., 4-functional thiol compound (pentaerythritol tetrakis (3-mercaptobutyrate)
*6: Karenz MT (registered trademark) BD1, manufactured by Showa Denko K.K., bifunctional thiol compound (1,4-bis(3-mercaptobutyryloxy)butane)
*7: Karenz MT (registered trademark) NR1, manufactured by Showa Denko K.K., trifunctional thiol compound (1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione)
*8: KS-66, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd. *9: Phthalocyanine blue, blue colorant *10: Omnirad 651, manufactured by IGM, benzyl ketal photopolymerization initiator *11: Aerosil #200, thixotropic agent, manufactured by Nippon Aerosil Co., Ltd., fine powder silica *12: Microace K-1, talc, manufactured by Fuji Talc Kogyo Co., Ltd.
実施例の結果より、本発明の紫外線硬化型レジスト組成物は、指触乾燥性、印刷性、ガラス密着性、エッチング液に対する耐性、剥離性の全てにおいて優れていることがわかる。このレジスト組成物を用いることにより得られるガラス等の基材の加工品も精度の良いエッチングが施されたものとされる。 The results of the examples show that the ultraviolet-curable resist composition of the present invention is excellent in all respects: dryness to touch, printability, adhesion to glass, resistance to etching solutions, and peelability. By using this resist composition, processed products made of substrates such as glass can also be considered to have been etched with high precision.
本発明は上記の実施の形態の構成及び実施例に限定されるものではなく、発明の要旨の範囲内で種々変形が可能である。 The present invention is not limited to the configurations and examples of the above-described embodiments, and various modifications are possible within the scope of the gist of the invention.
以上説明したように、本発明のレジスト組成物は、ガラス密着性、エッチング液に対する耐性、剥離性、解像性に優れ、タッチパネル、光学材料、および計測器等のガラス躯体（基板）のエッチングに適用される。また、ガラス以外の基材として、シリコンウェハ、チタンや金属酸化物等を含む基材に対しても密着性やフッ酸耐性に優れ、それらの基材のエッチングにも適用される。 As explained above, the resist composition of the present invention has excellent glass adhesion, resistance to etching solutions, peelability, and resolution, and is applicable to etching glass bodies (substrates) such as touch panels, optical materials, and measuring instruments. In addition, the resist composition has excellent adhesion and hydrofluoric acid resistance to substrates other than glass, such as silicon wafers and substrates containing titanium and metal oxides, and is also applicable to etching of these substrates.
本発明のレジスト組成物の基材への高い密着性により、基材上に描画された所望のレジストパターン通りの高精度のエッチングが行われるため、携帯電話等、意匠性を重視した製品への適用にも有用である。 The resist composition of the present invention has high adhesion to substrates, allowing highly accurate etching to be performed in accordance with the desired resist pattern drawn on the substrate, making it useful for application to products that place importance on design, such as mobile phones.
Claims (5)
（Ａ）カルボキシル基含有樹脂、
（Ｂ）多官能（メタ）アクリレートモノマー、
（Ｃ）多官能チオール化合物、
（Ｄ）光重合開始剤、および
（Ｅ）前記（Ａ）カルボキシル基含有樹脂１００質量部に対して２０～１００質量部のタルクを含み、
前記（Ｃ）多官能チオール化合物は、ペンタエリスリトールテトラキス（３-メルカプトブチレート)、および１，３，５-トリス（３-メルカプトブチリルオキシエチル）-１,３,５-トリアジン-２,４,６（１Ｈ，３Ｈ，５Ｈ）-トリオンのいずれか少なくとも一つであり、
前記（Ｃ）多官能チオール化合物を前記（Ａ）カルボキシル基含有樹脂１００質量部に対して１～１０質量部含むことを特徴とする、エッチングレジスト組成物。 An etching resist composition for use in forming a resist film that protects a substrate from etching using hydrofluoric acid alone or an etching solution containing hydrofluoric acid,
(A) a carboxyl group-containing resin,
(B) a polyfunctional (meth)acrylate monomer,
(C) a polyfunctional thiol compound,
(D) a photopolymerization initiator; and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the (A) carboxyl group-containing resin,
The polyfunctional thiol compound (C) is at least one of pentaerythritol tetrakis(3-mercaptobutyrate) and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione,
An etching resist composition comprising the polyfunctional thiol compound (C) in an amount of 1 to 10 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018239153 | 2018-12-21 | ||
| JP2018239153 | 2018-12-21 | ||
| PCT/JP2019/050256 WO2020130155A1 (en) | 2018-12-21 | 2019-12-23 | Hydrofluoric acid-resistant resist composition, and processed substrate product produced using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2020130155A1 JPWO2020130155A1 (en) | 2021-11-04 |
| JP7462573B2 true JP7462573B2 (en) | 2024-04-05 |
Family
ID=71101415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020561556A Active JP7462573B2 (en) | 2018-12-21 | 2019-12-23 | Etching resist composition and processed substrate obtained using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7462573B2 (en) |
| KR (1) | KR20210104754A (en) |
| CN (1) | CN113227010A (en) |
| WO (1) | WO2020130155A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007128052A (en) | 2005-10-05 | 2007-05-24 | Kansai Paint Co Ltd | Ultraviolet-curing resist composition for glass etching and glass etching processing method |
| JP2011164304A (en) | 2010-02-08 | 2011-08-25 | Taiyo Holdings Co Ltd | Photocurable resin composition, dry film and cured product of the same, and printed wiring board using the same |
| JP2014074924A (en) | 2013-12-02 | 2014-04-24 | Taiyo Holdings Co Ltd | Photosensitive dry film and laminate structure using the same |
| JP2014078045A (en) | 2014-01-24 | 2014-05-01 | Taiyo Holdings Co Ltd | Photocurable resin composition, dry film and cured product of the composition, and printed wiring board using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263404A (en) * | 2008-04-22 | 2009-11-12 | Toray Ind Inc | Paste composition and resin composition using the same |
| JP5890337B2 (en) * | 2013-02-13 | 2016-03-22 | 東京応化工業株式会社 | Radiation-sensitive resin composition, insulating film, and display device |
| JP6697222B2 (en) * | 2015-03-04 | 2020-05-20 | 太陽インキ製造株式会社 | Etching resist composition and dry film |
-
2019
- 2019-12-23 WO PCT/JP2019/050256 patent/WO2020130155A1/en active Application Filing
- 2019-12-23 CN CN201980083175.4A patent/CN113227010A/en active Pending
- 2019-12-23 KR KR1020217020923A patent/KR20210104754A/en unknown
- 2019-12-23 JP JP2020561556A patent/JP7462573B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007128052A (en) | 2005-10-05 | 2007-05-24 | Kansai Paint Co Ltd | Ultraviolet-curing resist composition for glass etching and glass etching processing method |
| JP2011164304A (en) | 2010-02-08 | 2011-08-25 | Taiyo Holdings Co Ltd | Photocurable resin composition, dry film and cured product of the same, and printed wiring board using the same |
| JP2014074924A (en) | 2013-12-02 | 2014-04-24 | Taiyo Holdings Co Ltd | Photosensitive dry film and laminate structure using the same |
| JP2014078045A (en) | 2014-01-24 | 2014-05-01 | Taiyo Holdings Co Ltd | Photocurable resin composition, dry film and cured product of the composition, and printed wiring board using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020130155A1 (en) | 2021-11-04 |
| WO2020130155A1 (en) | 2020-06-25 |
| KR20210104754A (en) | 2021-08-25 |
| CN113227010A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0909407B1 (en) | Photopolymerizable thermosetting resin composition | |
| KR101009081B1 (en) | Photo- and thermo-setting resin composition and printed wiring boards made by using the same | |
| CN101393394B (en) | Photo-cured and heat-cured resin composition and pcondensate thereof | |
| JP4584839B2 (en) | Photosensitive resin composition and cured product thereof | |
| JPH09157574A (en) | Photocuring, thermosetting delustering resist ink composition | |
| JP2017198746A (en) | Dry film, cured product and printed wiring board | |
| JP2019196444A (en) | Curable resin composition, dry film, cured product and electronic component | |
| KR102168004B1 (en) | Curable resin composition, cured product thereof, printed wiring board having same, and method for producing cured product | |
| KR102444761B1 (en) | The photosensitive resin composition, the soldering resist film using this photosensitive resin composition, a flexible printed wiring board, and an image display apparatus | |
| JP2002014466A (en) | Photosensitive resin composition | |
| JP4309225B2 (en) | Curable composition, cured product thereof and printed wiring board using the same | |
| JP7462573B2 (en) | Etching resist composition and processed substrate obtained using the same | |
| JP5608413B2 (en) | Curable resin composition | |
| JP2963069B2 (en) | Solder photoresist ink composition | |
| JPWO2003059975A1 (en) | Photosensitive resin composition and printed wiring board | |
| JP2005024659A (en) | Curable composition | |
| KR20210119893A (en) | Curable resin composition, dry film, cured product, and electronic component | |
| JP2003280189A (en) | Photosetting and thermosetting resin composition | |
| JPH0767008B2 (en) | Solder resist pattern forming method | |
| JP2002234932A (en) | Epoxy carboxylate compound soluble in alkali aqueous solution photosensitive resin composition using the same and its cured product | |
| JP2000292923A (en) | Photosensitive resin composition | |
| JP2003280191A (en) | Photosetting and thermosetting resin composition | |
| TWI424268B (en) | An alkaline developing type photosensitive resin composition | |
| JP2005105006A (en) | Photo-curing and heat-curing composition and its cured product and printed wiring board using the same | |
| JP2008063452A (en) | Curable composition and cured product therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220901 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230425 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20230621 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20230605 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230731 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231127 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240227 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240326 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7462573 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |