KR20210132148A - Photosensitive resin composition for microlens - Google Patents
Photosensitive resin composition for microlens Download PDFInfo
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- KR20210132148A KR20210132148A KR1020217030767A KR20217030767A KR20210132148A KR 20210132148 A KR20210132148 A KR 20210132148A KR 1020217030767 A KR1020217030767 A KR 1020217030767A KR 20217030767 A KR20217030767 A KR 20217030767A KR 20210132148 A KR20210132148 A KR 20210132148A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- structural unit
- component
- resin composition
- photosensitive resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- -1 diphenyl [4- (phenylthio) phenyl] sulfonium salt compound Chemical class 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000004292 cyclic ethers Chemical group 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 52
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- 239000004094 surface-active agent Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 238000011161 development Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- XXNDEOCNKXHSGK-UHFFFAOYSA-N 1-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOC(C)OC(=O)C(C)=C XXNDEOCNKXHSGK-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000004112 carboxyamino group Chemical group [H]OC(=O)N([H])[*] 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
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- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 2
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000002366 time-of-flight method Methods 0.000 description 2
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 2
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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- LWHOMMCIJIJIGV-UHFFFAOYSA-N (1,3-dioxobenzo[de]isoquinolin-2-yl) trifluoromethanesulfonate Chemical compound C1=CC(C(N(OS(=O)(=O)C(F)(F)F)C2=O)=O)=C3C2=CC=CC3=C1 LWHOMMCIJIJIGV-UHFFFAOYSA-N 0.000 description 1
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- ORPDKMPYOLFUBA-UHFFFAOYSA-M diphenyliodanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ORPDKMPYOLFUBA-UHFFFAOYSA-M 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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- 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
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- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- G—PHYSICS
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- 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
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
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- G—PHYSICS
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14625—Optical elements or arrangements associated with the device
- H01L27/14627—Microlenses
Abstract
[과제] 신규한 마이크로렌즈용 감광성 수지조성물을 제공하는 것이다.
[해결수단] 하기 (A)성분, 하기 (B)성분 및 하기 (C)성분을 함유하고, 이 (A)성분 100질량%에 대하여 이 (B)성분을 적어도 0.5질량% 함유하는 마이크로렌즈용 감광성 수지조성물이다.
(A): 하기 식(1)로 표시되는 구조단위, 하기 식(2)로 표시되는 구조단위 및 하기 식(3)으로 표시되는 구조단위를 갖는, 중량평균분자량 5000 내지 25000의 공중합체
(B): 광산발생제
(C): 용제
[식(1) 내지 식(3) 중, R1, R2 및 R3은 각각 독립적으로 수소원자 또는 메틸기를 나타내고, X1 및 X2는 각각 독립적으로 탄소원자수 2 내지 4의 알킬렌기를 나타내고, Z1은 산해리성기를 나타내고, Z2는 블록이소시아네이트기를 나타낸다.][Problem] To provide a novel photosensitive resin composition for microlenses.
[Solutions] For microlenses containing the following (A) component, the following (B) component, and the following (C) component, and containing at least 0.5 mass % of this (B) component with respect to 100 mass % of this (A) component It is a photosensitive resin composition.
(A): a copolymer having a weight average molecular weight of 5000 to 25000 having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3)
(B): photoacid generator
(C): solvent
[In Formulas (1) to (3), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, and X 1 and X 2 each independently represent an alkylene group having 2 to 4 carbon atoms. , Z 1 represents an acid dissociable group, Z 2 is It represents a block isocyanate group.]
Description
본 발명은, 특정의 알칼리가용성 폴리머, 광산발생제, 및 용제를 함유하는, 마이크로렌즈 형성용의 감광성 수지조성물에 관한 것이다. 특히 리플로우법에 의해 제작되는 마이크로렌즈용의 감광성 수지조성물에 관한 것이다.The present invention relates to a photosensitive resin composition for forming microlenses containing a specific alkali-soluble polymer, a photoacid generator, and a solvent. In particular, it relates to a photosensitive resin composition for microlenses produced by a reflow method.
고체촬상소자로서, CCD/CMOS 이미지센서가 알려져 있다. 최근, 새로운 이미지센서로서, 3차원(3D)카메라에 사용되는 TOF(Time of Flight)방식의 거리화상센서가 개발되고 있다. TOF방식이란, 광원으로부터 발생한 광이, 측정대상에서 반사되어, 센서로 수광할 때까지의 비행시간을 검출함으로써, 측정대상까지의 거리를 측정하는 방식이다. 이 TOF방식을 채용한 이미지센서는, 화소마다 거리정보를 검출함으로써, 고정밀도의 3차원 거리화상을 취득할 수 있다.As a solid-state image sensor, a CCD/CMOS image sensor is known. Recently, as a new image sensor, a TOF (Time of Flight) type distance image sensor used in a three-dimensional (3D) camera has been developed. The TOF method is a method of measuring the distance to the measurement object by detecting the flight time until the light generated from the light source is reflected from the measurement object and received by the sensor. An image sensor employing this TOF method can acquire a high-precision three-dimensional distance image by detecting distance information for each pixel.
종래부터, CCD/CMOS 이미지센서에는, 집광효율을 향상시키기 위해 마이크로렌즈가 마련되어 있다. 상기 마이크로렌즈의 제작방법의 하나로서, 리플로우법이 알려져 있다(예를 들어, 특허문헌 1을 참조). 즉, 감광성 수지조성물을 기판 상에 도포하고, 포토리소그래피법에 의해 단면형상이 직사각형상인 패턴을 형성한 후, 이 직사각형상의 패턴을 열처리에 의해 용융하여 유동시켜, 표면장력에 의해 렌즈형상을 제작하는 방법이다.BACKGROUND ART Conventionally, a CCD/CMOS image sensor is provided with a microlens in order to improve light collection efficiency. As one of the manufacturing methods of the said microlens, the reflow method is known (refer patent document 1, for example). That is, a photosensitive resin composition is applied on a substrate, a pattern having a rectangular cross-sectional shape is formed by a photolithography method, and the rectangular pattern is melted and flowed by heat treatment to produce a lens shape by surface tension. way.
한편, 중합체, 광산발생제, 용제, 및 티탄블랙을 포함하는 감광성 수지조성물이 알려져 있다(특허문헌 2를 참조). 특허문헌 2에 기재된 감광성 수지조성물 중의 중합체는, 산기가 산분해성기로 보호된 기를 갖는 제1의 구성단위 및 가교성기를 갖는 제2의 구성단위를 갖는 중합체, 그리고 제1의 구성단위를 갖는 중합체 및 제2의 구성단위를 갖는 중합체 중, 적어도 일방을 만족한다. 그러나, 상기 감광성 수지조성물이, 마이크로렌즈 형성용인 것, 특히 리플로우법에 의해 제작되는 마이크로렌즈 형성용인 것은, 특허문헌 2에 기재도 시사도 없다.On the other hand, a photosensitive resin composition containing a polymer, a photoacid generator, a solvent, and titanium black is known (refer to Patent Document 2). The polymer in the photosensitive resin composition described in Patent Document 2 is a polymer having a first structural unit having a group in which an acid group is protected by an acid-decomposable group and a second structural unit having a crosslinkable group, and a polymer having a first structural unit and At least one is satisfied among the polymers which have a 2nd structural unit. However, Patent Document 2 neither describes nor suggests that the photosensitive resin composition is for formation of microlenses, particularly that it is for formation of microlenses produced by a reflow method.
상기 TOF방식의 거리화상센서, 및 유기EL디스플레이 등의 전자표시 디바이스에, 마이크로렌즈를 탑재함으로써, 센서에의 집광효율 향상 및 디스플레이의 휘도향상이 기대된다.By mounting a microlens in the electronic display device such as the TOF-type distance image sensor and organic EL display, improvement of the light condensing efficiency of the sensor and improvement of the luminance of the display are expected.
마이크로렌즈 형성용 감광성 수지조성물은, 포토리소그래피법에 의해 원하는 형상의 패턴을 형성할 수 있는 것이 요구된다. 그리고, 원하는 형상의 패턴을 형성하기 위해, 알칼리성 현상액을 이용하여 현상한 후, 잔사의 발생이 억제되는 것이 요구된다. 나아가, 리플로우법에 의해 마이크로렌즈를 제작하기 위해서는, 상기 패턴이 리플로우 가능한 것이 필요하다. 또한, 제작된 마이크로렌즈 상에, 평탄화막 등의 피복막을 도포법에 의해 형성할 때, 사용하는 막형성용 조성물은 통상 용제를 포함하므로, 제작된 마이크로렌즈가 내용제성을 구비하는 것이 요구된다.The photosensitive resin composition for forming a microlens is required to be able to form a pattern of a desired shape by a photolithography method. And in order to form a pattern of a desired shape, it is calculated|required that generation|occurrence|production of a residue is suppressed after developing using an alkaline developing solution. Furthermore, in order to produce a microlens by the reflow method, it is necessary that the said pattern is reflowable. In addition, when forming a coating film such as a planarization film on the produced microlens by a coating method, the film-forming composition used usually contains a solvent, so that the produced microlens is required to have solvent resistance.
본 발명은, 상기의 과제를 모두 해결하는 것이다. 즉 본 발명은, 하기 (A)성분, 하기 (B)성분 및 하기 (C)성분을 함유하고, 이 (A)성분 100질량%에 대하여 이 (B)성분을 적어도 0.5질량% 함유하는 마이크로렌즈용 감광성 수지조성물이다.The present invention solves all of the above problems. That is, this invention contains the following (A) component, following (B) component, and following (C)component, The microlens which contains this (B) component at least 0.5 mass % with respect to 100 mass % of this (A) component It is a photosensitive resin composition for use.
(A): 하기 식(1)로 표시되는 구조단위, 하기 식(2)로 표시되는 구조단위 및 하기 식(3)으로 표시되는 구조단위를 갖는, 중량평균분자량 5000 내지 25000의 공중합체(A): a copolymer having a weight average molecular weight of 5000 to 25000 having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3)
(B): 광산발생제(B): photoacid generator
(C): 용제(C): solvent
[화학식 1][Formula 1]
[식(1) 내지 식(3) 중, R1, R2 및 R3은 각각 독립적으로 수소원자 또는 메틸기를 나타내고, X1 및 X2는 각각 독립적으로 탄소원자수 2 내지 4의 알킬렌기를 나타내고, Z1은 산해리성기를 나타내고, Z2는 블록이소시아네이트기를 나타낸다.][In Formulas (1) to (3), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, and X 1 and X 2 each independently represent an alkylene group having 2 to 4 carbon atoms. , Z 1 represents an acid dissociable group, and Z 2 represents a block isocyanate group.]
상기 산해리성기는, 예를 들어 하기 식(a)로 표시되는 기이다.The acid dissociable group is, for example, a group represented by the following formula (a).
[화학식 2][Formula 2]
(식 중, *은 산소원자와의 결합수를 나타내고, R4는 메틸기를 나타내고, R5는 탄소원자수 1 내지 6의 알킬기를 나타내고, 이 알킬기의 탄소원자수가 3 내지 6인 경우 분지구조를 가질 수도 있고, R5는 R4와 연결되어 환상 에테르구조를 형성할 수도 있다.)(wherein * represents the number of bonds with an oxygen atom, R 4 is represents a methyl group, and R 5 is Represents an alkyl group having 1 to 6 carbon atoms, and when the alkyl group has 3 to 6 carbon atoms, it may have a branched structure, and R 5 may be connected to R 4 to form a cyclic ether structure.)
상기 블록이소시아네이트기는, 예를 들어 하기 식(b) 또는 하기 식(c)로 표시되는 기이다.The said block isocyanate group is group represented by a following formula (b) or a following formula (c), for example.
[화학식 3][Formula 3]
[식(b) 및 식(c) 중, *은 상기 X2로 표시되는 알킬렌기와의 결합수를 나타내고, R6 및 R7은 각각 독립적으로 수소원자, 메틸기 또는 에틸기를 나타내고, R8은 메틸기를 나타내고, a는 0 내지 3의 정수를 나타낸다.][In formulas (b) and (c), * represents the number of bonds with the alkylene group represented by X 2 , R 6 and R 7 each independently represent a hydrogen atom, a methyl group or an ethyl group, and R 8 is represents a methyl group, and a represents an integer of 0 to 3.]
상기 공중합체는, 하기 식(4a)로 표시되는 구조단위 및 하기 식(4b)로 표시되는 구조단위 중 적어도 일방을 추가로 가질 수도 있다.The copolymer may further have at least one of a structural unit represented by the following formula (4a) and a structural unit represented by the following formula (4b).
[화학식 4][Formula 4]
[식(4a) 및 식(4b) 중, R9는 수소원자 또는 메틸기를 나타내고, R10은 탄소원자수 1 내지 6의 알킬기를 나타내고, 이 알킬기의 탄소원자수가 3 내지 6인 경우, 분지구조 또는 환구조를 가질 수도 있고, R11은 시클로헥실기 또는 페닐기를 나타낸다.][In formulas (4a) and (4b), R 9 represents a hydrogen atom or a methyl group, R 10 represents an alkyl group having 1 to 6 carbon atoms, and when the alkyl group has 3 to 6 carbon atoms, a branched structure or It may have a ring structure, and R 11 represents a cyclohexyl group or a phenyl group.]
상기 광산발생제는, 예를 들어, 디페닐[4-(페닐티오)페닐]설포늄염 화합물, 또는 N-(트리플루오로메탄설포닐옥시)-1,8-나프탈이미드 혹은 그의 유도체이다.The photoacid generator is, for example, a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound or N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or a derivative thereof. .
본 발명의 다른 태양은, 상기 마이크로렌즈용 감광성 수지조성물을 기판 상에 도포하고, 이 감광성 수지조성물을 프리베이크하여 수지막을 형성하는 공정, 마스크를 통해 상기 수지막을 노광하는 노광공정, 상기 노광공정 후의 수지막을 베이크하는 베이크공정, 상기 베이크 후의 수지막을, 알칼리성 현상액을 이용하여 현상하는 현상공정, 상기 현상공정 후 얻어진 패턴을 리플로우시키는 리플로우공정, 및 상기 리플로우공정 후의 패턴을 경화시켜 렌즈패턴을 형성하는 공정을 갖는, 마이크로렌즈의 제작방법이다.In another aspect of the present invention, the photosensitive resin composition for microlenses is applied on a substrate, and the photosensitive resin composition is pre-baked to form a resin film, an exposure process of exposing the resin film through a mask, after the exposure process A baking step of baking the resin film, a developing step of developing the resin film after the baking using an alkaline developer, a reflow step of reflowing the pattern obtained after the developing step, and curing the pattern after the reflow step to form a lens pattern It is a manufacturing method of a microlens which has the process of forming.
상기 리플로우공정은, 상기 현상 후 얻어진 패턴을 예를 들어 120℃ 내지 200℃의 온도로 가열하는 공정이다.The reflow step is a step of heating the pattern obtained after the development to a temperature of, for example, 120°C to 200°C.
본 발명의 마이크로렌즈용 감광성 수지조성물은, 포토리소그래피법에 의해 단면형상이 직사각형상(矩形狀)의 패턴을 형성할 수 있음과 함께, 현상 후에 패턴이 형성되어 있지 않은 노광부에 있어서 잔사가 발생하는 일 없이, 형성된 패턴의 엣지부(
본 발명은, (A)성분, (B)성분 및 (C)성분을 함유하고, 이 (A)성분 100질량%에 대하여 이 (B)성분을 적어도 0.5질량% 함유하는 마이크로렌즈용 감광성 수지조성물이다. 본 발명의 마이크로렌즈용 감광성 수지조성물은, 포지티브형 감광성 수지조성물이다. 이하, 본 발명의 각 성분의 상세를 설명한다. 본 발명의 마이크로렌즈용 감광성 수지조성물로부터 용제를 제외한 고형분은, 통상 1질량% 내지 50질량%이다. 본 명세서에 있어서, 용제를 제외한 본 발명의 마이크로렌즈용 감광성 수지조성물의 성분을, 고형분이라고 정의한다.This invention contains (A) component, (B) component, and (C)component, The photosensitive resin composition for microlenses containing this (B) component at least 0.5 mass % with respect to 100 mass % of this (A) component am. The photosensitive resin composition for microlenses of the present invention is a positive photosensitive resin composition. Hereinafter, the detail of each component of this invention is demonstrated. Solid content excluding a solvent from the photosensitive resin composition for microlenses of this invention is 1 mass % - 50 mass % normally. In this specification, the component of the photosensitive resin composition for microlens of this invention except a solvent is defined as solid content.
<(A)성분><(A) component>
본 발명의 마이크로렌즈용 감광성 수지조성물에 있어서의 (A)성분은, 상기 식(1)로 표시되는 구조단위, 상기 식(2)로 표시되는 구조단위 및 상기 식(3)으로 표시되는 구조단위를 갖는, 중량평균분자량 5000 내지 25000의 공중합체이다. 이 공중합체는, 3종의 모노머로부터 얻어지는 터폴리머(3원 공중합체)로 한정되지 않고, 4종의 모노머로부터 얻어지는 공중합체, 또는 5종의 모노머로부터 얻어지는 공중합체일 수도 있다. 상기 공중합체의 중량평균분자량은, 겔퍼미에이션 크로마토그래피(GPC)에 의해, 표준시료로서 폴리스티렌을 이용하여 얻어지는 값이다.The component (A) in the photosensitive resin composition for microlenses of the present invention comprises a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3). It is a copolymer having a weight average molecular weight of 5000 to 25000. This copolymer is not limited to the terpolymer (terpolymer) obtained from 3 types of monomers, The copolymer obtained from 4 types of monomers or the copolymer obtained from 5 types of monomers may be sufficient. The weight average molecular weight of the copolymer is a value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).
상기 식(1)로 표시되는 구조단위는, 예를 들어 하기 식(1a)로 표시된다. 이 식(1)로 표시되는 구조단위는, 산해리성기를 갖는 구조단위이면 하기 식(1a)로 표시되는 구조단위로 한정되지 않는다. 여기서, 산해리성기란, 산에 의해 해리하여 알칼리가용성기가 되는 기이다. 본 발명에 있어서, 상기 산은, 노광에 의해 (B)성분의 광산발생제로부터 발생하는 산이며, 상기 알칼리가용성기는 카르복시기이다.The structural unit represented by the formula (1) is, for example, represented by the following formula (1a). The structural unit represented by the formula (1) is not limited to the structural unit represented by the following formula (1a) as long as it has an acid dissociable group. Here, an acid-dissociable group is a group which dissociates with an acid and becomes an alkali-soluble group. In this invention, the said acid is an acid which generate|occur|produces from the photo-acid generator of (B) component by exposure, and the said alkali-soluble group is a carboxy group.
[화학식 5][Formula 5]
(식 중, R1은 수소원자 또는 메틸기를 나타내고, R4는 메틸기를 나타내고, R5는 탄소원자수 1 내지 6의 알킬기를 나타내고, 이 알킬기의 탄소원자수가 3 내지 6인 경우 분지구조를 가질 수도 있고, R5는 R4와 연결되어 환상 에테르구조를 형성할 수도 있다.)(Wherein, R 1 represents a hydrogen atom or a methyl group, R 4 represents a methyl group, R 5 represents an alkyl group having 1 to 6 carbon atoms, and when the alkyl group has 3 to 6 carbon atoms, it may have a branched structure and R 5 may be connected to R 4 to form a cyclic ether structure.)
상기 식(1)로 표시되는 구조단위를 형성하는 모노머의 구체예로서, 1-메톡시에틸(메트)아크릴레이트, 1-에톡시에틸(메트)아크릴레이트, 1-프로폭시에틸(메트)아크릴레이트, 1-이소프로폭시에틸(메트)아크릴레이트, 1-n-부톡시에틸(메트)아크릴레이트, 1-tert-부톡시에틸(메트)아크릴레이트, 1-n-헥실옥시에틸(메트)아크릴레이트, 1-시클로헥실옥시에틸(메트)아크릴레이트, 테트라하이드로-2H-피란-2-일(메트)아크릴레이트를 들 수 있다. 이들 모노머는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다. 본 명세서에 있어서, (메트)아크릴레이트는 메타크릴레이트 및 아크릴레이트를 의미한다.As specific examples of the monomer forming the structural unit represented by the formula (1), 1-methoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 1-propoxyethyl (meth) acrylic Rate, 1-isopropoxyethyl (meth)acrylate, 1-n-butoxyethyl (meth)acrylate, 1-tert-butoxyethyl (meth)acrylate, 1-n-hexyloxyethyl (meth) acrylate, 1-cyclohexyloxyethyl (meth)acrylate, and tetrahydro-2H-pyran-2-yl (meth)acrylate. These monomers may be used individually by 1 type, or may be used in combination of 2 or more type. In the present specification, (meth)acrylate means methacrylate and acrylate.
상기 식(2)로 표시되는 구조단위는, 가교성기로서 하이드록시기를 갖는 구조단위이다. 이 식(2)로 표시되는 구조단위를 형성하는 모노머의 구체예로서, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트를 들 수 있다. 이들 모노머는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다.The structural unit represented by the formula (2) is a structural unit having a hydroxyl group as a crosslinkable group. As specific examples of the monomer forming the structural unit represented by the formula (2), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acryl rate can be mentioned. These monomers may be used individually by 1 type, or may be used in combination of 2 or more type.
상기 식(3)으로 표시되는 구조단위는, 예를 들어 하기 식(3b) 또는 하기 식(3c)로 표시된다. 이 식(3)으로 표시되는 구조단위는, 블록이소시아네이트기를 갖는 구조단위이면 하기 식(3b) 또는 하기 식(3c)로 표시되는 구조단위로 한정되지 않는다. 여기서, 블록이소시아네이트기란, 이소시아네이트기(-NCO)가 열탈리 가능한 보호기에 의해 블록된 기, 즉, 이소시아네이트기에 블록제를 반응시킨 기이다.The structural unit represented by the formula (3) is, for example, represented by the following formula (3b) or the following formula (3c). The structural unit represented by the formula (3) is not limited to the structural unit represented by the following formula (3b) or (3c) as long as it is a structural unit having a block isocyanate group. Here, the blocked isocyanate group is a group in which an isocyanate group (-NCO) is blocked by a thermally detachable protecting group, ie, a group in which a blocking agent is reacted with an isocyanate group.
[화학식 6][Formula 6]
[식(3b) 및 식(3c) 중, R3은 수소원자 또는 메틸기를 나타내고, X2는 탄소원자수 2 내지 4의 알킬렌기를 나타내고, R6 및 R7은 각각 독립적으로 수소원자, 메틸기 또는 에틸기를 나타내고, R8은 메틸기를 나타내고, a는 0 내지 3의 정수를 나타낸다.][In formulas (3b) and (3c), R 3 represents a hydrogen atom or a methyl group, X 2 represents an alkylene group having 2 to 4 carbon atoms, and R 6 and R 7 are each independently a hydrogen atom, a methyl group or represents an ethyl group, R 8 represents a methyl group, and a represents an integer of 0 to 3.]
상기 식(3)으로 표시되는 구조단위를 형성하는 모노머의 구체예로서, 2-이소시아네이트에틸메타크릴레이트, 2-이소시아네이트에틸아크릴레이트 등의 이소시아네이트함유 (메트)아크릴레이트에, 메틸에틸케톤옥심, ε-카프로락탐, 3,5-디메틸피라졸, 말론산디에틸 등의 블록제를 부가한 화합물을 들 수 있다. 이들 모노머는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다.As a specific example of the monomer forming the structural unit represented by the formula (3), to isocyanate-containing (meth)acrylates such as 2-isocyanate ethyl methacrylate and 2-isocyanate ethyl acrylate, methyl ethyl ketone oxime, ε - The compound which added blocking agents, such as caprolactam, 3, 5- dimethylpyrazole, and diethyl malonate, is mentioned. These monomers may be used individually by 1 type, or may be used in combination of 2 or more type.
상기 (A)성분의 공중합체는, 상기 식(4a)로 표시되는 구조단위 및 상기 식(4b)로 표시되는 구조단위 중 적어도 일방을 추가로 가질 수도 있다. 이 식(4a)로 표시되는 구조단위를 형성하는 모노머의 구체예로서, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, n-펜틸(메트)아크릴레이트, 시클로펜틸(메트)아크릴레이트, n-헥실(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트를 들 수 있다. 상기 식(4b)로 표시되는 구조단위를 형성하는 모노머의 구체예로서, N-시클로헥실말레이미드, N-페닐말레이미드를 들 수 있다. 이들 모노머는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다.The copolymer of the component (A) may further have at least one of the structural unit represented by the formula (4a) and the structural unit represented by the formula (4b). As specific examples of the monomer forming the structural unit represented by the formula (4a), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-hexyl (meth) acrylic a rate and cyclohexyl (meth)acrylate are mentioned. Specific examples of the monomer forming the structural unit represented by the formula (4b) include N-cyclohexylmaleimide and N-phenylmaleimide. These monomers may be used individually by 1 type, or may be used in combination of 2 or more type.
상기 (A)성분의 공중합체에 있어서, 상기 식(1)로 표시되는 구조단위, 상기 식(2)로 표시되는 구조단위, 상기 식(3)으로 표시되는 구조단위, 상기 식(4a)로 표시되는 구조단위 및 상기 식(4b)로 표시되는 구조단위의 합 100mol%에 대하여, 상기 식(1)로 표시되는 구조단위의 함유율은 예를 들어 12mol% 내지 30mol%이고, 바람직하게는 17mol% 내지 25mol%, 상기 식(2)로 표시되는 구조단위의 함유율은 예를 들어 5mol% 내지 40mol%이고, 바람직하게는 10mol% 내지 30mol%, 상기 식(3)으로 표시되는 구조단위의 함유율은 예를 들어 5mol% 내지 40mol%이고, 바람직하게는 10mol% 내지 30mol%, 상기 식(4a)로 표시되는 구조단위의 함유율은 예를 들어 0mol% 내지 60mol%, 상기 식(4b)로 표시되는 구조단위의 함유율은 예를 들어 0mol% 내지 60mol%이다.In the copolymer of the component (A), the structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (3), the structural unit represented by the formula (4a) With respect to 100 mol% of the sum of the structural unit represented by the structural unit and the structural unit represented by the formula (4b), the content of the structural unit represented by the formula (1) is, for example, 12 mol% to 30 mol%, preferably 17 mol% to 25 mol%, the content rate of the structural unit represented by the formula (2) is, for example, 5 mol% to 40 mol%, preferably 10 mol% to 30 mol%, the content rate of the structural unit represented by the formula (3) is, for example, For example, 5 mol% to 40 mol%, preferably 10 mol% to 30 mol%, the content rate of the structural unit represented by the formula (4a) is, for example, 0 mol% to 60 mol%, the structural unit represented by the formula (4b) The content of is, for example, 0 mol% to 60 mol%.
상기 식(1)로 표시되는 구조단위의 함유율이 하한값보다도 작은 경우, 포토리소그래피법에 의해 패턴을 형성할 때, 현상액에 대한 노광부의 용해성이 부족하여, 원하는 형상의 패턴이 얻어지지 않을 우려가 있다. 상기 식(1)로 표시되는 구조단위의 함유율이 상한값보다도 큰 경우, 제작된 마이크로렌즈의 내용제성이 얻어지지 않을 우려가 있다. 상기 식(2)로 표시되는 구조단위 및 상기 식(3)으로 표시되는 구조단위의 함유율이 하한값보다도 작은 경우, 제작된 마이크로렌즈의 내용제성이 얻어지지 않을 우려가 있다. 상기 식(2)로 표시되는 구조단위 및 상기 식(3)으로 표시되는 구조단위의 함유율이 상한값보다도 많은 경우, 포토리소그래피법에 의해 패턴을 형성할 때, 현상액에 대한 노광부의 용해성이 부족하여, 원하는 형상의 패턴이 얻어지지 않을 우려가 있다. 상기 (A)성분의 공중합체는, 상기 식(2)로 표시되는 구조단위 및 상기 식(3)으로 표시되는 구조단위를 가짐으로써, 베이크에 의해 가교반응이 진행된다. 그러므로, 상기 식(2)로 표시되는 구조단위 및 상기 식(3)으로 표시되는 구조단위의 함유율은, 등몰인 것이 바람직하다. 상기 식(4a)로 표시되는 구조단위 및 상기 식(4b)로 표시되는 구조단위는, 그 함유율에 따라 상기 공중합체의 유리전이점(Tg)을 조정할 수 있으므로, 패턴의 리플로우성을 용이하게 제어할 수 있다.When the content rate of the structural unit represented by the formula (1) is smaller than the lower limit, when the pattern is formed by the photolithography method, the solubility of the exposed portion to the developer is insufficient, and there is a fear that a pattern having a desired shape may not be obtained. . When the content rate of the structural unit represented by the formula (1) is larger than the upper limit, there is a fear that the solvent resistance of the produced microlens cannot be obtained. When the content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is smaller than the lower limit, there is a fear that the solvent resistance of the produced microlens cannot be obtained. When the content rate of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is higher than the upper limit, the solubility of the exposed part to the developer is insufficient when forming the pattern by the photolithography method, There exists a possibility that the pattern of a desired shape may not be obtained. Since the copolymer of the component (A) has a structural unit represented by the formula (2) and a structural unit represented by the formula (3), a crosslinking reaction proceeds by baking. Therefore, it is preferable that the content rate of the structural unit represented by the said Formula (2) and the structural unit represented by said Formula (3) is equimolar. Since the structural unit represented by the formula (4a) and the structural unit represented by the formula (4b) can adjust the glass transition point (Tg) of the copolymer according to the content thereof, the reflow property of the pattern can be easily can be controlled
상기 (A)성분의 공중합체를 얻는 방법은 특별히 한정되지 않는다. 일반적으로는, 상기 식(1)로 표시되는 구조단위를 형성하는 모노머, 상기 식(2)로 표시되는 구조단위를 형성하는 모노머 및 상기 식(3)으로 표시되는 구조단위를 형성하는 모노머, 그리고, 임의로 상기 식(4a)로 표시되는 구조단위를 형성하는 모노머 및 상기 식(4b)로 표시되는 구조단위를 형성하는 모노머 중 적어도 일방을, 중합개시제 존재하의 용제 중에 있어서, 통상 50℃ 내지 120℃의 온도하에서 중합반응시킴으로써 얻어진다. 이와 같이 하여 얻어지는 공중합체는, 통상, 용제에 용해된 용액상태이며, 이 상태로 단리하는 일 없이, 본 발명의 마이크로렌즈용 감광성 수지조성물에 이용할 수 있다.The method of obtaining the copolymer of the said (A) component is not specifically limited. In general, a monomer forming the structural unit represented by the formula (1), a monomer forming the structural unit represented by the formula (2), and a monomer forming the structural unit represented by the formula (3), and , optionally at least one of the monomer forming the structural unit represented by the formula (4a) and the monomer forming the structural unit represented by the formula (4b) in a solvent in the presence of a polymerization initiator is usually 50 ° C. to 120 ° C. It is obtained by polymerization at a temperature of The copolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the photosensitive resin composition for microlenses of the present invention without isolating in this state.
<(B)성분><(B) component>
본 발명의 마이크로렌즈용 감광성 수지조성물에 있어서의 (B)성분은, 광산발생제이다. 이 광산발생제는, 노광에 의해 산이 발생하는 화합물이면 특별히 한정되지 않는다. 이 화합물의 구체예로서, 오늄염 화합물, 설폰이미드 화합물, 및 디설포닐디아조메탄 화합물을 들 수 있다.(B) component in the photosensitive resin composition for microlenses of this invention is a photo-acid generator. This photo-acid generator will not be specifically limited if it is a compound which an acid generate|occur|produces by exposure. Specific examples of this compound include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.
상기 오늄염 화합물의 구체예로서, 디페닐요오도늄헥사플루오로포스페이트, 디페닐요오도늄트리플루오로메탄설포네이트, 디페닐요오도늄노나플루오로-n-부탄설포네이트, 디페닐요오도늄퍼플루오로-n-옥탄설포네이트, 디페닐요오도늄캠퍼설포네이트, 비스(4-tert-부틸페닐)요오도늄캠퍼설포네이트, 비스(4-tert-부틸페닐)요오도늄트리플루오로메탄설포네이트 등의 요오도늄염 화합물, 및 트리페닐설포늄헥사플루오로포스페이트, 트리페닐설포늄트리스(펜타플루오로에틸)트리플루오로포스페이트, 트리페닐설포늄헥사플루오로안티모네이트, 트리페닐설포늄테트라키스(펜타플루오로페닐)보레이트, 트리페닐설포늄노나플루오로-n-부탄설포네이트, 트리페닐설포늄캠퍼설포네이트, 트리페닐설포늄트리플루오로메탄설포네이트, 디페닐[4-(페닐티오)페닐]설포늄헥사플루오로포스페이트, 디페닐[4-(페닐티오)페닐]설포늄트리스(펜타플루오로에틸)트리플루오로포스페이트, 디페닐[4-(페닐티오)페닐]설포늄헥사플루오로안티모네이트, 디페닐[4-(페닐티오)페닐]설포늄테트라키스(펜타플루오로페닐)보레이트 등의 설포늄염 화합물을 들 수 있다. 이 오늄염 화합물 중에서, 설포늄염 화합물이 바람직하고, i선(365nm)를 이용한 노광에 의해 산이 발생하는 화합물로는 디페닐[4-(페닐티오)페닐]설포늄염 화합물이 보다 바람직하다.As a specific example of the onium salt compound, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodo Nium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoro iodonium salt compounds such as lomethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfoniumtris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulf and sulfonium salt compounds such as phonium hexafluoroantimonate and diphenyl[4-(phenylthio)phenyl]sulfoniumtetrakis(pentafluorophenyl)borate. Among these onium salt compounds, a sulfonium salt compound is preferable, and a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound is more preferable as a compound that generates an acid upon exposure using i-ray (365 nm).
상기 설폰이미드 화합물의 구체예로서, N-(트리플루오로메탄설포닐옥시)석신이미드, N-(노나플루오로-n-부탄설포닐옥시)석신이미드, N-(캠퍼설포닐옥시)석신이미드, N-(트리플루오로메탄설포닐옥시)-1,8-나프탈이미드, N-(트리플루오로메탄설포닐옥시)-2-알킬-1,8-나프탈이미드, N-(트리플루오로메탄설포닐옥시)-3-알킬-1,8-나프탈이미드 및 N-(트리플루오로메탄설포닐옥시)-4-알킬-1,8-나프탈이미드를 들 수 있다. 이 설폰이미드 화합물 중에서, N-(트리플루오로메탄설포닐옥시)-1,8-나프탈이미드, 및 그의 유도체가 바람직하다.Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy) ) Succinimide, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide, N-(trifluoromethanesulfonyloxy)-2-alkyl-1,8-naphthalimide , N-(trifluoromethanesulfonyloxy)-3-alkyl-1,8-naphthalimide and N-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalimide can be heard Among these sulfonimide compounds, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide and derivatives thereof are preferable.
상기 디설포닐디아조메탄 화합물의 구체예로서, 비스(트리플루오로메틸설포닐)디아조메탄, 비스(시클로헥실설포닐)디아조메탄, 비스(페닐설포닐)디아조메탄, 비스(p-톨루엔설포닐)디아조메탄, 비스(2,4-디메틸벤젠설포닐)디아조메탄, 및 메틸설포닐-p-톨루엔설포닐디아조메탄을 들 수 있다.Specific examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p- toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
상기 광산발생제의 구체예로서, 아데카 아크르즈(アデカア-クルズ)(등록상표) SP-056, 동 SP-066, 동 SP-140, 동 SP-141, 동 SP-082, 동 SP-601, 동 SP-606, 동 SP-701, 동 SP-150, 동 SP-170, 동 SP-171(이상, (주)ADEKA제), CPI(등록상표)-110P, 동-110B, 동-310B, 동-210S, 동-100P, 동-101A, 동-200K(이상, 산아프로(주)제), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS-165, SI-105, NDI-105, NDI-109, NAI-105, NAI-109(이상, 미도리화학(주)제)를 들 수 있다. 이들 광산발생제는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다.As a specific example of the said photo-acid generator, Adeka Arcz (adeca-cruz) (trademark) SP-056, copper SP-066, copper SP-140, copper SP-141, copper SP-082, copper SP-601 , copper SP-606, copper SP-701, copper SP-150, copper SP-170, copper SP-171 (above, manufactured by ADEKA), CPI (registered trademark)-110P, copper-110B, copper-310B , Copper-210S, Copper-100P, Copper-101A, Copper-200K (above, manufactured by San-Apro), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105 , MPI-106, MPI-109, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301, TPS -102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-205, MDS-209 , BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS-165, SI-105, NDI-105, NDI -109, NAI-105, and NAI-109 (above, Midori Chemical Co., Ltd. product) are mentioned. These photo-acid generators may be used individually by 1 type, or may be used in combination of 2 or more type.
상기 (B)성분의 광산발생제는, 상기 (A)성분 100질량%에 대하여 적어도 0.5질량% 함유한다. 이 광산발생제의 함유량이 0.5질량%보다 적으면, 상기 (A)성분의 산해리성기가 해리하지 않고, 알칼리가용성기가 발현되지 않는다. 그러므로, 포토리소그래피법에 의해 패턴을 형성할 때, 노광부의 현상액에 대한 용해성이 부족하여, 원하는 형상의 패턴이 얻어지지 않을 우려가 있다. 상기 광산발생제의 함유량의 상한은, 노광에 의해 발생하는 산의 강도에 따라 변화한다. 예를 들어, 노광에 의해 광산발생제로부터 발생하는 산이 강산일수록, 이 광산발생제의 함유량의 상한을 작게 할 수 있다. 이 광산발생제로서 상기 아데카 아크르즈(등록상표) SP-606을 채용하는 경우, 그 함유량의 상한은, 상기 (A)성분 100질량%에 대하여, 예를 들어 5질량%이다. 이 광산발생제의 함유량이 너무 많으면, 포토리소그래피법에 의해 패턴을 형성할 때, 현상 후의 노광부에 이 광산발생제가 잔사로서 남기 쉽다.The photo-acid generator of the said (B) component contains at least 0.5 mass % with respect to 100 mass % of the said (A) component. When content of this photo-acid generator is less than 0.5 mass %, the acid-dissociable group of the said (A) component will not dissociate, and an alkali-soluble group will not be expressed. Therefore, when forming a pattern by the photolithography method, the solubility with respect to the developing solution of an exposure part is insufficient, and there exists a possibility that the pattern of a desired shape may not be obtained. The upper limit of content of the said photo-acid generator changes with the intensity|strength of the acid which generate|occur|produces by exposure. For example, the upper limit of content of this photo-acid generator can be made small, so that the acid which generate|occur|produces from a photo-acid generator by exposure is a strong acid. When employing the said ADEKA ACRUZ (trademark) SP-606 as this photo-acid generator, the upper limit of the content is 5 mass % with respect to 100 mass % of the said (A) component, for example. When there is too much content of this photo-acid generator, when forming a pattern by the photolithographic method, this photo-acid generator tends to remain as a residue in the exposed part after image development.
<(C)성분><(C)component>
본 발명의 마이크로렌즈용 감광성 수지조성물에 있어서의 (C)성분은, 용제이다. 상기 (A)성분, 상기 (B)성분, 및 후술하는 기타 성분을 용해하는 용제이면, 특별히 한정되지 않는다. 이 용제의 구체예로서, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 프로필렌글리콜, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜모노부틸에테르, 프로필렌글리콜모노부틸에테르아세테이트, 톨루엔, 자일렌, 메틸에틸케톤, 시클로펜탄온, 시클로헥사논, 2-하이드록시프로피온산에틸, 2-하이드록시-2-메틸프로피온산에틸, 에톡시아세트산에틸, 하이드록시아세트산에틸, 2-하이드록시-3-메틸부탄산메틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산메틸, 피루브산메틸, 아세트산에틸, 아세트산부틸, 유산에틸, 유산부틸, 2-헵탄온, γ-부티로락톤을 들 수 있다. 이들 용제는, 1종 단독으로 사용할 수도, 혹은 2종 이상을 조합하여 사용할 수도 있다.(C)component in the photosensitive resin composition for microlenses of this invention is a solvent. It will not specifically limit if it is a solvent in which the said (A) component, the said (B) component, and the other component mentioned later are melt|dissolved. Specific examples of this solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydride Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxy ethyl propionate, 3-ethoxy methyl propionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, and γ-butyrolactone. These solvents may be used individually by 1 type, or may be used in combination of 2 or more type.
<계면활성제><Surfactant>
본 발명의 마이크로렌즈용 감광성 수지조성물은, 기판에 대한 도포성을 향상시킬 목적으로, 계면활성제를 함유할 수도 있다. 이 계면활성제의 구체예로서, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌올레일에테르 등의 폴리옥시에틸렌알킬에테르류, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르 등의 폴리옥시에틸렌알킬아릴에테르류, 폴리옥시에틸렌·폴리옥시프로필렌블록코폴리머류, 솔비탄모노라우레이트, 솔비탄모노팔미테이트, 솔비탄모노스테아레이트, 솔비탄모노올리에이트, 솔비탄트리올리에이트, 솔비탄트리스테아레이트 등의 솔비탄지방산에스테르류, 폴리옥시에틸렌솔비탄모노라우레이트, 폴리옥시에틸렌솔비탄모노팔미테이트, 폴리옥시에틸렌솔비탄모노스테아레이트, 폴리옥시에틸렌솔비탄트리올리에이트, 폴리옥시에틸렌솔비탄트리스테아레이트 등의 폴리옥시에틸렌솔비탄지방산에스테르류 등의 비이온계 계면활성제, 에프톱(등록상표) EF301, 동 EF303, 동 EF352(이상, 미츠비시머테리얼전자화성(주)제), 메가팍(등록상표) F-171, 동 F-173, 동 R-30, 동 R-40, 동 R-40-LM(이상, DIC(주)제), 플루오라드 FC430, 동 FC431(이상, 쓰리엠재팬(주)제), 아사히가드(등록상표) AG710, 서플론(등록상표) S-382, 동 SC101, 동 SC102, 동 SC103, 동 SC104, 동 SC105, 동 SC106(AGC(주)제), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G 등 프터젠트 시리즈(フタ-ジェントシリ-ズ)((주)네오스제) 등의 불소계 계면활성제, 오가노실록산폴리머 KP341(신에쯔화학공업(주)제)을 들 수 있다.The photosensitive resin composition for microlenses of the present invention may contain a surfactant in order to improve the applicability to the substrate. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether; Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monool Sorbitan fatty acid esters such as ester, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, EFTOP (registered trademark) EF301, copper EF303, copper EF352 (above, Mitsubishi Material Electronics Chemical Co., Ltd.), Megapac (registered trademark) F-171, Dong F-173, Dong R-30, Dong R-40, Dong R-40-LM (above, manufactured by DIC Co., Ltd.) , Fluorad FC430, copper FC431 (above, manufactured by 3M Japan), Asahigard (registered trademark) AG710, Sufflon (registered trademark) S-382, copper SC101, copper SC102, copper SC103, copper SC104, copper SC105 , Copper SC106 (manufactured by AGC Co., Ltd.), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G Fluorine surfactants, such as Futa-gent series (manufactured by Neos Co., Ltd.), and organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.) are mentioned.
상기 계면활성제는, 1종 단독으로 또는 2종 이상을 조합하여 이용할 수 있다. 본 발명의 마이크로렌즈용 감광성 수지조성물이 이 계면활성제를 함유하는 경우, 그 함유량은, 이 조성물의 고형분 중의 함유량에 기초하여, 3질량% 이하이고, 바람직하게는 1질량% 이하이고, 보다 바람직하게는 0.5질량% 이하이다.The said surfactant can be used individually by 1 type or in combination of 2 or more type. When the photosensitive resin composition for microlenses of the present invention contains this surfactant, the content is 3% by mass or less, preferably 1% by mass or less, more preferably based on the content in the solid content of the composition. is 0.5 mass % or less.
<기타 첨가제><Other Additives>
본 발명의 마이크로렌즈용 감광성 수지조성물은, 본 발명의 효과를 손상시키지 않는 한에 있어서, 필요에 따라, 경화조제, 자외선흡수제, 증감제, 가소제, 산화방지제, 밀착조제, 또는 다가 페놀, 다가 카르본산 등의 용해촉진제를 기타 첨가제로서 포함할 수 있다. 한편, 본 발명의 마이크로렌즈용 감광성 수지조성물은, 상기 (A)성분의 공중합체가 자기가교성이므로, 가교제를 필요로 하지 않는다.The photosensitive resin composition for microlenses of the present invention may contain, if necessary, a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, or a polyhydric phenol, polyvalent carboxylate, as long as the effects of the present invention are not impaired. A dissolution accelerator such as main acid may be included as other additives. On the other hand, the photosensitive resin composition for microlenses of the present invention does not require a crosslinking agent because the copolymer of the component (A) is self-crosslinking.
<마이크로렌즈용 감광성 조성물 조제방법><Method for preparing photosensitive composition for microlens>
본 발명의 마이크로렌즈용 감광성 수지조성물의 조제방법은, 특별히 한정되지 않으나, 예를 들어, 상기 (A)성분의 공중합체의 용액 및 상기 (B)성분의 광산발생제를, 상기 (C)성분의 용제에 소정의 비율로 혼합하고, 균일한 용액으로 하는 방법을 들 수 있다. 나아가, 이 조제방법의 적당한 단계에 있어서, 임의로, 상기 계면활성제 및 상기 기타 첨가제를 추가로 첨가하여 혼합하는 방법을 들 수 있다.Although the preparation method of the photosensitive resin composition for microlens of this invention is not specifically limited, For example, the solution of the copolymer of the said (A) component, and the photo-acid generator of the said (B) component, the said (C)component The method of mixing with the solvent of a predetermined ratio and setting it as a uniform solution is mentioned. Furthermore, in a suitable step of this preparation method, optionally, a method of further adding and mixing the above-mentioned surfactant and the above-mentioned other additives is mentioned.
<마이크로렌즈의 제작><Production of microlenses>
기판[예를 들어, 산화규소막, 질화규소막 또는 산화질화규소막으로 피복되어 있을 수도 있는 실리콘 등의 반도체기판, 컬러필터, 평탄화막 등의 유기막으로 피복되어 있을 수도 있는 실리콘 등의 반도체기판, 질화갈륨(GaN), 비화갈륨(GaAs), 인화갈륨(GaP), 인화인듐(InP) 등의 화합물 반도체기판, 질화규소기판, 석영기판, 유리기판(무알칼리유리, 저알칼리유리, 결정화유리를 포함한다), ITO막이 형성된 유리기판] 상에, 스피너, 코터 등의 적당한 도포방법에 의해 본 발명의 마이크로렌즈용 감광성 수지조성물을 도포하고, 그 후, 핫플레이트 등의 가열수단을 이용하여 프리베이크함으로써, 수지막을 형성한다. 상기 프리베이크조건으로는, 베이크온도 80℃ 내지 150℃, 베이크시간 0.3분 내지 60분간에서 적당히 선택되고, 바람직하게는, 베이크온도 80℃ 내지 120℃, 베이크시간 0.5분 내지 5분간이다.Substrate [for example, a semiconductor substrate such as silicon which may be coated with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a semiconductor substrate such as silicon which may be coated with an organic film such as a color filter or a planarization film, nitride Compound semiconductor substrates such as gallium (GaN), gallium arsenide (GaAs), gallium phosphide (GaP), and indium phosphide (InP), silicon nitride substrates, quartz substrates, glass substrates (alkali-free glass, low alkali glass, crystallized glass) ), on a glass substrate on which an ITO film is formed], the photosensitive resin composition for microlenses of the present invention is applied by an appropriate coating method such as a spinner or a coater, and then pre-baked using a heating means such as a hot plate, to form a resin film. The pre-bake conditions are suitably selected from a baking temperature of 80° C. to 150° C. and a baking time of 0.3 minutes to 60 minutes, preferably, a baking temperature of 80° C. to 120° C., and a baking time of 0.5 minutes to 5 minutes.
본 발명의 마이크로렌즈용 감광성 수지조성물로부터 형성되는 수지막의 막두께로는, 0.005μm 내지 30μm이고, 바람직하게는 0.01μm 내지 20μm이다.The film thickness of the resin film formed from the photosensitive resin composition for microlenses of the present invention is 0.005 µm to 30 µm, preferably 0.01 µm to 20 µm.
다음에, 얻어진 상기 수지막에 대하여, 원하는 형상의 패턴을 형성하기 위한 마스크(레티클)를 통해 노광한다. 노광에는, g선, i선, KrF엑시머레이저 등의 근자외선 또는 가시광선을 사용할 수 있다. 추가로, 노광 후의 수지막에 대하여 베이크(Post Exposure Bake)를 행한다. 노광 후의 베이크조건으로는, 베이크온도 80℃ 내지 120℃, 베이크시간 0.3분 내지 60분간에서 적당히 선택된다.Next, the obtained resin film is exposed through a mask (reticle) for forming a pattern of a desired shape. For exposure, near-ultraviolet rays or visible rays such as g-rays, i-rays, and KrF excimer lasers can be used. Furthermore, baking (Post Exposure Bake) is performed with respect to the resin film after exposure. As baking conditions after exposure, it is suitably selected from a baking temperature of 80 degreeC - 120 degreeC, and a baking time of 0.3 minutes - 60 minutes.
그 후, 상기 수지막을, 알칼리성 현상액을 이용하여 현상한다. 그 결과, 상기 기판 상에 원하는 형상의 패턴이 형성된다. 이 알칼리성 현상액으로는, 예를 들어, 수산화칼륨, 수산화나트륨 등의 알칼리금속수산화물의 수용액, 수산화테트라메틸암모늄, 수산화테트라에틸암모늄, 콜린 등의 수산화4급 암모늄의 수용액, 에탄올아민, 프로필아민, 에틸렌디아민 등의 아민수용액 등의 알칼리성 수용액을 들 수 있다. 추가로, 이들 현상액에 계면활성제를 첨가할 수도 있다.Thereafter, the resin film is developed using an alkaline developer. As a result, a pattern of a desired shape is formed on the substrate. Examples of the alkaline developer include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, propylamine, and ethylene Alkaline aqueous solutions, such as amine aqueous solutions, such as diamine, are mentioned. Additionally, a surfactant may be added to these developing solutions.
상기 현상의 조건으로는, 현상온도 5℃ 내지 50℃, 현상시간 10초 내지 300초에서 적당히 선택된다. 상기 수지막은, 수산화테트라메틸암모늄수용액을 이용하여, 실온에서 용이하게 현상을 행할 수 있다. 현상 후, 린스액으로서 예를 들어 초순수를 이용하여, 적당히 린스를 행한다.The development conditions are appropriately selected from a developing temperature of 5° C. to 50° C. and a developing time of 10 seconds to 300 seconds. The said resin film can be developed easily at room temperature using tetramethylammonium hydroxide aqueous solution. After development, it is suitably rinsed using, for example, ultrapure water as a rinse liquid.
나아가, 형성된 상기 패턴을 1회째의 포스트베이크에 의해 리플로우시킨다. 상기 1회째의 포스트베이크조건으로는, 베이크온도 120℃ 내지 200℃, 베이크시간 0.3분 내지 60분간에서 적당히 선택된다. 그 후, g선, i선, KrF엑시머레이저 등의 근자외선 또는 가시광선을 이용하여, 리플로우 후의 상기 패턴을 전면(全面)노광할 수도 있다. 게다가, 전면노광 후에, 상기 패턴에 대하여 다시 노광 후 베이크를 행할 수도 있다. 이 노광 후 베이크조건으로서 예를 들어, 베이크온도 120℃ 내지 200℃, 베이크시간 0.3분 내지 60분간에서 적당히 선택된다. 마지막으로, 상기 리플로우 후의 패턴을 2회째의 포스트베이크에 의해 경화시켜 렌즈패턴을 형성한다. 상기 2회째의 포스트베이크조건으로는, 베이크온도 150℃ 내지 250℃, 베이크시간 0.3분 내지 60분간에서 적당히 선택된다.Furthermore, the formed said pattern is reflowed by the 1st post-baking. The conditions for the first post-baking are appropriately selected from a baking temperature of 120°C to 200°C and a baking time of 0.3 minutes to 60 minutes. Thereafter, the entire surface of the pattern after reflow may be exposed using near-ultraviolet rays or visible rays such as g-rays, i-rays, and KrF excimer lasers. In addition, after exposure to the entire surface, the pattern may be subjected to post-exposure baking again. As the baking conditions after this exposure, it is suitably selected from, for example, a baking temperature of 120 degreeC - 200 degreeC, and a baking time of 0.3 minutes - 60 minutes. Finally, the pattern after the reflow is cured by a second post-baking to form a lens pattern. The conditions for the second post-baking are appropriately selected from a baking temperature of 150° C. to 250° C. and a baking time of 0.3 minutes to 60 minutes.
실시예Example
이하, 합성예 및 실시예를 들어본 발명을 보다 상세히 설명하는데, 본 발명은 하기 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.
[중량평균분자량의 측정][Measurement of weight average molecular weight]
장치: 일본분광(주)제 GPC시스템Device: GPC system made by Nippon Spectroscopy Co., Ltd.
칼럼: Shodex〔등록상표〕 GPC KF-804L 및 GPC KF-803LColumn: Shodex [registered trademark] GPC KF-804L and GPC KF-803L
칼럼오븐: 40℃Column oven: 40℃
유량: 1ml/분Flow: 1ml/min
용리액: 테트라하이드로푸란Eluent: tetrahydrofuran
표준시료: 폴리스티렌Standard sample: polystyrene
[합성예 1][Synthesis Example 1]
1-부톡시에틸메타크릴레이트 7.0g, 2-하이드록시에틸메타크릴레이트 4.9g, 2-[0-(1’-메틸프로필리덴아미노)카르복시아미노]에틸메타크릴레이트[카렌즈 MOI-BM(등록상표)(쇼와덴코(주)제)] 9.1g, 메틸메타크릴레이트 7.5g, 및 2,2’-아조비스이소부티로니트릴 1.4g을 프로필렌글리콜모노메틸에테르 89.8g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 79.8g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시켰다. 반응용액을 냉각 후, 다량의 헥산용액에 투입하여 폴리머를 재침전하고, 가열건조하여, 하기 식(1-1)로 표시되는 구조단위, 하기 식(2-1)로 표시되는 구조단위, 하기 식(3-1)로 표시되는 구조단위 및 하기 식(4a-1)로 표시되는 구조단위를 갖는 공중합체를 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 16,000(폴리스티렌환산)이었다.1-butoxyethyl methacrylate 7.0 g, 2-hydroxyethyl methacrylate 4.9 g, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Carenz MOI-BM ( registered trademark) (manufactured by Showa Denko Co., Ltd.)] 9.1 g, methyl methacrylate 7.5 g, and 1.4 g of 2,2'-azobisisobutyronitrile were dissolved in 89.8 g of propylene glycol monomethyl ether, This solution was dripped over 3 hours in the flask which hold|maintained 79.8 g of propylene glycol monomethyl ether at 70 degreeC. After completion|finish of dripping, it was made to react for 18 hours. After cooling the reaction solution, it is added to a large amount of hexane solution to re-precipitate the polymer, and then dried by heating, a structural unit represented by the following formula (1-1), a structural unit represented by the following formula (2-1), a structural unit represented by the following formula (2-1), the following formula A copolymer having a structural unit represented by (3-1) and a structural unit represented by the following formula (4a-1) was obtained. The weight average molecular weight Mw of the obtained copolymer was 16,000 (in terms of polystyrene).
[화학식 7][Formula 7]
[합성예 2][Synthesis Example 2]
1-부톡시에틸메타크릴레이트 9.0g, 2-하이드록시에틸메타크릴레이트 3.1g, 2-[0-(1’-메틸프로필리덴아미노)카르복시아미노]에틸메타크릴레이트[카렌즈 MOI-BM(등록상표)(쇼와덴코(주)제] 5.9g, 메틸메타크릴레이트 12.1g, N-페닐말레이미드4.2g, 및 2,2’-아조비스이소부티로니트릴 1.7g을 프로필렌글리콜모노메틸에테르 36.0g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 18.0g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시킴으로써, 하기 식(1-1)로 표시되는 구조단위, 하기 식(2-1)로 표시되는 구조단위, 하기 식(3-1)로 표시되는 구조단위, 하기 식(4a-1)로 표시되는 구조단위 및 하기 식(4b-1)로 표시되는 구조단위를 갖는 공중합체의 용액(고형분농도 40질량%)을 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 22,000(폴리스티렌환산)이었다.1-Butoxyethyl methacrylate 9.0 g, 2-hydroxyethyl methacrylate 3.1 g, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Carenz MOI-BM ( Registered trademark) (manufactured by Showa Denko Co., Ltd.] 5.9 g, methyl methacrylate 12.1 g, N-phenylmaleimide 4.2 g, and 2,2'-azobisisobutyronitrile 1.7 g with propylene glycol monomethyl ether After dissolving in 36.0 g, 18.0 g of propylene glycol monomethyl ether was added dropwise over 3 hours to a flask maintained at 70° C. After completion of the dropping, the solution was allowed to react for 18 hours to obtain the following formula (1-1) The structural unit represented by the structural unit represented by the following formula (2-1), the structural unit represented by the following formula (3-1), the structural unit represented by the following formula (4a-1) and the following formula (4b-1) A solution (solid content concentration of 40 mass %) of a copolymer having the structural unit represented by ) was obtained.
[화학식 8][Formula 8]
[합성예 3][Synthesis Example 3]
1-부톡시에틸메타크릴레이트 8.5g, 2-하이드록시에틸메타크릴레이트 3.0g, 2-[0-(1’-메틸프로필리덴아미노)카르복시아미노]에틸메타크릴레이트[카렌즈 MOI-BM(등록상표)(쇼와덴코(주)제] 5.5g, 메틸메타크릴레이트 9.1g, N-페닐말레이미드 7.9g, 및 2,2’-아조비스이소부티로니트릴 1.7g을 프로필렌글리콜모노메틸에테르 35.7g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 17.9g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시킴으로써, 상기 식(1-1)로 표시되는 구조단위, 상기 식(2-1)로 표시되는 구조단위, 상기 식(3-1)로 표시되는 구조단위, 상기 식(4a-1)로 표시되는 구조단위 및 상기 식(4b-1)로 표시되는 구조단위를 갖는 공중합체의 용액(고형분농도 40질량%)을 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 19,000(폴리스티렌환산)이었다. 1-butoxyethyl methacrylate 8.5 g, 2-hydroxyethyl methacrylate 3.0 g, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Carenz MOI-BM ( Registered trademark) (Showa Denko Co., Ltd. product) 5.5 g, methyl methacrylate 9.1 g, N-phenylmaleimide 7.9 g, and 2,2'-azobisisobutyronitrile 1.7 g propylene glycol monomethyl ether After dissolving in 35.7 g, this solution was added dropwise over 3 hours to a flask in which 17.9 g of propylene glycol monomethyl ether was maintained at 70° C. After completion of the dropping, the solution was allowed to react for 18 hours to obtain the formula (1-1) The structural unit represented by the structural unit represented by the formula (2-1), the structural unit represented by the formula (3-1), the structural unit represented by the formula (4a-1) and the formula (4b-1) A solution (solid content concentration of 40 mass %) of a copolymer having the structural unit represented by ) was obtained.
[합성예 4][Synthesis Example 4]
1-부톡시에틸메타크릴레이트 9.5g, 메틸메타크릴레이트 20.4g, 및 2,2’-아조비스이소부티로니트릴 1.5g을 프로필렌글리콜모노메틸에테르 31.4g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 26.9g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시킴으로써, 하기 식(1-1)로 표시되는 구조단위 및 하기 식(4a-1)로 표시되는 구조단위를 갖는 공중합체의 용액(고형분농도 35질량%)을 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 16,000(폴리스티렌환산)이었다.After dissolving 9.5 g of 1-butoxyethyl methacrylate, 20.4 g of methyl methacrylate, and 1.5 g of 2,2'-azobisisobutyronitrile in 31.4 g of propylene glycol monomethyl ether, the solution was mixed with propylene 26.9 g of glycol monomethyl ether was dripped over 3 hours in the flask maintained at 70 degreeC. After completion of the dropwise addition, the reaction was conducted for 18 hours to obtain a solution (solid content concentration of 35% by mass) of a copolymer having a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (4a-1). The weight average molecular weight Mw of the obtained copolymer was 16,000 (in terms of polystyrene).
[화학식 9][Formula 9]
[합성예 5][Synthesis Example 5]
1-부톡시에틸메타크릴레이트 5.1g, 메틸메타크릴레이트 24.7g, 및 2,2’-아조비스이소부티로니트릴 1.5g을 프로필렌글리콜모노메틸에테르 31.3g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 26.8g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시킴으로써, 상기 식(1-1)로 표시되는 구조단위 및 상기 식(4a-1)로 표시되는 구조단위를 갖는 공중합체의 용액(고형분농도 35질량%)을 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 20,000(폴리스티렌환산)이었다.After dissolving 5.1 g of 1-butoxyethyl methacrylate, 24.7 g of methyl methacrylate, and 1.5 g of 2,2'-azobisisobutyronitrile in 31.3 g of propylene glycol monomethyl ether, the solution was mixed with propylene 26.8 g of glycol monomethyl ether was dripped over 3 hours in the flask maintained at 70 degreeC. After completion of the dropwise addition, the reaction was carried out for 18 hours to obtain a solution (solid content concentration of 35% by mass) of a copolymer having a structural unit represented by the formula (1-1) and a structural unit represented by the formula (4a-1). The weight average molecular weight Mw of the obtained copolymer was 20,000 (in terms of polystyrene).
[합성예 6][Synthesis Example 6]
1-부톡시에틸메타크릴레이트 8.4g, 2-하이드록시에틸메타크릴레이트 5.9g, 2-[0-(1’-메틸프로필리덴아미노)카르복시아미노]에틸메타크릴레이트[카렌즈 MOI-BM(등록상표)(쇼와덴코(주)제] 10.9g, 메틸메타크릴레이트 9.0g, 및 2,2’-아조비스이소부티로니트릴 1.7g을 프로필렌글리콜모노메틸에테르 35.9g에 용해시킨 후, 이 용액을, 프로필렌글리콜모노메틸에테르 18.0g을 70℃로 유지한 플라스크 중에 3시간에 걸쳐 적하하였다. 적하 종료 후, 18시간 반응시킴으로써, 상기 식(1-1)로 표시되는 구조단위, 상기 식(2-1)로 표시되는 구조단위, 상기 식(3-1)로 표시되는 구조단위 및 상기 식(4a-1)로 표시되는 구조단위를 갖는 공중합체의 용액(고형분농도 40질량%)을 얻었다. 얻어진 공중합체의 중량평균분자량Mw는 28,000(폴리스티렌환산)이었다.1-butoxyethyl methacrylate 8.4 g, 2-hydroxyethyl methacrylate 5.9 g, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Carenz MOI-BM ( Registered trademark) (manufactured by Showa Denko Co., Ltd.] 10.9 g of methyl methacrylate, and 1.7 g of 2,2'-azobisisobutyronitrile were dissolved in 35.9 g of propylene glycol monomethyl ether, The solution was added dropwise over 3 hours to a flask in which 18.0 g of propylene glycol monomethyl ether was kept at 70° C. After completion of the dropping, the solution was allowed to react for 18 hours, whereby the structural unit represented by the formula (1-1), the formula ( A solution (solid content concentration of 40% by mass) of a copolymer having a structural unit represented by 2-1), a structural unit represented by the formula (3-1), and a structural unit represented by the formula (4a-1) was obtained. The weight average molecular weight Mw of the obtained copolymer was 28,000 (in terms of polystyrene).
[실시예 1][Example 1]
합성예 1에서 얻어진 (A)성분인 공중합체 16.6g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.83g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0052g을, (C)성분인 프로필렌글리콜모노메틸에테르 29.1g 및 프로필렌글리콜모노메틸에테르아세테이트 3.2g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 실시예, 및 후술하는 실시예 2 내지 4, 8 및 9에서 사용한 광산발생제는, N-(트리플루오로메탄설포닐옥시)-1,8-나프탈이미드의 유도체에 해당한다.16.6 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.83 g of SP-606 (manufactured by ADEKA Corporation) as a photoacid generator as component (B), and DFX-18 (manufactured by Neos Corporation) as a surfactant ) 0.0052 g was dissolved in 29.1 g of propylene glycol monomethyl ether and 3.2 g of propylene glycol monomethyl ether acetate as (C) component to prepare a solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The photo-acid generators used in this Example and Examples 2 to 4, 8 and 9 described later correspond to derivatives of N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide.
[실시예 2][Example 2]
합성예 1에서 얻어진 (A)성분인 공중합체 18.6g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.37g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다.18.6 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.37 g of SP-606 (manufactured by ADEKA Corporation) as a photoacid generator as component (B), and DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant ) 0.0057g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses.
[실시예 3][Example 3]
합성예 1에서 얻어진 (A)성분인 공중합체 18.8g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.19g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다.18.8 g of the copolymer as (A) component obtained in Synthesis Example 1, 0.19 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as (B) component, and DFX-18 (Neos Co., Ltd. product) as a surfactant ) 0.0057g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses.
[실시예 4][Example 4]
합성예 1에서 얻어진 (A)성분인 공중합체 18.9g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.095g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다.18.9 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.095 g of SP-606 (manufactured by ADEKA Corporation) as a photoacid generator as component (B), and DFX-18 (manufactured by Neos Corporation) as a surfactant ) 0.0057g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses.
[실시예 5][Example 5]
합성예 1에서 얻어진 (A)성분인 공중합체 18.1g, (B)성분인 광산발생제로서 CPI-110B(산아프로(주)제) 0.91g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 실시예에서 사용한 광산발생제는, 디페닐[4-(페닐티오)페닐]설포늄염 화합물에 해당한다.18.1 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.91 g of CPI-110B (manufactured by San Apro Co., Ltd.) as a photoacid generator as component (B), and DFX-18 (Neos Co., Ltd.) as a surfactant 1) 0.0057 g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The photoacid generator used in this Example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
[실시예 6][Example 6]
합성예 1에서 얻어진 (A)성분인 공중합체 18.1g, (B)성분인 광산발생제로서 CPI-110P(산아프로(주)제) 0.91g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 실시예에서 사용한 광산발생제는, 디페닐[4-(페닐티오)페닐]설포늄염 화합물에 해당한다.18.1 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.91 g of CPI-110P (manufactured by San Apro Co., Ltd.) as a photoacid generator as component (B), and DFX-18 (Neos Co., Ltd.) as a surfactant 1) 0.0057 g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The photoacid generator used in this Example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
[실시예 7][Example 7]
합성예 1에서 얻어진 (A)성분인 공중합체 18.1g, (B)성분인 광산발생제로서 CPI-210S(산아프로(주)제) 0.91g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 실시예에서 사용한 광산발생제는, 디페닐[4-(페닐티오)페닐]설포늄염 화합물에 해당한다.18.1 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.91 g of CPI-210S (manufactured by San Apro Co., Ltd.) as a photoacid generator as component (B), and DFX-18 (Neos Co., Ltd.) as a surfactant 1) 0.0057 g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The photoacid generator used in this Example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
[실시예 8][Example 8]
합성예 2에서 얻어진 (A)성분인 공중합체의 용액(고형분농도 40질량%) 44.0g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.88g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0055g을, (C)성분인 프로필렌글리콜모노메틸에테르 1.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다.44.0 g of a solution (solid content concentration: 40 mass %) of the copolymer as (A) component obtained in Synthesis Example 2, (B) as a photo-acid generator as a component, SP-606 (manufactured by ADEKA Corporation) 0.88 g, and as a surfactant 0.0055 g of DFX-18 (Neos Co., Ltd. product) was dissolved in 1.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses.
[실시예 9][Example 9]
합성예 3에서 얻어진 (A)성분인 공중합체의 용액(고형분농도 40질량%) 44.0g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.88g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0055g을, (C)성분인 프로필렌글리콜모노메틸에테르 1.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다.44.0 g of a solution (solid content concentration: 40 mass %) of the copolymer as (A) component obtained in Synthesis Example 3, (B) as a photoacid generator as a component, SP-606 (manufactured by ADEKA) 0.88 g, and as a surfactant 0.0055 g of DFX-18 (Neos Co., Ltd. product) was dissolved in 1.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses.
[비교예 1][Comparative Example 1]
합성예 4에서 얻어진 공중합체의 용액(고형분농도 35질량%) 43.5g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.76g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0048g을, (C)성분인 프로필렌글리콜모노메틸에테르 2.3g 및 프로필렌글리콜모노메틸에테르아세테이트 3.4g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 비교예에서 이용한 공중합체는, 본 발명의 마이크로렌즈용 감광성 수지조성물의 (A)성분에 해당하지 않는다.43.5 g of a solution of the copolymer obtained in Synthesis Example 4 (solid content concentration of 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and DFX-18 (Neos) as a surfactant Co., Ltd. product 0.0048 g was dissolved in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The copolymer used in this comparative example does not correspond to (A) component of the photosensitive resin composition for microlenses of this invention.
[비교예 2][Comparative Example 2]
합성예 5에서 얻어진 공중합체의 용액(고형분농도 35질량%) 43.5g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.76g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0048g을, (C)성분인 프로필렌글리콜모노메틸에테르 2.3g 및 프로필렌글리콜모노메틸에테르아세테이트 3.4g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 비교예에서 이용한 공중합체는, 본 발명의 마이크로렌즈용 감광성 수지조성물의 (A)성분에 해당하지 않는다.43.5 g of a solution of the copolymer obtained in Synthesis Example 5 (solid content concentration of 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Corporation) as a photoacid generator as component (B), and DFX-18 (Neos) as a surfactant Co., Ltd. product 0.0048 g was dissolved in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The copolymer used in this comparative example does not correspond to (A) component of the photosensitive resin composition for microlenses of this invention.
[비교예 3][Comparative Example 3]
합성예 6에서 얻어진 공중합체의 용액(고형분농도 35질량%) 43.5g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.76g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0048g을, (C)성분인 프로필렌글리콜모노메틸에테르 2.3g 및 프로필렌글리콜모노메틸에테르아세테이트 3.4g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 비교예에서 이용한 공중합체는, 본 발명의 마이크로렌즈용 감광성 수지조성물의 (A)성분에 해당하지 않는다.43.5 g of a solution of the copolymer obtained in Synthesis Example 6 (solid content concentration of 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and DFX-18 (Neos) as a surfactant Co., Ltd. product 0.0048 g was dissolved in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. The copolymer used in this comparative example does not correspond to (A) component of the photosensitive resin composition for microlenses of this invention.
[비교예 4][Comparative Example 4]
합성예 1에서 얻어진 (A)성분인 공중합체 19.0g, (B)성분인 광산발생제로서 SP-606((주)ADEKA제) 0.019g, 및 계면활성제로서 DFX-18(네오스(주)제) 0.0057g을, (C)성분인 프로필렌글리콜모노메틸에테르 27.9g 및 프로필렌글리콜모노메틸에테르아세테이트 3.1g에 용해시켜 용액으로 하였다. 그 후, 이 용액을 구멍직경 1μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하여, 마이크로렌즈용 감광성 수지조성물을 조제하였다. 본 비교예의 마이크로렌즈용 감광성 수지조성물의 (B)성분의 함유량은, (A)성분 100질량%에 대하여 0.5질량%보다 적다.19.0 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.019 g of SP-606 (manufactured by ADEKA Corporation) as a photoacid generator as component (B), and DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant ) 0.0057g was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate which are (C)component, and it was set as the solution. Thereafter, this solution was filtered using a polyethylene microfilter having a pore diameter of 1 µm to prepare a photosensitive resin composition for microlenses. Content of (B) component of the photosensitive resin composition for microlenses of this comparative example is less than 0.5 mass % with respect to 100 mass % of (A) component.
[패턴 직사각형성 평가][Pattern Rectangularity evaluation]
실시예 1 내지 실시예 9 및 비교예 1 내지 비교예 4에서 조제한 마이크로렌즈용 감광성 수지조성물을 각각, 실리콘웨이퍼 상에 스핀코터를 이용하여 도포하고, 핫플레이트 상에 배치하여 100℃에서 90초간 프리베이크함으로써, 막두께 10μm의 수지막을 형성하였다. 상기 프리베이크는, 대기 중에서 실시하였다. 이어서, i선 스텝퍼 NSR-2205i12D(NA=0.63)((주)니콘제)에 의해, 바이너리 마스크를 개재하여 상기 수지막을 노광하고, 이어서 핫플레이트 상에 배치하여 100℃에서 90초간 노광 후 가열(Post Exposure Bake)을 행하였다. 그 후, 상기 수지막을, 2.38질량% 농도의 수산화테트라메틸암모늄(TMAH)수용액을 이용하여 50초간 현상하고, 초순수로 20초간 린스하고, 건조하였다. 그 결과, 패턴이 상기 실리콘웨이퍼 상에 형성되었다. 얻어진 패턴의 단면형상을 주사형 전자현미경 S-4800((주)히다치하이테크놀로지즈제)을 이용하여 관찰하였다. 상기 패턴의 단면형상이 직사각형이 아닌 경우는 “×”, 상기 패턴의 단면형상이 10μm×10μm의 직사각형인 경우는 “○”로 하여, 패턴의 직사각형성을 평가하였다. 그 결과를 표 1에 나타낸다. Each of the photosensitive resin compositions for microlenses prepared in Examples 1 to 9 and Comparative Examples 1 to 4 were coated on a silicon wafer using a spin coater, placed on a hot plate, and freed at 100° C. for 90 seconds. By baking, a resin film with a film thickness of 10 µm was formed. The said prebaking was performed in air|atmosphere. Next, the resin film is exposed through an i-line stepper NSR-2205i12D (NA=0.63) (manufactured by Nikon Corporation) through a binary mask, and then placed on a hot plate and exposed to 100° C. for 90 seconds followed by heating ( Post Exposure Bake) was performed. Thereafter, the resin film was developed for 50 seconds using an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass, rinsed with ultrapure water for 20 seconds, and dried. As a result, a pattern was formed on the silicon wafer. The cross-sectional shape of the obtained pattern was observed using the scanning electron microscope S-4800 (made by Hitachi High-Technologies Corporation). When the cross-sectional shape of the pattern was not a rectangle, it was defined as “x”, and when the cross-sectional shape of the pattern was a rectangle of 10 μm×10 μm, it was defined as “○”, and the rectangularity of the pattern was evaluated. The results are shown in Table 1.
[현상 후 잔사 평가][Evaluation of residue after development]
상기 실리콘웨이퍼 상에 형성된 패턴주변의 노광부를 관찰함으로써, 현상 후의 잔사를 평가하였다. 상기 패턴이 형성되어 있지 않은 노광부에 잔사가 많이 관찰되는 경우는 “×”, 이 패턴이 형성되어 있지 않은 노광부에 잔사는 관찰되지 않으나 이 패턴의 엣지부에 잔사가 관찰되는 경우는 “△”, 이 패턴이 형성되어 있지 않은 노광부 및 이 패턴의 엣지부에 전혀 잔사가 관찰되지 않는 경우는 “○”로 하여, 현상 후 잔사를 평가하였다. 평가결과를 표 1에 나타낸다.The residue after development was evaluated by observing the exposed portion around the pattern formed on the silicon wafer. When a large amount of residue is observed in the exposed portion on which the pattern is not formed, “×”, and when the residue is not observed in the exposed portion on which the pattern is not formed, but residue is observed in the edge portion of the pattern, “△ ”, when no residue was observed in the exposed portion where this pattern was not formed and in the edge portion of this pattern, it was set as “○”, and the residue after development was evaluated. Table 1 shows the evaluation results.
[패턴 리플로우성 평가][Pattern reflow evaluation]
실시예 1 내지 실시예 9, 비교예 1 및 비교예 3에서 조제한 마이크로렌즈용 감광성 수지조성물로부터 직사각형패턴이 형성된 실리콘웨이퍼를, 핫플레이트 상에 배치하여 140℃에서 5분간 포스트 베이크를 행하였다. 상기 포스트베이크 후, 얻어진 패턴의 단면형상을 주사형 전자현미경 S-4800((주)히다치하이테크놀로지즈제)을 이용하여 관찰하였다. 패턴의 단면형상이 전혀 변화하지 않는 경우는 “×”, 패턴의 단면형상이 변화하여 반원형이 되는 경우는 “○”로 하여, 패턴의 리플로우성을 평가하였다. 평가결과를 표 1에 나타낸다.Silicon wafers having rectangular patterns formed from the photosensitive resin compositions for microlenses prepared in Examples 1 to 9 and Comparative Examples 1 and 3 were placed on a hot plate, and post-baked at 140° C. for 5 minutes. After the said post-baking, the cross-sectional shape of the obtained pattern was observed using the scanning electron microscope S-4800 (made by Hitachi High-Technologies Corporation). When the cross-sectional shape of the pattern does not change at all, "x", when the cross-sectional shape of the pattern changes and becomes semi-circular, "○" was set, and the reflow property of the pattern was evaluated. Table 1 shows the evaluation results.
[내용제성 평가][Evaluation of solvent resistance]
실시예 1 내지 실시예 9, 비교예 1 및 비교예 3에서 조제한 마이크로렌즈용 감광성 수지조성물을 각각, 실리콘웨이퍼 상에 스핀코터를 이용하여 도포하고, 핫플레이트 상에 있어서 100℃에서 90초간 프리베이크함으로써, 막두께 10μm의 수지막을 형성하였다. 이어서, 핫플레이트 상에 있어서 100℃에서 90초간 베이크한 후, 계속해서 140℃에서 5분간, 추가로 220℃에서 5분간 포스트베이크함으로써, 상기 실리콘웨이퍼 상에 경화막을 형성하였다. 상기 프리베이크 및 포스트베이크는 모두, 대기 중에서 실시하였다. 이들 경화막에 대하여, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 유산에틸, 및 2.38질량% 농도의 수산화테트라메틸암모늄(TMAH)수용액 각각에, 23℃의 온도조건하, 5분간 침지하는 시험을 행하였다. 침지 전후에 있어서 상기 경화막의 막두께 변화를 측정하였다. 침지시험에 사용한 상기 용제 중 1개라도, 침지 전의 이 경화막의 막두께에 대하여5% 이상의 막두께 증감이 있었던 경우는 “×”, 모든 용제에 대해 막두께 증감이 5% 미만이었던 경우는 “○”로 하여, 내용제성을 평가하였다. 평가결과를 표 1에 나타낸다.Each of the photosensitive resin compositions for microlenses prepared in Examples 1 to 9, Comparative Example 1 and Comparative Example 3 were coated on a silicon wafer using a spin coater, and pre-baked at 100° C. for 90 seconds on a hot plate. Thus, a resin film having a film thickness of 10 µm was formed. Subsequently, on a hot plate, after baking at 100 degreeC for 90 second, the cured film was formed on the said silicon wafer by continuously post-baking at 140 degreeC for 5 minute(s), and also 220 degreeC for 5 minute(s). All of the said pre-baking and post-baking were performed in air|atmosphere. These cured films were immersed in each of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38 mass% under a temperature condition of 23 ° C. for 5 minutes. The test was done. Before and after immersion, the film thickness change of the said cured film was measured. In any of the above solvents used in the immersion test, “×” indicates a film thickness increase or decrease of 5% or more with respect to the film thickness of this cured film before immersion, and “○” if the film thickness increase or decrease was less than 5% for all solvents. ” to evaluate the solvent resistance. Table 1 shows the evaluation results.
[표 1][Table 1]
표 1에 나타내는 바와 같이, 실시예 1 내지 실시예 9에서 조제한 마이크로렌즈용 감광성 수지조성물로부터 형성되는 수지막은, 패턴 직사각형성, 현상 후 잔사의 정도 및 패턴 리플로우성의 점에서, 우수한 결과가 얻어져, 이 수지막으로부터 형성되는 경화막은, 우수한 내용제성을 나타냈다.As shown in Table 1, the resin film formed from the photosensitive resin composition for microlenses prepared in Examples 1 to 9 showed excellent results in terms of pattern rectangularity, the degree of residue after development and pattern reflow properties. and the cured film formed from this resin film showed the outstanding solvent resistance.
한편, 비교예 2 내지 비교예 4에서 조제한 마이크로렌즈용 감광성 수지조성물로부터 형성되는 수지막은, 패턴 직사각형성, 현상 후 잔사의 정도 및 패턴 리플로우성의 어느 하나의 점에서 양호한 결과가 얻어지지 않고, 비교예 1의 마이크로렌즈용 감광성 수지조성물로부터 형성되는 경화막은, 내용제성이 낮은 것이 확인되어, 본 발명의 우위성이 나타났다.On the other hand, in the resin film formed from the photosensitive resin composition for microlenses prepared in Comparative Examples 2 to 4, good results were not obtained in any one of the pattern rectangular property, the degree of residue after development, and the pattern reflow property, As for the cured film formed from the photosensitive resin composition for microlenses of Comparative Example 1, it was confirmed that solvent resistance was low, and the superiority of this invention was shown.
Claims (8)
(A): 하기 식(1)로 표시되는 구조단위, 하기 식(2)로 표시되는 구조단위 및 하기 식(3)으로 표시되는 구조단위를 갖는, 중량평균분자량 5000 내지 25000의 공중합체
(B): 광산발생제
(C): 용제
[화학식 1]
[식(1) 내지 식(3) 중, R1, R2 및 R3은 각각 독립적으로 수소원자 또는 메틸기를 나타내고, X1 및 X2는 각각 독립적으로 탄소원자수 2 내지 4의 알킬렌기를 나타내고, Z1은 산해리성기를 나타내고, Z2는 블록이소시아네이트기를 나타낸다.]The photosensitive resin composition for microlenses which contains following (A) component, following (B) component, and following (C)component, and contains this (B) component at least 0.5 mass % with respect to 100 mass % of this (A) component.
(A): a copolymer having a weight average molecular weight of 5000 to 25000 having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3)
(B): photoacid generator
(C): solvent
[Formula 1]
[In Formulas (1) to (3), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, and X 1 and X 2 each independently represent an alkylene group having 2 to 4 carbon atoms. , Z 1 represents an acid dissociable group, and Z 2 represents a block isocyanate group.]
상기 산해리성기는 하기 식(a)로 표시되는 기인, 마이크로렌즈용 감광성 수지조성물.
[화학식 2]
(식 중, *은 산소원자와의 결합수를 나타내고, R4는 메틸기를 나타내고, R5는 탄소원자수 1 내지 6의 알킬기를 나타내고, 이 알킬기의 탄소원자수가 3 내지 6인 경우 분지구조를 가질 수도 있고, R5는 R4와 연결되어 환상 에테르구조를 형성할 수도 있다.)According to claim 1,
The acid dissociable group is a group represented by the following formula (a), a photosensitive resin composition for microlenses.
[Formula 2]
(wherein * represents the number of bonds with an oxygen atom, R 4 represents a methyl group, R 5 represents an alkyl group having 1 to 6 carbon atoms, and when the alkyl group has 3 to 6 carbon atoms, it has a branched structure or R 5 may be connected to R 4 to form a cyclic ether structure.)
상기 블록이소시아네이트기는 하기 식(b) 또는 하기 식(c)로 표시되는 기인, 마이크로렌즈용 감광성 수지조성물.
[화학식 3]
[식(b) 및 식(c) 중, *은 상기 X2로 표시되는 알킬렌기와의 결합수를 나타내고, R6 및 R7은 각각 독립적으로 수소원자, 메틸기 또는 에틸기를 나타내고, R8은 메틸기를 나타내고, a는 0 내지 3의 정수를 나타낸다.]3. The method of claim 1 or 2,
The block isocyanate group is a group represented by the following formula (b) or the following formula (c), a photosensitive resin composition for microlenses.
[Formula 3]
[In formulas (b) and (c), * represents the number of bonds with the alkylene group represented by X 2 , R 6 and R 7 each independently represent a hydrogen atom, a methyl group or an ethyl group, and R 8 is represents a methyl group, and a represents an integer of 0 to 3.]
상기 공중합체는 하기 식(4a)로 표시되는 구조단위 및 하기 식(4b)로 표시되는 구조단위 중 적어도 일방을 추가로 갖는, 마이크로렌즈용 감광성 수지조성물.
[화학식 4]
[식(4a) 및 식(4b) 중, R9는 수소원자 또는 메틸기를 나타내고, R10은 탄소원자수 1 내지 6의 알킬기를 나타내고, 이 알킬기의 탄소원자수가 3 내지 6인 경우, 분지구조 또는 환구조를 가질 수도 있고, R11은 시클로헥실기 또는 페닐기를 나타낸다.]4. The method according to any one of claims 1 to 3,
The copolymer further has at least one of a structural unit represented by the following formula (4a) and a structural unit represented by the following formula (4b), a photosensitive resin composition for microlenses.
[Formula 4]
[In formulas (4a) and (4b), R 9 represents a hydrogen atom or a methyl group, R 10 represents an alkyl group having 1 to 6 carbon atoms, and when the alkyl group has 3 to 6 carbon atoms, a branched structure or It may have a ring structure, and R 11 is It represents a cyclohexyl group or a phenyl group.]
상기 광산발생제는 디페닐[4-(페닐티오)페닐]설포늄염 화합물인, 마이크로렌즈용 감광성 수지조성물. 5. The method according to any one of claims 1 to 4,
The photo-acid generator is a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound, the photosensitive resin composition for microlenses.
상기 광산발생제는 N-(트리플루오로메탄설포닐옥시)-1,8-나프탈이미드 또는 그의 유도체인, 마이크로렌즈용 감광성 수지조성물.5. The method according to any one of claims 1 to 4,
The photo-acid generator is N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or a derivative thereof, a photosensitive resin composition for microlenses.
마스크를 통해 상기 수지막을 노광하는 노광공정,
상기 노광공정 후의 수지막을 베이크하는 베이크공정,
상기 베이크공정 후의 수지막을, 알칼리성 현상액을 이용하여 현상하는 현상공정,
상기 현상공정 후 얻어진 패턴을 리플로우시키는 리플로우공정, 및
상기 리플로우공정 후의 패턴을 경화시켜 렌즈패턴을 형성하는 공정을 갖는, 마이크로렌즈의 제작방법.A step of applying the photosensitive resin composition for microlenses according to any one of claims 1 to 6 on a substrate, and prebaking the photosensitive resin composition to form a resin film;
an exposure process of exposing the resin film through a mask;
a baking step of baking the resin film after the exposure step;
A developing step of developing the resin film after the baking step using an alkaline developer;
A reflow process of reflowing the pattern obtained after the developing process, and
A method of manufacturing a microlens having a step of curing the pattern after the reflow step to form a lens pattern.
상기 리플로우공정은, 상기 현상공정 후 얻어진 패턴을 120℃ 내지 200℃의 온도로 가열하는 공정인, 마이크로렌즈의 제작방법.8. The method of claim 7,
The reflow process is a process of heating the pattern obtained after the developing process to a temperature of 120° C. to 200° C., a method of manufacturing a microlens.
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| JP2006337956A (en) | 2005-06-06 | 2006-12-14 | Iwate Toshiba Electronics Co Ltd | Manufacturing method of microlens array |
| WO2015125870A1 (en) | 2014-02-20 | 2015-08-27 | 富士フイルム株式会社 | Photosensitive resin composition, cured object and production method therefor, resin pattern production method, cured film, liquid crystal display device, organic el display device, infrared cutoff filter, and solid imaging device |
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| JP5003376B2 (en) * | 2007-09-20 | 2012-08-15 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
| US8796349B2 (en) * | 2010-11-30 | 2014-08-05 | Nissan Chemical Industries, Ltd. | Photosensitive resin composition for microlenses |
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