JP7445198B2 - Photosensitive resin composition for microlenses - Google Patents
Photosensitive resin composition for microlenses Download PDFInfo
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- JP7445198B2 JP7445198B2 JP2021501826A JP2021501826A JP7445198B2 JP 7445198 B2 JP7445198 B2 JP 7445198B2 JP 2021501826 A JP2021501826 A JP 2021501826A JP 2021501826 A JP2021501826 A JP 2021501826A JP 7445198 B2 JP7445198 B2 JP 7445198B2
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- 239000011342 resin composition Substances 0.000 title claims description 60
- -1 diphenyl[4-(phenylthio)phenyl]sulfonium salt compound Chemical class 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 238000011161 development Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- 239000000463 material Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 45
- 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 25
- 239000004094 surface-active agent Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 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
- 238000000034 method Methods 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
- 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
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000000206 photolithography 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
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 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
- 125000004112 carboxyamino group Chemical group [H]OC(=O)N([H])[*] 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 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 3
- 239000012953 triphenylsulfonium Substances 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 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
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 239000011248 coating agent Substances 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
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 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
- YUOCJTKDRNYTFJ-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)ON1C(=O)CCC1=O YUOCJTKDRNYTFJ-UHFFFAOYSA-N 0.000 description 1
- OKRLWHAZMUFONP-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)ON1C(=O)CCC1=O OKRLWHAZMUFONP-UHFFFAOYSA-N 0.000 description 1
- HHYVKZVPYXHHCG-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C HHYVKZVPYXHHCG-UHFFFAOYSA-M 0.000 description 1
- FJALTVCJBKZXKY-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triphenylsulfanium Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FJALTVCJBKZXKY-UHFFFAOYSA-M 0.000 description 1
- VLLPVDKADBYKLM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate;triphenylsulfanium Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VLLPVDKADBYKLM-UHFFFAOYSA-M 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- DPOPGHCRRJYPMP-UHFFFAOYSA-N 1-[diazo(methylsulfonyl)methyl]sulfonyl-4-methylbenzene Chemical compound CC1=CC=C(S(=O)(=O)C(=[N+]=[N-])S(C)(=O)=O)C=C1 DPOPGHCRRJYPMP-UHFFFAOYSA-N 0.000 description 1
- GYQQFWWMZYBCIB-UHFFFAOYSA-N 1-[diazo-(4-methylphenyl)sulfonylmethyl]sulfonyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1 GYQQFWWMZYBCIB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QFKJMDYQKVPGNM-UHFFFAOYSA-N [benzenesulfonyl(diazo)methyl]sulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=CC=C1 QFKJMDYQKVPGNM-UHFFFAOYSA-N 0.000 description 1
- GLGXSTXZLFQYKJ-UHFFFAOYSA-N [cyclohexylsulfonyl(diazo)methyl]sulfonylcyclohexane Chemical compound C1CCCCC1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1CCCCC1 GLGXSTXZLFQYKJ-UHFFFAOYSA-N 0.000 description 1
- FDTRPMUFAMGRNM-UHFFFAOYSA-N [diazo(trifluoromethylsulfonyl)methyl]sulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C(F)(F)F FDTRPMUFAMGRNM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VGZKCAUAQHHGDK-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 VGZKCAUAQHHGDK-UHFFFAOYSA-M 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking 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
- 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
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 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
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 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
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- 239000007788 liquid 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
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
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- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
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- 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
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate 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
- 238000002360 preparation method Methods 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
- 239000011541 reaction mixture Substances 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
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate 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
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
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- 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
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- 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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- 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
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- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- 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
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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
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/80—Constructional details of image sensors
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Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
本発明は、特定のアルカリ可溶性ポリマー、光酸発生剤、及び溶剤を含有する、マイクロレンズ形成用の感光性樹脂組成物に関する。特にリフロー法により作製されるマイクロレンズ用の感光性樹脂組成物に関する。 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, the present invention relates to a photosensitive resin composition for microlenses produced by a reflow method.
固体撮像素子として、ＣＣＤ／ＣＭＯＳイメージセンサが知られている。近年、新たなイメージセンサとして、三次元（３Ｄ）カメラに使用されるＴＯＦ（Ｔｉｍｅ ｏｆ Ｆｌｉｇｈｔ）方式の距離画像センサが開発されている。ＴＯＦ方式とは、光源から発生した光が、測定対象で反射し、センサで受光するまでの飛行時間を検出することで、測定対象までの距離を測定する方式である。このＴＯＦ方式を採用したイメージセンサは、画素ごとに距離情報を検出することで、高精度な三次元距離画像を取得できる。 A CCD/CMOS image sensor is known as a solid-state image sensor. In recent years, a TOF (Time of Flight) distance image sensor used in three-dimensional (3D) cameras has been developed as a new image sensor. The TOF method is a method for measuring the distance to a measurement target by detecting the flight time from when light generated from a light source is reflected by a measurement target until the light is received by a sensor. An image sensor that uses this TOF method can obtain highly accurate three-dimensional distance images by detecting distance information for each pixel.
従来より、ＣＣＤ／ＣＭＯＳイメージセンサには、集光効率を向上させるためにマイクロレンズが設けられている。前記マイクロレンズの作製方法の１つとして、リフロー法が知られている（例えば、特許文献１を参照）。すなわち、感光性樹脂組成物を基板上に塗布し、フォトリソグラフィー法により断面形状が矩形状のパターンを形成した後、該矩形状のパターンを熱処理により溶融し流動させて、表面張力によりレンズ形状を作製する方法である。 Conventionally, CCD/CMOS image sensors have been provided with microlenses to improve light collection efficiency. A reflow method is known as one of the methods for manufacturing the microlens (see, for example, Patent Document 1). That is, a photosensitive resin composition is applied onto a substrate, a pattern with a rectangular cross section is formed by photolithography, and then the rectangular pattern is melted and fluidized by heat treatment, and the lens shape is formed by surface tension. This is a method of manufacturing.
一方、重合体、光酸発生剤、溶剤、及びチタンブラックを含む感光性樹脂組成物が知られている（特許文献２を参照）。特許文献２に記載の感光性樹脂組成物中の重合体は、酸基が酸分解性基で保護された基を有する第１の構成単位及び架橋性基を有する第２の構成単位を有する重合体、並びに第１の構成単位を有する重合体及び第２の構成単位を有する重合体のうち、少なくとも一方を満たす。しかし、上記感光性樹脂組成物が、マイクロレンズ形成用であること、特にリフロー法により作製されるマイクロレンズ形成用であることは、特許文献２に記載も示唆もない。 On the other hand, a photosensitive resin composition containing a polymer, a photoacid generator, a solvent, and titanium black is known (see Patent Document 2). The polymer in the photosensitive resin composition described in Patent Document 2 is a polymer having a first structural unit having an acid group protected with an acid-decomposable group and a second structural unit having a crosslinkable group. At least one of a polymer having a first structural unit and a polymer having a second structural unit is satisfied. However, Patent Document 2 neither describes nor suggests that the photosensitive resin composition is used for forming microlenses, particularly for forming microlenses produced by a reflow method.
前記ＴＯＦ方式の距離画像センサ、及び有機ＥＬディスプレイ等の電子表示デバイスに、マイクロレンズを搭載することで、センサへの集光効率向上及びディスプレイの輝度向上が期待される。 By mounting a microlens on the TOF distance image sensor and an electronic display device such as an organic EL display, it is expected that the efficiency of light collection to the sensor and the brightness of the display will be improved.
マイクロレンズ形成用感光性樹脂組成物は、フォトリソグラフィー法により所望の形状のパターンを形成できることが要求される。そして、所望の形状のパターンを形成するために、アルカリ性現像液を用いて現像した後、残渣の発生が抑制されることが要求される。さらに、リフロー法によりマイクロレンズを作製するためには、前記パターンがリフロー可能であることが必要である。また、作製されたマイクロレンズ上に、平坦化膜等の被覆膜を塗布法により形成する際、使用する膜形成用組成物は通常溶剤を含むため、作製されたマイクロレンズが耐溶剤性を具備することが要求される。 The photosensitive resin composition for forming microlenses is required to be able to form a pattern of a desired shape by photolithography. In order to form a pattern with a desired shape, it is required that the generation of residues be suppressed after development using an alkaline developer. Furthermore, in order to produce a microlens by a reflow method, the pattern needs to be reflowable. In addition, when forming a coating film such as a flattening film on the fabricated microlens by a coating method, the film-forming composition used usually contains a solvent, so the fabricated microlens does not have solvent resistance. It is required to be equipped.
本発明は、前記の課題を全て解決するものである。すなわち本発明は、下記（Ａ）成分、下記（Ｂ）成分及び下記（Ｃ）成分を含有し、該（Ａ）成分１００質量％に対し該（Ｂ）成分を少なくとも０．５質量％含有するマイクロレンズ用感光性樹脂組成物である。
（Ａ）：下記式（１）で表される構造単位、下記式（２）で表される構造単位及び下記式（３）で表される構造単位を有する、重量平均分子量５０００乃至２５０００の共重合体
（Ｂ）：光酸発生剤
（Ｃ）：溶剤
(A): A polymer having a weight average molecular weight of 5,000 to 25,000 and 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). Polymer (B): Photoacid generator (C): Solvent
前記酸解離性基は、例えば下記式（ａ）で表される基である。
前記ブロックイソシアネート基は、例えば下記式（ｂ）又は下記式（ｃ）で表される基である。
前記共重合体は、下記式（４ａ）で表される構造単位及び下記式（４ｂ）で表される構造単位のうち少なくとも一方をさらに有してもよい。
前記光酸発生剤は、例えば、ジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物、又はＮ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミドもしくはその誘導体である。 The photoacid generator is, for example, a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound, or N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or a derivative thereof.
本発明の他の態様は、前記マイクロレンズ用感光性樹脂組成物を基板上に塗布し、該感光性樹脂組成物をプリベークして樹脂膜を形成する工程、マスクを通して前記樹脂膜を露光する露光工程、前記露光工程後の樹脂膜をベークするベーク工程、前記ベーク後の樹脂膜を、アルカリ性現像液を用いて現像する現像工程、前記現像工程後得られたパターンをリフローさせるリフロー工程、及び前記リフロー工程後のパターンを硬化させてレンズパターンを形成する工程を有する、マイクロレンズの作製方法である。 Other aspects of the present invention include a step of applying the photosensitive resin composition for microlenses onto a substrate and prebaking the photosensitive resin composition to form a resin film, and an exposure step of exposing the resin film to light through a mask. a baking step of baking the resin film after the exposure step; a developing step of developing the baked resin film using an alkaline developer; a reflow step of reflowing the pattern obtained after the developing step; This is a method for manufacturing a microlens, which includes a step of forming a lens pattern by curing a pattern after a reflow step.
前記リフロー工程は、前記現像後得られたパターンを例えば１２０℃乃至２００℃の温度で加熱する工程である。 The reflow process is a process of heating the pattern obtained after the development at a temperature of, for example, 120°C to 200°C.
本発明のマイクロレンズ用感光性樹脂組成物は、フォトリソグラフィー法により断面形状が矩形状のパターンを形成できると共に、現像後にパターンが形成されていない露光部において残渣が発生することなく、形成されたパターンの裾部においても残渣が発生しないようにできる。さらに、前記パターンはリフロー可能であり、本発明のマイクロレンズ用感光性樹脂組成物を用いて、耐溶剤性を具備する、厚膜（最大高さ１０μｍ乃至２０μｍ）のマイクロレンズを作製することができる。 The photosensitive resin composition for microlenses of the present invention can form a pattern having a rectangular cross-sectional shape by photolithography, and can be formed without generating any residue in exposed areas where no pattern is formed after development. It is possible to prevent residue from being generated even at the hem of the pattern. Furthermore, the pattern can be reflowed, and a thick film (maximum height of 10 μm to 20 μm) microlens with solvent resistance can be produced using the photosensitive resin composition for microlenses of the present invention. can.
本発明は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を含有し、該（Ａ）成分１００質量％に対し該（Ｂ）成分を少なくとも０．５質量％含有するマイクロレンズ用感光性樹脂組成物である。本発明のマイクロレンズ用感光性樹脂組成物は、ポジ型感光性樹脂組成物である。以下、本発明の各成分の詳細を説明する。本発明のマイクロレンズ用感光性樹脂組成物から溶剤を除いた固形分は、通常１質量％乃至５０質量％である。本明細書において、溶剤を除く本発明のマイクロレンズ用感光性樹脂組成物の成分を、固形分と定義する。 The present invention provides a photosensitive material for microlenses containing component (A), component (B), and component (C), and containing at least 0.5% by mass of component (B) based on 100% by mass of component (A). It is a synthetic resin composition. The photosensitive resin composition for microlenses of the present invention is a positive photosensitive resin composition. The details of each component of the present invention will be explained below. The solid content of the photosensitive resin composition for microlenses of the present invention excluding the solvent is usually 1% by mass to 50% by mass. In this specification, the components of the photosensitive resin composition for microlenses of the present invention excluding the solvent are defined as solid content.
＜（Ａ）成分＞
本発明のマイクロレンズ用感光性樹脂組成物における（Ａ）成分は、前記式（１）で表される構造単位、前記式（２）で表される構造単位及び前記式（３）で表される構造単位を有する、重量平均分子量５０００乃至２５０００の共重合体である。該共重合体は、３種のモノマーから得られるターポリマー（三元共重合体）に限定されず、４種のモノマーから得られる共重合体、又は５種のモノマーから得られる共重合体であってもよい。前記共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準試料としてポリスチレンを用いて得られる値である。
<(A) component>
Component (A) in the photosensitive resin composition for microlenses of the present invention includes a structural unit represented by the above formula (1), a structural unit represented by the above formula (2), and a structural unit represented by the above formula (3). It is a copolymer having a weight average molecular weight of 5,000 to 25,000. The copolymer is not limited to a terpolymer (ternary copolymer) obtained from three types of monomers, but may also be a copolymer obtained from four types of monomers or a copolymer obtained from five types of monomers. There may be. The weight average molecular weight of the copolymer is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.
前記式（１）で表される構造単位は、例えば下記式（１ａ）で表される。該式（１）で表される構造単位は、酸解離性基を有する構造単位であれば下記式（１ａ）で表される構造単位に限定されない。ここで、酸解離性基とは、酸により解離してアルカリ可溶性基となる基である。本発明において、前記酸は、露光により（Ｂ）成分の光酸発生剤から発生する酸であり、前記アルカリ可溶性基はカルボキシ基である。
前記式（１）で表される構造単位を形成するモノマーの具体例として、１－メトキシエチル（メタ）アクリレート、１－エトキシエチル（メタ）アクリレート、１－プロポキシエチル（メタ）アクリレート、１－イソプロポキシエチル（メタ）アクリレート、１－ｎ－ブトキシエチル（メタ）アクリレート、１－ｔｅｒｔ－ブトキシエチル（メタ）アクリレート、１－ｎ－ヘキシルオキシエチル（メタ）アクリレート、１－シクロヘキシルオキシエチル（メタ）アクリレート、テトラヒドロ－２Ｈ－ピラン－２－イル（メタ）アクリレートが挙げられる。これらのモノマーは、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。本明細書において、（メタ）アクリレートはメタクリレート及びアクリレートを意味する。 Specific examples of monomers forming the structural unit represented by formula (1) include 1-methoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 1-propoxyethyl (meth)acrylate, 1-iso Propoxyethyl (meth)acrylate, 1-n-butoxyethyl (meth)acrylate, 1-tert-butoxyethyl (meth)acrylate, 1-n-hexyloxyethyl (meth)acrylate, 1-cyclohexyloxyethyl (meth)acrylate , tetrahydro-2H-pyran-2-yl (meth)acrylate. These monomers may be used alone or in combination of two or more. As used herein, (meth)acrylate means methacrylate and acrylate.
前記式（２）で表される構造単位は、架橋性基としてヒドロキシ基を有する構造単位である。該式（２）で表される構造単位を形成するモノマーの具体例として、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレートが挙げられる。これらのモノマーは、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。 The structural unit represented by the formula (2) is a structural unit having a hydroxy group as a crosslinkable group. Specific examples of monomers forming the structural unit represented by formula (2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. These monomers may be used alone or in combination of two or more.
前記式（３）で表される構造単位は、例えば下記式（３ｂ）又は下記式（３ｃ）で表される。該式（３）で表される構造単位は、ブロックイソシアネート基を有する構造単位であれば下記式（３ｂ）又は下記式（３ｃ）で表される構造単位に限定されない。ここで、ブロックイソシアネート基とは、イソシアネート基（－ＮＣＯ）が熱脱離可能な保護基によりブロックされた基、すなわち、イソシアネート基にブロック剤を反応させた基である。
前記式（３）で表される構造単位を形成するモノマーの具体例として、２－イソシアネートエチルメタクリレート、２－イソシアネートエチルアクリレート等のイソシアネート含有（メタ）アクリレートに、メチルエチルケトンオキシム、ε－カプロラクタム、３，５－ジメチルピラゾール、マロン酸ジエチル等のブロック剤を付加した化合物が挙げられる。これらのモノマーは、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。 Specific examples of monomers forming the structural unit represented by the above formula (3) include isocyanate-containing (meth)acrylates such as 2-isocyanate ethyl methacrylate and 2-isocyanate ethyl acrylate, methyl ethyl ketone oxime, ε-caprolactam, 3, Examples include compounds to which blocking agents such as 5-dimethylpyrazole and diethyl malonate are added. These monomers may be used alone or in combination of two or more.
前記（Ａ）成分の共重合体は、前記式（４ａ）で表される構造単位及び前記式（４ｂ）で表される構造単位のうち少なくとも一方をさらに有してもよい。該式（４ａ）で表される構造単位を形成するモノマーの具体例として、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートが挙げられる。前記式（４ｂ）で表される構造単位を形成するモノマーの具体例として、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミドが挙げられる。これらのモノマーは、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。 The copolymer of component (A) may further include at least one of the structural unit represented by the formula (4a) and the structural unit represented by the formula (4b). Specific examples of monomers forming the structural unit represented by the formula (4a) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( Examples include meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, cyclopentyl(meth)acrylate, n-hexyl(meth)acrylate, and cyclohexyl(meth)acrylate. Specific examples of monomers forming the structural unit represented by formula (4b) include N-cyclohexylmaleimide and N-phenylmaleimide. These monomers may be used alone or in combination of two or more.
前記（Ａ）成分の共重合体において、前記式（１）で表される構造単位、前記式（２）で表される構造単位、前記式（３）で表される構造単位、前記式（４ａ）で表される構造単位及び前記式（４ｂ）で表される構造単位の和１００ｍｏｌ％に対し、前記式（１）で表される構造単位の含有率は例えば１２ｍｏｌ％乃至３０ｍｏｌ％であり、好ましくは１７ｍｏｌ％乃至２５ｍｏｌ％、前記式（２）で表される構造単位の含有率は例えば５ｍｏｌ％乃至４０ｍｏｌ％であり、好ましくは１０ｍｏｌ％乃至３０ｍｏｌ％、前記式（３）で表される構造単位の含有率は例えば５ｍｏｌ％乃至４０ｍｏｌ％であり、好ましくは１０ｍｏｌ％乃至３０ｍｏｌ％、前記式（４ａ）で表される構造単位の含有率は例えば０ｍｏｌ％乃至６０ｍｏｌ％、前記式（４ｂ）で表される構造単位の含有率は例えば０ｍｏｌ％乃至６０ｍｏｌ％である。 In the copolymer of the component (A), a structural unit represented by the formula (1), a structural unit represented by the formula (2), a structural unit represented by the formula (3), a structural unit represented by the formula ( The content of the structural unit represented by formula (1) is, for example, 12 mol% to 30 mol% with respect to the sum of 100 mol% of the structural unit represented by 4a) and the structural unit represented by formula (4b). , preferably 17 mol% to 25 mol%, the content of the structural unit represented by the formula (2) is, for example, 5 mol% to 40 mol%, preferably 10 mol% to 30 mol%, represented by the formula (3) The content of the structural unit is, for example, 5 mol% to 40 mol%, preferably 10 mol% to 30 mol%, and the content of the structural unit represented by the formula (4a) is, for example, 0 mol% to 60 mol%, the formula (4b) The content of the structural unit represented by is, for example, 0 mol% to 60 mol%.
前記式（１）で表される構造単位の含有率が下限値よりも小さい場合、フォトリソグラフィー法によりパターンを形成する際、現像液に対する露光部の溶解性が不足し、所望の形状のパターンが得られない虞がある。前記式（１）で表される構造単位の含有率が上限値よりも大きい場合、作製されたマイクロレンズの耐溶剤性が得られない虞がある。前記式（２）で表される構造単位及び前記式（３）で表される構造単位の含有率が下限値よりも小さい場合、作製されたマイクロレンズの耐溶剤性が得られない虞がある。前記式（２）で表される構造単位及び前記式（３）で表される構造単位の含有率が上限値よりも多い場合、フォトリソグラフィー法によりパターンを形成する際、現像液に対する露光部の溶解性が不足し、所望の形状のパターンが得られない虞がある。前記（Ａ）成分の共重合体は、前記式（２）で表される構造単位及び前記式（３）で表される構造単位を有することにより、ベークにより架橋反応が進行する。そのため、前記式（２）で表される構造単位及び前記式（３）で表される構造単位の含有率は、等モルであることが好ましい。前記式（４ａ）で表される構造単位及び前記式（４ｂ）で表される構造単位は、その含有率により前記共重合体のガラス転移点（Ｔｇ）を調整することができるため、パターンのリフロー性を容易に制御することができる。 If the content of the structural unit represented by the above formula (1) is smaller than the lower limit, when forming a pattern by photolithography, the solubility of the exposed area in the developer will be insufficient, resulting in a pattern with the desired shape. There is a possibility that you will not get it. If the content of the structural unit represented by the formula (1) is larger than the upper limit, there is a possibility that the produced microlens will not have sufficient solvent resistance. If the content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is lower than the lower limit, there is a possibility that the produced microlens will not have sufficient solvent resistance. . When the content of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3) is higher than the upper limit, when forming a pattern by the photolithography method, the exposure area to the developer is There is a possibility that the solubility is insufficient and a pattern with a desired shape cannot be obtained. The copolymer of component (A) has the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3), so that the crosslinking reaction proceeds by baking. Therefore, it is preferable that the contents of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) are equimolar. 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 depending on their content. Reflowability can be easily controlled.
前記（Ａ）成分の共重合体を得る方法は特に限定されない。一般的には、前記式（１）で表される構造単位を形成するモノマー、前記式（２）で表される構造単位を形成するモノマー及び前記式（３）で表される構造単位を形成するモノマー、並びに、任意で前記式（４ａ）で表される構造単位形成するモノマー及び前記式（４ｂ）で表される構造単位を形成するモノマーのうち少なくとも一方を、重合開始剤存在下の溶剤中において、通常５０℃乃至１２０℃の温度下で重合反応させることにより得られる。このようにして得られる共重合体は、通常、溶剤に溶解した溶液状態であり、この状態で単離することなく、本発明のマイクロレンズ用感光性樹脂組成物に用いることができる。 The method for obtaining the copolymer of component (A) is not particularly limited. Generally, monomers that form the structural unit represented by the above formula (1), monomers that form the structural unit represented by the above formula (2), and monomers that form the structural unit represented by the above formula (3) are used. and optionally at least one of the monomers forming the structural unit represented by the formula (4a) and the monomers forming the structural unit represented by the formula (4b), in a solvent in the presence of a polymerization initiator. It is obtained by carrying out a polymerization reaction at a temperature of usually 50°C to 120°C. The copolymer thus obtained is usually in the form of a solution dissolved in a solvent, and can be used in the photosensitive resin composition for microlenses of the present invention without being isolated in this state.
＜（Ｂ）成分＞
本発明のマイクロレンズ用感光性樹脂組成物における（Ｂ）成分は、光酸発生剤である。該光酸発生剤は、露光により酸が発生する化合物であれば特に限定されない。該化合物の具体例として、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物が挙げられる。
<(B) component>
Component (B) in the photosensitive resin composition for microlenses of the present invention is a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon exposure to light. Specific examples of the compound include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
前記オニウム塩化合物の具体例として、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ－ｎ－ブタンスルホネート、ジフェニルヨードニウムパーフルオロ－ｎ－オクタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムカンファースルホネート、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート等のヨードニウム塩化合物、及びトリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムノナフルオロ－ｎ－ブタンスルホネート、トリフェニルスルホニウムカンファースルホネート、トリフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムヘキサフルオロホスフェート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムヘキサフルオロアンチモネート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等のスルホニウム塩化合物が挙げられる。該オニウム塩化合物の中で、スルホニウム塩化合物が好ましく、ｉ線（３６５ｎｍ）を用いた露光により酸が発生する化合物としてはジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物がより好ましい。 Specific examples of the onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4- Iodonium salt compounds such as tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, Phenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl] ] Sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl] Examples include sulfonium salt compounds such as sulfonium tetrakis(pentafluorophenyl)borate. Among the onium salt compounds, sulfonium salt compounds are preferred, and diphenyl[4-(phenylthio)phenyl]sulfonium salt compounds are more preferred as compounds that generate acid upon exposure using i-line (365 nm).
前記スルホンイミド化合物の具体例として、Ｎ－（トリフルオロメタンスルホニルオキシ）スクシンイミド、Ｎ－（ノナフルオロ－ｎ－ブタンスルホニルオキシ）スクシンイミド、Ｎ－（カンファースルホニルオキシ）スクシンイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－２－アルキル－１，８－ナフタルイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－３－アルキル－１，８－ナフタルイミド及びＮ－（トリフルオロメタンスルホニルオキシ）－４－アルキル－１，８－ナフタルイミドが挙げられる。該スルホンイミド化合物の中で、Ｎ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド、及びその誘導体が好ましい。 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 is mentioned. Among the sulfonimide compounds, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide and its derivatives are preferred.
前記ジスルホニルジアゾメタン化合物の具体例として、ビス（トリフルオロメチルスルホニル）ジアゾメタン、ビス（シクロヘキシルスルホニル）ジアゾメタン、ビス（フェニルスルホニル）ジアゾメタン、ビス（ｐ－トルエンスルホニル）ジアゾメタン、ビス（２，４－ジメチルベンゼンスルホニル）ジアゾメタン、及びメチルスルホニル－ｐ－トルエンスルホニルジアゾメタンが挙げられる。 Specific examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and bis(2,4-dimethylbenzene). sulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
前記光酸発生剤の具体例として、アデカアークルズ（登録商標）ＳＰ－０５６、同ＳＰ－０６６、同ＳＰ－１４０、同ＳＰ－１４１、同ＳＰ－０８２、同ＳＰ－６０１、同ＳＰ－６０６、同ＳＰ－７０１、同ＳＰ－１５０、同ＳＰ－１７０、同ＳＰ－１７１（以上、（株）ＡＤＥＫＡ製）、ＣＰＩ（登録商標）－１１０Ｐ、同－１１０Ｂ、同－３１０Ｂ、同－２１０Ｓ、同－１００Ｐ、同－１０１Ａ、同－２００Ｋ（以上、サンアプロ（株）製）、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（以上、みどり化学（株）製）が挙げられる。これらの光酸発生剤は、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。 Specific examples of the photoacid generator include Adeka Arkles (registered trademark) SP-056, Adeka Arkles (registered trademark) SP-066, Adeka Arkles (registered trademark) SP-140, Adeka Arkles (registered trademark) SP-141, Adeka Arkles (registered trademark) SP-082, Adeka Arkles (registered trademark) SP-601, and Adeka Arkles (registered trademark) SP-606. , SP-701, SP-150, SP-170, SP-171 (made by ADEKA Co., Ltd.), CPI (registered trademark) -110P, -110B, -310B, -210S, -100P, -101A, -200K (manufactured by Sun-Apro Co., Ltd.), 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 (manufactured by Midori Kagaku Co., Ltd.). These photoacid generators may be used alone or in combination of two or more.
前記（Ｂ）成分の光酸発生剤は、前記（Ａ）成分１００質量％に対し少なくとも０．５質量％含有する。該光酸発生剤の含有量が０．５質量％より少ないと、前記（Ａ）成分の酸解離性基が解離せず、アルカリ可溶性基が発現しない。そのため、フォトリソグラフィー法によりパターンを形成する際、露光部の現像液に対する溶解性が不足し、所望の形状のパターンが得られない虞がある。前記光酸発生剤の含有量の上限は、露光により発生する酸の強さによって変化する。例えば、露光により光酸発生剤から発生する酸が強酸であるほど、該光酸発生剤の含有量の上限を小さくすることができる。該光酸発生剤として前記アデカアークルズ（登録商標）ＳＰ－６０６を採用する場合、その含有量の上限は、前記（Ａ）成分１００質量％に対し、例えば５質量％である。該光酸発生剤の含有量が多すぎると、フォトリソグラフィー法によりパターンを形成する際、現像後の露光部に該光酸発生剤が残渣として残りやすい。 The photoacid generator as the component (B) is contained in an amount of at least 0.5% by mass based on 100% by mass of the component (A). If the content of the photoacid generator is less than 0.5% by mass, the acid-dissociable group of the component (A) will not be dissociated and the alkali-soluble group will not be expressed. Therefore, when forming a pattern by photolithography, there is a possibility that the exposed portion may not have sufficient solubility in a developer, and a pattern with a desired shape may not be obtained. The upper limit of the content of the photoacid generator changes depending on the strength of the acid generated by exposure. For example, the stronger the acid generated from the photoacid generator upon exposure, the smaller the upper limit of the content of the photoacid generator can be. When the Adeka Arcles (registered trademark) SP-606 is used as the photoacid generator, the upper limit of its content is, for example, 5% by mass based on 100% by mass of the component (A). If the content of the photoacid generator is too large, the photoacid generator tends to remain as a residue in the exposed area after development when forming a pattern by photolithography.
＜（Ｃ）成分＞
本発明のマイクロレンズ用感光性樹脂組成物における（Ｃ）成分は、溶剤である。前記（Ａ）成分、前記（Ｂ）成分、及び後述するその他成分を溶解する溶剤であれば、特に限定されない。該溶剤の具体例として、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、２－ヘプタノン、γ－ブチロラクトンが挙げられる。これらの溶剤は、１種単独で使用しても、或いは２種以上を組み合わせて使用してもよい。
<(C) component>
Component (C) in the photosensitive resin composition for microlenses of the present invention is a solvent. The solvent is not particularly limited as long as it can dissolve the component (A), the component (B), and other components described below. Specific examples of the 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, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, acetic acid Examples include butyl, ethyl lactate, butyl lactate, 2-heptanone, and γ-butyrolactone. These solvents may be used alone or in combination of two or more.
＜界面活性剤＞
本発明のマイクロレンズ用感光性樹脂組成物は、基板に対する塗布性を向上させる目的で、界面活性剤を含有してもよい。該界面活性剤の具体例として、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（以上、三菱マテリアル電子化成（株）製）、メガファック（登録商標）Ｆ－１７１、同Ｆ－１７３、同Ｒ－３０、同Ｒ－４０、同Ｒ－４０－ＬＭ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（以上、スリーエムジャパン（株）製）、アサヒガード（登録商標）ＡＧ７１０、サーフロン（登録商標）Ｓ－３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（ＡＧＣ（株）製）、ＦＴＸ－２０６Ｄ、ＦＴＸ－２１２Ｄ、ＦＴＸ－２１８、ＦＴＸ－２２０Ｄ、ＦＴＸ－２３０Ｄ、ＦＴＸ－２４０Ｄ、ＦＴＸ－２１２Ｐ、ＦＴＸ－２２０Ｐ、ＦＴＸ－２２８Ｐ、ＦＴＸ－２４０Ｇ等フタージェントシリーズ（（株）ネオス製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）が挙げられる。
<Surfactant>
The photosensitive resin composition for microlenses of the present invention may contain a surfactant for the purpose of improving coating properties on a 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, and polyoxyethylene oleyl ether. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F-171 , F-173, R-30, R-40, R-40-LM (manufactured by DIC Corporation), Florado FC430, FC431 (manufactured by 3M Japan Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon (registered trademark) SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation), FTX-206D, FTX-212D, FTX- Fluorine surfactants such as Ftergent series (manufactured by Neos Co., Ltd.), organosiloxane Examples include polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
前記界面活性剤は、１種単独で又は２種以上を組み合わせて用いることができる。本発明のマイクロレンズ用感光性樹脂組成物が該界面活性剤を含有する場合、その含有量は、該組成物の固形分中の含有量に基づいて、３質量％以下であり、好ましくは１質量％以下であり、より好ましくは０．５質量％以下である。 The surfactants may be used alone or in combination of two or more. When the photosensitive resin composition for microlenses of the present invention contains the surfactant, the content is 3% by mass or less, preferably 1% by mass or less, based on the content in the solid content of the composition. It is not more than 0.5% by mass, more preferably not more than 0.5% by mass.
＜その他添加剤＞
本発明のマイクロレンズ用感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、硬化助剤、紫外線吸収剤、増感剤、可塑剤、酸化防止剤、密着助剤、又は多価フェノール、多価カルボン酸等の溶解促進剤をその他添加剤として含むことができる。なお、本発明のマイクロレンズ用感光性樹脂組成物は、前記（Ａ）成分の共重合体が自己架橋性であるため、架橋剤を必要としない。
<Other additives>
The photosensitive resin composition for microlenses of the present invention may contain curing aids, ultraviolet absorbers, sensitizers, plasticizers, antioxidants, adhesion aids, as necessary, as long as the effects of the present invention are not impaired. , or a solubility promoter such as polyhydric phenol or polycarboxylic acid may be included as other additives. Note that 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-crosslinkable.
＜マイクロレンズ用感光性組成物調製方法＞
本発明のマイクロレンズ用感光性樹脂組成物の調製方法は、特に限定されないが、例えば、前記（Ａ）成分の共重合体の溶液及び前記（Ｂ）成分の光酸発生剤を、前記（Ｃ）成分の溶剤に所定の割合で混合し、均一な溶液とする方法が挙げられる。さらに、この調製方法の適当な段階において、任意で、前記界面活性剤及び前記その他添加剤を更に添加して混合する方法が挙げられる。
<Method for preparing photosensitive composition for microlenses>
The method for preparing the photosensitive resin composition for microlenses of the present invention is not particularly limited, but for example, the solution of the copolymer of the component (A) and the photoacid generator of the component (B) are ) A method of mixing the components in a solvent at a predetermined ratio to form a uniform solution is mentioned. Furthermore, at an appropriate stage of this preparation method, the above-mentioned surfactant and the above-mentioned other additives may optionally be further added and mixed.
＜マイクロレンズの作製＞
基板［例えば、酸化珪素膜、窒化珪素膜又は酸化窒化珪素膜で被覆されていてもよいシリコン等の半導体基板、カラーフィルター、平坦化膜等の有機膜で被覆されていてもよいシリコン等の半導体基板、窒化ガリウム（ＧａＮ）、砒化ガリウム（ＧａＡｓ）、リン化ガリウム（ＧａＰ）、リン化インジウム（ＩｎＰ）等の化合物半導体基板、窒化珪素基板、石英基板、ガラス基板（無アルカリガラス、低アルカリガラス、結晶化ガラスを含む）、ＩＴＯ膜が形成されたガラス基板］上に、スピナー、コーター等の適当な塗布方法により本発明のマイクロレンズ用感光性樹脂組成物を塗布し、その後、ホットプレート等の加熱手段を用いてプリベークすることにより、樹脂膜を形成する。前記プリベーク条件としては、ベーク温度８０℃乃至１５０℃、ベーク時間０．３分乃至６０分間から適宜選択され、好ましくは、ベーク温度８０℃乃至１２０℃、ベーク時間０．５分乃至５分間である。
<Production of microlens>
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 such as silicon which may be covered with an organic film such as a color filter or a planarization film Substrates, compound semiconductor substrates such as gallium nitride (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), a glass substrate on which an ITO film is formed], the photosensitive resin composition for microlenses of the present invention is applied using an appropriate coating method such as a spinner or a coater, and then coated on a hot plate, etc. A resin film is formed by pre-baking using a heating means. The pre-bake conditions are appropriately selected from a bake temperature of 80° C. to 150° C. and a bake time of 0.3 minutes to 60 minutes, preferably a bake temperature of 80° C. to 120° C. and a bake time of 0.5 minutes to 5 minutes. .
本発明のマイクロレンズ用感光性樹脂組成物から形成される樹脂膜の膜厚としては、０．００５μｍ乃至３０μｍであり、好ましくは０．０１μｍ乃至２０μｍである。 The 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.
次に、得られた前記樹脂膜に対し、所望の形状のパターンを形成するためのマスク（レチクル）を通して露光する。露光には、ｇ線、ｉ線、ＫｒＦエキシマレーザー等の近紫外線又は可視光線を使用することができる。さらに、露光後の樹脂膜に対しベーク（Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｅ）を行う。露光後のベーク条件としては、ベーク温度８０℃乃至１２０℃、ベーク時間０．３分乃至６０分間から適宜選択される。 Next, the obtained resin film is exposed to light through a mask (reticle) for forming a pattern of a desired shape. For exposure, near ultraviolet light or visible light such as g-line, i-line, KrF excimer laser, etc. can be used. Furthermore, the exposed resin film is subjected to a post exposure bake. The baking conditions after exposure are appropriately selected from a baking temperature of 80° C. to 120° C. and a baking time of 0.3 minutes to 60 minutes.
その後、前記樹脂膜を、アルカリ性現像液を用いて現像する。その結果、前記基板上に所望の形状のパターンが形成される。該アルカリ性現像液としては、例えば、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリン等の水酸化四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミン等のアミン水溶液等のアルカリ性水溶液を挙げることができる。さらに、これらの現像液に界面活性剤を加えることもできる。 Thereafter, the resin film is developed using an alkaline developer. As a result, a pattern with a desired shape is formed on the substrate. Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and ethanolamine. , alkaline aqueous solutions such as amine aqueous solutions such as propylamine and ethylenediamine. Furthermore, surfactants can also be added to these developers.
前記現像の条件としては、現像温度５℃乃至５０℃、現像時間１０秒乃至３００秒から適宜選択される。前記樹脂膜は、水酸化テトラメチルアンモニウム水溶液を用いて、室温で容易に現像を行うことができる。現像後、リンス液として例えば超純水を用いて、適宜リンスを行う。 The conditions for the development are appropriately selected from a development temperature of 5° C. to 50° C. and a development time of 10 seconds to 300 seconds. The resin film can be easily developed at room temperature using a tetramethylammonium hydroxide aqueous solution. After development, rinsing is performed as appropriate using, for example, ultrapure water as a rinsing liquid.
さらに、形成された前記パターンを１回目のポストベークによりリフローさせる。前記１回目のポストベーク条件としては、ベーク温度１２０℃乃至２００℃、ベーク時間０．３分乃至６０分間から適宜選択される。その後、ｇ線、ｉ線、ＫｒＦエキシマレーザー等の近紫外線又は可視光線を用い、リフロー後の前記パターンを全面露光してもよい。さらに、全面露光の後に、前記パターンに対して再び露光後ベークを行ってもよい。この露光後ベーク条件として例えば、ベーク温度１２０℃乃至２００℃、ベーク時間０．３分乃至６０分間から適宜選択される。最後に、前記リフロー後のパターンを２回目のポストベークにより硬化させてレンズパターンを形成する。前記２回目のポストベーク条件としては、ベーク温度１５０℃乃至２５０℃、ベーク時間０．３分乃至６０分間から適宜選択される。 Furthermore, the formed pattern is reflowed by a first post-bake. The first post-bake conditions are appropriately selected from a bake temperature of 120° C. to 200° C. and a bake 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 light such as g-line, i-line, KrF excimer laser, etc. Further, after the entire surface is exposed, the pattern may be subjected to post-exposure baking again. The post-exposure baking conditions are appropriately selected from, for example, a baking temperature of 120° C. to 200° C. and a baking time of 0.3 minutes to 60 minutes. Finally, the reflowed pattern is cured by a second post-bake to form a lens pattern. The second post-bake conditions are appropriately selected from a bake temperature of 150° C. to 250° C. and a bake time of 0.3 minutes to 60 minutes.
以下、合成例及び実施例を挙げて本発明をより詳細に説明するが、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples.
［重量平均分子量の測定］
装置：日本分光（株）製ＧＰＣシステム
カラム：Ｓｈｏｄｅｘ〔登録商標〕ＧＰＣ ＫＦ－８０４Ｌ及びＧＰＣ ＫＦ－８０３Ｌ
カラムオーブン：４０℃
流量：１ｍｌ／分
溶離液：テトラヒドロフラン
標準試料：ポリスチレン
[Measurement of weight average molecular weight]
Equipment: GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) GPC KF-804L and GPC KF-803L
Column oven: 40℃
Flow rate: 1 ml/min Eluent: Tetrahydrofuran Standard sample: Polystyrene
［合成例１］
１－ブトキシエチルメタクリレート７．０ｇ、２－ヒドロキシエチルメタクリレート４．９ｇ、２－［０－（１’－メチルプロピリデンアミノ）カルボキシアミノ］エチルメタクリレート［カレンズＭＯＩ－ＢＭ（登録商標）（昭和電工（株）製）］９．１ｇ、メチルメタクリレート７．５ｇ、及び２，２’－アゾビスイソブチロニトリル１．４ｇをプロピレングリコールモノメチルエーテル８９．８ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル７９．８ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させた。反応溶液を冷却後、多量のヘキサン溶液に投入してポリマーを再沈殿し、加熱乾燥して、下記式（１－１）で表される構造単位、下記式（２－１）で表される構造単位、下記式（３－１）で表される構造単位及び下記式（４ａ－１）で表される構造単位を有する共重合体を得た。得られた共重合体の重量平均分子量Ｍｗは１６，０００（ポリスチレン換算）であった。
7.0 g of 1-butoxyethyl methacrylate, 4.9 g of 2-hydroxyethyl methacrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Karens MOI-BM (registered trademark) (Showa Denko Co., Ltd.)], 7.5 g of methyl methacrylate, and 1.4 g of 2,2'-azobisisobutyronitrile were dissolved in 89.8 g of propylene glycol monomethyl ether. 79.8 g of monomethyl ether was added dropwise over 3 hours into a flask maintained at 70°C. After the dropwise addition was completed, the reaction was continued for 18 hours. After cooling the reaction solution, the polymer is reprecipitated by pouring it into a large amount of hexane solution, and is heated and dried to obtain a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (2-1). A copolymer having a structural unit represented by the following formula (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).
［合成例２］
１－ブトキシエチルメタクリレート９．０ｇ、２－ヒドロキシエチルメタクリレート３．１ｇ、２－［０－（１’－メチルプロピリデンアミノ）カルボキシアミノ］エチルメタクリレート［カレンズＭＯＩ－ＢＭ（登録商標）（昭和電工（株）製］５．９ｇ、メチルメタクリレート１２．１ｇ、Ｎ－フェニルマレイミド４．２ｇ、及び２，２’－アゾビスイソブチロニトリル１．７ｇをプロピレングリコールモノメチルエーテル３６．０ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル１８．０ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させることにより、下記式（１－１）で表される構造単位、下記式（２－１）で表される構造単位、下記式（３－１）で表される構造単位、下記式（４ａ－１）で表される構造単位及び下記式（４ｂ－１）で表される構造単位を有する共重合体の溶液（固形分濃度４０質量％）を得た。得られた共重合体の重量平均分子量Ｍｗは２２，０００（ポリスチレン換算）であった。
9.0 g of 1-butoxyethyl methacrylate, 3.1 g of 2-hydroxyethyl methacrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Karens MOI-BM (registered trademark) (Showa Denko Co., Ltd.], 12.1 g of methyl methacrylate, 4.2 g of N-phenylmaleimide, and 1.7 g of 2,2'-azobisisobutyronitrile were dissolved in 36.0 g of propylene glycol monomethyl ether. This solution was added dropwise over 3 hours into a flask in which 18.0 g of propylene glycol monomethyl ether was kept at 70°C.After the dropwise addition was completed, the reaction was carried out for 18 hours to form a compound represented by the following formula (1-1). Structural units, structural units represented by the following formula (2-1), structural units represented by the following formula (3-1), structural units represented by the following formula (4a-1), and the following formula (4b- A solution (solid content concentration: 40% by mass) of a copolymer having the structural unit represented by 1) was obtained.The weight average molecular weight Mw of the obtained copolymer was 22,000 (in terms of polystyrene).
［合成例３］
１－ブトキシエチルメタクリレート８．５ｇ、２－ヒドロキシエチルメタクリレート３．０ｇ、２－［０－（１’－メチルプロピリデンアミノ）カルボキシアミノ］エチルメタクリレート［カレンズＭＯＩ－ＢＭ（登録商標）（昭和電工（株）製］５．５ｇ、メチルメタクリレート９．１ｇ、Ｎ－フェニルマレイミド７．９ｇ、及び２，２’－アゾビスイソブチロニトリル１．７ｇをプロピレングリコールモノメチルエーテル３５．７ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル１７．９ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させることにより、前記式（１－１）で表される構造単位、前記式（２－１）で表される構造単位、前記式（３－１）で表される構造単位、前記式（４ａ－１）で表される構造単位及び前記式（４ｂ－１）で表される構造単位を有する共重合体の溶液（固形分濃度４０質量％）を得た。得られた共重合体の重量平均分子量Ｍｗは１９，０００（ポリスチレン換算）であった。
[Synthesis example 3]
8.5 g of 1-butoxyethyl methacrylate, 3.0 g of 2-hydroxyethyl methacrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Karens MOI-BM (registered trademark) (Showa Denko Co., Ltd.], 9.1 g of methyl methacrylate, 7.9 g of N-phenylmaleimide, and 1.7 g of 2,2'-azobisisobutyronitrile were dissolved in 35.7 g of propylene glycol monomethyl ether. This solution was added dropwise over a period of 3 hours into a flask in which 17.9 g of propylene glycol monomethyl ether was kept at 70°C.After the completion of the dropwise addition, by reacting for 18 hours, the reaction mixture represented by the formula (1-1) was obtained. Structural unit, 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- A solution (solid content concentration: 40% by mass) of a copolymer having the structural unit represented by 1) was obtained.The weight average molecular weight Mw of the obtained copolymer was 19,000 (in terms of polystyrene).
［合成例４］
１－ブトキシエチルメタクリレート９．５ｇ、メチルメタクリレート２０．４ｇ、及び２，２’－アゾビスイソブチロニトリル１．５ｇをプロピレングリコールモノメチルエーテル３１．４ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル２６．９ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させることにより、下記式（１－１）で表される構造単位及び下記式（４ａ－１）で表される構造単位を有する共重合体の溶液（固形分濃度３５質量％）を得た。得られた共重合体の重量平均分子量Ｍｗは１６，０００（ポリスチレン換算）であった。
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, this solution was dissolved in propylene glycol monomethyl ether. 26.9 g of monomethyl ether was added dropwise over 3 hours into a flask maintained at 70°C. After the dropwise addition, a solution 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) (solid content concentration 35 mass%) was obtained. The weight average molecular weight Mw of the obtained copolymer was 16,000 (in terms of polystyrene).
［合成例５］
１－ブトキシエチルメタクリレート５．１ｇ、メチルメタクリレート２４．７ｇ、及び２，２’－アゾビスイソブチロニトリル１．５ｇをプロピレングリコールモノメチルエーテル３１．３ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル２６．８ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させることにより、前記式（１－１）で表される構造単位及び前記式（４ａ－１）で表される構造単位を有する共重合体の溶液（固形分濃度３５質量％）を得た。得られた共重合体の重量平均分子量Ｍｗは２０，０００（ポリスチレン換算）であった。
[Synthesis example 5]
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, this solution was dissolved in propylene glycol monomethyl ether. 26.8 g of monomethyl ether was added dropwise over 3 hours into a flask maintained at 70°C. After the dropwise addition, a solution of a copolymer having a structural unit represented by the above formula (1-1) and a structural unit represented by the above formula (4a-1) (solid content concentration 35 mass%) was obtained. The weight average molecular weight Mw of the obtained copolymer was 20,000 (in terms of polystyrene).
［合成例６］
１－ブトキシエチルメタクリレート８．４ｇ、２－ヒドロキシエチルメタクリレート５．９ｇ、２－［０－（１’－メチルプロピリデンアミノ）カルボキシアミノ］エチルメタクリレート［カレンズＭＯＩ－ＢＭ（登録商標）（昭和電工（株）製］１０．９ｇ、メチルメタクリレート９．０ｇ、及び２，２’－アゾビスイソブチロニトリル１．７ｇをプロピレングリコールモノメチルエーテル３５．９ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル１８．０ｇを７０℃に保持したフラスコ中に３時間かけて滴下した。滴下終了後、１８時間反応させることにより、前記式（１－１）で表される構造単位、前記式（２－１）で表される構造単位、前記式（３－１）で表される構造単位及び前記式（４ａ－１）で表される構造単位を有する共重合体の溶液（固形分濃度４０質量％）を得た。得られた共重合体の重量平均分子量Ｍｗは２８，０００（ポリスチレン換算）であった。
[Synthesis example 6]
8.4 g of 1-butoxyethyl methacrylate, 5.9 g of 2-hydroxyethyl methacrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate [Karens MOI-BM (registered trademark) (Showa Denko Co., Ltd.], 9.0 g of methyl methacrylate, and 1.7 g of 2,2'-azobisisobutyronitrile were dissolved in 35.9 g of propylene glycol monomethyl ether. 18.0 g of ether was added dropwise into a flask kept at 70°C over 3 hours.After the dropwise addition, the reaction was carried out for 18 hours to form a structural unit represented by the formula (1-1) and the formula (2- A solution of a copolymer having the structural unit represented by 1), the structural unit represented by the above formula (3-1), and the structural unit represented by the above formula (4a-1) (solid content concentration 40% by mass) ) was obtained.The weight average molecular weight Mw of the obtained copolymer was 28,000 (in terms of polystyrene).
［実施例１］
合成例１で得られた（Ａ）成分である共重合体１６．６ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．８３ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５２ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２９．１ｇ及びプロピレングリコールモノメチルエーテルアセテート３．２ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本実施例、及び後述する実施例２乃至４、８及び９で使用した光酸発生剤は、Ｎ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミドの誘導体に該当する。
[Example 1]
16.6 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.83 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and as a surfactant. 0.0052 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 29.1 g of propylene glycol monomethyl ether and 3.2 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The photoacid generator used in this example and Examples 2 to 4, 8, and 9 below corresponds to a derivative of N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide.
［実施例２］
合成例１で得られた（Ａ）成分である共重合体１８．６ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．３７ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。
[Example 2]
18.6 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.37 g of SP-606 (made by ADEKA Co., Ltd.) as a photoacid generator as component (B), and as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens.
［実施例３］
合成例１で得られた（Ａ）成分である共重合体１８．８ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．１９ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。
[Example 3]
18.8 g of the copolymer as component (A) obtained in Synthesis Example 1, 0.19 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens.
［実施例４］
合成例１で得られた（Ａ）成分である共重合体１８．９ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０９５ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。
[Example 4]
18.9 g of the copolymer (A) component obtained in Synthesis Example 1, 0.095 g of SP-606 (manufactured by ADEKA Co., Ltd.) as the photoacid generator (B) component, and as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens.
［実施例５］
合成例１で得られた（Ａ）成分である共重合体１８．１ｇ、（Ｂ）成分である光酸発生剤としてＣＰＩ－１１０Ｂ（サンアプロ（株）製）０．９１ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本実施例で使用した光酸発生剤は、ジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物に該当する。
[Example 5]
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 as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The photoacid generator used in this example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
［実施例６］
合成例１で得られた（Ａ）成分である共重合体１８．１ｇ、（Ｂ）成分である光酸発生剤としてＣＰＩ－１１０Ｐ（サンアプロ（株）製）０．９１ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本実施例で使用した光酸発生剤は、ジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物に該当する。
[Example 6]
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 as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The photoacid generator used in this example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
［実施例７］
合成例１で得られた（Ａ）成分である共重合体１８．１ｇ、（Ｂ）成分である光酸発生剤としてＣＰＩ－２１０Ｓ（サンアプロ（株）製）０．９１ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本実施例で使用した光酸発生剤は、ジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物に該当する。
[Example 7]
18.1 g of the copolymer as the component (A) obtained in Synthesis Example 1, 0.91 g of CPI-210S (manufactured by San-Apro Co., Ltd.) as the photoacid generator as the component (B), and as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The photoacid generator used in this example corresponds to a diphenyl[4-(phenylthio)phenyl]sulfonium salt compound.
［実施例８］
合成例２で得られた（Ａ）成分である共重合体の溶液（固形分濃度４０質量％）４４．０ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．８８ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５５ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル１．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。
[Example 8]
44.0 g of the copolymer solution (solid content concentration 40% by mass), which is the component (A) obtained in Synthesis Example 2, and SP-606 (manufactured by ADEKA Co., Ltd.) as the photoacid generator, which is the component (B). ) and 0.0055 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 1.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate as component (C). It was made into a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens.
［実施例９］
合成例３で得られた（Ａ）成分である共重合体の溶液（固形分濃度４０質量％）４４．０ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．８８ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５５ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル１．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。
[Example 9]
44.0 g of a solution (solid content concentration 40% by mass) of the copolymer as component (A) obtained in Synthesis Example 3, and SP-606 (manufactured by ADEKA Co., Ltd.) as the photoacid generator as component (B). ) and 0.0055 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 1.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate as component (C). It was made into a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens.
［比較例１］
合成例４で得られた共重合体の溶液（固形分濃度３５質量％）４３．５ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．７６ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００４８ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２．３ｇ及びプロピレングリコールモノメチルエーテルアセテート３．４ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本比較例で用いた共重合体は、本発明のマイクロレンズ用感光性樹脂組成物の（Ａ）成分に該当しない。
[Comparative example 1]
43.5 g of the copolymer solution obtained in Synthesis Example 4 (solid content concentration 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and A solution was prepared by dissolving 0.0048 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate as component (C). Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The copolymer used in this comparative example does not correspond to component (A) of the photosensitive resin composition for microlenses of the present invention.
［比較例２］
合成例５で得られた共重合体の溶液（固形分濃度３５質量％）４３．５ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．７６ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００４８ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２．３ｇ及びプロピレングリコールモノメチルエーテルアセテート３．４ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本比較例で用いた共重合体は、本発明のマイクロレンズ用感光性樹脂組成物の（Ａ）成分に該当しない。
[Comparative example 2]
43.5 g of the copolymer solution obtained in Synthesis Example 5 (solid content concentration 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and A solution was prepared by dissolving 0.0048 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate as component (C). Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The copolymer used in this comparative example does not correspond to component (A) of the photosensitive resin composition for microlenses of the present invention.
［比較例３］
合成例６で得られた共重合体の溶液（固形分濃度３５質量％）４３．５ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．７６ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００４８ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２．３ｇ及びプロピレングリコールモノメチルエーテルアセテート３．４ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本比較例で用いた共重合体は、本発明のマイクロレンズ用感光性樹脂組成物の（Ａ）成分に該当しない。
[Comparative example 3]
43.5 g of the copolymer solution obtained in Synthesis Example 6 (solid content concentration 35% by mass), 0.76 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator as component (B), and A solution was prepared by dissolving 0.0048 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant in 2.3 g of propylene glycol monomethyl ether and 3.4 g of propylene glycol monomethyl ether acetate as component (C). Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The copolymer used in this comparative example does not correspond to component (A) of the photosensitive resin composition for microlenses of the present invention.
［比較例４］
合成例１で得られた（Ａ）成分である共重合体１９．０ｇ、（Ｂ）成分である光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０１９ｇ、及び界面活性剤としてＤＦＸ－１８（ネオス（株）製）０．００５７ｇを、（Ｃ）成分であるプロピレングリコールモノメチルエーテル２７．９ｇ及びプロピレングリコールモノメチルエーテルアセテート３．１ｇに溶解させ溶液とした。その後、該溶液を孔径１μｍのポリエチレン製ミクロフィルターを用いてろ過して、マイクロレンズ用感光性樹脂組成物を調製した。本比較例のマイクロレンズ用感光性樹脂組成物の（Ｂ）成分の含有量は、（Ａ）成分１００質量％に対し０．５質量％より少ない。
[Comparative example 4]
19.0 g of the copolymer (A) component obtained in Synthesis Example 1, 0.019 g of SP-606 (manufactured by ADEKA Co., Ltd.) as the photoacid generator (B) component, and as a surfactant. 0.0057 g of DFX-18 (manufactured by Neos Co., Ltd.) was dissolved in 27.9 g of propylene glycol monomethyl ether and 3.1 g of propylene glycol monomethyl ether acetate, which are component (C), to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 1 μm to prepare a photosensitive resin composition for a microlens. The content of component (B) in the photosensitive resin composition for microlenses of this comparative example is less than 0.5% by mass based on 100% by mass of component (A).
［パターン矩形性評価］
実施例１乃至実施例９及び比較例１乃至比較例４で調製したマイクロレンズ用感光性樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上に配置し１００℃で９０秒間プリベークすることにより、膜厚１０μｍの樹脂膜を形成した。前記プリベークは、大気中で実施した。次いで、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）により、バイナリーマスクを介して前記樹脂膜を露光し、次いでホットプレート上に配置し１００℃で９０秒間露光後加熱（Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｅ）を行った。その後、前記樹脂膜を、２．３８質量％濃度の水酸化テトラメチルアンモニウム（ＴＭＡＨ）水溶液を用い５０秒間現像し、超純水で２０秒間リンスし、乾燥した。その結果、パターンが前記シリコンウエハー上に形成された。得られたパターンの断面形状を走査型電子顕微鏡Ｓ－４８００（（株）日立ハイテクノロジーズ製）を用いて観察した。前記パターンの断面形状が矩形でない場合は“×”、前記パターンの断面形状が１０μｍ×１０μｍの矩形である場合は“○”として、パターンの矩形性を評価した。その結果を表１に示す。
[Pattern rectangularity evaluation]
The photosensitive resin compositions for microlenses prepared in Examples 1 to 9 and Comparative Examples 1 to 4 were each applied onto a silicon wafer using a spin coater, placed on a hot plate, and heated at 100°C. By prebaking for 90 seconds, a resin film with a thickness of 10 μm was formed. The prebaking was performed in the atmosphere. Next, the resin film was exposed to light through a binary mask using an i-line stepper NSR-2205i12D (NA=0.63) (manufactured by Nikon Corporation), and then placed on a hot plate and exposed at 100° C. for 90 seconds. Heating (Post Exposure Bake) was performed. Thereafter, the resin film was developed for 50 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), 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 a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). The rectangularity of the pattern was evaluated as "x" if the cross-sectional shape of the pattern was not rectangular, and as "○" if the cross-sectional shape of the pattern was a 10 μm x 10 μm rectangle. The results are shown in Table 1.
［現像後残渣評価］
前記シリコンウエハー上に形成されたパターン周辺の露光部を観察することにより、現像後の残渣を評価した。前記パターンが形成されていない露光部に残渣が多く観察される場合は“×”、該パターンが形成されていない露光部に残渣は観察されないが該パターンの裾部に残渣が観察される場合は“△”、該パターンが形成されていない露光部及び該パターンの裾部に全く残渣が観察されない場合は“○”として、現像後残渣を評価した。評価結果を表１に示す。
[Post-development residue evaluation]
The residue after development was evaluated by observing the exposed area around the pattern formed on the silicon wafer. If a lot of residue is observed in the exposed area where the pattern is not formed, mark it as "x". If no residue is observed in the exposed area where the pattern is not formed, but residue is observed at the bottom of the pattern, mark it as "x". The residue after development was evaluated as "△" and "○" when no residue was observed in the exposed area where the pattern was not formed and the bottom of the pattern. The evaluation results are shown in Table 1.
［パターンリフロー性評価］
実施例１乃至実施例９、比較例１及び比較例３で調製したマイクロレンズ用感光性樹脂組成物から矩形パターンが形成されたシリコンウエハーを、ホットプレート上に配置し１４０℃で５分間ポストベークを行った。前記ポストベーク後、得られたパターンの断面形状を走査型電子顕微鏡Ｓ－４８００（（株）日立ハイテクノロジーズ製）を用いて観察した。パターンの断面形状が全く変化しない場合は“×”、パターンの断面形状が変化し半円形となる場合は“○”として、パターンのリフロー性を評価した。評価結果を表１に示す。
[Pattern reflow evaluation]
Silicon wafers on which rectangular patterns were formed from the photosensitive resin compositions for microlenses prepared in Examples 1 to 9, Comparative Examples 1 and 3 were placed on a hot plate and post-baked at 140° C. for 5 minutes. I did it. After the post-baking, the cross-sectional shape of the obtained pattern was observed using a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). The reflowability of the pattern was evaluated as "x" if the cross-sectional shape of the pattern did not change at all, and as "○" if the cross-sectional shape of the pattern changed and became semicircular. The evaluation results are shown in Table 1.
［耐溶剤性評価］
実施例１乃至実施例９、比較例１及び比較例３で調製したマイクロレンズ用感光性樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において１００℃で９０秒間プリベークすることにより、膜厚１０μｍの樹脂膜を形成した。次いで、ホットプレート上において１００℃で９０秒間ベークした後、続けて１４０℃で５分間、さらに２２０℃で５分間ポストベークすることにより、前記シリコンウエハー上に硬化膜を形成した。前記プリベーク及びポストベークはいずれも、大気中で実施した。これらの硬化膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、及び２．３８質量％濃度の水酸化テトラメチルアンモニウム（ＴＭＡＨ）水溶液それぞれに、２３℃の温度条件下、５分間浸漬する試験を行った。浸漬前後において前記硬化膜の膜厚変化を測定した。浸漬試験に使用した上記溶剤のうち１つでも、浸漬前の該硬化膜の膜厚に対して５％以上の膜厚増減があった場合は“×”、全ての溶剤について膜厚増減が５％未満であった場合は“○”として、耐溶剤性を評価した。評価結果を表１に示す。
[Solvent resistance evaluation]
The photosensitive resin compositions for microlenses prepared in Examples 1 to 9, Comparative Example 1, and Comparative Example 3 were each applied onto a silicon wafer using a spin coater, and then placed on a hot plate at 100°C for 90 seconds. By prebaking, a resin film with a thickness of 10 μm was formed. Next, a cured film was formed on the silicon wafer by baking on a hot plate at 100° C. for 90 seconds, followed by post-baking at 140° C. for 5 minutes and further at 220° C. for 5 minutes. Both the pre-baking and post-baking were performed in the atmosphere. These cured films were treated with propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and an aqueous solution of tetramethylammonium hydroxide (TMAH) with a concentration of 2.38% by mass at a temperature of 23°C for 5 minutes. A test was conducted in which the sample was immersed for 1 minute. Changes in the thickness of the cured film were measured before and after immersion. If even one of the above-mentioned solvents used in the immersion test had a film thickness increase or decrease of 5% or more with respect to the film thickness of the cured film before immersion, it would be marked "x", and the film thickness increase or decrease of 5% for all solvents. If it was less than %, it was evaluated as "○" and the solvent resistance was evaluated. The evaluation results are shown in Table 1.
表１に示すように、実施例１乃至実施例９で調製したマイクロレンズ用感光性樹脂組成物から形成される樹脂膜は、パターン矩形性、現像後残渣の程度及びパターンリフロー性の点で、優れた結果が得られ、該樹脂膜から形成される硬化膜は、優れた耐溶剤性を示した。
一方、比較例２乃至比較例４で調製したマイクロレンズ用感光性樹脂組成物から形成される樹脂膜は、パターン矩形性、現像後残渣の程度及びパターンリフロー性のいずれかの点で良好な結果が得られず、比較例１のマイクロレンズ用感光性樹脂組成物から形成される硬化膜は、耐溶剤性が低いことが確認され、本発明の優位性が示された。
As shown in Table 1, the resin films formed from the photosensitive resin compositions for microlenses prepared in Examples 1 to 9 had poor pattern rectangularity, degree of post-development residue, and pattern reflowability. Excellent results were obtained, and the cured film formed from the resin film showed excellent solvent resistance.
On the other hand, the resin films formed from the photosensitive resin compositions for microlenses prepared in Comparative Examples 2 to 4 had good results in terms of pattern rectangularity, degree of post-development residue, and pattern reflowability. was not obtained, and it was confirmed that the cured film formed from the photosensitive resin composition for microlenses of Comparative Example 1 had low solvent resistance, demonstrating the superiority of the present invention.
Claims (9)
（Ａ）：下記式（１）で表される構造単位、下記式（２）で表される構造単位及び下記式（３）で表される構造単位を有し、下記式（４ａ）で表される構造単位及び下記式（４ｂ）で表される構造単位のうち少なくとも一方をさらに有し、前記式（１）で表される構造単位、前記式（２）で表される構造単位、前記式（３）で表される構造単位、前記式（４ａ）で表される構造単位及び前記式（４ｂ）で表される構造単位の和１００ｍｏｌ％に対し、前記式（１）で表される構造単位の含有率は１２ｍｏｌ％乃至３０ｍｏｌ％、前記式（２）で表される構造単位の含有率は５ｍｏｌ％乃至４０ｍｏｌ％、前記式（３）で表される構造単位の含有率は５ｍｏｌ％乃至４０ｍｏｌ％、前記式（４ａ）で表される構造単位の含有率は０ｍｏｌ％乃至６０ｍｏｌ％、前記式（４ｂ）で表される構造単位の含有率は０ｍｏｌ％乃至６０ｍｏｌ％である（但し、前記式（４ａ）で表される構造単位の含有率及び前記式（４ｂ）で表される構造単位の含有率がいずれも０ｍｏｌ％である場合を除く。）、重量平均分子量５０００乃至２５０００の共重合体
（Ｂ）：光酸発生剤
（Ｃ）：溶剤
(A): It has 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), and is represented by the following formula (4a). and a structural unit represented by the following formula (4b), the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the above Relative to 100 mol% of the sum of the structural unit represented by formula (3), the structural unit represented by formula (4a), and the structural unit represented by formula (4b), the compound represented by formula (1) The content of structural units is 12 mol% to 30 mol%, the content of structural units represented by formula (2) is 5 mol% to 40 mol%, and the content of structural units represented by formula (3) is 5 mol%. The content of the structural unit represented by the formula (4a) is 0 mol% to 60 mol%, and the content of the structural unit represented by the formula (4b) is 0 mol% to 60 mol% (however, (Excluding the case where the content of the structural unit represented by the above formula (4a) and the content of the structural unit represented by the above formula (4b) are both 0 mol%), a weight average molecular weight of 5000 to 25000. Polymer (B): Photoacid generator (C): Solvent
マスクを通して前記樹脂膜を露光する露光工程、
前記露光工程後の樹脂膜をベークするベーク工程、
前記ベーク工程後の樹脂膜を、アルカリ性現像液を用いて現像する現像工程、
前記現像工程後得られたパターンをリフローさせるリフロー工程、及び
前記リフロー工程後のパターンを硬化させてレンズパターンを形成する工程を有する、マイクロレンズの作製方法。 A step of applying the photosensitive resin composition for a microlens according to any one of claims 1 to 5 on a substrate and prebaking the photosensitive resin composition to form a resin film;
an exposure step 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 method for producing a microlens, comprising a reflow step of reflowing the pattern obtained after the development step, and a step of curing the pattern after the reflow step to form a lens pattern.
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| PCT/JP2020/004145 WO2020175036A1 (en) | 2019-02-25 | 2020-02-04 | Photosensitive resin composition for microlenses |
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| WO2007086249A1 (en) | 2006-01-25 | 2007-08-02 | Nissan Chemical Industries, Ltd. | Positive photosensitive resin composition and cured film obtained therefrom |
| JP2009075329A (en) | 2007-09-20 | 2009-04-09 | Jsr Corp | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
| WO2014126088A1 (en) | 2013-02-13 | 2014-08-21 | 富士フイルム株式会社 | Photosensitive resin composition, production method for cured film using same, cured film, liquid crystal display device, and organic el display device |
| WO2018021049A1 (en) | 2016-07-28 | 2018-02-01 | 日産化学工業株式会社 | Resin composition |
| US20180284609A1 (en) | 2017-03-28 | 2018-10-04 | Promerus, Llc | Photosensitive compositions, color filter and microlens derived therefrom |
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| JP2006337956A (en) | 2005-06-06 | 2006-12-14 | Iwate Toshiba Electronics Co Ltd | Manufacturing method of microlens array |
| JP5696858B2 (en) * | 2010-11-30 | 2015-04-08 | 日産化学工業株式会社 | Photosensitive resin composition for microlenses |
| KR101852528B1 (en) * | 2011-07-07 | 2018-04-27 | 닛산 가가쿠 고교 가부시키 가이샤 | Resin compositions |
| WO2013035569A1 (en) * | 2011-09-05 | 2013-03-14 | 日産化学工業株式会社 | Resin composition |
| CN104870499B (en) * | 2012-12-14 | 2016-11-23 | 昭和电工株式会社 | Copolymer, photosensitive polymer combination containing this copolymer and resin molding |
| KR101856554B1 (en) | 2014-02-20 | 2018-05-10 | 후지필름 가부시키가이샤 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007086249A1 (en) | 2006-01-25 | 2007-08-02 | Nissan Chemical Industries, Ltd. | Positive photosensitive resin composition and cured film obtained therefrom |
| JP2009075329A (en) | 2007-09-20 | 2009-04-09 | Jsr Corp | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
| WO2014126088A1 (en) | 2013-02-13 | 2014-08-21 | 富士フイルム株式会社 | Photosensitive resin composition, production method for cured film using same, cured film, liquid crystal display device, and organic el display device |
| WO2018021049A1 (en) | 2016-07-28 | 2018-02-01 | 日産化学工業株式会社 | Resin composition |
| US20180284609A1 (en) | 2017-03-28 | 2018-10-04 | Promerus, Llc | Photosensitive compositions, color filter and microlens derived therefrom |
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| WO2020175036A1 (en) | 2020-09-03 |
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