CN114397797A - Negative photoresist composition containing nano particles - Google Patents
Negative photoresist composition containing nano particles Download PDFInfo
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- CN114397797A CN114397797A CN202210028765.0A CN202210028765A CN114397797A CN 114397797 A CN114397797 A CN 114397797A CN 202210028765 A CN202210028765 A CN 202210028765A CN 114397797 A CN114397797 A CN 114397797A
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 68
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000004642 Polyimide Substances 0.000 claims abstract description 27
- 229920001721 polyimide Polymers 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 60
- -1 amino, mercapto, carboxyl Chemical group 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- 125000005375 organosiloxane group Chemical group 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 84
- 239000010408 film Substances 0.000 description 63
- 230000015572 biosynthetic process Effects 0.000 description 39
- 239000002904 solvent Substances 0.000 description 37
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 34
- 238000002156 mixing Methods 0.000 description 29
- 239000000654 additive Substances 0.000 description 22
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 20
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 19
- 239000011148 porous material Substances 0.000 description 18
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000001883 metal evaporation Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
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- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- 150000000191 1,4-naphthoquinones Chemical class 0.000 description 1
- VFBJLGFFRRYLLV-UHFFFAOYSA-N 1-(6-benzoyl-9-ethylcarbazol-3-yl)octan-1-one Chemical compound C1=C2C3=CC(C(=O)CCCCCCC)=CC=C3N(CC)C2=CC=C1C(=O)C1=CC=CC=C1 VFBJLGFFRRYLLV-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- CWRBWLKXTXSMEH-UHFFFAOYSA-N 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C CWRBWLKXTXSMEH-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- YQZZHMXSIYMFDK-UHFFFAOYSA-N 2-[bis(2-prop-2-enoyloxyethoxy)phosphoryloxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOP(=O)(OCCOC(=O)C=C)OCCOC(=O)C=C YQZZHMXSIYMFDK-UHFFFAOYSA-N 0.000 description 1
- VVPLLZZDAKVSSO-UHFFFAOYSA-N 2-[bis[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(=O)(OCCOC(=O)C(C)=C)OCCOC(=O)C(C)=C VVPLLZZDAKVSSO-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- AISGCPJYLZUZOS-UHFFFAOYSA-N 2-hydroxy-1,2-bis(2-methylphenyl)ethanone Chemical compound CC1=CC=CC=C1C(O)C(=O)C1=CC=CC=C1C AISGCPJYLZUZOS-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- YJVIKVWFGPLAFS-UHFFFAOYSA-N 9-(2-methylprop-2-enoyloxy)nonyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCOC(=O)C(C)=C YJVIKVWFGPLAFS-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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Abstract
A negative photoresist composition containing nano particles comprises one or more mixtures of acrylic copolymer resin, organic siloxane oligomer and polyimide precursor polymer, nano particles M, acrylic multifunctional monomer with more than two functionalities and photoinitiator. The negative photoresist composition containing the nano particles can form an insulating film with specific hardness, and the nano particles can increase the roughness of the surface of the insulating film, so that the insulating film has excellent adhesion with metal when metal is evaporated on the insulating film, thereby minimizing adverse effects caused by deformation of a flexible plate and remarkably improving the production efficiency.
Description
Technical Field
The present invention relates to a negative photoresist composition for nanoparticles. More particularly, the present invention relates to a nanoparticle-containing negative photoresist composition for forming an insulating film pattern or a protective film pattern of a display element and on which metal is evaporated.
Background
In the display manufacturing process, it is necessary to form an insulating film pattern or a protective film pattern. A photoresist formed using a photosensitive resin composition for forming the insulating film pattern or the protective film pattern. The photoresist composition contains a photoinitiator, so that the photoresist composition can perform a photocuring reaction when irradiated with light.
The photosensitive photoresist composition is firstly coated on a substrate to form a photosensitive resin film. Then, a photolithography process is performed on the photosensitive resin film to form a photosensitive resin film pattern. The photosensitive resin film pattern can be used as an insulating film or a protective film.
The exposure process in the photolithography process may include a crosslinking reaction by photo-curing and thermal curing. After the exposure process is completed, a developing process is performed on the resin film pattern using the dissolution property of the alkaline aqueous solution.
The nanoparticle-containing negative photoresist composition is classified into a POSITIVE TYPE (POSITIVE TYPE) and a negative TYPE (NEGATIVE TYPE) according to the solubility of the photosensitive part to the aqueous alkaline solution in the developing process. The Positive (Positive) photoresist composition contains a photosensitizer diazonaphthoquinone (diazonaphthoquinone), and the azo group of the diazonaphthoquinone is red, so that the Positive photoresist has low light transmittance, and the Positive photoresist can be damaged by an organic solvent. Therefore, how to form an organic insulating film using a negative (negative) photoresist composition is a hot spot of research.
With the development of display technology, especially the continuous update of flexible display technology, the negative photoresist composition requires the deposition of metal on the surface of an organic insulating film formed on a flexible substrate to form a designed circuit. However, the conventional negative resin has poor adhesion to metal after being cured into an insulating film, and the metal circuit is easily detached from the surface thereof, thereby causing a problem that the metal circuit is broken when the flexible substrate is deformed.
Therefore, there is a need to develop a negative photoresist material capable of achieving evaporation of metal on the surface of an insulating film and having good adhesion to the metal.
Disclosure of Invention
Technical problem
The invention aims to provide a negative photoresist composition containing nano particles, which can realize metal evaporation on the surface of an insulating film and has good adhesion with metal.
Technical scheme
An embodiment of the invention provides a negative photoresist composition containing nanoparticles for a metal evaporation underlayer, comprising: a nanoparticle-containing negative photoresist composition, comprising: a resin matrix composed of one or more of an acrylic copolymer resin represented by chemical formula 1, an organosiloxane oligomer represented by one or more of chemical formulae 2A, 2B, and 2C, a polyimide precursor polymer represented by chemical formula 3, nanoparticles M represented by chemical formula 4, an acrylic multifunctional monomer having two or more functionalities, and a photoinitiator,
[ chemical formula 1]
Wherein R1, R2, R3 and R4 in the chemical formula 1 are represented by the following chemical formula 5, m ranges from 0 to 100, the weight average molecular weight of the acrylic copolymer resin is 1000-50000,
[ chemical formula 2A ]
[ chemical formula 2B ]
[ chemical formula 2C ]
Wherein X in the chemical formulas 2A, 2B and 2C are respectively and independently selected from R1, R2, R3 and R4 shown in the chemical formula 5, n in the chemical formula 2A ranges from 5 to 100, the weight average molecular weight of the organic siloxane oligomer is 500-50000,
[ chemical formula 3]
Wherein A is1、A2Each independently selected from R1, R2, R3 and R4 shown in chemical formula 5, n ranges from 1 to 100, and the weight average molecular weight of the polyimide precursor polymer is 1000-20000, X1Is 1-20 atoms and contains C, S, O, Si, C (CF)3)2A chain aliphatic chain or an aromatic chain of (a),
[ chemical formula 4]
Wherein n ranges from 0 to 1000000,
wherein R5 is a chain structure containing one or more of C, O, Si and S elements and having a weight average molecular weight of 0-5000, R6 is a terminal group selected from epoxy, amino, mercapto, carboxyl, phosphate, sulfonic acid and hydroxyl,
[ chemical formula 5]
R1:-H,-CH3
R3,R4:
Wherein, X1Is 1-20 atoms and contains C, S, O, Si, C (CF)3)2A chain aliphatic chain or an aromatic chain of (a),
wherein X in chemical formula 31And X in chemical formula 51The same is true.
The nanoparticles M in the nanoparticle-containing negative photoresist composition may include SiO2、C aO、CaCO3、TiO2、BaSO4、Al2O3、ZrO2、MgO、ZnO、Fe2O3、Fe3O4And Cu O, and the diameter of the nano particles M is in the range of 1-100 nm.
The photoinitiator of the nanoparticle-containing negative photoresist composition may include at least one of an O-acyl oxime-based photoinitiator, an acetophenone-based photoinitiator, and a benzophenone-based photoinitiator.
The negative photoresist composition containing the nano particles can also comprise at least one of a leveling agent, a curing agent and a silane coupling agent.
In the negative photoresist composition containing nanoparticles, the nanoparticles M range from 0.0001 to 30 parts by weight relative to 100 parts by weight of the resin matrix.
In the nanoparticle-containing negative photoresist composition, the acrylic multifunctional monomer is in the range of 50 to 150 parts by weight with respect to 100 parts by weight of the resin matrix.
In the negative photoresist composition containing the nanoparticles, the photoinitiator of the negative photoresist composition containing the nanoparticles comprises 0.1 to 10.0 parts by weight of an O-acyl oxime photoinitiator, 0.1 to 10.0 parts by weight of a benzophenone photoinitiator, and 0.1 to 10.0 parts by weight of at least one of the benzophenone photoinitiator, and the acetophenone photoinitiator, based on 100 parts by weight of the resin matrix.
In the negative photoresist composition containing nanoparticles, the weight average molecular weight (M w) of the resin matrix is 500 to 200000.
The nanoparticle-containing negative-working photoresist composition is configured to be developed in an aqueous alkaline solution to obtain a specific photoresist pattern.
Technical effects
The negative photoresist composition containing nano-particles of the invention can form an insulating film with specific hardness. Since the nanoparticles can increase the roughness of the surface of the insulating film, the insulating film has excellent adhesion to the metal when the metal is deposited thereon. By adopting the photoresist composition, adverse effects caused by deformation of the flexible plate can be minimized, and the production efficiency is obviously improved.
Drawings
Fig. 1 is a surface scanning electron micrograph of a developed pattern formed using a negative photoresist composition containing nanoparticles of an example.
Detailed Description
The following examples are given to illustrate the present invention. However, the embodiments of the present invention may be modified into various other forms, and therefore, the scope of the present invention is not limited to the following embodiments.
The negative photoresist composition containing the nano particles comprises the following components:
[A] acrylic copolymer
The acrylic copolymer may be represented by the following chemical formula 1.
[ chemical formula 1]
Wherein, R1 is hydrogen or methyl, R2 is benzene or p-hydroxybenzene, R3, R4 can be hydrogen, hydroxyl, methyl, phenyl, epoxy-containing, vinyl-containing, (meth) acryloxy-containing, carboxyl-containing, hydroxyl-containing, amine-containing aliphatic side chains, and specifically, refer to the structural formula in chemical formula 5. Wherein, the selection of R1, R2, R3 and R4, namely the size of the groups, the space position of the groups and the like do not influence the formation of the insulating film, and the nanoparticles can increase the roughness of the surface of the insulating film, thereby leading the insulating film and the metal to have excellent adhesion.
[B] Organosiloxane oligomers
The organosiloxane oligomer may be represented by the following chemical formulas 2A, 2B, 2C.
[ chemical formula 2A ]
[ chemical formula 2B ]
[ chemical formula 2C ]
Wherein X in the chemical formulas 2A, 2B and 2C are each independently selected from R1, R2, R3 and R4 shown in the chemical formula 5, n in the chemical formula 2A ranges from 5 to 100, and the weight average molecular weights of the organosiloxane oligomers shown in the chemical formulas 2A, 2B and 2C are all 500-50000. The technical effects can be realized by using the three substances 2A, 2B and 2C in any combination. Also, the selection of each optional group in the organosiloxane oligomer, etc. does not affect the formation of the insulating film, and the nanoparticles can increase the roughness of the surface of the insulating film, thereby enabling excellent adhesion between the insulating film and the metal.
[C] Polyimide precursor polymer
The polyimide precursor polymer may be represented by the following chemical formula 3.
[ chemical formula 3]
Wherein A is1、A2Each independently selected from R1, R2, R3 and R4 shown in chemical formula 5, n of the oligomer shown in chemical formula 3 is 1-100, weight average molecular weight is 1000-20000, X1Is 1-20 atoms and contains C, S, O, Si, C (CF)3)2A chain aliphatic chain or an aromatic chain. Similarly, the selection of various optional groups in the polyimide precursor polymer and the like do not influence the formation of the insulating film, and the nanoparticles can increase the roughness of the surface of the insulating film, so that the insulating film and the metal have excellent adhesion.
X1The following may be included: -CH2-,-S-,-O-,-C(CF3)2-, -Si-, -O-Si-, and aromatic-containing structures. Wherein the aromatic containing structure may include: phenyl, biphenyl, fluorene.
The acrylic copolymer resin (a) represented by the above chemical formula 1, the organosiloxane oligomer (B) represented by the chemical formulae 2A, 2B, and 2C, and the polyimide precursor polymer (C) represented by the chemical formula 3 may be used alone or in combination of two or more to form a resin matrix. The selection of any combination and the like do not influence the formation of the insulating film, and the nanoparticles can increase the roughness of the surface of the insulating film, so that the insulating film and the metal have excellent adhesion. Any two or three of A, B and C are mixed, the range is 0-100%, namely the mixture can be mixed at any proportion.
[D] Nanoparticles
[ chemical formula 4]
Wherein the nanoparticles comprise SiO2、CaO、CaCO3、TiO2、BaSO4、Al2O3、ZrO2、MgO、ZnO、Fe2O3、Fe3O4One or more of CuO and the like are mixed and used, and the diameter range of the nano particles is 1-100 nm. The content and the particle size of the nano particles can influence the storage stability and the transmittance of the product, and the smaller the particle size is, the better the dispersion is and the better the storage stability and the transmittance are. In the surface modification component, R5 is one or more elements of oxygen, silicon, sulfur, carbon and the like, a chain structure with the weight average molecular weight of 0-5000 is contained in the chain, and R6 is an end group selected from epoxy, amino, sulfydryl, carboxyl, phosphate, sulfonic acid and hydroxyl.
R5 may include: - (CH)2)n-,-(CH2) n-O-, fatty chains containing-COO-ester groups, -O-Si (C H)3)n-(CH2)n-,-O-Si-,-S-,-O-,-C(CF3)2And aromatic-containing chain structures, wherein n is in the range: between 0 and 500, the aromatic-containing chain structure may include: phenyl, biphenyl, fluorene.
The selection of each optional group in the nano particles does not influence the formation of the insulating film, and the nano particles can increase the roughness of the surface of the insulating film, so that the insulating film and the metal have excellent adhesion.
[E] Acrylic polyfunctional monomer
Although the acrylic polyfunctional monomer is not particularly limited, a di-or tri-functional or higher (meth) acrylate monomer is preferable because it has good reactivity and the strength of the resulting insulating film is higher, and a tri-or higher (meth) acrylate monomer is particularly preferable.
The difunctional (meth) acrylate-based monomers are, for example: ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, bisphenoxyethanolfluorene diacrylate, bisphenoxyethanolfluorene dimethacrylate, and the like.
The (meth) acrylate monomer having a mesoscopic property or higher includes, for example: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris (2-acryloxyethyl) phosphate, tris (2-methacryloxyethyl) phosphate, and the like. The monofunctional, difunctional or higher (meth) acrylate monomer may be used alone or in combination of two or more.
As for the amount of the acrylic polyfunctional monomer used, 50 to 150 parts by weight, preferably 50 to 120 parts by weight, and most preferably 70 to 100 parts by weight are used per 100 parts by weight of the resin matrix composed of one or more of the acrylic copolymer resin, the organosiloxane oligomer, and the polyimide precursor polymer. When the amount is within this range, the film thickness of the photosensitive resin obtained can be easily controlled, and a high-adhesion and high-sensitivity resin composition having excellent strength and adhesion can be obtained.
[F] Photoinitiator
As one kind of the photoinitiator, O-acyloxime compounds such as ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- [ 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl ] -9H-carbazol-3-yl ] -1- (O-acetyloxime), 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl ] -1, 2-nonane-2-oxime-O-benzoate, and mixtures thereof, 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl ] -1, 2-nonane-2-oxime-O-acetate, 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl ] -1, 2-pentane-2-oxime-O-acetate, 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl ] -octane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-benzoate, processes for their preparation and their use, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-acetate, 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, and the like.
As the O-acyloxime photoinitiator, other photoinitiators may be added in an amount of 50 to 250 parts by weight based on the total weight of the photoinitiator, and for example, acyloximes, acylethers, acetophenones, benzophenones, quinones, halogen compounds, acylphosphine oxides, peroxides, and the like may be used in general.
Examples of the other photoinitiators include benzyl alcohol (benzyl), diacetyl, benzoin, 2-hydroxy-1, 2-bis (2-methylphenyl) ethanone (o-Toluoi), 4-dimethylbenzoic acid (p-Toluoi), anisoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, acetophenone, p-dimethylaminoacetophenone, α '-dimethoxyacetoxybenzophenone, 4-bis- (diethylamino) -benzophenone, 2' -dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) but-1-yl -ketones, anthraquinones, 1, 4-naphthoquinones, phenacyl chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, benzoyl peroxide, di-t-butyl peroxide and the like.
As for the addition amount of the photoinitiator used in the present invention, 0.1 to 10 parts by weight, more preferably 1.0 to 5.0 parts by weight, based on 100 parts by weight of the resin matrix composed of one or more of the acrylic copolymer resin, the organosiloxane oligomer, and the polyimide precursor polymer, is used. When used in this range, a photosensitive resin composition having an excellent balance among heat resistance, solvent resistance and pattern shape controllability after development can be obtained.
[G] Additives [ silane coupling agent (E-1), flatting agent (E-2), thermal polymerization inhibitor and sensitizer
The photosensitive resin composition of the present invention may contain, as required, 0.1 to 5 parts by weight of an additive other than the components [ A ] to [ F ] based on 100 parts by weight of a resin matrix comprising one or more of an acrylic copolymer resin, an organosiloxane oligomer, and a polyimide precursor polymer, within a range not to impair the effects of the present invention.
The additive may employ a silane coupling agent (G-1) which improves adhesion to the substrate. The silane coupling agent may be a silane coupling agent having a reactive functional group such as a carboxyl group, a methylpropanoyl group, an isocyanate group, and an epoxy group, and more specifically, trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 2- (3',4' -epoxycyclohexyl) ethyltrimethoxysilane, and the like. The silane coupling agent may be used singly or in combination. As for the blending amount, 0.1 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight, based on 100 parts by weight of the resin base constituted of one or more of the acrylic copolymer resin, the organosiloxane oligomer and the polyimide precursor polymer, is used.
Another of the above additives is a leveling agent (G-2) for improving coatability. Examples of levelling agents which are marketed are: r-08, R-475, R-30 (manufactured by DIC), BM-1000, BM-1100 (manufactured by BMCHEMI E), FLUORADE FC-135, FLUORADE FC-170C, FLUORADE F C-430, FLUORADE FC-431 (manufactured by Sumitomo 3M Co., Ltd.), SAFLON S-112, SAFLON S-113, SAFLON S-131, SAFLON S-141, SAFLON S-145, fluorine-based or silicon-based surfactants such as SAFLON S-382, SAFLON SC-101, SAFLON SC-102, SAFLON SC-103, SAFLON SC-104, SAFLON SC-105, SAFLON SC-106 (available from Niglass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC190 (available from Toray silica Co., Ltd.). These leveling agents may be used alone or in combination of two or more. Other additives such as thermal polymerization inhibitors and sensitizers may also be used. The amount of the leveling agent, the thermal polymerization inhibitor and the sensitizer is in the range of 0.1 to 3.0 parts by weight based on 100 parts by weight of the resin matrix composed of one or more of an acrylic copolymer resin, an organosiloxane oligomer and a polyimide precursor polymer.
In addition to the above additives, the curable composition further contains an amine curing agent (G-3) and an imidazole curing accelerator. Further, a photosensitizer, a thermal polymerization inhibitor, a defoaming agent, etc. may be used as needed, and the content thereof may be used in a range of 0.1 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight, based on 100 parts by weight of a resin matrix composed of one or more of an acrylic copolymer resin, an organosiloxane oligomer, and a polyimide precursor polymer.
[ Synthesis example 1]
Synthesis of acrylic copolymer [ A1]
After a flask equipped with a mechanical stirrer, a thermometer and a cooling jacket was prepared, 240g of propylene glycol monomethyl ether, 30g of acrylic acid, 50g of methyl methacrylate, 30g of styrene and 2g of azobisisobutyronitrile were added under a nitrogen stream, and then the temperature of the reactor was raised to 65 ℃ to allow the reaction to proceed for 6 hours. Then, the reaction solution was poured into water to obtain a precipitate with water, and the precipitate was dried in a vacuum oven to obtain a polymer resin having a weight average molecular weight of 5000 [ A1 ].
[ Synthesis example 2]
Synthesis of acrylic copolymer [ A2]
After a flask equipped with a mechanical stirrer, a thermometer and a cooling jacket was prepared, 240g of propylene glycol monomethyl ether, 30g of acrylic acid, 50g of methyl methacrylate, 20g of styrene, 20g of glycidyl acrylate and 2g of azobisisobutyronitrile were added under a nitrogen stream, and then the temperature of the reactor was raised to 65 ℃ to allow the reaction to proceed for 10 hours. Then, the reaction mixture was poured into water to obtain a precipitate with water, and the precipitate was dried in a vacuum oven to obtain a polymer resin [ A2] having a weight average molecular weight of 10000.
[ Synthesis example 3]
Synthesis of organosiloxane oligomer [ B1]
Preparing a flask with a mechanical stirrer, a thermometer and a cooling jacket, adding 200g of propylene glycol monomethyl ether, 20g of methyltriethoxysilane, 20g of methyltrimethoxysilane and 20g of phenyltrimethoxysilane under the condition of nitrogen flow, adding 10g of acetic acid and 5g of deionized water at room temperature to perform silane polycondensation reaction, dropwise adding dilute hydrochloric acid in the process, keeping the pH at 4-5, adding 20g of 3-methacryloxypropyltrimethoxysilane after 5 hours of reaction, adding the reactant into methanol after 2 hours of reaction, precipitating, drying in a vacuum drying oven to obtain the organosiloxane oligomer [ B-1] with the weight average molecular weight of 5000
[ Synthesis example 4]
Synthesis of organosiloxane oligomer [ B2]
Preparing a flask with a mechanical stirrer, a thermometer and a cooling jacket, adding 200g of propylene glycol monomethyl ether, 20g of methyltriethoxysilane, 20g of methyltrimethoxysilane, 20g of phenyltrimethoxysilane and 20g of hydroxyl-containing silsesquioxane (POSS) under the nitrogen flow, adding 10g of acetic acid and 5g of deionized water at room temperature to perform silane polycondensation reaction, dropwise adding dilute hydrochloric acid in the process, keeping the pH at 4-5, adding 20g of 3-methacryloxypropyltrimethoxysilane after 5 hours of reaction, adding reactants into methanol after 2 hours of reaction, precipitating, and drying in a vacuum drying oven to obtain the organosiloxane oligomer [ B2] with the weight average molecular weight of 10000
[ Synthesis example 5]
Synthesis of polyimide precursor oligomer [ C1]
20.0g (0.1mol) of 4, 4' -diaminodiphenyl ether was dissolved in 200g of Tetrahydrofuran (THF) under a stream of dry nitrogen gas, and 21.8g (0.1mol) of pyromellitic anhydride and 20g of pyridine were added thereto and reacted at 60 ℃ for 6 hours. After the reaction was completed, the solution was put into 1L of water for precipitation, and the resulting precipitate was collected by filtration. The collected polymer solid was dried by a vacuum drier to obtain a polyimide precursor oligomer having a weight average molecular weight of 2000 [ C1 ].
[ Synthesis example 6]
Synthesis of polyimide precursor oligomer [ C2]
20.0g (0.1mol) of 4,4 '-diaminodiphenyl ether was dissolved in 200g of Tetrahydrofuran (THF) under a stream of dry nitrogen gas, 44.4g (0.1mol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride and 40g of pyridine were added thereto, and the mixture was reacted at 60 ℃ for 10 hours. After the reaction was completed, the solution was put into 1L of water for precipitation, and the resulting precipitate was collected by filtration. The collected polymer solid was dried by a vacuum drier to obtain a polyimide precursor oligomer having a weight average molecular weight of 5000 [ C2 ].
Preparation of negative photoresist composition containing nanoparticles
[ example 1]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer was added [ Synthesis example 1]The resulting acrylic copolymer [ A1]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. On the upper partAfter the components are mixed evenly, 10 parts by weight of 20n m parts of TiO are added2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 2]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, the following composition example 2 was added]The resulting acrylic copolymer [ A2]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed well, 10 parts by weight of 15n m parts of ZrO was added2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 3]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, the following [ Synthesis example 3]]The obtained organosiloxane oligomer [ B1]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of the otherOne of the additives is a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1]]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. Mixing the above components uniformly, adding 10 weight parts of 40nm SiO2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 4]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, Synthesis example 4]The obtained organosiloxane oligomer [ B2]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. Mixing the above components, adding 10 weight parts of 20nm TiO2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 5]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, the following [ Synthesis example 5]]The obtained polyimide precursor [ C1]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiatorEthanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, 10 parts by weight of 40n m parts of SiO was added2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 6]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, Synthesis example 6]The obtained polyimide precursor [ C2]]100 parts by weight (solid content), trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha)) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, 10 parts by weight of 20n m parts of TiO was added2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 7]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer was added [ Synthesis example 1]The resulting acrylic copolymer [ A1]]And [ SynthesisExample 3]The obtained organosiloxane Polymer [ B1]]100 parts by weight (solid content) of this mixture, trimethylolpropane triacrylate (product name: TMPTA, Nippon Kagaku Co., Ltd.) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, K EMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. Mixing the above components uniformly, adding 10 weight parts of 40nm SiO2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 8]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer was added [ Synthesis example 1]The resulting acrylic copolymer [ A1]]And [ Synthesis example 5]The obtained polyimide precursor Polymer [ C1]]100 parts by weight (solid matter) of this mixture, trimethylolpropane triacrylate (product name: TMP TA, Nippon Kagaku Co., Ltd.) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) as a photoinitiator [ F-2]]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. Mixing the above componentsAfter homogenization, 10 parts by weight of 40nm SiO were added2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
[ example 9]
To a mixing tank equipped with an ultraviolet ray-blocking film and a stirrer, the following [ Synthesis example 3]]The resulting organosiloxane oligomer [ B1]]And [ Synthesis example 5]The obtained polyimide precursor Polymer [ C1]]100 parts by weight (solid content) of this mixture, trimethylolpropane triacrylate (product name: TMPT A, Nippon Kagaku Co., Ltd.) [ E-1]50 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma strain) as a polyfunctional monomer [ E-2]]40 parts by weight of photoinitiator of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-radical]-1- (O-acetyloxime) (product name: OXE-02, BASF (strain)) [ F-1]]3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EM K, KEMAX (strain)) as a photoinitiator [ F-2]5 parts by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of the other additives]1 part by weight of BYK-333[ G-2] as a leveling agent]After 0.5 part by weight, propylene glycol monomethyl ether acetate as a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. Mixing the above components uniformly, adding 10 weight parts of 40nm SiO2Mixing the nanometer particles uniformly, and filtering by using a microporous filter with the pore diameter of 0.45 mu m to prepare the negative photoresist composition containing the nanometer particles.
The following is a comparative example of a negative photoresist without nanoparticles.
Comparative example 1
100 parts by weight (solid content) of the acrylic copolymer [ A1] obtained in [ Synthesis example 1], 50 parts by weight of trimethylolpropane triacrylate (product name: TMPTA, Kakkiso Co., Ltd.) [ E-1] of a polyfunctional monomer, 40 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Co., Ltd.) [ E-2] of a polyfunctional monomer, 3 parts by weight of ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Co., Ltd.) [ F-1 ]), 3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK) of a photoinitiator, KEMAX (strain)) [ F-2]5 parts by weight, a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1]1 part by weight as one of the other additives, and BYK-333[ G-2]0.5 part by weight as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. The negative photoresist composition containing no nanoparticles was prepared by filtration through a microporous filter having a pore size of 0.45. mu.m.
Comparative example 2
100 parts by weight (solid content) of the acrylic copolymer [ A2] obtained in [ Synthesis example 2], 50 parts by weight of trimethylolpropane triacrylate (product name: TMPTA, Kakkiso Co., Ltd.) [ E-1] of a polyfunctional monomer, 40 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Co., Ltd.) [ E-2] of a polyfunctional monomer, 3 parts by weight of ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Co., Ltd.) [ F-1 ]), 3 parts by weight of 4, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK) of a photoinitiator, KEMAX (strain)) [ F-2]5 parts by weight, a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1]1 part by weight as one of the other additives, and BYK-333[ G-2]0.5 part by weight as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 3
100 parts by weight (solid content) of the organosiloxane oligomer [ B1] obtained in [ Synthesis example 3], 50 parts by weight of trimethylolpropane triacrylate (product name: TMPTA, Nippon Chemicals, Ltd.) [ E-1] of a polyfunctional monomer, 40 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Ltd.) [ E-2] of a polyfunctional monomer, 3 parts by weight of ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Ltd.) [ F-1] of a photoinitiator, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK) of a photoinitiator, KEMAX (strain)) [ F-2]5 parts by weight, a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1]1 part by weight as one of the other additives, and BYK-333[ G-2]0.5 part by weight as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 4
100 parts by weight (solid content) of the organosiloxane oligomer [ B2] obtained in [ Synthesis example 4], 50 parts by weight of trimethylolpropane triacrylate (product name: TMPTA, Nippon Chemicals, Ltd.) [ E-1] of a polyfunctional monomer, 40 parts by weight of dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Ltd.) [ E-2] of a polyfunctional monomer, 3 parts by weight of ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Ltd.) [ F-1] of a photoinitiator, 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK) of a photoinitiator, KEMAX (strain)) [ F-2]5 parts by weight, a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1]1 part by weight as one of the other additives, and BYK-333[ G-2]0.5 part by weight as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 5
100 parts by weight (solid content) of the polyimide precursor polymer [ C1] obtained in [ Synthesis example 5], 50 parts by weight of a polyfunctional monomer trimethylolpropane triacrylate (product name: TMPTA, Kakkiso Co., Ltd.) [ E-1], 40 parts by weight of a polyfunctional monomer dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Co., Ltd.) [ E-2], 3 parts by weight of a photoinitiator ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Co., Ltd.) [ F-1], and 4 parts by weight of a photoinitiator were charged into a mixing tank equipped with an ultraviolet ray blocking film and a stirrer, 5 parts by weight of 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) [ F-2], 1 part by weight of gamma-glycidoxypropyltrimethoxysilane [ G-1] which is a silane coupling agent and 0.5 part by weight of BYK-333[ G-2] which is a leveling agent, and then propylene glycol monomethyl ether acetate which is a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 6
100 parts by weight (solid content) of the polyimide precursor polymer [ C2] obtained in [ Synthesis example 6], 50 parts by weight of a polyfunctional monomer trimethylolpropane triacrylate (product name: TMPTA, Kakkiso Co., Ltd.) [ E-1], 40 parts by weight of a polyfunctional monomer dipentaerythritol pentaacrylate (product name: SR-399NS, Sadoma (Co., Ltd.) [ E-2], 3 parts by weight of a photoinitiator ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (Co., Ltd.) [ F-1], and 4 parts by weight of a photoinitiator were charged into a mixing tank equipped with an ultraviolet ray blocking film and a stirrer, 5 parts by weight of 4-bis- (diethylamino) -benzophenone (product name: Hycure EMK, KEMAX (strain)) [ F-2], 1 part by weight of gamma-glycidoxypropyltrimethoxysilane [ G-1] which is a silane coupling agent and 0.5 part by weight of BYK-333[ G-2] which is a leveling agent, and then propylene glycol monomethyl ether acetate which is a solvent was added while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 7
To a mixing tank equipped with an ultraviolet ray blocking film and a stirrer were added 100 parts by weight (solid content) of the acrylic copolymer [ A1] obtained in [ Synthesis example 1] and the organosiloxane polymer [ B1] obtained in [ Synthesis example 3], 50 parts by weight of trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPTA, Nippon Kabushiki Kaisha) [ E-1], 40 parts by weight of dipentaerythritol pentaacrylate of a polyfunctional monomer (product name: SR-399NS, Saedoma Kabushiki Kaisha) [ E-2], ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) of a photoinitiator (product name: OXE-02, BASF (ltd)) [ F-1]3 parts by weight, 4-bis- (diethylamino) -benzophenone as a photoinitiator (product name: 5 parts by weight of Hycure EMK, K EMAX (available from K.K.) [ F-2], 1 part by weight of gamma-glycidoxypropyltrimethoxysilane [ G-1] as a silane coupling agent as one of other additives, and 0.5 part by weight of BYK-333[ G-2] as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 8
To a mixing tank equipped with an ultraviolet ray blocking film and a stirrer were added 100 parts by weight (solid content) of the acrylic copolymer [ A1] obtained in [ Synthesis example 1] and the polyimide precursor polymer [ C1] obtained in [ Synthesis example 5], 50 parts by weight of trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMP TA, Nippon Kasei Co., Ltd.) [ E-1], 40 parts by weight of dipentaerythritol pentaacrylate of a polyfunctional monomer (product name: SR-399NS, Saedoma Co., Ltd.) [ E-2], ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (ltd)) [ F-1]3 parts by weight, 4-bis- (diethylamino) -benzophenone as a photoinitiator (product name: 5 parts by weight of Hycure EMK, KEMAX (strain)) [ F-2], 1 part by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of other additives, and 0.5 part by weight of BYK-333[ G-2] as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
Comparative example 9
To a mixing tank equipped with an ultraviolet ray blocking film and a stirrer were added 100 parts by weight (solid content) of the silicone copolymer [ B1] obtained in [ Synthesis example 3] and the polyimide precursor polymer [ C1] obtained in [ Synthesis example 5], 50 parts by weight of trimethylolpropane triacrylate of a polyfunctional monomer (product name: TMPT A, Nippon Kabushiki Kaisha) ] [ E-1], 40 parts by weight of dipentaerythritol pentaacrylate of a polyfunctional monomer (product name: SR-399NS, Saedoma Kabushiki Co.) [ E-2], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) of a photoinitiator (product name: OXE-02, BASF (ltd)) [ F-1]3 parts by weight, 4-bis- (diethylamino) -benzophenone as a photoinitiator (product name: 5 parts by weight of Hycure EM K, KEMAX (strain)) [ F-2], 1 part by weight of a silane coupling agent gamma-glycidoxypropyltrimethoxysilane [ G-1] as one of other additives, and 0.5 part by weight of BYK-333[ G-2] as a leveling agent, followed by addition of propylene glycol monomethyl ether acetate as a solvent while stirring. The amount of solvent was adjusted so that the viscosity of the composition was 15 cPs. After the above components were mixed uniformly, the mixture was filtered through a microporous filter having a pore size of 0.45 μm to prepare a negative photoresist composition containing no nanoparticles.
The specific components and their composition ratios are summarized in table 1.
[ TABLE 1]
Wherein the content of the first and second substances,
[D] is nano-particles
[ E-1 ]: trimethylolpropane triacrylate (product name: TMPTA, Nippon Kabushiki Kaisha)),
[ E-2 ]: dipentaerythritol pentaacrylate (product name: SR-399NS, Saedoma (L))
[ F-1 ]: ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (product name: OXE-02, BASF (strain))
[ F-2 ]: 4, 4-bis- (diethylamino) -benzophenone (product name: HYCURE EMK, KEMEX strain)
[G-1]: silane coupling agent (gamma-glycidoxypropyltrimethoxysilane, product name: XIAMERETER)TMOFS-6040 Silane,DOW)
[ G-2 ]: leveling agent (Leveling agent) (product name: BYK-333, BYKCHEMIE (strain))
Forming an insulating film pattern
After the negative photoresist composition solutions of examples 1 to 9 and comparative examples 1 to 9 were spin-coated or slit-coated on one side of a transparent substrate, the coated side was heated (prebaked) to form a thin film.
The transparent substrate for forming a pattern was a glass substrate, and after the composition was applied, it was prebaked at 100 ℃ for 90 seconds, and then the formed film was exposed to light through a photomask having a pattern of 15 μm. After exposure, after development by an aqueous solution of 0.042% (weight fraction) potassium hydroxide at 25 ℃ for 60 seconds, washing with pure water for 1 minute, and heating in an oven at 230 ℃ for 30 minutes to form a pattern, wherein the baking temperature of examples 5, 6, 8, 9 and comparative examples 5, 6, 8, 9 was 300 degrees for 60 minutes.
The following evaluations were carried out on the photosensitive resin compositions prepared in examples and comparative examples.
(1) Evaluation of hardness
The cured film was subjected to a hardness test using a pencil hardness tester using the same cured film as the pattern except that no photomask was used.
The hardness test was carried out by scratching with a standard pencil (Mitsubishi pencil/uni: 1-6H, HB, 1-6B) under a load of 1 kg. Hardness was expressed based on a pencil when no scratch was made. The hardness is preferably HB or more.
(2) Evaluation of adhesion to substrate
The cured film was subjected to the same procedure as the pattern except that no photomask was used, and the adhesion of the cured film to the flexible substrate was tested by a cross-cut test.
The cured film was peeled off from the substrate with a 3M adhesive tape after 100 checkerboard marks were formed on the cured film by the checkerboard tape method using the ATSM-D3359 method. When 100 pieces of the peeled checkerboard were measured, the adhesion was found to be good at 5B. The criteria are shown in table 2 below.
[ TABLE 2]
100 | ≥80 | ≥60 | ≥40 | ≥20 | ≥0% | |
Classification | 5B | 4B | 3B | 2B | 1B | 0 |
Determination | Is excellent in | Failure of the product | Failure of the product | Failure of the product | Failure of the product | Failure of the product |
(3) Evaluation of transmittance
The cured film was patterned identically except that no photomask was used, and the transmittance of the cured film at a wavelength of 400nm was measured using a UV-Vis spectrometer. The light transmittance is preferably 90% or more, and the light transmittance is preferably 90% or less.
(4) Evaluation of Metal adhesion
And (3) after respectively evaporating metal copper, molybdenum, aluminum and titanium with the thickness of 2 microns on the upper layer of the cured film, evaluating the adhesion between the metal on the upper layer of the surface layer and the negative photoresist on the bottom layer by using the same evaluation method as the method (3).
(5) Evaluation of storage stability
The photosensitive resin composition was left in a clean room at 25 ℃ for one week, and the rate of change in viscosity was measured. When the viscosity increase rate is less than 5%, the storage stability is good, and when the viscosity increase rate is 5% or more, the storage stability is poor.
The evaluation results for the items (1) to (5) are shown in [ table 3] and [ table 4 ].
[ TABLE 3]
【4】
Very good: excellent, ●: good, X: it is not good.
Claims (9)
1. A nanoparticle-containing negative photoresist composition, comprising: a resin matrix composed of one or more of an acrylic copolymer resin represented by chemical formula 1, an organosiloxane oligomer represented by one or more of chemical formulae 2A, 2B, and 2C, a polyimide precursor polymer represented by chemical formula 3, nanoparticles M represented by chemical formula 4, an acrylic multifunctional monomer having two or more functionalities, and a photoinitiator,
[ chemical formula 1]
Wherein R1, R2, R3 and R4 in the chemical formula 1 are represented by the following chemical formula 5, m ranges from 0 to 100, the weight average molecular weight of the acrylic copolymer resin is 1000-50000,
[ chemical formula 2A ]
[ chemical formula 2B ]
[ chemical formula 2C ]
Wherein X in the chemical formulas 2A, 2B and 2C are respectively and independently selected from R1, R2, R3 and R4 shown in the chemical formula 5, n in the chemical formula 2A ranges from 5 to 100, the weight average molecular weights of the organosiloxane oligomers shown in the chemical formulas 2A, 2B and 2C are all 500-50000,
[ chemical formula 3]
Wherein A is1、A2Each independently selected from R1, R2, R3 and R4 shown in chemical formula 5, n ranges from 1 to 100, and the weight average molecular weight of the polyimide precursor polymer is 1000-20000, X1Is 1-20 atoms and contains C, S, O, Si, C (CF)3)2A chain aliphatic chain or an aromatic chain of (a),
[ chemical formula 4]
Wherein n ranges from 0 to 1000000,
wherein R5 is a chain structure containing one or more of C, O, Si and S elements and having a weight average molecular weight of 0-5000, R6 is a terminal group selected from epoxy, amino, mercapto, carboxyl, phosphate, sulfonic acid and hydroxyl,
[ chemical formula 5]
R1:-H,-CH3
R3,R4:
Wherein, X1Is 1-20 atoms and contains C, S, O, Si, C (CF)3)2Or an aliphatic chain or an aromatic-containing chain.
2. The nanoparticle-containing negative photoresist composition according to claim 1,
the nanoparticles M comprise SiO2、CaO、CaCO3、TiO2、BaSO4、Al2O3、ZrO2、MgO、ZnO、Fe2O3、Fe3O4And CuO, the diameter of the nano particles M is in the range of 1-100 nm.
3. The nanoparticle-containing negative photoresist composition according to claim 1,
the photoinitiator of the nanoparticle-containing negative photoresist composition comprises at least one of an O-acyl oxime photoinitiator, an acetophenone photoinitiator and a benzophenone photoinitiator.
4. The nanoparticle-containing negative photoresist composition according to claim 1,
the negative photoresist composition containing the nano particles also comprises at least one of a leveling agent, a curing agent and a silane coupling agent.
5. The nanoparticle-containing negative photoresist composition according to claim 1,
the range of the nanoparticles M is 0.0001 to 30 parts by weight with respect to 100 parts by weight of the resin matrix.
6. The nanoparticle-containing negative photoresist composition according to claim 1,
the acrylic multifunctional monomer ranges from 50 to 150 parts by weight with respect to 100 parts by weight of the resin matrix.
7. The nanoparticle-containing negative photoresist composition according to claim 3,
the photoinitiator of the negative photoresist composition containing the nanoparticles comprises an O-acyl oxime photoinitiator, an acetophenone photoinitiator and a benzophenone photoinitiator, wherein the content of the O-acyl oxime photoinitiator is 0.1 to 10.0 parts by weight, and the content of at least one of the acetophenone photoinitiator and the benzophenone photoinitiator is 0.1 to 10.0 parts by weight, relative to 100 parts by weight of the resin matrix.
8. The nanoparticle-containing negative photoresist composition according to claim 1,
the weight average molecular weight (Mw) of the resin matrix is 500 to 200000.
9. The nanoparticle-containing negative-working photoresist composition of claim 1, wherein the nanoparticle-containing negative-working photoresist composition is configured to be developed in an aqueous alkaline solution to obtain a particular photoresist pattern.
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JP2018120069A (en) * | 2017-01-25 | 2018-08-02 | 東レ株式会社 | Negative photosensitive resin composition, cured film and touch panel member |
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US20080311308A1 (en) * | 2004-08-13 | 2008-12-18 | Hae-Wook Lee | Composition for Functional Coatings, Film Formed Therefrom and Method for Forming the Composition and the Film |
JP2009020520A (en) * | 2007-07-16 | 2009-01-29 | Korea Electrotechnology Research Inst | Organic-inorganic hybrid photosensitive resin composition and liquid crystal display element using cured product thereof |
JP2010013572A (en) * | 2008-07-04 | 2010-01-21 | Nippon Kayaku Co Ltd | Photosensitive resin composition and antireflection film |
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