WO2011114995A1 - Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component - Google Patents
Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component Download PDFInfo
- Publication number
- WO2011114995A1 WO2011114995A1 PCT/JP2011/055680 JP2011055680W WO2011114995A1 WO 2011114995 A1 WO2011114995 A1 WO 2011114995A1 JP 2011055680 W JP2011055680 W JP 2011055680W WO 2011114995 A1 WO2011114995 A1 WO 2011114995A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- photosensitive resin
- silane coupling
- coupling agent
- negative photosensitive
- Prior art date
Links
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 80
- 239000011342 resin composition Substances 0.000 title claims description 109
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 76
- 239000000243 solution Substances 0.000 description 57
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 53
- 239000011259 mixed solution Substances 0.000 description 46
- -1 sheets Substances 0.000 description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- 238000011156 evaluation Methods 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 238000011161 development Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 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 10
- 239000002253 acid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 208000009322 hypertrophic pyloric stenosis Diseases 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 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 3
- XONHRWVRGDYLMG-UHFFFAOYSA-N 3-(tert-butylcarbamoyl)-6-trimethoxysilylhexanoic acid Chemical compound CO[Si](OC)(OC)CCCC(CC(O)=O)C(=O)NC(C)(C)C XONHRWVRGDYLMG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 2
- WGQGVNPPSCMSLJ-UHFFFAOYSA-N 2-[2-(tert-butylamino)-2-oxoethyl]-5-triethoxysilylpentanoic acid Chemical compound C(C)(C)(C)NC(CC(C(=O)O)CCC[Si](OCC)(OCC)OCC)=O WGQGVNPPSCMSLJ-UHFFFAOYSA-N 0.000 description 2
- UDKNOHSXYQTBOS-UHFFFAOYSA-N 2-[2-oxo-2-(propan-2-ylamino)ethyl]-5-trimethoxysilylpentanoic acid Chemical compound C(C)(C)NC(CC(C(=O)O)CCC[Si](OC)(OC)OC)=O UDKNOHSXYQTBOS-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
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- XSGRJZPPQFXMIX-UHFFFAOYSA-N 3-(2-methylbutan-2-ylcarbamoyl)-6-trimethoxysilylhexanoic acid Chemical compound C(C)(C)(CC)NC(=O)C(CC(=O)O)CCC[Si](OC)(OC)OC XSGRJZPPQFXMIX-UHFFFAOYSA-N 0.000 description 2
- YKJUEVDNMCEERC-UHFFFAOYSA-N 3-(propan-2-ylcarbamoyl)-6-trimethoxysilylhexanoic acid Chemical compound C(C)(C)NC(=O)C(CC(=O)O)CCC[Si](OC)(OC)OC YKJUEVDNMCEERC-UHFFFAOYSA-N 0.000 description 2
- WQHJTHWEUSYDPW-UHFFFAOYSA-N 3-(tert-butylcarbamoyl)-6-triethoxysilylhexanoic acid Chemical compound C(C)(C)(C)NC(=O)C(CC(=O)O)CCC[Si](OCC)(OCC)OCC WQHJTHWEUSYDPW-UHFFFAOYSA-N 0.000 description 2
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 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 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MRJXZRBBFSDWFR-UHFFFAOYSA-N diethoxy-methyl-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethoxy]silane Chemical compound C1C(C(C)O[Si](C)(OCC)OCC)CCC2OC21 MRJXZRBBFSDWFR-UHFFFAOYSA-N 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical group CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- PBDDFKGMGASJHE-UHFFFAOYSA-N dimethoxy-methyl-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxy)silane Chemical compound C1C(CO[Si](C)(OC)OC)CCC2OC21 PBDDFKGMGASJHE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000013212 metal-organic material Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QAEDNLDMOUKNMI-UHFFFAOYSA-O (4-hydroxyphenyl)-dimethylsulfanium Chemical compound C[S+](C)C1=CC=C(O)C=C1 QAEDNLDMOUKNMI-UHFFFAOYSA-O 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- FPWTYNVSDHXYDF-UHFFFAOYSA-N 1-[4-(sulfanylmethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(CS)C=C1 FPWTYNVSDHXYDF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PBNDUFBHPISRDY-UHFFFAOYSA-N 2-(3-phenylprop-2-enoxymethyl)oxirane Chemical compound C=1C=CC=CC=1C=CCOCC1CO1 PBNDUFBHPISRDY-UHFFFAOYSA-N 0.000 description 1
- AHNLTPNNRFETEC-UHFFFAOYSA-N 2-(3-trimethoxysilylpropyl)butanedioic acid Chemical compound CO[Si](OC)(OC)CCCC(C(O)=O)CC(O)=O AHNLTPNNRFETEC-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- VQMHSKWEJGIXGA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O VQMHSKWEJGIXGA-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- WZYITJZDLDRVAK-UHFFFAOYSA-N 2-(tert-butylcarbamoyl)-5-(2-trimethoxysilylethyl)cyclohexane-1-carboxylic acid Chemical compound C(C)(C)(C)NC(=O)C1C(CC(CC1)CC[Si](OC)(OC)OC)C(=O)O WZYITJZDLDRVAK-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 1
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 1
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 1
- AJJLBMIIDVIQIA-UHFFFAOYSA-N 2-[1-(2-ethenylphenyl)ethoxymethyl]oxirane Chemical compound C=1C=CC=C(C=C)C=1C(C)OCC1CO1 AJJLBMIIDVIQIA-UHFFFAOYSA-N 0.000 description 1
- WZPIYCSDWSSKRZ-UHFFFAOYSA-N 2-[1-(3-ethenylphenyl)ethoxymethyl]oxirane Chemical compound C=1C=CC(C=C)=CC=1C(C)OCC1CO1 WZPIYCSDWSSKRZ-UHFFFAOYSA-N 0.000 description 1
- GBQNGHNVAOQHBN-UHFFFAOYSA-N 2-[1-(4-ethenylphenyl)ethoxymethyl]oxirane Chemical compound C=1C=C(C=C)C=CC=1C(C)OCC1CO1 GBQNGHNVAOQHBN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- NXEOWHHSWZHJPU-UHFFFAOYSA-N 2-[2-(2-methylbutan-2-ylamino)-2-oxoethyl]-5-trimethoxysilylpentanoic acid Chemical compound C(C)(C)(CC)NC(CC(C(=O)O)CCC[Si](OC)(OC)OC)=O NXEOWHHSWZHJPU-UHFFFAOYSA-N 0.000 description 1
- XEWRMLCETSBBCQ-UHFFFAOYSA-N 2-[2-oxo-2-(propylamino)ethyl]-5-trimethoxysilylpentanoic acid Chemical compound O=C(CC(C(=O)O)CCC[Si](OC)(OC)OC)NCCC XEWRMLCETSBBCQ-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- BWONDYSHSJIGBM-UHFFFAOYSA-N 2-[[2-ethenyl-3,5-bis(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C1=C(COCC2OC2)C=C(COCC2OC2)C(C=C)=C1COCC1CO1 BWONDYSHSJIGBM-UHFFFAOYSA-N 0.000 description 1
- DZYCUUFNXNXWBU-UHFFFAOYSA-N 2-[[2-ethenyl-3,6-bis(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C1=CC(COCC2OC2)=C(COCC2OC2)C(C=C)=C1COCC1CO1 DZYCUUFNXNXWBU-UHFFFAOYSA-N 0.000 description 1
- NAHOABUATCSPEQ-UHFFFAOYSA-N 2-[[2-ethenyl-3-(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C1=CC=C(COCC2OC2)C(C=C)=C1COCC1CO1 NAHOABUATCSPEQ-UHFFFAOYSA-N 0.000 description 1
- LOXIWIOCGARHCY-UHFFFAOYSA-N 2-[[2-ethenyl-4-(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C=1C=C(COCC2OC2)C(C=C)=CC=1COCC1CO1 LOXIWIOCGARHCY-UHFFFAOYSA-N 0.000 description 1
- JHLMJWVEODHXFB-UHFFFAOYSA-N 2-[[3-ethenyl-2,6-bis(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1=C(COCC2OC2)C(C=C)=CC=C1COCC1CO1 JHLMJWVEODHXFB-UHFFFAOYSA-N 0.000 description 1
- HBJKAXHCQPNZBZ-UHFFFAOYSA-N 2-[[4-ethenyl-2,6-bis(oxiran-2-ylmethoxymethyl)phenyl]methoxymethyl]oxirane Chemical compound C1OC1COCC=1C(COCC2OC2)=CC(C=C)=CC=1COCC1CO1 HBJKAXHCQPNZBZ-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229940013085 2-diethylaminoethanol Drugs 0.000 description 1
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- JPEIGKQUFGYBSU-UHFFFAOYSA-N 3-(2-methylpropylcarbamoyl)-6-trimethoxysilylhexanoic acid Chemical compound C(C(C)C)NC(=O)C(CC(=O)O)CCC[Si](OC)(OC)OC JPEIGKQUFGYBSU-UHFFFAOYSA-N 0.000 description 1
- JRGQKLFZSNYTDX-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOCC1CO1 JRGQKLFZSNYTDX-UHFFFAOYSA-N 0.000 description 1
- DAJFVZRDKCROQC-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tripropoxysilane Chemical compound CCCO[Si](OCCC)(OCCC)CCCOCC1CO1 DAJFVZRDKCROQC-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- IOSONAGXTXMCDY-UHFFFAOYSA-N 4-(benzylsulfanylmethyl)phenol Chemical compound C1=CC(O)=CC=C1CSCC1=CC=CC=C1 IOSONAGXTXMCDY-UHFFFAOYSA-N 0.000 description 1
- VVSRECWZBBJOTG-UHFFFAOYSA-N 4-Hydroxy-3-methyl-2-butanone Chemical compound OCC(C)C(C)=O VVSRECWZBBJOTG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- STCQADFDVULNEN-UHFFFAOYSA-N 4-[(2-methylphenyl)methylsulfanylmethyl]phenol Chemical compound CC1=CC=CC=C1CSCC1=CC=C(O)C=C1 STCQADFDVULNEN-UHFFFAOYSA-N 0.000 description 1
- KOIXTNPKJXMOMW-UHFFFAOYSA-N 4-ethoxy-4-oxo-2-trimethoxysilylbutanoic acid Chemical compound C(C)OC(CC(C(=O)O)[Si](OC)(OC)OC)=O KOIXTNPKJXMOMW-UHFFFAOYSA-N 0.000 description 1
- JSHPTIGHEWEXRW-UHFFFAOYSA-N 5-hydroxypentan-2-one Chemical compound CC(=O)CCCO JSHPTIGHEWEXRW-UHFFFAOYSA-N 0.000 description 1
- OKIDBAXESNNOLZ-UHFFFAOYSA-N 7-[2-(tert-butylcarbamoyl)-4-(2-trimethoxysilylethyl)cyclohexyl]heptanoic acid Chemical compound CC(C)(C)NC(=O)C1CC(CCC1CCCCCCC(=O)O)CC[Si](OC)(OC)OC OKIDBAXESNNOLZ-UHFFFAOYSA-N 0.000 description 1
- YMKUUZGDKGHFIV-UHFFFAOYSA-N 7-[2-(tert-butylcarbamoyl)-5-(2-trimethoxysilylethyl)cyclohexyl]heptanoic acid Chemical compound CC(C)(C)NC(=O)C1CCC(CC1CCCCCCC(=O)O)CC[Si](OC)(OC)OC YMKUUZGDKGHFIV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- LVUDWRFBOPCJHC-UHFFFAOYSA-N C(C)(C)(C)N1C(C(CC1=O)[Si](OC)(OC)OC)=O Chemical compound C(C)(C)(C)N1C(C(CC1=O)[Si](OC)(OC)OC)=O LVUDWRFBOPCJHC-UHFFFAOYSA-N 0.000 description 1
- DJFXEDBWOCBVPC-UHFFFAOYSA-N C(C1CO1)OCC1=C(C=C)C=CC(=C1)COCC1CO1.C(C1CO1)OCC1=C(C=C)C=CC=C1COCC1CO1 Chemical compound C(C1CO1)OCC1=C(C=C)C=CC(=C1)COCC1CO1.C(C1CO1)OCC1=C(C=C)C=CC=C1COCC1CO1 DJFXEDBWOCBVPC-UHFFFAOYSA-N 0.000 description 1
- OQJZNTGVKQBTQX-UHFFFAOYSA-N C1(=CC=CC=C1)NC(CC(C(=O)O)CCC[Si](OC)(OC)OC)=O Chemical compound C1(=CC=CC=C1)NC(CC(C(=O)O)CCC[Si](OC)(OC)OC)=O OQJZNTGVKQBTQX-UHFFFAOYSA-N 0.000 description 1
- ZHNLKUPMNNABSY-UHFFFAOYSA-N CC(CCC[Si](OC)(OC)OC)CC(=O)NC(C)(C)C Chemical compound CC(CCC[Si](OC)(OC)OC)CC(=O)NC(C)(C)C ZHNLKUPMNNABSY-UHFFFAOYSA-N 0.000 description 1
- SXNICUVVDOTUPD-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 SXNICUVVDOTUPD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- BRHJUILQKFBMTL-UHFFFAOYSA-N [4,4-bis(dimethylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound C1=CC(N(C)C)(N(C)C)CC=C1C(=O)C1=CC=CC=C1 BRHJUILQKFBMTL-UHFFFAOYSA-N 0.000 description 1
- VFXVSCAZEBOMCW-UHFFFAOYSA-N [4-[(2-methylphenyl)methylsulfanylmethyl]phenyl] benzoate Chemical compound CC1=CC=CC=C1CSCC(C=C1)=CC=C1OC(=O)C1=CC=CC=C1 VFXVSCAZEBOMCW-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
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- HFLZEANEEYUWOE-UHFFFAOYSA-N anthracen-1-yl(trimethoxy)silane Chemical compound C1=CC=C2C=C3C([Si](OC)(OC)OC)=CC=CC3=CC2=C1 HFLZEANEEYUWOE-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 239000006227 byproduct Substances 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- JJFFNQSUUAIWHB-UHFFFAOYSA-N carbamic acid;prop-2-enoic acid Chemical compound NC(O)=O.OC(=O)C=C JJFFNQSUUAIWHB-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- 150000002170 ethers Chemical class 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- XPKFLEVLLPKCIW-UHFFFAOYSA-N ethyl 4-(diethylamino)benzoate Chemical compound CCOC(=O)C1=CC=C(N(CC)CC)C=C1 XPKFLEVLLPKCIW-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical compound CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 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
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FQYWWLSIKWDAEC-UHFFFAOYSA-N tributoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOCC1CO1 FQYWWLSIKWDAEC-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BOVWGKNFLVZRDU-UHFFFAOYSA-N triethoxy(trifluoromethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)F BOVWGKNFLVZRDU-UHFFFAOYSA-N 0.000 description 1
- OHKFEBYBHZXHMM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CCC)OCC1CO1 OHKFEBYBHZXHMM-UHFFFAOYSA-N 0.000 description 1
- SJQPASOTJGFOMU-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)C(C)OCC1CO1 SJQPASOTJGFOMU-UHFFFAOYSA-N 0.000 description 1
- NFRRMEMOPXUROM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CC)OCC1CO1 NFRRMEMOPXUROM-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- FVMMYGUCXRZVPJ-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(CC)OCC1CO1 FVMMYGUCXRZVPJ-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- NLKPPXKQMJDBFO-UHFFFAOYSA-N triethoxy-[3-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(CCC[Si](OCC)(OCC)OCC)CCC2OC21 NLKPPXKQMJDBFO-UHFFFAOYSA-N 0.000 description 1
- KPNCYSTUWLXFOE-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC(C)OCC1CO1 KPNCYSTUWLXFOE-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- PSUKBUSXHYKMLU-UHFFFAOYSA-N triethoxy-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](OCC)(OCC)OCC)CCC2OC21 PSUKBUSXHYKMLU-UHFFFAOYSA-N 0.000 description 1
- GSUGNQKJVLXBHC-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCOCC1CO1 GSUGNQKJVLXBHC-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- ORVBHOQTQDOUIW-UHFFFAOYSA-N trimethoxy(trifluoromethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)F ORVBHOQTQDOUIW-UHFFFAOYSA-N 0.000 description 1
- FFJVMNHOSKMOSA-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCCC([Si](OC)(OC)OC)OCC1CO1 FFJVMNHOSKMOSA-UHFFFAOYSA-N 0.000 description 1
- DAVVOFDYOGMLNQ-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)C(C)OCC1CO1 DAVVOFDYOGMLNQ-UHFFFAOYSA-N 0.000 description 1
- FNBIAJGPJUOAPB-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)C(CC)OCC1CO1 FNBIAJGPJUOAPB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- KKFKPRKYSBTUDV-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CC(CC)OCC1CO1 KKFKPRKYSBTUDV-UHFFFAOYSA-N 0.000 description 1
- HTVULPNMIHOVRU-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C)OCC1CO1 HTVULPNMIHOVRU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- ZOWVSEMGATXETK-UHFFFAOYSA-N trimethoxy-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](OC)(OC)OC)CCC2OC21 ZOWVSEMGATXETK-UHFFFAOYSA-N 0.000 description 1
- GUKYSRVOOIKHHB-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCOCC1CO1 GUKYSRVOOIKHHB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000012953 triphenylsulfonium Substances 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
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- G02B1/105—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Definitions
- the present invention relates to a resin composition for forming a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film such as a touch panel sensor element, or an interlayer insulating film of a semiconductor element.
- TFT thin film transistor
- the present invention relates to a silane coupling agent suitable for the above.
- it is related with the negative photosensitive composition using the same, the cured film formed from it, and the member for touch panels which has the cured film.
- hard coat materials there are various uses for hard coat materials. For example, it is used to improve the surface hardness of automobile parts, containers for cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat material include heat resistance, weather resistance, adhesiveness, etc. in addition to hardness and scratch resistance.
- a radical polymerization type UV curable hard coat material for example, see Non-Patent Document 1.
- the composition of the hard coat material is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives.
- Oligomer and monomer are cross-linked by radical polymerization by UV irradiation to obtain a high hardness film. Since this hard coat material requires a short time for curing, use of this hard coat material improves productivity. Furthermore, since a negative photosensitive material having a general radical polymerization mechanism can be used, there is an advantage that the manufacturing cost is reduced.
- the capacitive touch panel which has been attracting attention in recent years, is one of the uses of hard coat materials.
- the capacitance type touch panel has a pattern made of an ITO (Indium Tin Oxide) film on glass.
- ITO Indium Tin Oxide
- a film having high hardness is required.
- a method of adding a silane coupling agent is well known.
- a silane coupling agent having an imide group see Patent Document 1 and Patent Document 2
- Patent Document 3 a silane coupling agent suitable for the heat resistant resin precursor composition
- a compound having a carboxyl group and an ester group or a carboxyl group and an amide group see Patent Document 3
- organosilicon compound having an amic acid structure has a structure in which an amino group-containing silane coupling agent is added to an aromatic ring anhydride.
- This organosilicon compound is strongly colored and is not suitable for touch panel applications, and the adhesion-improving curing is not sufficient.
- An object of the present invention is to provide a cured film having excellent adhesion to a substrate surface composed of metal or inorganic material, high hardness, and excellent resolution. Furthermore, another object of the present invention is to provide a cured film having a low curing shrinkage rate and good flatness.
- the present invention has the following configuration. That is, it is a silane coupling agent represented by the following general formula (1).
- Each R 1 may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.
- the alkyl group may further have a substituent.
- N represents 0 or 1.
- R 2 represents carbon.
- R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and phenoxy (In addition, among these groups of R 3 , those other than the hydroxyl group may further have a substituent.)
- the cured film containing the silane coupling agent of the present invention has the effect of improving the adhesion with the substrate surface made of metal or inorganic material, having high hardness and excellent resolution. Furthermore, the cured film containing the silane coupling agent of the present invention has an effect that the curing shrinkage rate is low and the flatness is good.
- the silane coupling agent of the present invention has a structure represented by the following general formula (1).
- Each R 1 may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.
- the alkyl group may further have a substituent.
- N represents 0 or 1.
- R 2 represents carbon. Represents a trivalent organic group having 3 to 30.
- R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and phenoxy (In addition, among these groups of R 3 , those other than the hydroxyl group may further have a substituent.)
- R 1 a methyl group, an ethyl group, and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable from the viewpoint of obtaining raw materials.
- R 1 may have a substituent such as an alkoxy group, an aryl group, a phenoxy group, or a halogen group.
- R 2 is preferably a trivalent organic group having 3 to 30 carbon atoms, and more preferably a trivalent organic group having 3 to 10 carbon atoms from the viewpoint of solubility in an organic solvent.
- silane coupling agent represented by the general formula (1) of the present invention examples include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butyl).
- silane coupling agents When these silane coupling agents are added to the negative photosensitive resin, they may be used alone or mixed.
- silane coupling agents As a method for producing these silane coupling agents, a method of producing by reacting a silane coupling agent containing an acid anhydride with an alkylamine is preferable from the viewpoint of ease of production.
- a silane coupling agent containing an acid anhydride two types of silane coupling agents of the present invention are generated simultaneously.
- a small amount of oligomer or the like can be replicated in this synthesis method, it does not significantly affect the adhesion improving effect and need not be considered.
- the addition amount is preferably 1 to 15% by mass, preferably 3 to 10% by mass with respect to the total amount of the resin component of the negative photosensitive resin composition, that is, (B) alkali-soluble resin and (C) polyfunctional acrylic monomer. % Is more preferable. If the amount is less than 1% by mass, the effect of improving the adhesiveness is not sufficient.
- the negative photosensitive resin composition using the silane coupling agent of the present invention comprises at least (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, and (C) a polyfunctional acrylic. It contains a monomer and (D) a photoradical polymerization initiator.
- the negative photosensitive composition of the present invention contains (B) an alkali-soluble resin.
- the alkali-soluble resin By having the alkali-soluble resin, the negative photosensitive resin composition is excellent in alkali solubility (developability), and a good pattern can be formed while suppressing the residue after development. Moreover, by having an ethylenically unsaturated double bond group, a crosslinking density can be improved and the hardness of a cured film can be improved.
- alkali-soluble resin examples include polysiloxane, acrylic resin, vinyl ether resin, polyhydroxystyrene, novolac resin, polyimide, polyamide, and the like.
- alkali-soluble resin it is preferable that at least a part of the ethylenically unsaturated double bond group is introduced in order to increase the hardness of the cured film.
- polysiloxanes and acrylic resins are more preferred because of the ease of introduction of ethylenically unsaturated double bond groups. Moreover, you may contain 2 or more types of these polymers.
- alkali-soluble resin it is not limited to this.
- a reaction product obtained by hydrolyzing and condensing a trifunctional alkoxysilane compound is particularly preferable.
- the following are mentioned as a trifunctional alkoxysilane compound.
- the ethylenically unsaturated double bond group can be easily introduced into the polysiloxane, and the hardness of the cured film is increased. Is more preferable.
- (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, (meth) acrylic acid 2- (4-methoxycyclohexyl)
- Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and ⁇ -methylstyrene may be copolymerized with the above (meth) acrylic acid or (meth) acrylic acid ester. .
- an ethylenically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth) acrylic acid.
- an epoxy compound having an ethylenically unsaturated double bond group include the following compounds.
- the content of the (B) alkali-soluble resin is not particularly limited, and can be arbitrarily selected depending on the desired film thickness and application.
- the alkali-soluble resin is preferably added in an amount of 10 to 60% by mass based on the solid content of the negative photosensitive resin composition.
- the negative photosensitive composition of the present invention contains (C) a polyfunctional monomer.
- the polyfunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, a multi-sensitive monomer having an acrylic group is preferable.
- Specific examples include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester, propylene phthalate anhydride Oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, oligomer such as alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythrine Ritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dip
- the negative photosensitive resin composition of the present invention contains (D) a photo radical polymerization initiator.
- a photo radical polymerization initiator Any radical photopolymerization initiator may be used as long as it is decomposed and / or reacted by light (including ultraviolet rays and electron beams) to generate radicals.
- light including ultraviolet rays and electron beams
- ⁇ -aminoalkylphenone compounds include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-( 2,4,4-trimethylpentyl) -phosphine oxide and the like.
- oxime ester compound examples include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O -Benzoyloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.
- benzophenone compound having an amino group examples include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone.
- benzoic acid ester compound having an amino group examples include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.
- the content of the radical photopolymerization initiator is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition. Moreover, 20 mass% or less is preferable and 10 mass% or less is more preferable. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.
- the negative photosensitive resin composition of the present invention may contain a polymerization inhibitor.
- a polymerization inhibitor By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development is improved in applications requiring pattern processing.
- Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.
- the content of the polymerization inhibitor is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition.
- it is preferably 5% by mass or less, and more preferably 1% by mass or less.
- the negative photosensitive resin composition of the present invention may contain a thermal acid generator.
- the effect of improving the adhesion of the silane coupling agent can be further enhanced by the thermal acid generator.
- Specific examples of the thermal acid generator preferably used include triphenylsulfonium, 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl- Examples include 4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, and the like.
- SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-200, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI -150L, SI-160L, SI-180L are also preferably used. Two or more of these may be contained.
- the content of the thermal acid generator is preferably 0.1 to 3% by mass based on the total amount of the resin component of the negative photosensitive resin composition, that is, (B) alkali-soluble resin and (C) polyfunctional acrylic monomer. . If the amount is less than 0.1% by mass, the effect of improving the adhesiveness is small. If the amount is more than 3% by mass, the pattern becomes larger than the mask pattern and the resolution is lowered.
- the siloxane resin composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber By containing the ultraviolet absorber, the light resistance of the resulting cured film is improved, and the resolution after development is improved in applications that require pattern processing.
- a ultraviolet absorber There is no limitation in particular as a ultraviolet absorber, A well-known thing can be used.
- benzotriazole compounds benzophenone compounds, and triazine compounds are preferably used.
- ultraviolet absorbers for benzotriazole compounds include 2- (2H benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-t-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 And '-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole.
- UV absorbers for benzophenone compounds include 2-hydroxy-4-methoxybenzophenone.
- Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.
- the negative photosensitive resin composition of the present invention may contain a solvent.
- a compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be contained. Further, a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable.
- boiling point By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.
- Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2- Butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl Examples include ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol.
- diacetone alcohol is preferable from the viewpoint of storage stability
- propylene glycol mono t-butyl ether is preferable from the viewpoint of step coverage.
- cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, Examples include cycloheptanone. Among these, ⁇ -butyrolactone is preferable.
- the negative photosensitive resin composition of the present invention may contain various solvents such as acetates, ketones and ethers other than those described above.
- the content of the solvent is not particularly limited, and any amount can be used depending on the coating method.
- the amount of solvent is generally 50 to 95% by mass of the entire negative photosensitive resin composition.
- the negative photosensitive resin composition of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing.
- the curing agent is not particularly limited and known ones can be used. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used in view of the stability of the curing agent and the processability of the obtained coating film.
- the negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
- various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
- a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Two or more of these may be used.
- fluorosurfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink & Chemicals, Inc.) NBX-15 and FTX-218 (manufactured by Neos) are preferably used.
- silicone surfactants BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Japan Japan Co., Ltd.) are preferably used.
- a typical method for producing the negative photosensitive resin composition of the present invention will be described.
- a silane coupling agent represented by the general formula (1) (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, (D) a photoradical polymerization initiator, and other additives as necessary. Is added to an arbitrary solvent and dissolved by stirring, and then the resulting solution is filtered to obtain a negative photosensitive resin composition.
- the method for forming a cured film using the negative photosensitive resin composition of the present invention will be described with an example.
- the negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, Pre-bake with a heating device such as an oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
- exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
- the exposure intensity is about 10 to 4000 J / m 2 (wavelength 365 nm exposure amount conversion), and this light is irradiated through or without a desired mask.
- the exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.
- the exposed portion can be dissolved by development to obtain a negative pattern.
- a developing method it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle.
- a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammonium salts such as choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.
- this film is heated in a range of 150 to 450 ° C. for about 20 minutes to 1 hour with a heating device such as a hot plate or an oven.
- the cured film obtained by curing the negative photosensitive resin composition of the present invention is used as a touch panel protective film, a touch panel insulating film, various hard coat materials, an antireflection film, and an optical filter. Further, since it has negative photosensitivity, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, column materials, etc. for liquid crystal and organic EL displays. Among these, in particular, it can be suitably used as a touch panel protective film or a touch panel insulating film that requires adhesion after heat treatment and chemical treatment to a substrate not containing Si, such as ITO or molybdenum.
- Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. Since especially high hardness is calculated
- the hardness is preferably 4H or more
- the transmittance is 95% or more
- the resolution is preferably 20 ⁇ m or less.
- the hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.
- PGMEA propylene glycol monomethyl ether acetate
- DAA diacetone alcohol
- Synthesis Example 1 Synthesis of Silane Coupling Agent Mixed Solution (a-1) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine, and the mixture was allowed to warm to room temperature for a while. And stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butylamino) ) -2-Oxoethyl) -5- (trimethoxysilyl) pentanoic acid mixed solution (a-1) was obtained.
- Synthesis Example 2 Synthesis of Silane Coupling Agent Mixed Solution (a-2) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of t-pentylamine were added for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (t-pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- ( A mixed solution (a-2) of tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
- Synthesis Example 3 Synthesis of Silane Coupling Agent Mixed Solution (a-3) To 200 g of PGMEA were added 41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 9.45 g (160 mmol) of isopropylamine at room temperature for a while. After stirring, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (tert- A mixed solution (a-3) of isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
- Synthesis Example 4 Synthesis of Silane Coupling Agent Mixed Solution (a-4) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of n-propylamine for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (propylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (propyl A mixed solution (a-4) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
- Synthesis Example 5 Synthesis of Silane Coupling Agent Mixed Solution (a-5) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 14.90 g (160 mmol) of aniline were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (phenylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (phenyl A mixed solution (a-5) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
- Synthesis Example 6 Synthesis of Silane Coupling Agent Mixed Solution (a-6) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 7.37 g (160 mmol) of ethanol were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
- the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 4-ethoxy-4-oxo-2- (trimethoxysilyl) butanoic acid, 4-ethoxy-4-oxo-3- (tri A mixed solution (a-6) of methoxysilyl) butanoic acid was obtained.
- Synthesis Example 7 Synthesis of Silane Coupling Agent Solution (a-7) 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine were added to 400 g of PGMEA at room temperature for a while. After stirring, the mixture was stirred at 60 ° C. for 2 hours. Then, it heated up to 140 degreeC and made it react for 6 hours, azeotropically boiling PGMEA and water. The resulting solution was diluted with PGMEA so that the solid content concentration was 20% to obtain a 1- (tert-butyl) -3-trimethoxysilylpyrrolidine-2,5-dione solution (a-7).
- Synthesis Example 8 Synthesis of Siloxane Resin Solution (b-1) 13.62 g (0.1 mol) of methyltrimethoxysilane, 118.98 g (0.6 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 39 .39 g (0.15 mol), ⁇ -methacryloxypropyltrimethoxysilane 35.16 g, and DAA 140.87 g were added to a 500 ml three-necked flask.
- ITO substrate A cured film having a film thickness of 1.5 ⁇ m produced on this substrate (hereinafter referred to as ITO substrate) is made of ITO and a cured film according to JIS “K5400” 8.5.2 (1990) cross-cut tape method. Adhesion was evaluated. On the surface of the cured film on the glass substrate, 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm ⁇ 1 mm were produced. .
- Example 1 Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd. (hereinafter referred to as IC907) .)) 1.557 g, 4,4-bis (diethylamino) benzophenone (hereinafter referred to as EK) 0.173 g was dissolved in 21.618 g DAA and 34.489 g PGMEA. To this solution, dipentaerythritol hexaacrylate (trade name “Kayarad DPHA”, Shin Nippon Kayaku Co., Ltd.
- DPHA silane coupling agent mixed solution
- a-1 silane coupling agent mixed solution
- b-1 siloxane resin solution
- BYK-333 which is a silicone surfactant (manufactured by BYK Japan Japan Co., Ltd.) 1.500 g of a 1% by weight PGMEA solution was added and stirred, followed by filtration with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-1).
- the obtained negative photosensitive resin composition (N-1) was spin-coated on a glass substrate and an ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 ⁇ m.
- the mask Using the parallel light mask aligner (PLA-501F manufactured by Canon Inc.) as the light source and the ultrahigh pressure mercury lamp as the light source, the mask having a one-to-one width of 5, 10, 20, 30, 40, 50 ⁇ m width
- the exposure was performed at an exposure amount of 200 mJ (i-line) and a mask gap of 100 ⁇ m.
- an automatic developing device AD-2000, manufactured by Takizawa Sangyo Co., Ltd.
- shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (Mitsubishi Gas Chemical Co., Ltd.).
- ELM-D Mitsubishi Gas Chemical Co., Ltd.
- rinsed with water for 30 seconds.
- a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). About the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the said method.
- Example 2 A negative photosensitive resin composition (N-2) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-2).
- Example 3 A negative photosensitive resin composition (N-3) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-3) was evaluated in the same manner as in Example 1.
- Example 4 A negative photosensitive resin composition (Example 1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was changed to 0.433 g and the addition amount of PGMEA was changed to 38.382 g. N-4) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-4).
- Example 5 The negative photosensitive resin composition (N-1) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 1.730 g and the addition amount of PGMEA was 37.085 g. -5) was obtained. Using the obtained negative photosensitive resin composition (N-5), evaluation was performed in the same manner as in Example 1.
- Example 6 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 10.382 g and the addition amount of PGMEA was 28.433 g. -6) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-6).
- Negative photosensitive resin composition (N-1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 14.708 g and the addition amount of PGMEA was 24.107 g. -7) was obtained. Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-7).
- Example 8 The negative photosensitive resin composition (N-1) (30.000 g) is triphenylsulfonium trifluoromethanesulfonate (trade name “WPAG-281”, manufactured by Big Chemie Japan Co., Ltd. (hereinafter referred to as WPAG-281). 0.052 g) was added and stirred to obtain a negative photosensitive resin composition (N-8), and the obtained negative photosensitive resin composition (N-8) was used as an example. Evaluation was performed in the same manner as in Example 1.
- WPAG-281 triphenylsulfonium trifluoromethanesulfonate
- Example 9 The negative photosensitive resin composition (N-9) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-1) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-9).
- Example 10 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (21.629 g). In this solution, DPHA 8.652 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 21.629 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-10). Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-10).
- Example 11 A negative photosensitive resin composition (N-11) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-11).
- Example 12 A negative photosensitive resin composition (N-12) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-12), evaluation was performed in the same manner as in Example 1.
- Example 13 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (24.108 g).
- DPHA 10.382 g silane coupling agent mixed solution (a-1) 4.326 g, 4-tert-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 17.303 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-13). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-13).
- Example 14 A negative photosensitive resin composition (N-14) was obtained in the same manner as in Example 13, except that 0.052 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-13). . Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-14).
- Example 15 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (18.917 g). In this solution, DPHA 6.921 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1 mass% solution 8.652 g, acrylic resin solution (b-2) 25.955 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-15). Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-15).
- Example 16 Under a yellow light, 1.730 g of the quinonediazide compound (q-1) was dissolved in 6.045 g of DAA and 43.141 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a positive photosensitive resin composition (P-1).
- a-1 silane coupling agent mixed solution
- b-1 siloxane resin solution
- BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Next,
- the obtained positive photosensitive resin composition (P-1) was spin-coated on a glass substrate and an ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 ⁇ m.
- the mask Using the parallel light mask aligner (PLA-501F manufactured by Canon Inc.) as the light source and the ultrahigh pressure mercury lamp as the light source, the mask having a one-to-one width of 5, 10, 20, 30, 40, 50 ⁇ m width
- the exposure was performed at an exposure amount of 200 mJ (i line) and a mask gap of 100 ⁇ m.
- an unexposed portion having a sufficient area for hardness and adhesion measurement was secured.
- an automatic developing device AD-2000, manufactured by Takizawa Sangyo Co., Ltd.
- shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (Mitsubishi Gas Chemical Co., Ltd.).
- a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). About the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the said method.
- Example 17 It was dissolved in 6.045 g of DAA and 44.871 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain a thermosetting resin composition (U-1).
- a-1 silane coupling agent mixed solution
- b-1 siloxane resin solution
- BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain
- thermosetting resin composition (U-1) was spin-coated on a glass substrate and an ITO substrate, respectively, using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of revolutions. A 5 ⁇ m film was prepared. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). Curing shrinkage was calculated by the above method, and hardness and adhesion were evaluated.
- Comparative Example 2 A negative photosensitive resin composition (N-17) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-17) was used for evaluation in the same manner as in Example 1.
- Comparative Example 3 A negative photosensitive resin composition (N-18) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-18).
- Comparative Example 4 The negative photosensitive resin composition (N-19) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-17) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-19).
- the negative photosensitive resin composition (N-20) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-16) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-20).
- Example 9 A negative photosensitive resin composition (N-24) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-24), evaluation was performed in the same manner as in Example 1.
- Comparative Example 10 A negative photosensitive resin composition (N-25) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-25).
- Comparative Example 11 A negative photosensitive resin composition (N-26) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-6) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-26).
- Comparative Example 12 A negative photosensitive resin composition (N-27) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-27).
- Comparative Example 13 A positive photosensitive resin composition (P-2) was prepared in the same manner as in Example 16 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 16 using the obtained positive photosensitive resin composition (P-2).
- thermosetting resin composition (U-2) was obtained in the same manner as in Example 17 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). It was. Evaluation was performed in the same manner as in Example 17 using the obtained thermosetting resin composition (U-2).
- Reference example 1 A negative photosensitive resin composition (N-1 (using a silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed. Spin coated. Thereafter, prebaking was performed at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a film having a thickness of 1.5 ⁇ m. The produced film was exposed at an exposure amount of 200 mJ (i-line) using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.) and an ultrahigh pressure mercury lamp as a light source.
- N-1 using a silane coupling agent (a-1)
- a spin coater (1H-360S manufactured by Mikasa Co., Ltd.)
- prebaking was performed at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen M
- Reference example 2 A positive photosensitive resin composition (P-1 (using silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of rotations. A film having a thickness of 1.5 ⁇ m was formed by spin coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.).
- SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.
- the curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the curing shrinkage ratio was 16%, and the planarization ability was poor. Evaluation was performed in the same manner as described above except that (P-2) was used instead of the positive photosensitive resin composition (P-1). As a result, the curing shrinkage ratio was 13% and the planarization ability was good.
- the planarization performance tends to be lowered particularly by adding the silane coupling agent (a-1) of the present invention instead of the conventional silane coupling agent. It was seen.
- thermosetting resin composition (U-1 (using silane coupling agent (a-1))) on a silicon wafer substrate at an arbitrary rotation speed using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.).
- a film having a thickness of 1.5 ⁇ m was prepared by coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222).
- the curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the cure shrinkage ratio was 18%, and the planarization ability was poor.
- thermosetting resin composition by adding the silane coupling agent (a-1) of the present invention instead of the conventional silane coupling agent, the curing shrinkage rate and the planarization performance are lowered. There was a trend.
- the present invention is suitably used for a silane coupling agent, a negative photosensitive resin composition containing the same, a cured film using the same, and a touch panel device having the same.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
すなわち、下記一般式(1)で表されるシランカップリング剤である。 In order to solve the above problems, the present invention has the following configuration.
That is, it is a silane coupling agent represented by the following general formula (1).
ここで、R1としては、メチル基、エチル基、ブチル基が好ましく、特に原料入手の点からメチル基、エチル基が好ましい。R1はアルコキシ基、アリール基、フェノキシ基、ハロゲン基などの置換基を有していても良い。R2としては、炭素数3~30の3価の有機基が好ましく、有機溶剤への溶解性の点からは炭素数3~10の3価の有機基がより好ましい。 (Each R 1 may be the same or different and represents an alkyl group having 1 to 6 carbon atoms. The alkyl group may further have a substituent. N represents 0 or 1. R 2 represents carbon. Represents a trivalent organic group having 3 to 30. R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and phenoxy (In addition, among these groups of R 3 , those other than the hydroxyl group may further have a substituent.)
Here, as R 1 , a methyl group, an ethyl group, and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable from the viewpoint of obtaining raw materials. R 1 may have a substituent such as an alkoxy group, an aryl group, a phenoxy group, or a halogen group. R 2 is preferably a trivalent organic group having 3 to 30 carbon atoms, and more preferably a trivalent organic group having 3 to 10 carbon atoms from the viewpoint of solubility in an organic solvent.
DAA:ジアセトンアルコール。 PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とt-ブチルアミン11.70g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、3-(tert-ブチルカルバモイル)-6-(トリメトキシシリル)へキサン酸、2-(2-(tert-ブチルアミノ)―2-オキソエチル)-5-(トリメトキシシリル)ペンタン酸の混合溶液(a-1)を得た。 Synthesis Example 1 Synthesis of Silane Coupling Agent Mixed Solution (a-1) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine, and the mixture was allowed to warm to room temperature for a while. And stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butylamino) ) -2-Oxoethyl) -5- (trimethoxysilyl) pentanoic acid mixed solution (a-1) was obtained.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とt-ペンチルアミン9.45g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、2-(2-(t-ペンチルアミノ)―2-オキソエチル)-5-(トリメトキシシリル)ペンタン酸、3-(tert-ペンチルカルバモイル)-6-(トリメトキシシリル)へキサン酸の混合溶液(a-2)を得た。 Synthesis Example 2 Synthesis of Silane Coupling Agent Mixed Solution (a-2) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of t-pentylamine were added for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (t-pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- ( A mixed solution (a-2) of tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とイソプロピルアミン9.45g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、2-(2-(イソプロピルアミノ)―2-オキソエチル)-5-(トリメトキシシリル)ペンタン酸、3-(tert-イソプロピルカルバモイル)-6-(トリメトキシシリル)へキサン酸の混合溶液(a-3)を得た。 Synthesis Example 3 Synthesis of Silane Coupling Agent Mixed Solution (a-3) To 200 g of PGMEA were added 41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 9.45 g (160 mmol) of isopropylamine at room temperature for a while. After stirring, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (tert- A mixed solution (a-3) of isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とn-プロピルアミン9.45g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、2-(2-オキソ-2-(プロピルアミノ)エチル)-5-(トリメトキシシリル)ペンタン酸、3-(プロピルカルバモイル)-6-(トリメトキシシリル)へキサン酸の混合溶液(a-4)を得た。 Synthesis Example 4 Synthesis of Silane Coupling Agent Mixed Solution (a-4) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of n-propylamine for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (propylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (propyl A mixed solution (a-4) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とアニリン14.90g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、2-(2-オキソ-2-(フェニルアミノ)エチル)-5-(トリメトキシシリル)ペンタン酸、3-(フェニルカルバモイル)-6-(トリメトキシシリル)へキサン酸の混合溶液(a-5)を得た。 Synthesis Example 5 Synthesis of Silane Coupling Agent Mixed Solution (a-5) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 14.90 g (160 mmol) of aniline were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (phenylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (phenyl A mixed solution (a-5) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
PGMEA200gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とエタノール7.37g(160mmol)を加えてしばらく室温にて撹拌した後、40℃にて2時間撹拌した。その後、80℃まで昇温し、6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、4-エトキシ-4-オキソ-2-(トリメトキシシリル)ブタン酸、4-エトキシ-4-オキソ-3-(トリメトキシシリル)ブタン酸の混合溶液(a-6)を得た。 Synthesis Example 6 Synthesis of Silane Coupling Agent Mixed Solution (a-6) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 7.37 g (160 mmol) of ethanol were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours. The resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 4-ethoxy-4-oxo-2- (trimethoxysilyl) butanoic acid, 4-ethoxy-4-oxo-3- (tri A mixed solution (a-6) of methoxysilyl) butanoic acid was obtained.
PGMEA400gに3-トリメトキシシリルプロピルコハク酸無水物41.97g(160mmol)とt-ブチルアミン11.70g(160mmol)を加えてしばらく室温にて撹拌した後、60℃にて2時間撹拌した。その後、140℃まで昇温し、PGMEAと水を共沸しながら6時間反応させた。得られた溶液を固形分濃度が20%になるようにPGMEAで希釈し、1-(tert-ブチル)-3-トリメトキシシリルピロリジン-2,5-ジオン溶液(a-7)を得た。 Synthesis Example 7 Synthesis of Silane Coupling Agent Solution (a-7) 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine were added to 400 g of PGMEA at room temperature for a while. After stirring, the mixture was stirred at 60 ° C. for 2 hours. Then, it heated up to 140 degreeC and made it react for 6 hours, azeotropically boiling PGMEA and water. The resulting solution was diluted with PGMEA so that the solid content concentration was 20% to obtain a 1- (tert-butyl) -3-trimethoxysilylpyrrolidine-2,5-dione solution (a-7).
メチルトリメトキシシラン13.62g(0.1モル)、フェニルトリメトキシシラン118.98g(0.6モル)、3-トリメトキシシリルプロピルコハク酸39.39g(0.15モル)、γ-メタクリルオキシプロピルトリメトキシシラン35.16g、DAA140.87gを500mlの三口フラスコに加えた。その後、混合液を室温で攪拌しながら、水59.4gにリン酸0.106g(仕込みモノマに対して0.05質量%)を溶かしたリン酸水溶液を30分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、さらに45分加熱攪拌した(内温は100~110℃)。反応中に副生成物であるメタノール、水が合計89g留出した。得られたポリシロキサンのDAA溶液に対し、ポリマー濃度が40質量%となるようにDAAを加えてシロキサン樹脂溶液(b-1)を得た。得られたポリマーの重量平均分子量は7500であった。 Synthesis Example 8 Synthesis of Siloxane Resin Solution (b-1) 13.62 g (0.1 mol) of methyltrimethoxysilane, 118.98 g (0.6 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 39 .39 g (0.15 mol), γ-methacryloxypropyltrimethoxysilane 35.16 g, and DAA 140.87 g were added to a 500 ml three-necked flask. Thereafter, an aqueous phosphoric acid solution in which 0.106 g of phosphoric acid (0.05% by mass with respect to the charged monomer) was dissolved in 59.4 g of water was added over 30 minutes while the mixture was stirred at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and further heated and stirred for 45 minutes (the internal temperature was 100 to 110 ° C.). During the reaction, 89 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by mass to obtain a siloxane resin solution (b-1). The weight average molecular weight of the obtained polymer was 7500.
500mlのフラスコに2,2’-アゾビス(イソブチロニトリル)を3g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を30g、スチレンを22.48g、シクロヘキシルメタクリレートを25.13g加えた。その後、混合液を室温でしばらく攪拌し、フラスコ内を窒素置換した後、70℃で5時間加熱攪拌した。次に、得られた溶液にメタクリル酸グリシジルを15g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱攪拌した。得られたアクリル樹脂溶液の固形分濃度が40質量%になるようにPGMEAを加え、アクリル樹脂溶液(b-2)を得た。アクリル樹脂の重量平均分子量は13500、酸価は100mgKOH/gであった。 Synthesis Example 9 Synthesis of Acrylic Resin Solution (b-2) A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 30 g of methacrylic acid, 22.48 g of styrene, and 25.13 g of cyclohexyl methacrylate were added. Thereafter, the mixture was stirred at room temperature for a while, and the atmosphere in the flask was replaced with nitrogen, followed by heating and stirring at 70 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. PGMEA was added so that the solid content concentration of the obtained acrylic resin solution was 40% by mass to obtain an acrylic resin solution (b-2). The weight average molecular weight of the acrylic resin was 13500, and the acid value was 100 mgKOH / g.
乾燥窒素気流下、TrisP-PA(商品名、本州化学工業(株)製)21.23g(0.05mol)と5-ナフトキノンジアジドスルホニル酸クロリド37.62g(0.14mol)を1,4-ジオキサン450gに溶解させ、室温にした。この溶液に、1,4-ジオキサン50gと混合したトリエチルアミン15.58g(0.154mol)を、系内が35℃以上にならないように滴下した。滴下終了後、30℃で2時間攪拌した。トリエチルアミン塩を濾過し、濾液を水に投入した。その後、析出した沈殿を濾過で集めた。この沈殿を真空乾燥機で乾燥させ、キノンジアジド化合物(q-1)を得た。 Synthesis Example 10 Synthesis of quinonediazide compound (q-1) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidesulfonyl acid chloride 37. 62 g (0.14 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this solution, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35 ° C. After completion of dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (q-1).
(1)硬度の測定
5cm角のガラス基板上に作製した膜厚1.5μmの硬化膜について、「JIS K5600-5-4(1999年)」に準拠して鉛筆硬度を測定した。ただし、負荷加重を500gとした。 The evaluation methods in each example and comparative example are shown below.
(1) Measurement of hardness Pencil hardness was measured on a cured film having a thickness of 1.5 μm produced on a 5 cm square glass substrate in accordance with “JIS K5600-5-4 (1999)”. However, the load weight was 500 g.
無アルカリガラス基板(ガラス厚み0.7mm)上にITOを膜厚200オングストローム、抵抗値100Ω/□となるように基板を形成した。この基板(以下、ITO基板と記載する)上に作製した膜厚1.5μmの硬化膜について、JIS「K5400」8.5.2(1990年)碁盤目テープ法に準じてITOと硬化膜の接着性を評価した。ガラス基板上の硬化膜表面に、カッターナイフでガラス板の素地に到達するように、直交する縦横11本ずつの平行な直線を1mm間隔で引いて、1mm×1mmのマス目を100個作製した。切られた硬化膜表面にセロハン粘着テ-プ(幅=18mm、粘着力=3.7N/10mm)を張り付け、消しゴム(JIS S6050合格品)で擦って密着させた。そして、テープの一端を持ち、板に直角に保ち瞬間的に剥離した際のマス目の残存数を目視によって評価した。マス目の剥離面積により以下のように判定した。
5:剥離面積 0%
4:剥離面積 0~<5%
3:剥離面積 5~15%
2:剥離面積 15~35%
1:剥離面積 35~65%
0:剥離面積 65~100%。 (2) Evaluation of ITO Adhesion A substrate was formed on an alkali-free glass substrate (glass thickness 0.7 mm) so that ITO had a thickness of 200 Å and a resistance value of 100Ω / □. A cured film having a film thickness of 1.5 μm produced on this substrate (hereinafter referred to as ITO substrate) is made of ITO and a cured film according to JIS “K5400” 8.5.2 (1990) cross-cut tape method. Adhesion was evaluated. On the surface of the cured film on the glass substrate, 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm were produced. . A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was attached to the cut surface of the cured film, and rubbed with an eraser (JIS S6050-accepted product) for adhesion. Then, one end of the tape was held, and the number of cells remaining when the tape was instantaneously peeled off was evaluated by visual observation. The determination was made as follows according to the peeled area of the cells.
5: peeling area 0%
4: Stripping area 0 to <5%
3: Peeling area 5-15%
2: Peeling area 15-35%
1: Peeling area 35-65%
0: Peeling area 65 to 100%.
1対1の幅のラインアンドスペースパターンマスクを使用し、最小パターンを形成可能なマスクパターンの幅を測定した。 (3) Resolution Using a line-and-space pattern mask having a width of 1: 1, the width of a mask pattern capable of forming a minimum pattern was measured.
前記(1)記載の方法でシリコンウエハ上に作製した硬化膜について、キュア前後の硬化収縮率を算出した。この値が0~15%の場合、平坦化性能は良好といえる。硬化収縮率は以下の式に従って算出した。
硬化収縮率(%)=(1-キュアで得られた硬化膜の膜厚÷現像後の膜厚)×100
ただし、非感光性樹脂組成物の硬化収縮率を算出する場合は、現像工程を行わないため、「現像後の膜厚」を「プリベーク後の膜厚」として算出した。膜厚測定にはラムダエースSTM-602(商品名 大日本スクリーン製造(株)製)を用いた。屈折率は測定物によらず1.52とし、プリベーク後の膜厚、現像後の膜厚、およびキュアで得られた硬化膜の膜厚を測定した。 (4) Evaluation of planarization performance About the cured film produced on the silicon wafer by the method of said (1), the cure shrinkage rate before and behind hardening was computed. When this value is 0 to 15%, the planarization performance is good. The cure shrinkage was calculated according to the following formula.
Curing shrinkage (%) = (1−cured film thickness obtained by curing ÷ film thickness after development) × 100
However, in the case of calculating the curing shrinkage rate of the non-photosensitive resin composition, since the development step was not performed, “film thickness after development” was calculated as “film thickness after pre-baking”. Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used for film thickness measurement. The refractive index was 1.52, irrespective of the measured object, and the film thickness after pre-baking, the film thickness after development, and the film thickness of the cured film obtained by curing were measured.
黄色灯下にて2-メチル-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン(商品名「イルガキュア907」チバスペシャリティケミカル(株)社製、(以下、IC907と記載する。))1.557g、4,4-ビス(ジエチルアミノ)ベンゾフェノン(以下、EKと記載する。)0.173gをDAA21.618g、PGMEA34.489gに溶解させた。この溶液に、ジペンタエリスリトールヘキサアクリレート(商品名「カヤラッド DPHA」新日本化薬(株)社製(以下、DPHAと記載する。)10.382g、シランカップリング剤混合溶液(a-1)4.326g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、シロキサン樹脂溶液(b-1)17.303g、シリコーン系界面活性剤であるBYK-333(ビックケミー・ジャパン(株)製)のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-1)を得た。 Example 1
Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd. (hereinafter referred to as IC907) .)) 1.557 g, 4,4-bis (diethylamino) benzophenone (hereinafter referred to as EK) 0.173 g was dissolved in 21.618 g DAA and 34.489 g PGMEA. To this solution, dipentaerythritol hexaacrylate (trade name “Kayarad DPHA”, Shin Nippon Kayaku Co., Ltd. (hereinafter referred to as DPHA) 10.382 g, silane coupling agent mixed solution (a-1) 4 .326 g, 8.652 g of a 1% by weight PGMEA solution of 4-t-butylcatechol, 17.303 g of a siloxane resin solution (b-1), BYK-333 which is a silicone surfactant (manufactured by BYK Japan Japan Co., Ltd.) 1.500 g of a 1% by weight PGMEA solution was added and stirred, followed by filtration with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-1).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-2)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-2)を得た。得られたネガ型感光性樹脂組成物(N-2)を用いて、実施例1と同様にして評価を行った。 Example 2
A negative photosensitive resin composition (N-2) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-2).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-3)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-3)を得た。得られたネガ型感光性樹脂組成物(N-3)を用いて、実施例1と同様にして評価を行った。 Example 3
A negative photosensitive resin composition (N-3) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-3) was evaluated in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の添加量を0.433gに、およびPGMEAの添加量を38.382gに変更する以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-4)を得た。得られたネガ型感光性樹脂組成物(N-4)を用いて、実施例1と同様にして評価を行った。 Example 4
A negative photosensitive resin composition (Example 1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was changed to 0.433 g and the addition amount of PGMEA was changed to 38.382 g. N-4) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-4).
シランカップリング剤混合溶液(a-1)の添加量を1.730gに、およびPGMEAの添加量を37.085gにする以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-5)を得た。得られたネガ型感光性樹脂組成物(N-5)を用いて、実施例1と同様にして評価を行った。 Example 5
The negative photosensitive resin composition (N-1) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 1.730 g and the addition amount of PGMEA was 37.085 g. -5) was obtained. Using the obtained negative photosensitive resin composition (N-5), evaluation was performed in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の添加量を10.382gに、およびPGMEAの添加量を28.433gにする以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-6)を得た。得られたネガ型感光性樹脂組成物(N-6)を用いて、実施例1と同様にして評価を行った。 Example 6
A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 10.382 g and the addition amount of PGMEA was 28.433 g. -6) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-6).
シランカップリング剤混合溶液(a-1)の添加量を14.708gに、およびPGMEAの添加量を24.107gにする以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-7)を得た。得られたネガ型感光性樹脂組成物(N-7)を用いて、実施例1と同様にして評価を行った。 Example 7
Negative photosensitive resin composition (N-1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 14.708 g and the addition amount of PGMEA was 24.107 g. -7) was obtained. Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-7).
ネガ型感光性樹脂組成物(N-1)30.000gにトリフェニルスルホニウムトリフルオロメタンスルホン酸塩(商品名「WPAG-281」ビックケミー・ジャパン(株)社製(以下、WPAG-281と記載する。)を0.052g添加し、攪拌することで、ネガ型感光性樹脂組成物(N-8)を得た。得られたネガ型感光性樹脂組成物(N-8)を用いて、実施例1と同様にして評価を行った。 Example 8
The negative photosensitive resin composition (N-1) (30.000 g) is triphenylsulfonium trifluoromethanesulfonate (trade name “WPAG-281”, manufactured by Big Chemie Japan Co., Ltd. (hereinafter referred to as WPAG-281). 0.052 g) was added and stirred to obtain a negative photosensitive resin composition (N-8), and the obtained negative photosensitive resin composition (N-8) was used as an example. Evaluation was performed in the same manner as in Example 1.
ネガ型感光性樹脂組成物(N-1)30.000gにWPAG-281を0.208g添加し、攪拌することで、ネガ型感光性樹脂組成物(N-9)を得た。得られたネガ型感光性樹脂組成物(N-9)を用いて、実施例1と同様にして評価を行った。 Example 9
The negative photosensitive resin composition (N-9) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-1) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-9).
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA 21.629gに溶解させた。この溶液に、DPHA 8.652g、シランカップリング剤混合溶液(a-1)4.326g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)21.629g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-10)を得た。得られたネガ型感光性樹脂組成物(N-10)を用いて、実施例1と同様にして評価を行った。 Example 10
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (21.629 g). In this solution, DPHA 8.652 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 21.629 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Subsequently, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-10). Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-10).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-2)を用いる以外は実施例10と同様に行い、ネガ型感光性樹脂組成物(N-11)を得た。得られたネガ型感光性樹脂組成物(N-11)を用いて、実施例1と同様にして評価を行った。 Example 11
A negative photosensitive resin composition (N-11) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-11).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-3)を用いる以外は実施例10と同様に行い、ネガ型感光性樹脂組成物(N-12)を得た。得られたネガ型感光性樹脂組成物(N-12)を用いて、実施例1と同様にして評価を行った。 Example 12
A negative photosensitive resin composition (N-12) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-12), evaluation was performed in the same manner as in Example 1.
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA24.108gに溶解させた。この溶液に、DPHA 10.382g、シランカップリング剤混合溶液(a-1)4.326g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)17.303g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-13)を得た。得られたネガ型感光性樹脂組成物(N-13)を用いて、実施例1と同様にして評価を行った。 Example 13
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (24.108 g). In this solution, DPHA 10.382 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-tert-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 17.303 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-13). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-13).
ネガ型感光性樹脂組成物(N-13)30.000gにWPAG-281を0.052g添加する以外は実施例13と同様に行い、ネガ型感光性樹脂組成物(N-14)を得た。得られたネガ型感光性樹脂組成物(N-14)を用いて、実施例1と同様にして評価を行った。 Example 14
A negative photosensitive resin composition (N-14) was obtained in the same manner as in Example 13, except that 0.052 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-13). . Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-14).
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA 18.917gに溶解させた。この溶液に、DPHA 6.921g、シランカップリング剤混合溶液(a-1)4.326g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)25.955g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-15)を得た。得られたネガ型感光性樹脂組成物(N-15)を用いて、実施例1と同様にして評価を行った。 Example 15
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (18.917 g). In this solution, DPHA 6.921 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1 mass% solution 8.652 g, acrylic resin solution (b-2) 25.955 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-15). Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-15).
黄色灯下にてキノンジアジド化合物(q-1)1.730gをDAA 6.045g、PGMEA 43.141gに溶解させた。この溶液に、シランカップリング剤混合溶液(a-1)4.326g、シロキサン樹脂溶液(b-1)43.258g、シリコーン系界面活性剤であるBYK-333(ビックケミー・ジャパン(株)製)のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ポジ型感光性樹脂組成物(P-1)を得た。
得られたポジ型感光性樹脂組成物(P-1)をガラス基板、およびITO基板にそれぞれスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートした。その後、これらの基板をホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて110℃で2分間プリベークし、膜厚1.5μmの膜を作製した。 Example 16
Under a yellow light, 1.730 g of the quinonediazide compound (q-1) was dissolved in 6.045 g of DAA and 43.141 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a positive photosensitive resin composition (P-1).
The obtained positive photosensitive resin composition (P-1) was spin-coated on a glass substrate and an ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 μm.
DAA 6.045g、PGMEA 44.871gに溶解させた。この溶液に、シランカップリング剤混合溶液(a-1)4.326g、シロキサン樹脂溶液(b-1)43.258g、シリコーン系界面活性剤であるBYK-333(ビックケミー・ジャパン(株)製)のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、熱硬化性樹脂組成物(U-1)を得た。
得られた熱硬化性樹脂組成物(U-1)をガラス基板、およびITO基板にそれぞれにスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートし膜厚1.5μmの膜を作製した。その後、ホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて110℃で2分間プリベークした。最後に、オーブン(エスペック(株)製IHPS-222)を用いて空気中260℃で1時間キュアして硬化膜を作製した。前記方法で硬化収縮率を算出し、硬度、接着性を評価した。 Example 17
It was dissolved in 6.045 g of DAA and 44.871 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Subsequently, filtration was performed with a 0.45 μm filter to obtain a thermosetting resin composition (U-1).
The obtained thermosetting resin composition (U-1) was spin-coated on a glass substrate and an ITO substrate, respectively, using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of revolutions. A 5 μm film was prepared. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). Curing shrinkage was calculated by the above method, and hardness and adhesion were evaluated.
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 21.618g、PGMEA 38.815gに溶解させた。この溶液に、DPHA 10.382g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、シロキサン樹脂溶液(b-1)17.303g、シリコーン系界面活性剤であるBYK-333(ビックケミー・ジャパン(株)製)のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-16)を得た。得られたネガ型感光性樹脂組成物(N-16)を用いて、実施例1と同様にして評価を行った。 Comparative Example 1
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (21.618 g) and PGMEA (38.815 g). To this solution, DPHA 10.382 g, 4-tert-butylcatechol PGMEA 1% by weight solution 8.652 g, siloxane resin solution (b-1) 17.303 g, silicone surfactant BYK-333 (BIC Chemie Japan) 1.500 g of 1 mass% PGMEA solution (manufactured by Co., Ltd.) was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-16). The obtained negative photosensitive resin composition (N-16) was used for evaluation in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-4)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-17)を得た。得られたネガ型感光性樹脂組成物(N-17)を用いて、実施例1と同様にして評価を行った。 Comparative Example 2
A negative photosensitive resin composition (N-17) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-17) was used for evaluation in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-5)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-18)を得た。得られたネガ型感光性樹脂組成物(N-18)を用いて、実施例1と同様にして評価を行った。 Comparative Example 3
A negative photosensitive resin composition (N-18) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-18).
ネガ型感光性樹脂組成物(N-17)30.000gにWPAG-281を0.208g添加し、攪拌することで、ネガ型感光性樹脂組成物(N-19)を得た。得られたネガ型感光性樹脂組成物(N-19)を用いて、実施例1と同様にして評価を行った。 Comparative Example 4
The negative photosensitive resin composition (N-19) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-17) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-19).
ネガ型感光性樹脂組成物(N-16)30.000gにWPAG-281を0.208g添加し、攪拌することで、ネガ型感光性樹脂組成物(N-20)を得た。得られたネガ型感光性樹脂組成物(N-20)を用いて、実施例1と同様にして評価を行った。 Comparative Example 5
The negative photosensitive resin composition (N-20) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-16) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-20).
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA 25.955gに溶解させた。この溶液に、DPHA 8.652g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)21.629g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-21)を得た。得られたネガ型感光性樹脂組成物(N-21)を用いて、実施例1と同様にして評価を行った。 Comparative Example 6
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (25.955 g). To this solution, 8.652 g of DPHA, 8.652 g of PGMEA 1% by mass of 4-t-butylcatechol, 21.629 g of acrylic resin solution (b-2), 1.500 g of PGMEA 1% by mass of BYK-333 were added, Stir. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-21). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-21).
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA 28.434gに溶解させた。この溶液に、DPHA 10.382g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)17.303g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-22)を得た。得られたネガ型感光性樹脂組成物(N-22)を用いて、実施例1と同様にして評価を行った。 Comparative Example 7
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (28.434 g). To this solution, 10.382 g of DPHA, 8.652 g of PGMEA 1 mass% solution of 4-t-butylcatechol, 17.303 g of acrylic resin solution (b-2), 1.500 g of PGMEA 1 mass% solution of BYK-333, Stir. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-22). Using the obtained negative photosensitive resin composition (N-22), evaluation was performed in the same manner as in Example 1.
黄色灯下にて、IC907 1.557g、EK 0.173gをDAA 32.000g、PGMEA 23.243gに溶解させた。この溶液に、DPHA 6.921g、4-t-ブチルカテコールのPGMEA1質量%溶液8.652g、アクリル樹脂溶液(b-2)25.955g、BYK-333のPGMEA1質量%溶液1.500gを加え、撹拌した。次いで0.45μmのフィルターでろ過を行い、ネガ型感光性樹脂組成物(N-23)を得た。得られたネガ型感光性樹脂組成物(N-23)を用いて、実施例1と同様にして評価を行った。 Comparative Example 8
Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (23.243 g). To this solution was added DPHA 6.921 g, 4-tert-butylcatechol PGMEA 1% by weight solution 8.652 g, acrylic resin solution (b-2) 25.955 g, BYK-333 1% by weight PGMEA 1% by weight solution, Stir. Next, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-23). Using the obtained negative photosensitive resin composition (N-23), evaluation was conducted in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-4)を用いる以外は実施例10と同様に行い、ネガ型感光性樹脂組成物(N-24)を得た。得られたネガ型感光性樹脂組成物(N-24)を用いて、実施例1と同様にして評価を行った。 Comparative Example 9
A negative photosensitive resin composition (N-24) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-24), evaluation was performed in the same manner as in Example 1.
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-5)を用いる以外は実施例10と同様に行い、ネガ型感光性樹脂組成物(N-25)を得た。得られたネガ型感光性樹脂組成物(N-25)を用いて、実施例1と同様にして評価を行った。 Comparative Example 10
A negative photosensitive resin composition (N-25) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-25).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-6)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-26)を得た。得られたネガ型感光性樹脂組成物(N-26)を用いて、実施例1と同様にして評価を行った。 Comparative Example 11
A negative photosensitive resin composition (N-26) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-6) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-26).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-7)を用いる以外は実施例1と同様に行い、ネガ型感光性樹脂組成物(N-27)を得た。得られたネガ型感光性樹脂組成物(N-27)を用いて、実施例1と同様にして評価を行った。 Comparative Example 12
A negative photosensitive resin composition (N-27) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-27).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-7)を用いる以外は実施例16と同様に行い、ポジ型感光性樹脂組成物(P-2)を得た。得られたポジ型感光性樹脂組成物(P-2)を用いて、実施例16と同様にして評価を行った。 Comparative Example 13
A positive photosensitive resin composition (P-2) was prepared in the same manner as in Example 16 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 16 using the obtained positive photosensitive resin composition (P-2).
シランカップリング剤混合溶液(a-1)の代わりにシランカップリング剤混合溶液(a-7)を用いる以外は実施例17と同様に行い、熱硬化性樹脂組成物(U-2)を得た。得られた熱硬化性樹脂組成物(U-2)を用いて、実施例17と同様にして評価を行った。 Comparative Example 14
A thermosetting resin composition (U-2) was obtained in the same manner as in Example 17 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). It was. Evaluation was performed in the same manner as in Example 17 using the obtained thermosetting resin composition (U-2).
ネガ型感光性樹脂組成物(N-1(シランカップリング剤(a-1)を使用))をシリコンウエハ基板にスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートした。その後、ホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて110℃で2分間プリベークし、膜厚1.5μmの膜を作製した。作製した膜をパラレルライトマスクアライナー(キヤノン(株)製PLA-501F)を用いて超高圧水銀灯を光源とし、露光量200mJ(i線)で露光した。その後、自動現像装置(AD-2000、滝沢産業(株)製)を用いて、0.4質量%水酸化テトラメチルアンモニウム水溶液ELM-D(三菱ガス化学(株)製)で90秒間シャワー現像し、次いで水で30秒間リンスした。最後に、オーブン(エスペック(株)製IHPS-222)を用いて空気中220℃で1時間キュアして硬化膜を作製した。前記方法で硬化収縮率を算出し、平坦化能を評価した。その結果、硬化収縮率は11%で、平坦化能は良好であった。 Reference example 1
A negative photosensitive resin composition (N-1 (using a silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed. Spin coated. Thereafter, prebaking was performed at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a film having a thickness of 1.5 μm. The produced film was exposed at an exposure amount of 200 mJ (i-line) using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.) and an ultrahigh pressure mercury lamp as a light source. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (Mitsubishi Gas Chemical Co., Ltd.). Then rinsed with water for 30 seconds. Finally, a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). The curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the cure shrinkage ratio was 11% and the planarization ability was good.
ポジ型感光性樹脂組成物(P-1(シランカップリング剤(a-1)を使用))をシリコンウエハ基板にスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートし、膜厚1.5μmの膜を作製した。その後、ホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて110℃で2分間プリベークした。自動現像装置(AD-2000、滝沢産業(株)製)を用いて、0.4質量%水酸化テトラメチルアンモニウム水溶液ELM-D(三菱ガス化学(株)製)で90秒間シャワー現像し、次いで水で30秒間リンスした。次に、パラレルライトマスクアライナー(キヤノン(株)製PLA-501F)を用いて超高圧水銀灯を光源とし、露光量6000mJ(i線)で露光した。最後に、オーブン(エスペック(株)製IHPS-222)を用いて空気中220℃で1時間キュアして硬化膜を作製した。前記方法で硬化収縮率を算出し、平坦化能を評価した。その結果、硬化収縮率は16%で、平坦化能は不良であった。
ポジ型感光性樹脂組成物(P-1)の代わりに(P-2)を用いる以外は、上記と同様にして評価を行った。その結果、硬化収縮率は13%で、平坦化能は良好であった。 Reference example 2
A positive photosensitive resin composition (P-1 (using silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of rotations. A film having a thickness of 1.5 μm was formed by spin coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed for 90 seconds with a 0.4 mass% tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Rinse with water for 30 seconds. Next, using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.), an ultrahigh pressure mercury lamp was used as a light source, and exposure was performed at an exposure amount of 6000 mJ (i line). Finally, a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). The curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the curing shrinkage ratio was 16%, and the planarization ability was poor.
Evaluation was performed in the same manner as described above except that (P-2) was used instead of the positive photosensitive resin composition (P-1). As a result, the curing shrinkage ratio was 13% and the planarization ability was good.
熱硬化性樹脂組成物(U-1(シランカップリング剤(a-1)を使用))をシリコンウエハ基板にスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートし膜厚1.5μmの膜を作製した。その後、ホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて110℃で2分間プリベークした。最後に、オーブン(エスペック(株)製IHPS-222)を用いて空気中260℃で1時間キュアして硬化膜を作製した。前記方法で硬化収縮率を算出し、平坦化能を評価した。その結果、硬化収縮率は18%で、平坦化能は不良であった。 Reference example 3
Spin the thermosetting resin composition (U-1 (using silane coupling agent (a-1))) on a silicon wafer substrate at an arbitrary rotation speed using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.). A film having a thickness of 1.5 μm was prepared by coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). The curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the cure shrinkage ratio was 18%, and the planarization ability was poor.
Claims (7)
- 一般式(1)で表されるシランカップリング剤。
- 一般式(1)においてn=0であることを特徴とする請求項1に記載のシランカップリング剤。 The silane coupling agent according to claim 1, wherein n = 0 in the general formula (1).
- 少なくとも(A)請求項1または2に記載のシランカップリング剤、(B)アルカリ可溶性樹脂、(C)多官能アクリルモノマ、(D)光ラジカル重合開始剤、を含有することを特徴とするネガ型感光性樹脂組成物。 A negative containing at least (A) the silane coupling agent according to claim 1, (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) a photoradical polymerization initiator. Type photosensitive resin composition.
- (A)アルカリ可溶性樹脂がエチレン性不飽和基を有するシロキサン樹脂であることを特徴とする請求項3に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 3, wherein (A) the alkali-soluble resin is a siloxane resin having an ethylenically unsaturated group.
- (A)アルカリ可溶性樹脂がエチレン性不飽和基を有するアクリル樹脂であることを特徴とする請求項3に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 3, wherein the alkali-soluble resin (A) is an acrylic resin having an ethylenically unsaturated group.
- 請求項3~5のいずれかに記載のネガ型感光性樹脂組成物を硬化させてなる硬化膜。 A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 3 to 5.
- 請求項6に記載の硬化膜を有するタッチパネル用部材。 The member for touchscreens which has the cured film of Claim 6.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG2012068672A SG184100A1 (en) | 2010-03-17 | 2011-03-10 | Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component |
JP2011526326A JP5459315B2 (en) | 2010-03-17 | 2011-03-10 | Silane coupling agent, negative photosensitive resin composition, cured film, and touch panel member |
KR1020127024097A KR101839397B1 (en) | 2010-03-17 | 2011-03-10 | Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component |
CN201180014187.5A CN102803274B (en) | 2010-03-17 | 2011-03-10 | Silane coupling agent, negative light-sensitive resin combination, cured film and touch panel component |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010060298 | 2010-03-17 | ||
JP2010-060298 | 2010-03-17 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/627,663 Continuation US9191137B2 (en) | 2010-03-30 | 2012-09-26 | Transmission apparatus, reception apparatus, transmission method, and reception method |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011114995A1 true WO2011114995A1 (en) | 2011-09-22 |
Family
ID=44649090
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/055680 WO2011114995A1 (en) | 2010-03-17 | 2011-03-10 | Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP5459315B2 (en) |
KR (1) | KR101839397B1 (en) |
CN (1) | CN102803274B (en) |
SG (1) | SG184100A1 (en) |
TW (1) | TWI505031B (en) |
WO (1) | WO2011114995A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013031753A1 (en) * | 2011-08-29 | 2013-03-07 | 東レ株式会社 | Colored resin composition and resin black matrix substrate |
WO2013151167A1 (en) * | 2012-04-06 | 2013-10-10 | Azエレクトロニックマテリアルズマニュファクチャリング株式会社 | Negative photosensitive siloxane composition |
JP2014005437A (en) * | 2011-11-21 | 2014-01-16 | Toyo Ink Sc Holdings Co Ltd | Resin composition, and protective film and touch panel insulating film using the same |
JP2014066809A (en) * | 2012-09-25 | 2014-04-17 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
JP2014137394A (en) * | 2013-01-15 | 2014-07-28 | Hitachi Chemical Co Ltd | Photosensitive transparent material for protective film of touch panel electrode |
WO2014126013A1 (en) * | 2013-02-14 | 2014-08-21 | 東レ株式会社 | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
JP2015021029A (en) * | 2013-07-17 | 2015-02-02 | 東レ株式会社 | Composition, antireflection layer using the same and method for forming the same, glass having the same and solar cell module |
JP2015137271A (en) * | 2014-01-24 | 2015-07-30 | 信越化学工業株式会社 | Silane coupling agent, method of making the same, primer composition, and coating composition |
WO2015194639A1 (en) * | 2014-06-20 | 2015-12-23 | 大阪有機化学工業株式会社 | Photosensitive composition and cured film of same |
WO2018021049A1 (en) * | 2016-07-28 | 2018-02-01 | 日産化学工業株式会社 | Resin composition |
JP2019194709A (en) * | 2019-06-05 | 2019-11-07 | 日立化成株式会社 | Method for manufacturing base material for touch panel with cured film, photosensitive resin composition, photosensitive element and touch panel |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI567498B (en) | 2012-04-06 | 2017-01-21 | Az電子材料盧森堡有限公司 | Negative-type photosensitive siloxane composition |
WO2014045856A1 (en) * | 2012-09-21 | 2014-03-27 | 日本合成化学工業株式会社 | Laminate and use thereof |
KR101418026B1 (en) * | 2014-02-06 | 2014-08-08 | 동우 화인켐 주식회사 | Thermosetting ink composition |
CN104793384B (en) * | 2015-04-03 | 2017-07-28 | 京东方科技集团股份有限公司 | A kind of ultra-thin LCD and preparation method thereof |
CN105237037A (en) * | 2015-11-24 | 2016-01-13 | 烟台顺隆化工科技有限公司 | Water-proofing agent for natural stone building |
KR20200079231A (en) * | 2017-11-21 | 2020-07-02 | 도레이 카부시키가이샤 | Siloxane resin composition, cured film and display device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006316032A (en) * | 2005-05-16 | 2006-11-24 | Asahi Kasei Electronics Co Ltd | Silane coupling agent |
WO2009096050A1 (en) * | 2008-01-28 | 2009-08-06 | Toray Industries, Inc. | Siloxane resin compositions |
WO2010055154A1 (en) * | 2008-11-17 | 2010-05-20 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Dialkoxy- or dihydroxyphenyl radicals containing silanes, adhesives produced therefrom and method for producing silanes and adhesives |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002062654A (en) * | 2000-08-16 | 2002-02-28 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
TW584785B (en) * | 2001-07-04 | 2004-04-21 | Showa Denko Kk | Curable flame-retardant resist composition and cured product thereof |
DE102005056622A1 (en) * | 2005-11-25 | 2007-05-31 | Merck Patent Gmbh | Modified zinc oxide nanoparticles are formed by method placing precursor and silica modifier on organic solvent and growing until spectral absorption edge reaches the desired value |
KR101345475B1 (en) * | 2007-09-28 | 2013-12-27 | 도오꾜오까고오교 가부시끼가이샤 | Copolymer, resin composition, spacer for display panel, planarization film, thermosetting protective film, microlens, and process for producing copolymer |
-
2011
- 2011-03-10 JP JP2011526326A patent/JP5459315B2/en active Active
- 2011-03-10 WO PCT/JP2011/055680 patent/WO2011114995A1/en active Application Filing
- 2011-03-10 KR KR1020127024097A patent/KR101839397B1/en active IP Right Grant
- 2011-03-10 SG SG2012068672A patent/SG184100A1/en unknown
- 2011-03-10 CN CN201180014187.5A patent/CN102803274B/en active Active
- 2011-03-15 TW TW100108634A patent/TWI505031B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006316032A (en) * | 2005-05-16 | 2006-11-24 | Asahi Kasei Electronics Co Ltd | Silane coupling agent |
WO2009096050A1 (en) * | 2008-01-28 | 2009-08-06 | Toray Industries, Inc. | Siloxane resin compositions |
WO2010055154A1 (en) * | 2008-11-17 | 2010-05-20 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Dialkoxy- or dihydroxyphenyl radicals containing silanes, adhesives produced therefrom and method for producing silanes and adhesives |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5234230B1 (en) * | 2011-08-29 | 2013-07-10 | 東レ株式会社 | Colored resin composition and resin black matrix substrate |
WO2013031753A1 (en) * | 2011-08-29 | 2013-03-07 | 東レ株式会社 | Colored resin composition and resin black matrix substrate |
JP2014005437A (en) * | 2011-11-21 | 2014-01-16 | Toyo Ink Sc Holdings Co Ltd | Resin composition, and protective film and touch panel insulating film using the same |
JPWO2013151167A1 (en) * | 2012-04-06 | 2015-12-17 | アーゼッド・エレクトロニック・マテリアルズ(ルクセンブルグ)ソシエテ・ア・レスポンサビリテ・リミテ | Negative photosensitive siloxane composition |
WO2013151167A1 (en) * | 2012-04-06 | 2013-10-10 | Azエレクトロニックマテリアルズマニュファクチャリング株式会社 | Negative photosensitive siloxane composition |
CN104246612B (en) * | 2012-04-06 | 2019-06-11 | Az电子材料(卢森堡)有限公司 | Negative-type photosensitive silicone composition |
KR20140144275A (en) * | 2012-04-06 | 2014-12-18 | 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. | Negative photosensitive siloxane composition |
CN104246612A (en) * | 2012-04-06 | 2014-12-24 | Az电子材料(卢森堡)有限公司 | Negative photosensitive siloxane composition |
KR102002761B1 (en) | 2012-04-06 | 2019-07-23 | 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. | Negative photosensitive siloxane composition |
JP2014066809A (en) * | 2012-09-25 | 2014-04-17 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
JP2014137394A (en) * | 2013-01-15 | 2014-07-28 | Hitachi Chemical Co Ltd | Photosensitive transparent material for protective film of touch panel electrode |
KR102145232B1 (en) * | 2013-02-14 | 2020-08-18 | 도레이 카부시키가이샤 | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
CN104969126A (en) * | 2013-02-14 | 2015-10-07 | 东丽株式会社 | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
KR20150118091A (en) * | 2013-02-14 | 2015-10-21 | 도레이 카부시키가이샤 | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
CN104969126B (en) * | 2013-02-14 | 2019-10-01 | 东丽株式会社 | Negative-type photosensitive coloured composition, cured film, the manufacturing method of touch panel light-shielding pattern and touch panel |
US9651865B2 (en) | 2013-02-14 | 2017-05-16 | Toray Industries, Inc. | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
JPWO2014126013A1 (en) * | 2013-02-14 | 2017-02-02 | 東レ株式会社 | Negative photosensitive coloring composition, cured film, light shielding pattern for touch panel, and method for manufacturing touch panel |
WO2014126013A1 (en) * | 2013-02-14 | 2014-08-21 | 東レ株式会社 | Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method |
JP2015021029A (en) * | 2013-07-17 | 2015-02-02 | 東レ株式会社 | Composition, antireflection layer using the same and method for forming the same, glass having the same and solar cell module |
US9221849B2 (en) | 2014-01-24 | 2015-12-29 | Shin-Etsu Chemical Co., Ltd. | Silane coupling agent, making method, primer composition, and coating composition |
KR20150088733A (en) | 2014-01-24 | 2015-08-03 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silane coupling agent and method for preparing the same, primer composition, and coating composition |
JP2015137271A (en) * | 2014-01-24 | 2015-07-30 | 信越化学工業株式会社 | Silane coupling agent, method of making the same, primer composition, and coating composition |
JPWO2015194639A1 (en) * | 2014-06-20 | 2017-05-25 | 大阪有機化学工業株式会社 | Photosensitive composition and cured film thereof |
TWI656407B (en) * | 2014-06-20 | 2019-04-11 | 日商大阪有機化學工業股份有限公司 | Photosensitive composition and cured film thereof |
KR20170019371A (en) | 2014-06-20 | 2017-02-21 | 오사카 유키가가쿠고교 가부시키가이샤 | Photosensitive composition and cured film of same |
WO2015194639A1 (en) * | 2014-06-20 | 2015-12-23 | 大阪有機化学工業株式会社 | Photosensitive composition and cured film of same |
KR102053369B1 (en) | 2014-06-20 | 2019-12-06 | 오사카 유키가가쿠고교 가부시키가이샤 | Photosensitive composition and cured film of same |
WO2018021049A1 (en) * | 2016-07-28 | 2018-02-01 | 日産化学工業株式会社 | Resin composition |
JP2019194709A (en) * | 2019-06-05 | 2019-11-07 | 日立化成株式会社 | Method for manufacturing base material for touch panel with cured film, photosensitive resin composition, photosensitive element and touch panel |
Also Published As
Publication number | Publication date |
---|---|
CN102803274B (en) | 2015-07-29 |
JPWO2011114995A1 (en) | 2013-06-27 |
TW201142504A (en) | 2011-12-01 |
JP5459315B2 (en) | 2014-04-02 |
KR101839397B1 (en) | 2018-03-16 |
KR20130061124A (en) | 2013-06-10 |
CN102803274A (en) | 2012-11-28 |
TWI505031B (en) | 2015-10-21 |
SG184100A1 (en) | 2012-10-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5459315B2 (en) | Silane coupling agent, negative photosensitive resin composition, cured film, and touch panel member | |
JP5867083B2 (en) | Negative photosensitive resin composition and protective film using the same | |
JP5589387B2 (en) | Siloxane resin composition and protective film for touch panel using the same | |
JP5504689B2 (en) | Negative photosensitive resin composition and touch panel material using the same | |
JP5423004B2 (en) | Negative photosensitive resin composition and touch panel material using the same | |
JP5327345B2 (en) | Negative photosensitive resin composition, cured film, and touch panel member. | |
JP5407210B2 (en) | Siloxane resin composition and cured film using the same | |
WO2013146130A1 (en) | Silane coupling agent, light-sensitive resin composition, cured film, and touch panel member | |
WO2011129312A1 (en) | Negative photosensitive resin composition, cured film, and member for touch panel | |
JP5671936B2 (en) | Negative photosensitive resin composition and cured film using the same | |
JP6489288B1 (en) | Transparent resin composition, transparent film and transparent resin-coated glass substrate | |
JP7119390B2 (en) | Negative photosensitive resin composition and cured film using the same | |
JP2022064302A (en) | Negative siloxane resin composition, cured film, and element | |
JPWO2019102655A1 (en) | Siloxane resin composition, cured film and display device | |
JP2018120069A (en) | Negative photosensitive resin composition, cured film and touch panel member | |
JP6458902B1 (en) | Photosensitive siloxane resin composition, cured film and touch panel member | |
JP2020100819A (en) | Resin composition, cured film and method for producing the same | |
JP2023136705A (en) | Photosensitive resin composition, cured film and touch panel | |
JP2017187754A (en) | Negative siloxane resin composition, photospacer, color filter substrate, and liquid crystal display device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180014187.5 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011526326 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11756181 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127024097 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11756181 Country of ref document: EP Kind code of ref document: A1 |