JP5013003B2 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP5013003B2 JP5013003B2 JP2011011768A JP2011011768A JP5013003B2 JP 5013003 B2 JP5013003 B2 JP 5013003B2 JP 2011011768 A JP2011011768 A JP 2011011768A JP 2011011768 A JP2011011768 A JP 2011011768A JP 5013003 B2 JP5013003 B2 JP 5013003B2
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- JP
- Japan
- Prior art keywords
- compound
- acrylate
- meth
- group
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 43
- -1 oxime compounds Chemical class 0.000 claims description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 125000006850 spacer group Chemical group 0.000 claims description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004973 liquid crystal related substance Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 1
- 229940014800 succinic anhydride Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GBOJZXLCJZDBKO-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 GBOJZXLCJZDBKO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- JKVSAZTYCZKNDX-UHFFFAOYSA-N 1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C1=CC(C(=O)CCC)=CC=C1N1CCOCC1 JKVSAZTYCZKNDX-UHFFFAOYSA-N 0.000 description 1
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical compound C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- VYMSWGOFSKMMCE-UHFFFAOYSA-N 10-butyl-2-chloroacridin-9-one Chemical compound ClC1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 VYMSWGOFSKMMCE-UHFFFAOYSA-N 0.000 description 1
- UIJSCOPBBPNHFC-UHFFFAOYSA-N 2,2-dichloro-2-phenylethanethioic s-acid Chemical compound SC(=O)C(Cl)(Cl)C1=CC=CC=C1 UIJSCOPBBPNHFC-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- XAMXITINZBKDFX-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylethanethioic S-acid Chemical compound COC(C(=S)O)(C1=CC=CC=C1)OC XAMXITINZBKDFX-UHFFFAOYSA-N 0.000 description 1
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- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
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- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 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
- 239000003599 detergent Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- QGVQVNIIRBPOAM-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 QGVQVNIIRBPOAM-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
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- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 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
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000006353 oxyethylene group Chemical group 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229960004599 sodium borate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-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
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F7/0295—Photolytic halogen compounds
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- 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
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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Description
本発明は、感光性樹脂組成物に関する。 The present invention relates to a photosensitive resin composition.
液晶表示装置やタッチパネルなど、表示装置を構成するカラーフィルタとアレイ基板との間には、両基板の間隔を保持するためにスペーサーが設けられている。このスペーサーとしては、従来、ガラスビーズ、プラスチックビーズ等の球形粒子が使用されている。
しかしながら、このような球形粒子を使用した場合、ガラス基板上に無秩序に散布されるため、TFT素子や電極などに損傷を与えたり、透過画素部内に存在すると、入射光の散乱により、液晶表示素子のコントラストが低下したりすることがあった。そこで、球形粒子を散布する代わりに、感光性樹脂組成物を用いてスペーサーを形成することが提案されている。この方法により、任意の場所にスペーサーを形成することができるので、前述の問題点を解決することができる。このような感光性樹脂組成物としては、従来、カルボキシル基とエポキシ基とを有するアクリル共重合体からなるバインダー樹脂を含有するスペーサー形成用組成物が知られており、現像後のポストベーク時にエポキシ基とカルボキシル基との間で架橋し、耐溶剤性、耐熱性に優れたスペーサーパターンを得ることができる(特許文献1)。
また、スペーサー形成用組成物として、(メタ)アクリロイル基とカルボキシル基を有する感放射線硬化性樹脂を含有するスペーサー形成用組成物が知られている(特許文献2)。
A spacer is provided between the color filter constituting the display device, such as a liquid crystal display device or a touch panel, and the array substrate in order to maintain the distance between the two substrates. Conventionally, spherical particles such as glass beads and plastic beads are used as the spacer.
However, when such spherical particles are used, the liquid crystal display element is scattered randomly on the glass substrate. If the TFT element or the electrode is damaged or exists in the transmissive pixel portion, the liquid crystal display element is scattered due to scattering of incident light. In some cases, the contrast of the image was lowered. Therefore, it has been proposed to form a spacer using a photosensitive resin composition instead of spraying spherical particles. By this method, since the spacer can be formed at an arbitrary place, the above-mentioned problems can be solved. As such a photosensitive resin composition, conventionally, a spacer forming composition containing a binder resin made of an acrylic copolymer having a carboxyl group and an epoxy group is known, and an epoxy is used during post-baking after development. A spacer pattern excellent in solvent resistance and heat resistance can be obtained by crosslinking between a group and a carboxyl group (Patent Document 1).
Further, a spacer forming composition containing a radiation-sensitive curable resin having a (meth) acryloyl group and a carboxyl group is known as a spacer forming composition (Patent Document 2).
しかしながら、特許文献1に記載された組成物によって形成されるスペーサーは形成後の性能は良好であるものの、組成物を長期に渡って保存すると、増粘やゲル化が生じてしまうということを本発明者は見いだした。
また、特許文献2に記載された感放射線硬化樹脂においては、(メタ)アクリロイル基を導入する際に、イソシアナート化合物が用いられており、得られる感放射線硬化樹脂、さらにはそれを使用したスペーサー形成用組成物を取り扱う際にはイソシアナート化合物に起因する臭気の問題があることも本発明者は見いだした。
However, although the spacer formed by the composition described in Patent Document 1 has good performance after formation, it is important to note that if the composition is stored for a long period of time, thickening or gelation will occur. The inventor found.
In addition, in the radiation-sensitive curable resin described in Patent Document 2, an isocyanate compound is used when a (meth) acryloyl group is introduced, and the resulting radiation-sensitive curable resin, and further a spacer using the isocyanate compound The inventor has also found that there is an odor problem due to isocyanate compounds when handling the forming composition.
本発明の目的は、貯蔵安定性が良好であり、臭気の問題がない感光性樹脂組成物を提供するとともに本発明の感光性樹脂組成物を用いて形成した硬化樹脂パターンの、耐溶剤性が良好で、表面平滑性に優れ、粒状異物等の塗布欠陥が発生せず、微細なパターンまで解像可能であり、さらに、回復率に優れたフォトスペーサーのようなパターンを形成しうる感光性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a photosensitive resin composition having good storage stability and no odor problem, and having a solvent resistance of a cured resin pattern formed using the photosensitive resin composition of the present invention. Photosensitive resin that is good, has excellent surface smoothness, does not cause coating defects such as granular foreign matter, can be resolved to fine patterns, and can form a pattern like a photo spacer with excellent recovery rate An object is to provide a composition.
本発明者は、前記の課題を解決しうる新たな手段について鋭意検討の結果、特定の樹脂と特定の光重合開始剤とを含む感光性樹脂組成物が前述の課題を解決できることを見出し、本発明に至った。
すなわち本発明は、バインダー樹脂(A)、光重合性化合物(B)、光重合開始剤(C)および溶剤(D)を含有する感光性樹脂組成物において、
バインダー樹脂(A)が、下記(A1)、(A2)および(A4)を共重合させて共重合体1を得て、得られた共重合体1と(A3)とを共重合体1の(A4)に由来するエポキシ基の部位で反応させて共重合体2を得て、さらに得られた共重合体2と(A5)とを共重合体1の(A4)と(A3)の反応により生成した水酸基の部位に反応させて得られる共重合体であり、光重合開始剤(C)が、アセトフェノン系化合物、ビイミダゾール系化合物、オキシム系化合物およびトリアジン系化合物からなる群から選ばれる少なくとも一種の化合物であり、フォトスペーサーを形成するために用いられる感光性樹脂組成物を提供する。
(A1);一分子中にトリシクロデカン骨格およびジシクロペンタジエン骨格からなる群から選ばれる少なくとも1種の骨格と、不飽和結合とを有する化合物
(A2);(A1)および(A4)と共重合可能な不飽和結合を有する化合物
(A3);不飽和結合を有するカルボン酸
(A4);一分子中に不飽和結合とエポキシ基とを有する化合物
(A5);酸無水物
ただし、(A1)〜(A5)は、それぞれ、同一ではない。
As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have found that a photosensitive resin composition containing a specific resin and a specific photopolymerization initiator can solve the above-mentioned problems. Invented.
That is, the present invention relates to a photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D).
The binder resin (A) is obtained by copolymerizing the following (A1), (A2) and (A4) to obtain a copolymer 1, and the obtained copolymer 1 and (A3) are combined into the copolymer 1. The copolymer 2 is obtained by reacting at the site of the epoxy group derived from (A4), and the obtained copolymer 2 and (A5) are further reacted with (A4) and (A3) of the copolymer 1 The photopolymerization initiator (C) is a copolymer obtained by reacting with a hydroxyl group produced by the above, at least selected from the group consisting of acetophenone compounds, biimidazole compounds, oxime compounds and triazine compounds. A photosensitive resin composition that is a kind of compound and is used for forming a photospacer is provided.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A4) Compound (A3) having polymerizable unsaturated bond; Carboxylic acid (A4) having unsaturated bond; Compound (A5) having unsaturated bond and epoxy group in one molecule; Acid anhydride provided that (A1) ~ (A5) are not the same.
また、本発明は、前記の感光性樹脂組成物を用いて形成されるパターン、前記の感光性樹脂組成物を用いて形成されるフォトスペーサー、前記のフォトスペーサーを含んでなるカラーフィルタならびに前記のカラーフィルタを具備する表示装置を提供する。
Further, the present invention, the photosensitive resin composition of the patterns formed by using the photo spacers are formed using the photosensitive resin composition, a color filter and said comprising said full Otosupesa over A display device including the color filter is provided.
本発明の感光性樹脂組成物は、貯蔵安定性が良好であり、臭気の問題がなく、形成された塗膜やパターンは、耐溶剤性が良好で、表面平滑性が優れ、粒状異物等の塗布欠陥が発生せず、微細なパターンまで解像可能であり、さらに、フォトスペーサーのようなパターンを残すことに適している。 The photosensitive resin composition of the present invention has good storage stability, no odor problem, the formed coating film or pattern has good solvent resistance, excellent surface smoothness, particulate foreign matter, etc. A coating defect does not occur, it is possible to resolve a fine pattern, and it is suitable for leaving a pattern like a photo spacer.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の感光性樹脂組成物は、バインダー樹脂(A)、光重合性化合物(B)および光重合開始剤(C)、さらに任意にその他の添加剤(E)が、溶剤(D)に溶解または分散されてなる。 In the photosensitive resin composition of the present invention, the binder resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), and optionally other additives (E) are dissolved in the solvent (D). Or distributed.
バインダー樹脂(A)は、光や熱の作用による反応性およびアルカリ溶解性を有するものである。本発明の感光性樹脂組成物に用いられるバインダー樹脂(A)は、下記下記(A1)、(A2)および(A4)を共重合させて共重合体1を得て、得られた共重合体1と(A3)とを共重合体1の(A4)に由来するエポキシ基の部位で反応させて共重合体2を得て、さらに得られた共重合体2と(A5)とを共重合体1の(A4)と(A3)の反応により生成した水酸基の部位に反応させて得られる共重合体である。
(A1);一分子中にトリシクロデカン骨格およびジシクロペンタジエン骨格からなる群から選ばれる少なくとも1種の骨格と、不飽和結合とを有する化合物
(A2);(A1)および(A4)と共重合可能な不飽和結合を有する化合物
(A3);不飽和結合を有するカルボン酸
(A4);一分子中に不飽和結合とエポキシ基とを有する化合物
(A5);酸無水物
ただし、(A1)〜(A5)は、それぞれ、互いに同一ではない。
The binder resin (A) has reactivity and alkali solubility due to the action of light and heat. The binder resin (A) used in the photosensitive resin composition of the present invention is obtained by copolymerizing the following (A1), (A2) and (A4) to obtain a copolymer 1, and the obtained copolymer 1 and (A3) are reacted at the site of the epoxy group derived from (A4) of copolymer 1 to obtain copolymer 2, and the obtained copolymer 2 and (A5) are copolymerized. This is a copolymer obtained by reacting with the site of the hydroxyl group produced by the reaction of (A4) and (A3) of the coalescence 1.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A4) Compound (A3) having polymerizable unsaturated bond; Carboxylic acid (A4) having unsaturated bond; Compound (A5) having unsaturated bond and epoxy group in one molecule; Acid anhydride provided that (A1) -(A5) are not mutually the same.
一分子中に不飽和結合とトリシクロデカン骨格およびジシクロペンタジエン骨格からなる群から選ばれる少なくとも1種の骨格と、不飽和結合とを有する化合物(A1)としては、具体的には、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニルオキシエチル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレートが挙げられる。これらは、それぞれ単独で、または両者を組合せて用いることができる。ここで、本明細書中における(メタ)アクリレートの記載は、アクリレートおよび/またはメタクリレートを表す。 As the compound (A1) having an unsaturated bond, at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule, and an unsaturated bond, specifically, dicyclo Examples include pentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination. Here, description of (meth) acrylate in this specification represents an acrylate and / or a methacrylate.
(A1)および(A4)と共重合可能な不飽和結合を有する化合物(A2)としては、具体的には、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレートおよびアミノエチル(メタ)アクリレートのような不飽和カルボン酸の無置換または置換アルキルエステル;
シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、シクロヘプチル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、メンチル(メタ)アクリレート、シクロペンテニル(メタ)アクリレート、シクロヘキセニル(メタ)アクリレート、シクロヘプテニル(メタ)アクリレート、シクロオクテニル(メタ)アクリレート、メンタジエニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ピナニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ノルボルネニル(メタ)アクリレート、ピネニル(メタ)アクリレートのような不飽和カルボン酸の脂環式基を含むエステル化合物;
オリゴエチレングリコールモノアルキル(メタ)アクリレートのようなグリコール類のモノ飽和カルボン酸エステル化合物;
ベンジル(メタ)アクリレート、フェノキシ(メタ)アクリレートのような不飽和カルボン酸の芳香環を含むエステル化合物;
スチレン、α−メチルスチレン、α−フェニルスチレンおよびビニルトルエンのような芳香族ビニル化合物;
酢酸ビニルおよびプロピオン酸ビニルのようなカルボン酸ビニルエステル;
(メタ)アクリロニトリルおよびα−クロロアクリロニトリルのようなシアン化ビニル化合物;
N−シクロヘキシルマレイミドやN−フェニルマレイミド、N−ベンジルマレイミドのようなN−置換マレイミド化合物などが挙げられる。これらは、それぞれ単独で、または組合せて用いることができる。
Specific examples of the compound (A2) having an unsaturated bond copolymerizable with (A1) and (A4) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as ethyl (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. These can be used alone or in combination.
不飽和結合を有するカルボン酸(A3)としては、具体的には、アクリル酸およびメタクリル酸が挙げられる。アクリル酸およびメタクリル酸は、それぞれ単独で、または両者を組合せて用いることができる。また、これらのアクリル酸やメタクリル酸に加えて、その他の不飽和基を有するカルボン酸を用いることができる。その他の不飽和基を有するカルボン酸としては、具体的に、クロトン酸、イタコン酸、マレイン酸、フマル酸などが挙げられる。また、α−(ヒドロキシメチル)アクリル酸のような、同一分子中にヒドロキシ基およびカルボキシル基を含有する不飽和基を有するカルボン酸を併用することもできる。 Specific examples of the carboxylic acid (A3) having an unsaturated bond include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other carboxylic acids having an unsaturated group can be used. Specific examples of other carboxylic acid having an unsaturated group include crotonic acid, itaconic acid, maleic acid, and fumaric acid. In addition, a carboxylic acid having an unsaturated group containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can be used in combination.
一分子中に不飽和結合とエポキシ基とを有する化合物(A4)としては、(メタ)アクリル酸グリシジル、(メタ)アクリル酸−β−メチルグリシジル、(メタ)アクリル酸−β−エチルグリシジル、(メタ)アクリル酸−β−プロピルグリシジル、α−エチルアクリル酸−β−メチルグリシジル、(メタ)アクリル酸−3−メチル−3,4−エポキシブチル、(メタ)アクリル酸−3−エチル−3,4−エポキシブチル、(メタ)アクリル酸−4−メチル−4,5−エポキシペンチル、(メタ)アクリル酸−5−メチル−5,6−エポキシヘキシル、グリシジルビニルエーテルなどが挙げられ、好ましくは(メタ)アクリル酸グリシジルが挙げられる。 As the compound (A4) having an unsaturated bond and an epoxy group in one molecule, glycidyl (meth) acrylate, (meth) acrylic acid-β-methylglycidyl, (meth) acrylic acid-β-ethylglycidyl, ( (Meth) acrylic acid-β-propylglycidyl, α-ethylacrylic acid-β-methylglycidyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl, (meth) acrylic acid-3-ethyl-3, Examples include 4-epoxybutyl, (meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid-5-methyl-5,6-epoxyhexyl, and glycidyl vinyl ether. ) Glycidyl acrylate.
酸無水物(A5)は、分子中に酸無水物基を1個有する化合物であり、具体的には、マレイン酸無水物、コハク酸無水物、イタコン酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルエンドメチレンテトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、トリメリット酸無水物などが挙げられ、好ましくはテトラヒドロフタル酸無水物が挙げられる。 The acid anhydride (A5) is a compound having one acid anhydride group in the molecule, specifically, maleic acid anhydride, succinic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid. Examples of the acid anhydride include hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, and the like. Tetrahydrophthalic anhydride is preferable.
本発明に使用されるバインダー樹脂(A)は、(A1)、(A2)および(A4)を共重合させて共重合体1を得て、得られた共重合体1と(A3)とを反応させて共重合体2を得て、さらに得られた共重合体2と(A5)とを反応させて得られる共重合体である。 The binder resin (A) used in the present invention is obtained by copolymerizing (A1), (A2) and (A4) to obtain a copolymer 1, and the obtained copolymer 1 and (A3) It is a copolymer obtained by reacting to obtain a copolymer 2, and further reacting the obtained copolymer 2 with (A5).
まず、共重合体1を得るために、(A1)、(A2)および(A4)を共重合させる。
この共重合時は、通常の条件下で行なわれる。例えば、撹拌機、温度計、還流冷却管、滴下ロートおよび窒素導入管を備えたフラスコに、(A1)、(A2)および(A4)の合計量に対して、質量基準で、0.5〜20倍量の溶剤を導入し、フラスコ内雰囲気を空気から窒素に置換する。その後、溶剤を40〜140℃に昇温した後、(A1)、(A2)および(A4)の所定量、(A1)、(A2)および(A4)の合計量に対して、質量基準で、0〜20倍量の溶剤、およびアゾビスイソブチロニトリルやベンゾイルパーオキサイドなどの重合開始剤を、(A1)、(A2)および(A4)の合計モル数に対して、0.1〜10モル%添加した溶液(室温または加熱下にて撹拌溶解)を滴下ロートから0.1〜8時間かけて前記のフラスコに滴下し、さらに40〜140℃で1〜10時間撹拌する。
なお、上記の工程において、重合開始剤の一部または全量をフラスコ側に仕込んでもよいし、(A1)、(A2)および(A4)の一部または全量をフラスコ側に仕込んでもよい。また、分子量や分子量分布を制御するために、α−メチルスチレンダイマーやメルカプト化合物を連鎖移動剤として使用してもよい。α−メチルスチレンダイマーやメルカプト化合物の使用量は、(A1)〜(A3)の合計量に対して、質量基準で、0.005〜5%である。なお、上記した重合条件は、製造設備や重合による発熱量等などを考慮し、仕込み方法や反応温度を適宜調整してもよい。
First, in order to obtain the copolymer 1, (A1), (A2) and (A4) are copolymerized.
This copolymerization is performed under ordinary conditions. For example, in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 0.5 to 0.5 on a mass basis with respect to the total amount of (A1), (A2) and (A4). A 20-fold amount of solvent is introduced, and the atmosphere in the flask is replaced with nitrogen from air. Then, after heating up a solvent to 40-140 degreeC, it is a mass reference | standard with respect to the predetermined amount of (A1), (A2) and (A4), and the total amount of (A1), (A2) and (A4). 0 to 20 times the amount of solvent, and a polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide are added in an amount of 0.1 to the total number of moles of (A1), (A2) and (A4). A solution added with 10 mol% (stirred and dissolved at room temperature or under heating) is dropped from the dropping funnel into the flask over 0.1 to 8 hours, and further stirred at 40 to 140 ° C. for 1 to 10 hours.
In the above step, a part or the whole amount of the polymerization initiator may be charged to the flask side, and a part or the whole amount of (A1), (A2) and (A4) may be charged to the flask side. Moreover, in order to control molecular weight and molecular weight distribution, you may use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% on a mass basis with respect to the total amount of (A1)-(A3). In addition, the above-described polymerization conditions may be appropriately adjusted in the preparation method and the reaction temperature in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
それぞれから導かれる構成成分の比率としては、前記の共重合体1を構成する構成成分の合計モル数に対してモル分率で、以下の範囲にあることが好ましい。 The ratio of the component derived from each is preferably in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the copolymer 1.
(A1)から導かれる構成単位;2〜40モル%
(A2)から導かれる構成単位;2〜95モル%
(A4)から導かれる構成単位;3〜65モル%
Structural units derived from (A1); 2 to 40 mol%
Structural units derived from (A2); 2 to 95 mol%
Structural units derived from (A4); 3 to 65 mol%
また、前記の構成成分の比率が以下の範囲であると、より好ましい。 Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
(A1)から導かれる構成単位;5〜35モル%
(A2)から導かれる構成単位;5〜80モル%
(A4)から導かれる構成単位;15〜60モル%
Structural units derived from (A1); 5-35 mol%
Structural units derived from (A2); 5 to 80 mol%
Structural units derived from (A4); 15-60 mol%
前記の構成比率が、上記の範囲にあると、可とう性および耐熱性のバランスが良好であり、好ましい幹ポリマーが得られる。 When the composition ratio is in the above range, the balance between flexibility and heat resistance is good, and a preferable trunk polymer is obtained.
次に、前記の共重合体1に(A3)を付加してバインダー樹脂(A)に光/熱硬化性を付与する。 Next, (A3) is added to the copolymer 1 to impart light / thermosetting properties to the binder resin (A).
共重合体1と(A3)との反応は、例えば、特開2001−89533号公報に記載の条件で行われることができる。具体的には、フラスコ内雰囲気を窒素から空気に置換し、前記共重合体1の(A4)から導かれる構成単位に対して、モル分率で、5〜100モル%の(A3)、カルボキシル基とエポキシ基の反応触媒として、例えば、トリスジメチルアミノメチルフェノールを(A1)〜(A4)の合計量に対して、質量基準で、0.01〜5%、および重合禁止剤として、例えば、ハイドロキノンを(A1)〜(A4)の合計量に対して、質量基準で、0.001〜5%をフラスコ内に入れて、60〜130℃で、1〜10時間反応することにより、前記の共重合体1と(A3)とを反応させることができる。なお、重合条件と同様に、製造設備や重合による発熱量等などを考慮し、仕込み方法や反応温度を適宜調整してもよい。 Reaction of the copolymer 1 and (A3) can be performed on the conditions as described in Unexamined-Japanese-Patent No. 2001-89533, for example. Specifically, the atmosphere in the flask is replaced with air from nitrogen, and 5 to 100 mol% of (A3), carboxyl with respect to the structural unit derived from (A4) of the copolymer 1 As a reaction catalyst for a group and an epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% on a mass basis with respect to the total amount of (A1) to (A4), and as a polymerization inhibitor, for example, By adding 0.001 to 5% in a flask on a mass basis with respect to the total amount of (A1) to (A4), the hydroquinone is reacted at 60 to 130 ° C. for 1 to 10 hours. Copolymer 1 and (A3) can be reacted. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
(A3)の付加量は、(A1)、(A2)および(A4)を共重合させて得られた樹脂中のエポキシ基(A4成分に由来)に対して、5〜100モル%、好ましくは10〜95モル%である。
(A4)の組成比が上記範囲内にあると、十分な光硬化性や熱硬化性が得られ、信頼性に優れるので好ましい。
The amount of (A3) added is 5 to 100 mol%, preferably 5 to 100 mol%, based on the epoxy group (derived from the A4 component) in the resin obtained by copolymerizing (A1), (A2) and (A4). 10 to 95 mol%.
It is preferable that the composition ratio of (A4) is in the above range because sufficient photocurability and thermosetting can be obtained and the reliability is excellent.
次に、前記共重合体2と(A5)とを反応させてバインダー樹脂(A)にアルカリ溶解性を付与する。 Next, the copolymer 2 and (A5) are reacted to impart alkali solubility to the binder resin (A).
共重合体2と(A5)との反応は、例えば、特開2001−89533号公報に記載の条件で行われることができる。具体的には、前記共重合体2の(A3)から導かれる構成単位に対して、モル分率で、5〜100モル%の(A5)、反応触媒として、例えば、トリエチルアミンを(A1)〜(A4)の合計量に対して、質量基準で、0.01〜5%をフラスコ内に入れて、60〜130℃で、1〜10時間反応することにより、前記の共重合体2と(A5)とを反応させることができる。なお、重合条件と同様に、製造設備や重合による発熱量等などを考慮し、仕込み方法や反応温度を適宜調整してもよい。 The reaction between the copolymer 2 and (A5) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, with respect to the structural unit derived from (A3) of the copolymer 2, (A5) having a molar fraction of 5 to 100 mol%, for example, triethylamine is used as the reaction catalyst (A1) to With respect to the total amount of (A4), 0.01 to 5% is put in a flask on a mass basis and reacted at 60 to 130 ° C. for 1 to 10 hours. A5) can be reacted. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
(A5)の付加量は、共重合体2のアルコール性水酸基のモル数(A3成分に由来)に対して、5〜100モル%、好ましくは10〜95モル%である。 The addition amount of (A5) is 5 to 100 mol%, preferably 10 to 95 mol%, based on the number of moles of the alcoholic hydroxyl group of copolymer 2 (derived from component A3).
前記のバインダー樹脂(A)のポリスチレン換算の重量平均分子量は、好ましくは3,000〜100,000であり、より好ましくは5,000〜30,000である。バインダー樹脂(A)の重量平均分子量が、前記の範囲にあると、塗布性が良好であり、また現像時に膜減りが生じにくく、さらに現像時に未露光部分の抜け性が良好である傾向にあり、好ましい。 The weight average molecular weight in terms of polystyrene of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the binder resin (A) is within the above range, the coating property is good, the film is not easily reduced during development, and the unexposed part tends to be easily removed during development. ,preferable.
バインダー樹脂(A)の分子量分布[重量平均分子量(Mw)/数平均分子量(Mn)]は、好ましくは1.5〜6.0であり、より好ましくは1.8〜4.0である。分子量分布が、前記の範囲にあると、現像性に優れるので好ましい。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. The molecular weight distribution in the above range is preferable because the developability is excellent.
本発明の感光性樹脂組成物に用いられるバインダー樹脂(A)の含有量は、感光性樹脂組成物の固形分に対して質量分率で、通常、5〜90質量%、好ましくは10〜70質量%である。バインダー樹脂(A)の含有量が、前記の範囲にあると、現像液への溶解性が十分であり、未露光部分の基板上に現像残渣が発生しにくく、また現像時に露光部の膜減りが生じにくく、未露光部分の抜け性が良好な傾向にあり、好ましい。 Content of binder resin (A) used for the photosensitive resin composition of this invention is a mass fraction with respect to solid content of the photosensitive resin composition, and is 5-90 mass% normally, Preferably it is 10-70. % By mass. When the content of the binder resin (A) is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the unexposed part of the substrate, and the film thickness of the exposed part is reduced during development. This is preferable because the non-exposed portion tends to be easily removed.
なお、本発明のように、バインダー樹脂の側鎖に(メタ)アクリル基を導入したバインダー樹脂としては、本発明のバインダー樹脂(A)の他に、カルボキシル基を有するバインダー樹脂と、一分子中にエポキシ基と(メタ)アクリル基とを含有する化合物とを反応させたタイプがある。このタイプのものは、側鎖の(メタ)アクリル基含有量を高くするためには、カルボキシル基比率が高いバインダー樹脂を使用しなければならない。ところが、カルボキシル基比率が高いバインダー樹脂は、溶液粘度が高く、合成上および取り扱いにおいて、問題がある。本発明は、カルボキシル基を含有しない幹ポリマーを使用するので、前述のような問題点はない。 As in the present invention, the binder resin having a (meth) acryl group introduced into the side chain of the binder resin, in addition to the binder resin (A) of the present invention, a binder resin having a carboxyl group, and in one molecule There is a type in which an epoxy group and a compound containing a (meth) acryl group are reacted. In this type, in order to increase the content of the (meth) acrylic group in the side chain, a binder resin having a high carboxyl group ratio must be used. However, a binder resin having a high carboxyl group ratio has a high solution viscosity, which causes problems in synthesis and handling. Since the present invention uses a trunk polymer that does not contain a carboxyl group, there is no problem as described above.
本発明の感光性樹脂組成物に含まれる光重合性化合物(B)は、単官能モノマーの他、2官能、その他の多官能モノマーであることができる。
単官能モノマーの具体例としては、ノニルフェニルカルビトールアクリレート、2−ヒドロキシ−3−フェノキシプロピルアクリレート、2−エチルヘキシルカルビトールアクリレート、2−ヒドロキシエチルアクリレート、N−ビニルピロリドンなどが挙げられる。
また2官能モノマーの具体例としては、1,6−ヘキサンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ビスフェノールAのビス(アクリロイロキシエチル)エーテル、3−メチルペンタンジオールジ(メタ)アクリレートなどが挙げられる。
その他の多官能モノマーの具体例としては、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレートと酸無水物との反応物、ジペンタエリスリトールペンタ(メタ)アクリレートと酸無水物との反応物などが挙げられる。なかでも、2官能以上の多官能モノマーが好ましく用いられる。
光重合性化合物(B)の含有量は、感光性樹脂組成物中のバインダー樹脂(A)および光重合性化合物(B)の合計100質量部に対して、好ましくは1〜70質量部、より好ましくは5〜60質量部である。光重合性化合物(B)の含有量が、前記の範囲にあると、組成物を用いて形成された構造物の強度や平滑性、信頼性が良好になる傾向があり、好ましい。
The photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention can be a bifunctional or other polyfunctional monomer in addition to a monofunctional monomer.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Examples thereof include a reaction product of meth) acrylate, pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like. Of these, polyfunctional monomers having two or more functions are preferably used.
The content of the photopolymerizable compound (B) is preferably 1 to 70 parts by mass with respect to 100 parts by mass in total of the binder resin (A) and the photopolymerizable compound (B) in the photosensitive resin composition. Preferably it is 5-60 mass parts. When the content of the photopolymerizable compound (B) is within the above range, the strength, smoothness and reliability of the structure formed using the composition tend to be favorable, which is preferable.
本発明の感光性樹脂組成物に含まれる光重合開始剤(C)としては、アセトフェノン系化合物、ビイミダゾール系化合物、オキシム系化合物、トリアジン系化合物、またはこれらの混合物が用いられる。前記の光重合開始剤と、光重合開始助剤(C−1)とを併用することで、感光性樹脂組成物は更に高感度となり、これを用いてパターンを形成する際の生産性が向上するので、好ましい。しかし、光重合開始助剤(C−1)の吸収波長が光重合開始剤(C)の吸収波長よりも長波長側にある場合、形成した膜の透過率が低くなるので、本発明の効果を損なわない程度であれば使用することができる。 As the photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention, an acetophenone compound, a biimidazole compound, an oxime compound, a triazine compound, or a mixture thereof is used. By using the photopolymerization initiator and the photopolymerization initiation aid (C-1) in combination, the photosensitive resin composition becomes more sensitive, and the productivity when forming a pattern using this is improved. Therefore, it is preferable. However, when the absorption wavelength of the photopolymerization initiator auxiliary agent (C-1) is on the longer wavelength side than the absorption wavelength of the photopolymerization initiator (C), the transmittance of the formed film is lowered, and thus the effect of the present invention. Can be used as long as it does not damage the surface.
前記のアセトフェノン系化合物としては、ジエトキシアセトフェノン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、ベンジルジメチルケタール、2−ヒドロキシ−1−〔4−(2−ヒドロキシエトキシ)フェニル〕−2−メチルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)ブタン−1−オン、アセトフェノン系としては、具体的には、2−(2−メチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(3−メチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(4−メチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−エチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−プロピルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−ブチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2、3−ジメチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2、4−ジメチルベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−クロロベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−ブロモベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(3−クロロベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(4−クロロベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(3−ブロモベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(4−ブロモベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−メトキシベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(3−メトキシベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(4−メトキシベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−メチル−4−メトキシベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−メチル−4−ブロモベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−(2−ブロモ−4−メトキシベンジル)−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン、2−ヒドロキシ−2−メチル−1−〔4−(1−メチルビニル)フェニル〕プロパン−1−オンのオリゴマーなどが挙げられる。 Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- Specific examples of (4-morpholinophenyl) butan-1-one and acetophenone include 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, -(4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenze ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) ) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl)- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2 -Methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer and the like.
前記のビイミダゾール化合物としては、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニルビイミダゾール、2,2’−ビス(2、3−ジクロロフェニル)−4,4’,5,5’−テトラフェニルビイミダゾール(例えば、特開平6−75372号公報、特開平6−75373号公報など参照。)、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニルビイミダゾール、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラ(アルコキシフェニル)ビイミダゾール、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラ(ジアルコキシフェニル)ビイミダゾール、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラ(トリアルコキシフェニル)ビイミダゾール(例えば、特公昭48−38403号公報、特開昭62−174204号公報など参照。)、4,4’5,5’−位のフェニル基がカルボアルコキシ基により置換されているイミダゾール化合物(例えば、特開平7−10913号公報など参照。)などが挙げられ、好ましくは2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニルビイミダゾール、2,2’−ビス(2、3−ジクロロフェニル)−4,4’,5,5’−テトラフェニルビイミダゾールが挙げられる。 Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913) and the like, preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole may be mentioned.
前記のオキシム化合物としては、O−エトキシカルボニル−α−オキシイミノ−1−フェニルプロパン−1−オン、式(a)で表される化合物、式(b)で表される化合物などが挙げられる。 Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by formula (a), a compound represented by formula (b), and the like.
前記のトリアジン系化合物としては、2,4−ビス(トリクロロメチル)−6−(4−メトキシフェニル)−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−(4−メトキシナフチル)−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−ピペロニル−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−(4−メトキシスチリル)−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−〔2−(5−メチルフラン−2−イル)エテニル〕−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−〔2−(フラン−2−イル)エテニル〕−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−〔2−(4−ジエチルアミノ−2−メチルフェニル)エテニル〕−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−〔2−(3,4−ジメトキシフェニル)エテニル〕−1,3,5−トリアジンなどが挙げられる。 Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) Thenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
また、本発明の効果を損なわない程度であれば、この分野で通常用いられている光重合開始剤等をさらに併用することができ、例えば、ベンゾイン系化合物、ベンゾフェノン系化合物、チオキサントン系化合物、アントラセン系化合物などの光重合開始剤が挙げられる。
より具体的には以下のような化合物を挙げることができ、これらをそれぞれ単独で、または2種以上組合せて用いることができる。
In addition, a photopolymerization initiator or the like commonly used in this field can be used in combination as long as the effect of the present invention is not impaired. For example, a benzoin compound, a benzophenone compound, a thioxanthone compound, an anthracene And photopolymerization initiators such as a series compound.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.
前記のベンゾイン系化合物としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルなどが挙げられる。 Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
前記のベンゾフェノン系化合物としては、例えば、ベンゾフェノン、o−ベンゾイル安息香酸メチル、4−フェニルベンゾフェノン、4−ベンゾイル−4’−メチルジフェニルサルファイド、3,3’,4,4’−テトラ(tert−ブチルパーオキシカルボニル)ベンゾフェノン、2,4,6−トリメチルベンゾフェノンなどが挙げられる。 Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
前記のチオキサントン系化合物としては、例えば、2−イソプロピルチオキサントン、4−イソプロピルチオキサントン、2,4−ジエチルチオキサントン、2,4−ジクロロチオキサントン、1−クロロ−4−プロポキシチオキサントンなどが挙げられる。 Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
前記のアントラセン系化合物としては、例えば、9,10−ジメトキシアントラセン、2−エチル−9,10−ジメトキシアントラセン、9,10−ジエトキシアントラセン、2−エチル−9,10−ジエトキシアントラセンなどが挙げられる。 Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done.
その他にも、2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキシド、10−ブチル−2−クロロアクリドン、2−エチルアントラキノン、ベンジル、9,10−フェナンスレンキノン、カンファーキノン、フェニルグリオキシル酸メチル、チタノセン化合物などの光重合開始剤を併用することができる。 In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate A photopolymerization initiator such as a titanocene compound can be used in combination.
また、連鎖移動を起こしうる基を有する光重合開始剤として、特表2002−544205号公報に記載されているものを併用することができる。
前記の連鎖移動を起こしうる基を有する光重合開始剤としては、例えば、下記式(2)〜(7)のものが挙げられる。
Moreover, what is described in Tokushu 2002-544205 gazette can be used together as a photoinitiator which has the group which can raise | generate a chain transfer.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the thing of following formula (2)-(7) is mentioned, for example.
前記の連鎖移動を起こしうる基を有する光重合開始剤は、共重合体1の構成成分(A2)として使用することができる。そして、(A2)を用いて得られるバインダー樹脂(A)は、本発明のバインダー樹脂に併用することができる。 The photopolymerization initiator having a group capable of causing chain transfer can be used as the constituent component (A2) of the copolymer 1. And binder resin (A) obtained using (A2) can be used together with the binder resin of this invention.
また、光重合開始剤に光重合開始助剤(C−1)を組合せて用いることもできる。光重合開始助剤としては、アミン化合物および下記のカルボン酸化合物が好ましく、アミン化合物は芳香族アミン化合物がより好ましい。しかし、光重合開始助剤(C−1)の吸収波長が光重合開始剤(C)の吸収波長よりも長波長側にある場合、形成した膜の透過率が低くなるので、本発明の効果を損なわない程度であれば使用することができる。
光重合開始助剤の具体例としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミンなどの脂肪族アミン化合物、4−ジメチルアミノ安息香酸メチル、4−ジメチルアミノ安息香酸エチル、4−ジメチルアミノ安息香酸イソアミル、4−ジメチルアミノ安息香酸2−エチルヘキシル、安息香酸2−ジメチルアミノエチル、N,N−ジメチルパラトルイジン、4,4’−ビス(ジメチルアミノ)ベンゾフェノン(通称;ミヒラーズケトン)、4,4’−ビス(ジエチルアミノ)ベンゾフェノンのような芳香族アミン化合物が挙げられる。
前記のカルボン酸化合物としては、フェニルチオ酢酸、メチルフェニルチオ酢酸、エチルフェニルチオ酢酸、メチルエチルフェニルチオ酢酸、ジメチルフェニルチオ酢酸、メトキシフェニルチオ酢酸、ジメトキシフェニルチオ酢酸、クロロフェニルチオ酢酸、ジクロロフェニルチオ酢酸、N−フェニルグリシン、フェノキシ酢酸、ナフチルチオ酢酸、N−ナフチルグリシン、ナフトキシ酢酸などの芳香族ヘテロ酢酸類が挙げられる。
In addition, the photopolymerization initiator may be used in combination with a photopolymerization initiation assistant (C-1). As the photopolymerization initiation assistant, an amine compound and the following carboxylic acid compound are preferable, and the amine compound is more preferably an aromatic amine compound. However, when the absorption wavelength of the photopolymerization initiator auxiliary agent (C-1) is on the longer wavelength side than the absorption wavelength of the photopolymerization initiator (C), the transmittance of the formed film is lowered, and thus the effect of the present invention. Can be used as long as it does not damage the surface.
Specific examples of the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid. Isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′- Examples include aromatic amine compounds such as bis (diethylamino) benzophenone.
Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Examples include aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
光重合開始剤(C)の含有量は、バインダー樹脂(A)および光重合性化合物(B)の合計100質量部に対して、好ましくは0.1〜40質量部、より好ましくは1〜30質量部である。
また、光重合開始助剤(C−1)を用いる場合、その含有量は、前記の基準で、好ましくは0.1〜50質量部、より好ましくは0.1〜40質量部である。
光重合開始剤(C)の含有量が前記の範囲にあると、感光性樹脂組成物が高感度となり、前記の感光性樹脂組成物を用いて形成した構造物の強度や、前記の構造物の表面における平滑性が良好になる傾向があり、好ましい。前記に加えて、光重合開始助剤(C−1)の量が前記の範囲にあると、得られる感光性樹脂組成物の感度がさらに高くなり、前記の感光性樹脂組成物を用いて形成するパターン基板の生産性が向上する傾向にあり、好ましい。
The content of the photopolymerization initiator (C) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts with respect to 100 parts by mass in total of the binder resin (A) and the photopolymerizable compound (B). Part by mass.
Moreover, when using photoinitiator adjuvant (C-1), the content is 0.1-50 mass parts on the said reference | standard, More preferably, it is 0.1-40 mass parts.
When the content of the photopolymerization initiator (C) is in the above range, the photosensitive resin composition becomes highly sensitive, the strength of the structure formed using the photosensitive resin composition, and the structure There is a tendency that the smoothness on the surface of the film becomes good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained photosensitive resin composition is further increased, and the photosensitive resin composition is formed using the photosensitive resin composition. This is preferable because the productivity of the patterned substrate tends to be improved.
本発明の感光性樹脂組成物は溶剤(D)を含む。前記の溶剤(D)としては、感光性樹脂組成物の分野で用いられている各種の有機溶剤を用いることができる。その具体例としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテルおよびエチレングリコールモノブチルエーテルなどのエチレングリコールモノアルキルエーテル類;
ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテルおよびジエチレングリコールジブチルエーテルなどのジエチレングリコールジアルキルエーテル類;
メチルセロソルブアセテートおよびエチルセロソルブアセテートなどのエチレングリコールアルキルエーテルアセテート類;
プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、メトキシブチルアセテートおよびメトキシペンチルアセテートなどのアルキレングリコールアルキルエーテルアセテート類;
ベンゼン、トルエン、キシレンおよびメシチレンのような芳香族炭化水素類;
メチルエチルケトン、アセトン、メチルアミルケトン、メチルイソブチルケトンおよびシクロヘキサノンなどのケトン類;
エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコールおよびグリセリンなどのアルコール類;
3−エトキシプロピオン酸エチルおよび3−メトキシプロピオン酸メチルなどのエステル類;
γ−ブチロラクトンなどの環状エステル類などが挙げられる。
上記の溶剤のうち、塗布性、乾燥性の点から、好ましくは上記溶剤の中で沸点が100〜200℃の有機溶剤が挙げられ、より好ましくは、アルキレングリコールアルキルエーテルアセテート類、ケトン類、3−エトキシプロピオン酸エチルおよび3−メトキシプロピオン酸メチルのようなエステル類が挙げられ、とりわけ好ましくは、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、シクロヘキサノン、3−エトキシプロピオン酸エチル、3−メトキシプロピオン酸メチルが挙げられる。
これらの溶剤(D)は、それぞれ単独で、または2種類以上混合して用いることができる。
本発明の感光性樹脂組成物における溶剤(D)の含有量は、感光性樹脂組成物に対して質量分率で、通常、60〜90質量%、好ましくは70〜85質量%である。溶剤(D)の含有量が、前記の範囲にあると、スピンコーター、スリット&スピンコーター、スリットコーター(ダイコーター、カーテンフローコーターとも呼ばれることがある。)、インクジェットなどの塗布装置で塗布したときに塗布性が良好になる傾向があり、好ましい。
The photosensitive resin composition of the present invention contains a solvent (D). As said solvent (D), the various organic solvent currently used in the field | area of the photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
Among the above solvents, organic solvents having a boiling point of 100 to 200 ° C. are preferable among the above solvents from the viewpoints of coating properties and drying properties, and more preferable are alkylene glycol alkyl ether acetates, ketones, 3 -Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, particularly preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy And methyl propionate.
These solvents (D) can be used alone or in admixture of two or more.
Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition, and is 60-90 mass% normally, Preferably it is 70-85 mass%. When the content of the solvent (D) is within the above range, when applied by a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), an ink jet or the like. The coating property tends to be good, which is preferable.
本発明の感光性樹脂組成物には、必要に応じて、充填剤、他の高分子化合物、界面活性剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止材、凝集剤、連鎖移動剤などの添加剤(E)を併用することもできる。
充填剤としては、ガラス、シリカ、アルミナなどが例示される。
他の高分子化合物としては、エポキシ樹脂、マレイミド樹脂などの硬化性樹脂やポリビニルアルコール、ポリアクリル酸、ポリエチレングリコールモノアルキルエーテル、ポリフルオロアルキルアクリレート、ポリエステル、ポリウレタン等の熱可塑性樹脂などが例示される。
界面活性剤としては、市販の界面活性剤を用いることができ、例えば、シリコーン系、フッ素系、エステル系、カチオン系、アニオン系、ノニオン系、両性などの界面活性剤などが挙げられ、それぞれ単独でまたは2種以上を組合せて用いられる。前記の界面活性剤の例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリエチレングリコールジエステル類、ソルビタン脂肪酸エステル類、脂肪酸変性ポリエステル類、3級アミン変性ポリウレタン類、ポリエチレンイミン類等のほか、商品名でKP(信越化学工業(株)製)、ポリフロー(共栄化学(株)製)、エフ
トップ(トーケムプロダクツ社製)、メガファック(大日本インキ化学工業(株)製)、フロラード(住友スリーエム(株)製)、アサヒガード、サーフロン(以上、旭硝子(株)製)、ソルスパース(ゼネカ(株)製)、EFKA(EFKA CHEMICALS社製)、PB82
1(味の素(株)製)などが挙げられる。
密着促進剤として具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2−メトキシエトキシ)シラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−クロロプロピルメチルジメトキシシラン、3−クロロプロピルトリメトキシシラン、3−メタクリロイロキシプロピルトリメトキシシラン、3−メルカプトプロピルトリメトキシシランなどが挙げられる。
酸化防止剤として具体的には、2,2’−チオビス(4−メチル−6−tert−ブチルフェノール)、2,6−ジ−tert−ブチル−4−メチルフェノールなどが挙げられる。
紫外線吸収剤として具体的には、2−(3−tert−ブチル−2−ヒドロキシ−5−メチルフェニル)−5−クロロベンゾトリアゾール、アルコキシベンゾフェノンなどが挙げられる。
また凝集剤として具体的には、ポリアクリル酸ナトリウムなどが挙げられる。
連鎖移動剤としては、ドデシルメルカプタン、2,4−ジフェニル−4−メチル−1−ペンテンなどが挙げられる。
In the photosensitive resin composition of the present invention, if necessary, a filler, other polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation material, an aggregating agent, a chain transfer An additive (E) such as an agent can also be used in combination.
Examples of the filler include glass, silica, and alumina.
Examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. .
As the surfactant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Or a combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.) ), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB82
1 (manufactured by Ajinomoto Co., Inc.).
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
Specific examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the flocculant include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.
本発明の感光性樹脂組成物は、特許文献1に記載されるような樹脂成分を含まないので、貯蔵前の粘度に対する貯蔵後の粘度の変化率が小さく、好ましい。 Since the photosensitive resin composition of the present invention does not contain a resin component as described in Patent Document 1, the rate of change in viscosity after storage with respect to the viscosity before storage is small, which is preferable.
本発明の感光性樹脂組成物は、前記(A)〜(D)の各成分、必要に応じて(E)成分を任意の順序で混合するなどの方法により、容易に調整することができる。 The photosensitive resin composition of this invention can be easily adjusted by methods, such as mixing each component of said (A)-(D) and (E) component in arbitrary orders as needed.
感光性樹脂組成物は、例えば、以下のようにして基材(例えば、カラーフィルタや液晶駆動用回路が基板上に形成されたもの。)上または基板(例えば、ガラス、プラスチック、シリコンなど。)上に塗布し、光硬化および現像を行って、パターンを形成することができる。まず、この組成物を基板または先に形成された感光性樹脂組成物の固形分からなる層の上に塗布する。塗布は、スピンコーター、スリットコーター、カーテンフローコーター、バーコーターなど、公知の装置を用いて行われる。
塗布された感光性樹脂組成物層は、プリベークすることにより溶剤などの揮発成分が除去されて、平滑な塗膜を得る。このときの塗膜の厚さは、通常、1〜6μm程度である。
このようにして得られた塗膜に、目的のパターンを形成するためのマスクを介して紫外線を照射する。この際、露光部全体に均一に平行光線が照射され、かつマスクと基板の正確な位置合わせが行われるよう、マスクアライナーやステッパーなどの装置を使用するのが好ましい。さらにこの後、硬化の終了した塗膜をアルカリ水溶液に接触させて未露光部を溶解させ、現像することにより、目的とするパターン形状が得られる。現像方法は、液盛り法、ディッピング法、スプレー法等のいずれでも良い。さらに現像時に基板を任意の角度に傾けても良い。現像後、水洗を行い、さらに必要に応じて150〜230℃で10〜60分のポストベークを施すこともできる。
The photosensitive resin composition is, for example, on a substrate (for example, a color filter or a liquid crystal driving circuit formed on a substrate) or a substrate (for example, glass, plastic, silicon, etc.) as follows. The pattern can be formed by coating on top, photocuring and developing. First, this composition is apply | coated on the layer which consists of solid content of the photosensitive resin composition formed previously in the board | substrate. The coating is performed using a known apparatus such as a spin coater, a slit coater, a curtain flow coater, or a bar coater.
The applied photosensitive resin composition layer is pre-baked to remove volatile components such as a solvent to obtain a smooth coating film. The thickness of the coating film at this time is usually about 1 to 6 μm.
The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the unexposed portion and developed, whereby the intended pattern shape is obtained. The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development. After the development, it is washed with water, and further post-baked at 150 to 230 ° C. for 10 to 60 minutes, if necessary.
パターニング露光後の現像に使用する現像液は、通常、アルカリ性化合物と界面活性剤を含む水溶液である。
アルカリ性化合物は、無機および有機のアルカリ性化合物のいずれでもよい。無機アルカリ性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、燐酸水素二ナトリウム、燐酸二水素ナトリウム、燐酸水素二アンモニウム、燐酸二水素アンモニウム、燐酸二水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ホウ酸ナトリウム、ホウ酸カリウム、アンモニアなどが挙げられる。
また、有機アルカリ性化合物の具体例としては、テトラメチルアンモニウムヒドロキシド、2−ヒドロキシエチルトリメチルアンモニウムヒドロキシド、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、エタノールアミンなどが挙げられる。これらの無機および有機アルカリ性化合物は、それぞれ単独でまたは2種以上組合せて用いることができる。アルカリ現像液中のアルカリ性化合物の濃度は、好ましくは0.01〜10質量%であり、より好ましくは0.03〜5質量%である。
The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
またアルカリ現像液中の界面活性剤は、ノニオン系界面活性剤、アニオン系界面活性剤またはカチオン系界面活性剤のいずれでもよい。
ノニオン系界面活性剤の具体例としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリールエーテル、ポリオキシエチレンアルキルアリールエーテル、その他のポリオキシエチレン誘導体、オキシエチレン/オキシプロピレンブロックコポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミンなどが挙げられる。
アニオン系界面活性剤の具体例としては、ラウリルアルコール硫酸エステルナトリウムやオレイルアルコール硫酸エステルナトリウムのような高級アルコール硫酸エステル塩類、ラウリル硫酸ナトリウムやラウリル硫酸アンモニウムのようなアルキル硫酸塩類、ドデシルベンゼンスルホン酸ナトリウムやドデシルナフタレンスルホン酸ナトリウムのようなアルキルアリールスルホン酸塩類などが挙げられる。
カチオン系界面活性剤の具体例としては、ステアリルアミン塩酸塩やラウリルトリメチルアンモニウムクロライドのようなアミン塩または第四級アンモニウム塩などが挙げられる。
これらの界面活性剤は、それぞれ単独で用いることも、また2種以上組合せて用いることもできる。
アルカリ現像液中の界面活性剤の濃度は、通常、0.01〜10質量%、好ましくは0.05〜8質量%、より好ましくは0.1〜5質量%である。
The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.
以上のような感光性樹脂液の塗布、乾燥、得られる乾燥塗膜へのパターニング露光、そして現像という各操作を経て、基板上あるいはカラーフィルタ基板上に硬化樹脂パターンを形成することができる。
また、この硬化樹脂パターンは、液晶表示装置に使用されるフォトスペーサーとして有用である。
The cured resin pattern can be formed on the substrate or the color filter substrate through the operations such as application of the photosensitive resin liquid, drying, patterning exposure to the resulting dried coating film, and development.
Moreover, this cured resin pattern is useful as a photospacer used in a liquid crystal display device .
そして、本発明の感光性樹脂組成物を用いて製造されたカラーフィルタは、面内の膜厚差が小さく、例えば1〜6μmの膜厚で、面内膜厚差を0.15μm以下、さらには0.05μm以下とすることができる。したがって、こうして得られるカラーフィルタは、平滑性に優れたものであり、また該カラーフィルタを、例えば、特開平11−264969号に記載されたように、カラー液晶表示装置に組み込むことにより、優れた品質の液晶表示装置を高い歩留りで製造することができる。 And the color filter manufactured using the photosensitive resin composition of this invention has a small in-plane film thickness difference, for example, is a film thickness of 1-6 micrometers, and an in-plane film thickness difference is 0.15 micrometer or less, Furthermore, Can be 0.05 μm or less. Therefore, the color filter obtained in this way is excellent in smoothness, and is excellent by incorporating the color filter into a color liquid crystal display device as described in, for example, JP-A-11-264969. A quality liquid crystal display device can be manufactured with a high yield.
上記において、本発明の実施の形態について説明を行ったが、上記に開示された本発明の実施の形態は、あくまで例示であって、本発明の範囲はこれらの実施の形態に限定されない。本発明の範囲は、特許請求の範囲によって示され、さらに特許請求の範囲の記載と均等の意味および範囲内でのすべての変更を含むものである。以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
実施例1、実施例2および比較例1に使用したバインダー樹脂の構造等を、式(X)、式(Y)および表1に示す。表1中、a〜hは、モル比を示す。 The structure and the like of the binder resin used in Example 1, Example 2, and Comparative Example 1 are shown in Formula (X), Formula (Y), and Table 1. In Table 1, a to h indicate molar ratios.
バインダー樹脂には、イソシアナート化合物が用いられていないので、イソシアナート化合物に起因する特有の臭気はなかった。 Since no isocyanate compound was used in the binder resin, there was no peculiar odor caused by the isocyanate compound.
構成単位の説明
a:共重合体1における(A1)から導かれる構成単位。
b:共重合体1における(A2)から導かれる構成単位。
c:共重合体1における(A4)から導かれる構成単位に、(A3)を反応させて導かれる構成単位。
d:共重合体2における(A3)に由来する部位に(A5)を反応させて導かれる構成単位。
e:(A1)、(A2)および(A3)を反応させて得られる共重合体の(A1)から導かれる構成単位。
f:(A1)、(A2)および(A3)を反応させて得られる共重合体の(A2)から導かれる構成単位。
g:(A1)、(A2)および(A3)を反応させて得られる共重合体の(A3)から導かれる構成単位。
h:(A1)、(A2)および(A3)を反応させて得られる共重合体の(A3)から導かれる構成単位に、(A4)から導かれる構成単位を反応させた構成単位。
Explanation of Structural Units a: Structural units derived from (A1) in the copolymer 1.
b: A structural unit derived from (A2) in the copolymer 1.
c: A structural unit derived by reacting (A3) with the structural unit derived from (A4) in the copolymer 1.
d: A structural unit derived by reacting (A5) with a site derived from (A3) in copolymer 2.
e: A structural unit derived from (A1) of the copolymer obtained by reacting (A1), (A2) and (A3).
f: A structural unit derived from (A2) of the copolymer obtained by reacting (A1), (A2) and (A3).
g: A structural unit derived from (A3) of the copolymer obtained by reacting (A1), (A2) and (A3).
h: a structural unit obtained by reacting the structural unit derived from (A4) with the structural unit derived from (A3) of the copolymer obtained by reacting (A1), (A2) and (A3).
上記のバインダーポリマーのポリスチレン換算重量平均分子量(Mw)および数平均分子量(Mn)の測定については、GPC法を用いて、以下の条件で行った。
装置;HLC-8120GPC(東ソー(株)製)
カラム;TSK−GELG4000HXL+TSK−GELG2000HXL(直列接続)
カラム温度;40℃
溶媒;THF
流速;1.0ml/min
注入量;50μl
検出器;RI
測定試料濃度;0.6質量%(溶媒;THF)
校正用標準物質;TSK STANDARD POLYSTYRENE F−40、F−4、F−1、A−2500、A−500(東ソー(株)製)
上記で得られた重量平均分子量および数平均分子量の比を分子量分布(Mw/Mn)とした。
About the measurement of polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of said binder polymer, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw / Mn).
実施例および比較例の配合組成を表2に示す。表2中の数値は質量部数を表す。 Table 2 shows the compositions of the examples and comparative examples. Numerical values in Table 2 represent parts by mass.
2インチ角のガラス基板(コーニング社製、#1737)を、中性洗剤、水およびアルコールで順次洗浄してから乾燥した。このガラス基板上に、感光性樹脂組成物(表2)を、100mJ/cm2の露光量(365nm)で露光し、現像、水洗、ポストベーク後の膜厚が4.7μmになるようにスピンコートし、次にクリーンオーブン中、100℃で3分間プリベークした。冷却後、この感光性樹脂組成物を塗布した基板と石英ガラス製フォトマスク(一辺が20μmである正方形とスペース部が1:2の比率のパターンを有する)との間隔を50μmとし、超高圧水銀ランプ(USH−250D;ウシオ電機(株)製)を用いて大気雰囲気下、100mJ/cm2の露光量(365nm)で光照射した。その後、非イオン系界面活性剤0.12質量%と水酸化カリウム0.05質量%を含む水系現像液に上記塗膜を23℃で撹拌(マグネティクスターラーで300rpm)している現像液中で80秒間浸漬して現像し、水洗後、220℃で30分間ポストベークを行って、硬化樹脂パターンを得た。 A 2-inch square glass substrate (manufactured by Corning, # 1737) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition (Table 2) is exposed at an exposure amount (365 nm) of 100 mJ / cm 2 and spinned so that the film thickness after development, water washing and post-baking becomes 4.7 μm. Coated and then prebaked at 100 ° C. for 3 minutes in a clean oven. After cooling, the space between the substrate coated with the photosensitive resin composition and a quartz glass photomask (a square with a side of 20 μm and a space portion having a pattern with a ratio of 1: 2) is set to 50 μm, and ultra-high pressure mercury Using a lamp (USH-250D; manufactured by Ushio Electric Co., Ltd.), light was irradiated with an exposure amount (365 nm) of 100 mJ / cm 2 in an air atmosphere. Thereafter, in the developer in which the coating film is stirred at 23 ° C. (300 rpm with a magnetic stirrer) in an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.05% by mass of potassium hydroxide. It was developed by dipping for 80 seconds, washed with water, and post-baked at 220 ° C. for 30 minutes to obtain a cured resin pattern.
得られた硬化樹脂パターンの下記の項目において測定等を行った結果を表3に示す。 Table 3 shows the results of measurement and the like in the following items of the obtained cured resin pattern.
(表3中の説明)
耐NMP性;露光工程において、フォトマスクを使用しない以外は、実施例に記載したのと同様の操作を行い、塗膜を作製した。作製した塗膜をN−メチルピロリドン(30℃×30分)に浸漬し、浸漬前後の膜厚変化を測定した。浸漬前後での膜厚変化(=(浸漬後の膜厚(μm)/浸漬前の膜厚(μm))×100)が103%以下の場合を○、103%を越えた場合を×とした。
表面平滑性;表面平滑性の基準は、目視により表面を観察して、光沢があると○、白濁(不透明)していると×を表す。
粒状異物;目視により表面を観察して、異物がなければ○、あれば×を表す。
線幅;パターンのボトム部における二辺の寸法を、SEM(型番S−4100;(株)日立製作所製)を用いて測定し、得られた二辺の平均値を求めた。
形状;パターンの基板等に対して垂直な断面に対する断面を、上記と同じSEMを用いて観察した。
回復率;ダイナミック超微小硬度計(DUH−W201S;(株)島津製作所製)を用いて、総変位量(μm)および弾性変位量(μm)を、以下の条件で測定し、得られた数値から回復率を算出した。
(Explanation in Table 3)
NMP resistance: In the exposure step, a coating film was prepared by performing the same operation as described in Examples except that no photomask was used. The prepared coating film was immersed in N-methylpyrrolidone (30 ° C. × 30 minutes), and the change in film thickness before and after immersion was measured. Change in film thickness before and after immersion (= (film thickness after immersion (μm) / film thickness before immersion (μm)) × 100) is 103% or less, and ○ is over 103%. .
Surface smoothness: The standard of the surface smoothness indicates that the surface is visually observed, ◯ if it is glossy, and x if it is cloudy (opaque).
Particulate foreign matter: The surface is visually observed.
Line width: The dimension of two sides in the bottom part of the pattern was measured using SEM (model number S-4100; manufactured by Hitachi, Ltd.), and the average value of the obtained two sides was determined.
Shape: A cross section with respect to a cross section perpendicular to the substrate of the pattern was observed using the same SEM as described above.
Recovery rate: using a dynamic ultra-micro hardness meter (DUH-W201S; manufactured by Shimadzu Corporation), the total displacement (μm) and the elastic displacement (μm) were measured under the following conditions, and obtained. The recovery rate was calculated from the numerical values.
試験モード ;負荷−除荷試験
試験力 ;5gf(SI単位換算値;0.049N)
負荷速度 ;0.45gf/秒(SI単位換算値;0.0044N/秒)
保持時間 ;5秒
圧子 ;円錐台圧子(直径50mmφ)
回復率(%)=(弾性変位量(μm)/総変位量(μm))×100
Test mode: Load-unloading test test force: 5 gf (SI unit converted value; 0.049 N)
Load speed: 0.45 gf / sec (SI unit conversion value: 0.0044 N / sec)
Holding time: 5-second indenter; truncated cone indenter (diameter 50 mmφ)
Recovery rate (%) = (elastic displacement (μm) / total displacement (μm)) × 100
保存安定性;23℃で3ヶ月保管前後の粘度変化率を次式によって求めた。
粘度変化率(%)=[(保管後粘度)/(保管前粘度)]×100
Storage stability: Viscosity change rate before and after storage for 3 months at 23 ° C. was determined by the following formula.
Viscosity change rate (%) = [(viscosity after storage) / (viscosity before storage)] × 100
本発明のバインダー樹脂を含む実施例1および2の感光性樹脂組成物では、耐NMP性、表面平滑性、パターン形状、回復率およびに優れるパターンおよび塗膜が得られることがわかるが、本発明のバインダー樹脂を含まない比較例1の感光性樹脂組成物では、耐NMP性に劣る。 In the photosensitive resin compositions of Examples 1 and 2 containing the binder resin of the present invention, it is understood that a pattern and a coating film excellent in NMP resistance, surface smoothness, pattern shape, recovery rate and the like can be obtained. The photosensitive resin composition of Comparative Example 1 that does not contain the binder resin is inferior in NMP resistance.
本発明の感光性樹脂組成物は、液晶表示装置におけるフォトスペーサーの形成に用いることができる。 The photosensitive resin composition of this invention can be used for formation of the photo spacer in a liquid crystal display device.
Claims (9)
バインダー樹脂(A)が、下記(A1)、(A2)および(A4)を共重合させて共重合体1を得て、得られた共重合体1と(A3)とを共重合体1の(A4)に由来するエポキシ基の部位で反応させて共重合体2を得て、さらに得られた共重合体2と(A5)とを共重合体1の(A4)と(A3)の反応により生成した水酸基の部位に反応させて得られる共重合体であり、
光重合開始剤(C)が、アセトフェノン系化合物、ビイミダゾール系化合物、オキシム系化合物およびトリアジン系化合物からなる群から選ばれる少なくとも一種の化合物であり、
フォトスペーサーを形成するために用いられる感光性樹脂組成物から形成されたフォトスペーサー。
(A1);一分子中にトリシクロデカン骨格およびジシクロペンタジエン骨格からなる群から選ばれる少なくとも1種の骨格と、不飽和結合とを有する化合物
(A2);(A1)および(A4)と共重合可能な不飽和結合を有する化合物
(A3);不飽和結合を有するカルボン酸
(A4);一分子中に不飽和結合とエポキシ基とを有する化合物
(A5);酸無水物
ただし、(A1)〜(A5)は、それぞれ、互いに同一ではない。 A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D) ,
The binder resin (A) is obtained by copolymerizing the following (A1), (A2) and (A4) to obtain a copolymer 1, and the obtained copolymer 1 and (A3) are combined into the copolymer 1. The copolymer 2 is obtained by reacting at the site of the epoxy group derived from (A4), and the obtained copolymer 2 and (A5) are further reacted with (A4) and (A3) of the copolymer 1 Is a copolymer obtained by reacting with the hydroxyl group produced by
The photopolymerization initiator (C) is at least one compound selected from the group consisting of acetophenone compounds, biimidazole compounds, oxime compounds and triazine compounds,
A photospacer formed from a photosensitive resin composition used to form a photospacer .
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A4) Compound (A3) having polymerizable unsaturated bond; Carboxylic acid (A4) having unsaturated bond; Compound (A5) having unsaturated bond and epoxy group in one molecule; Acid anhydride provided that (A1) -(A5) are not mutually the same.
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