CN101470350B - Photo sensitive resin compositon, optical spacer, protective film, coloring pattern, display device and substrate thereof - Google Patents
Photo sensitive resin compositon, optical spacer, protective film, coloring pattern, display device and substrate thereof Download PDFInfo
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- CN101470350B CN101470350B CN2008101852446A CN200810185244A CN101470350B CN 101470350 B CN101470350 B CN 101470350B CN 2008101852446 A CN2008101852446 A CN 2008101852446A CN 200810185244 A CN200810185244 A CN 200810185244A CN 101470350 B CN101470350 B CN 101470350B
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- China
- Prior art keywords
- resin
- photosensitive polymer
- polymer combination
- mentioned
- methyl
- 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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- 229920005989 resin Polymers 0.000 title claims abstract description 181
- 239000011347 resin Substances 0.000 title claims abstract description 181
- 239000000758 substrate Substances 0.000 title claims abstract description 93
- 125000006850 spacer group Chemical group 0.000 title claims abstract description 87
- 230000001681 protective effect Effects 0.000 title abstract description 4
- 238000004040 coloring Methods 0.000 title abstract 2
- 230000003287 optical effect Effects 0.000 title abstract 2
- 229920000642 polymer Polymers 0.000 claims abstract description 91
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 51
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 51
- 230000002378 acidificating effect Effects 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims description 94
- -1 (methyl) acryloxy Chemical group 0.000 claims description 63
- 230000015572 biosynthetic process Effects 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 5
- 239000004606 Fillers/Extenders Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 95
- 239000004973 liquid crystal related substance Substances 0.000 description 54
- 239000010408 film Substances 0.000 description 40
- 238000005755 formation reaction Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- 238000000059 patterning Methods 0.000 description 30
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 28
- 239000000178 monomer Substances 0.000 description 27
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 22
- 239000012530 fluid Substances 0.000 description 21
- 239000011159 matrix material Substances 0.000 description 19
- 238000011084 recovery Methods 0.000 description 19
- 125000004185 ester group Chemical group 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 238000010023 transfer printing Methods 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 15
- 230000003252 repetitive effect Effects 0.000 description 15
- 230000008859 change Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229920005992 thermoplastic resin Polymers 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000001118 alkylidene group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 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 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- 102000004232 Mitogen-Activated Protein Kinase Kinases Human genes 0.000 description 3
- 108090000744 Mitogen-Activated Protein Kinase Kinases Proteins 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- XXCYLOYGDHVIBR-UHFFFAOYSA-N (1-methyl-4-propan-2-ylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(C)C1CCC(C)(OC(=O)C(C)=C)CC1 XXCYLOYGDHVIBR-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- LWEAHXKXKDCSIE-UHFFFAOYSA-M 2,3-di(propan-2-yl)naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S([O-])(=O)=O)=C(C(C)C)C(C(C)C)=CC2=C1 LWEAHXKXKDCSIE-UHFFFAOYSA-M 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000011293 Brassica napus Nutrition 0.000 description 2
- 240000008100 Brassica rapa Species 0.000 description 2
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- YDGMGEXADBMOMJ-LURJTMIESA-N N(g)-dimethylarginine Chemical group CN(C)C(\N)=N\CCC[C@H](N)C(O)=O YDGMGEXADBMOMJ-LURJTMIESA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000007877 V-601 Substances 0.000 description 2
- REUQOSNMSWLNPD-UHFFFAOYSA-N [2-(diethylamino)phenyl]-phenylmethanone Chemical compound CCN(CC)C1=CC=CC=C1C(=O)C1=CC=CC=C1 REUQOSNMSWLNPD-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000004653 anthracenylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YDGMGEXADBMOMJ-UHFFFAOYSA-N asymmetrical dimethylarginine Natural products CN(C)C(N)=NCCCC(N)C(O)=O YDGMGEXADBMOMJ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229940041616 menthol Drugs 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- CDUQMGQIHYISOP-RMKNXTFCSA-N (e)-2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C\C1=CC=CC=C1 CDUQMGQIHYISOP-RMKNXTFCSA-N 0.000 description 1
- VNGVIDOMLGIDMI-UHFFFAOYSA-N (sulfoamino)phosphonic acid Chemical compound S(=O)(=O)(O)NP(O)(O)=O VNGVIDOMLGIDMI-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- IJSVVICYGLOZHA-UHFFFAOYSA-N 2-methyl-n-phenylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1 IJSVVICYGLOZHA-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- DLAXSFQUZITJGP-UHFFFAOYSA-N 2-methylbutan-2-yl 2-methylprop-2-enoate Chemical compound CCC(C)(C)OC(=O)C(C)=C DLAXSFQUZITJGP-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- CGRJJOYCFCCGPX-UHFFFAOYSA-N 3-ethyloxetane Chemical class CCC1COC1 CGRJJOYCFCCGPX-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- FUWFDADDJOUNDL-UHFFFAOYSA-N 9,10-diethoxy-2-ethylanthracene Chemical compound CCC1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 FUWFDADDJOUNDL-UHFFFAOYSA-N 0.000 description 1
- GJNKQJAJXSUJBO-UHFFFAOYSA-N 9,10-diethoxyanthracene Chemical compound C1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 GJNKQJAJXSUJBO-UHFFFAOYSA-N 0.000 description 1
- JWJMBKSFTTXMLL-UHFFFAOYSA-N 9,10-dimethoxyanthracene Chemical compound C1=CC=C2C(OC)=C(C=CC=C3)C3=C(OC)C2=C1 JWJMBKSFTTXMLL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 0 CC(*N)C(N)=C Chemical compound CC(*N)C(N)=C 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- OMFKRKWGCMBJFW-UHFFFAOYSA-N [2-[ethyl(methyl)amino]phenyl]-phenylmethanone Chemical compound CCN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 OMFKRKWGCMBJFW-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-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
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000549 coloured material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- DBQGARDMYOMOOS-UHFFFAOYSA-N methyl 4-(dimethylamino)benzoate Chemical class COC(=O)C1=CC=C(N(C)C)C=C1 DBQGARDMYOMOOS-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 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
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical compound CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—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
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Optical Filters (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a photosensitive resin compound, an optical spacer, a protective film, a coloring pattern, a display device and a substrate thereof. The photosensitive resin compound provided by the invention comprises the following components: (A) a resin which is provided with branched structure and/or alicyclic ring structure on the side chain, acidic group and substituted alkyl that is provided with two ethylenic linkage type unsaturated bonds, (B) a polymeric compound which is provided with ethylenic linkage type unsaturated bond, and (C) a photopolymerization initiating agent. The photosensitive resin compound can form a pattern structure or protective film which has the advantages of high sensitivity, excellent storability in liquid state, excellent ageing stability and mechanical characteristic of photosensitive film after film forming.
Description
Technical field
The present invention relates to photosensitive polymer combination, light spacer (photo spacer) and forming method thereof, diaphragm, colored pattern, base board for display device and display device.
Background technology
In recent years, due to the large tracts of land of liquid crystal indicator and the raising of throughput rate etc., the maximization of plain glass (Mother Glass) substrate advances.With regard to substrate size (680 * 880mm left and right) in the past, less than mask size, just energy is corresponding so utilize the mode of exposing in the lump due to substrate size.Yet, maximization along with in recent years device, needs to large substrate (for example about 1500 * 1800mm) constantly increase, but the mask size that will prepare with aforesaid substrate size equal extent is almost impossible, utilizes the mode of exposure in the lump to be difficult to corresponding.
Therefore, as the Exposure mode of corresponding large substrate, the substep Exposure mode has been proposed.
Yet, in the substep Exposure mode, carrying out multiexposure, multiple exposure on a substrate, it all will carry out aligned in position each time, shifts the needed time so produced step.Therefore, the substep Exposure mode is compared with Exposure mode in the lump, can worry that throughput descends.In addition, in Exposure mode in the lump, can allow at 3000J/m
2The left and right can Butut exposure sensitivity, but in the substep Exposure mode, require to have at 1500J/m
2Below can carry out the exposure sensitivity of good Butut.But existing material is with 1500J/m
2Following exposure is difficult to obtain good sept (spacer) shape and thickness.
In addition, the controlled required value of the shape of relevant sept, thickness becomes more and more stricter in recent years, the shape that produces for the process variations when forming sept, the change of thickness, follow the shape of the rheological parameters' change with time of composition solution, the stability of thickness, also have room for improvement.Particularly, at 1500J/m
2Following exposure zone, with respect to exposure to shape, the thickness of sept control aspect also have problem.
And then, in recent years, the photosensitive resin combination that uses in the manufacturing of display panels is during preservation or in using, composition generation crystallizations in composition etc. and the problems such as foreign matter, polluting device that produce become seriously are so wish the photosensitive resin combination that can reduce pollution problem.
Relevant photosensitive polymer combination, various researchs have been carried out in the past, for example, a kind of photosensitive polymer combination is disclosed, it contains the curable resin that the multipolymer by fatty family cyclic hydrocarbon group consists of, the multipolymer of described fatty family cyclic hydrocarbon group has following molecular structure, that is: will have the aliphatics cyclic hydrocarbon group structural unit, have the structural unit of acidic functionality and have the molecular structure (for example, with reference to JP 2002-296775 communique) that the structural unit of free-radical polymerised base links.In addition, a kind of curable resin that is made of the multipolymer of fatty family cyclic hydrocarbon group is also disclosed, the multipolymer of described fatty family cyclic hydrocarbon group has following molecular structure, that is: will have the aliphatics cyclic hydrocarbon group of ad hoc structure structural unit, have the structural unit of acidic functionality and have the molecular structure (for example, with reference to JP 2002-293837 communique) that the structural unit of free-radical polymerised base links.
Summary of the invention
The invention provides photosensitive polymer combination, light spacer and forming method thereof, diaphragm, colored pattern, base board for display device and display device.The first form of the present invention is to provide a kind of photosensitive polymer combination; it contains: (A) have the resin that branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl have 2 ethylenic unsaturated links on side chain; (B) has the polymerizable compound of ethylenic unsaturated link; (C) that Photoepolymerizationinitiater initiater, this photosensitive polymer combination can form is highly sensitive, the keeping quality under liquid is good and film forming after patterning body or the diaphragm of exhibiting excellent stability with time of photosensitive film.The second form of the present invention is to provide a kind of formation method of light spacer, and it contains following operation: use the photosensitive polymer combination of above-mentioned the first form to form the operation of tunicle on substrate; The operation that at least a portion of above-mentioned tunicle is exposed; With the above-mentioned tunicle operation of developing after exposure; And the operation that heats of the above-mentioned tunicle after developing.The 3rd form of the present invention is to provide light spacer, diaphragm or the colored pattern of the photosensitive polymer combination formation of using above-mentioned the first form.The display device that the 4th form of the present invention is to provide at least a base board for display device in light spacer, diaphragm or the colored pattern that possesses above-mentioned the 3rd form and possesses this substrate.
But; use above-mentioned photosensitive polymer combination in the past (for example to form the patterning body on substrate; light spacer, colored pattern etc.; below identical) or during diaphragm; may not necessarily obtain be used to the sensitivity and the polymerisation reactivity that obtain good shape etc., also insufficient aspect the ageing stability of the photosensitive film after fluid preservation or film forming.
The present invention In view of the foregoing completes, to realize that following purpose is as problem.
Namely the purpose of this invention is to provide the good patterning body of a kind of ageing stability that can form the photosensitive film after the good and film forming of keeping quality under highly sensitive, liquid and mechanical characteristic or the photosensitive polymer combination of diaphragm.
In addition, even the purpose of this invention is to provide a kind of in the situation that form with low sensitivity, also have light spacer and the manufacture method thereof of good high homogeneity and uniform cross sectional shape.
In addition, even the purpose of this invention is to provide a kind of in the situation that form with low sensitivity, also have diaphragm or the colored pattern of good film thickness uniformity and uniform cross sectional shape.
In addition, the purpose of this invention is to provide a kind of can suppress to show uneven base board for display device and the uneven display device that suppresses that obtained of demonstration when being used for display device.
The present invention for the means that solve above-mentioned problem is:
＜1〉a kind of photosensitive polymer combination, it contains: (A) have the resin that branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl have 2 ethylenic unsaturated links on the side chain, (B) have the polymerizable compound of ethylenic unsaturated link, (C) Photoepolymerizationinitiater initiater.
＜2〉according to above-mentioned＜1〉described photosensitive polymer combination, wherein, described substituted alkyl is the group with following general formula (1) expression.
General formula (1)
(in general formula (1),
*The side that expression is combined with the main chain of resin, A1 represents that carbon number is dibasic alkyl of 1～9.B1 and B2 represent independently respectively singly-bound, urethane bond (the main chain side :-O-CO-NHR-), ester bond (the main chain side :-CO-O-), R represents that carbon number is 1～3 alkyl.In addition, X1 and X2 represent independently respectively ester bond (the main chain side :-O-CO-).R
1And R
2Represent independently respectively hydrogen atom or methyl.)
＜3〉according to above-mentioned＜1〉or＜2〉described photosensitive polymer combination, wherein, the substituting group of described substituted alkyl is (methyl) acryloxy.
＜4〉according to above-mentioned＜1 〉～＜3〉the middle described photosensitive polymer combination of any one, wherein, described group with branching and/or alicyclic structure has the group of following general formula (3) expression,
General formula (3)
In general formula (3), X represents the organic concatenating group of divalence, can also substituting group can be arranged by unsubstituted.Y represent 1 or 2, n represent 0～15 integer.
＜5〉according to above-mentioned＜1 〉～＜4〉the middle described photosensitive polymer combination of any one, wherein, described (A) to have the weight-average molecular weight that branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl has the resin of 2 ethylenic unsaturated links on side chain be 12000～60000 scope.
＜6〉according to above-mentioned＜1 〉～＜5〉the middle described photosensitive polymer combination of any one, wherein, described (A) to have the glass transition temperature (Tg) that branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl has a resin of 2 ethylenic unsaturated links on side chain be 40～180 ℃.
＜7〉according to above-mentioned＜1 〉～＜6〉the middle described photosensitive polymer combination of any one, wherein, described (A) is more than 20mgKOH/g at the acid number that has branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl on side chain and have the resin of 2 ethylenic unsaturated links.
＜8〉according to above-mentioned＜1 〉～＜7〉the middle described photosensitive polymer combination of any one, wherein, described (B) polymerizable compound is 0.5～2.0 with respect to the quality ratio (ratio of (B)/(A)) of described (A) resin.
＜9〉according to above-mentioned＜1 〉～＜8〉the middle described photosensitive polymer combination of any one, it further contains the extender pigment that mean grain size is 5～50nm.
＜10〉a kind of light spacer, its use above-mentioned＜1 〉～＜9 in the described photosensitive polymer combination of any one and forming.
＜11〉a kind of formation method of light spacer, it contains following operation (i)～(iii) at least:
(i) form above-mentioned＜1 on substrate 〉～＜9 in the operation of tunicle of the described photosensitive polymer combination of any one;
The operation of (ii) at least a portion of described tunicle being exposed;
(iii) operation of developing of the described tunicle after exposing;
(iv) operation that heats of the described tunicle after developing.
＜12〉a kind of diaphragm, its use above-mentioned＜1 〉～＜9 in the described photosensitive polymer combination of any one and forming.
＜13〉a kind of colored pattern, its use above-mentioned＜1 〉～＜9 in the described photosensitive polymer combination of any one and forming.
＜14〉a kind of base board for display device, it possess be selected from above-mentioned＜11 described light spacer, above-mentioned＜12 described diaphragm and above-mentioned＜13 at least a in described colored pattern.
＜15〉a kind of display device, it possesses above-mentioned＜14〉described base board for display device.
Embodiment
Below, photosensitive polymer combination of the present invention is elaborated, and then light spacer of having used this photosensitive polymer combination and forming method thereof, diaphragm, colored pattern, base board for display device and display device are also described.
" photosensitive polymer combination "
Photosensitive polymer combination of the present invention contains: (A) have branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has the resin (following also only be called " (A) resin ") of 2 ethylenic unsaturated links, (B) have the polymerizable compound of ethylenic unsaturated link, (C) Photoepolymerizationinitiater initiater.
Generally when use photosensitive polymer combination forms on substrate the patterning body (for example, light spacer, colored pattern etc., below identical) or during diaphragm, if only with exposing, polymerizing curable is insufficient.In addition, the ageing stability of the keeping quality under the liquid state and the photosensitive film after film forming also may not be abundant.
And then; when carrying out high-temperature heating treatment in order to ensure the ageing stability of the photosensitive film after above-mentioned film forming in exposure with after developing, might make the patterning body that will form or diaphragm deteriorated or make patterning body or the deteriorated phenomenon of diaphragm that is formed on substrate.For example, when forming light spacer on having the filter substrate of colored pattern, might make the light spacer that will form deteriorated or make the deteriorated phenomenon of colored pattern that is formed on substrate.
Therefore; by photosensitive polymer combination being set for the formation of the invention described above, photosensitive polymer combination of the present invention can form that polymerization-curable highly sensitive, when viscosity rise, exposure be difficult for to occur improves, the keeping quality under liquid is good and film forming after patterning body or the diaphragm of exhibiting excellent stability with time of photosensitive film.
Below, the polymerizable compound, (C) Photoepolymerizationinitiater initiater and other composition that (A) resin, (B) are had the ethylenic unsaturated link describe.
＜(A) resin 〉
(A) formation of resin is to have branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has (being substituted) 2 ethylenic unsaturated links.
Described (A) resin has acidic groups and possesses developability, simultaneously owing to having the substituted alkyl that contains 2 ethylenic unsaturated links, so have high sensitivity thereby possess high polymerisation reactivity, and have under good fluid preservation and dry film state through the time keeping quality, the patterning body can be controlled to be the controlled of desired shape and thickness (height etc.) so can give.
In addition, owing to having branching and/or alicyclic structure, so the compressive modulus of elasticity in the time of can improving formed patterning body and be subject to external force, from the elastic recovery of compression deformation.Thus, be useful when the patterning bodies such as light spacer that configuration example such as display device are used.
Here, branching and/or alicyclic structure, acidic groups and the substituted alkyl with 2 ethylenic unsaturated links can contain respectively in different side chains, also can part combination and contain in identical side chain, also can all contain in identical side chain.
In addition; in this instructions; (methyl) acryloyl group represents acryloyl group or methacryl; (methyl) acrylate represents acrylate or methacrylate; (methyl) propenyl represents propenyl or methylpropenyl; (methyl) acrylamide represents acrylamide or Methacrylamide, and (methyl) acrylanilide represents acrylanilide or metering system anilid.
(branching and/or alicyclic structure)
(A) resin is containing at least a branching and/or alicyclic structure on side chain that the main chain of resin is combined.Branching and/or alicyclic structure can contain a plurality of in the side chain of (A) resin.In addition, branching and/or alicyclic structure also can and/or have with acidic groups and contain in the side chain of (A) resin together with the substituted alkyl of 2 ethylenic unsaturated links.
In addition, branching and/or alicyclic structure can only consist of with the direct combination of the main chain of (A) resin the side chain of (A) resin with branching and/or alicyclic structure, also can be combined with the main chain of (A) resin by the organic concatenating group of divalence, consist of the side chain of (A) resin as the group with branching and/or alicyclic structure.
As the organic concatenating group of above-mentioned divalence, be preferably selected from a kind of or combination in alkylidene, arlydene, ester group, amide group and ether.As above-mentioned alkylidene, preferred total carbon atom number is 1～20 alkylidene, and more preferably total carbon atom number is 1～10 alkylidene.Can list particularly methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl etc., they also can have branching/ring texture, functional group, more preferably methylene, ethylidene, Ya Xinji.As above-mentioned arlydene, preferred total carbon atom number is 6～20 arlydene, and more preferably total carbon atom number is 6～12 arlydene.Can list phenylene, biphenylene, naphthylene, anthrylene etc. particularly, they also can have side chain, functional group, more preferably phenylene, biphenylene.
From the viewpoint of developability and elastic recovery rate, branching and/or alicyclic structure are preferably at least by the ester group (form of main chain side-COO-) be combined with the main chain of (A) resin.This form is not limited to branching and/or alicyclic structure, and only (form of main chain side-COO-) be combined with the main chain of (A) resin can also be branching and/or alicyclic structure by containing the ester group (form that the bivalence linking base of main chain side-COO-) is combined with the main chain of (A) resin by ester group.That is, between branching and/or alicyclic structure and ester chain and/or ester chain and (A) also can comprise other atom or other linking group between the main chain of resin.
As above-mentioned branched structure, can list carbon number and be the branch-like alkyl of 3～12, preference such as isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 2-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, isopentyl, tertiary pentyl, 3-octyl group, uncle's octyl group etc.Wherein, more preferably isopropyl, sec-butyl, the tert-butyl group, isopentyl etc., particularly preferably isopropyl, sec-butyl, the tert-butyl group etc.
As above-mentioned alicyclic structure, can list carbon number and be the alicyclic ring shape alkyl of 5～20, preference such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, adamantyl, three ring decyls, dicyclopentenyl, two cyclopentyl, three cyclopentenyls, three cyclopentyl etc. and the groups with them.Wherein, more preferably dicyclopentenyl, cyclohexyl, norborny, isobornyl, adamantyl, three encircle decyls, three cyclopentenyls, three cyclopentyl etc., further preferred dicyclopentenyl, cyclohexyl, norborny, isobornyl, three cyclopentenyls etc., particularly preferably dicyclopentenyl, three cyclopentenyls.
And then, as the group with branching and/or alicyclic structure, preferably have the group of following general formula (3) expression and the form that consists of.
General formula (3)
In general formula (3), X represents the organic concatenating group of divalence, can also substituting group can be arranged by unsubstituted.Y represent 1 or 2, n represent 0～15 integer.
As the organic concatenating group of above-mentioned divalence, be preferably selected from a kind of or combination in alkylidene, arlydene, ester group, amide group and ether, they also can have substituting group.
As above-mentioned alkylidene, preferred total carbon atom number is 1～20 alkylidene, and more preferably total carbon atom number is 1～10 alkylidene.Can list particularly the groups such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl, they also can have branching/ring texture, functional group, more preferably methylene, ethylidene, Ya Xinji.
As above-mentioned arlydene, preferred total carbon atom number is 6～20 arlydene, and more preferably total carbon atom number is 6～12 arlydene.Can list phenylene, biphenylene, naphthylene, anthrylene etc. particularly, they also can have side chain, functional group, more preferably phenylene, biphenylene.
Substituting group when being substituted as above-mentioned group can list alkyl, hydroxyl, amino, halogen radical, fragrant cyclic group, have the group of alicyclic structure etc.
As be used for importing the monomer of branching and/or alicyclic structure on side chain in (A) resin synthetic, can list phenylethylene, (methyl) esters of acrylic acid, vinyl ethers, vinyl ester, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl ester, (methyl) acrylic amide, more preferably (methyl) esters of acrylic acid.
as be used for importing the concrete monomer of branched structure on side chain in (A) resin synthetic, can list (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) acrylic acid tert-pentyl ester, the secondary isopentyl ester of (methyl) acrylic acid, (methyl) acrylic acid 2-monooctyl ester, (methyl) acrylic acid 3-monooctyl ester, (methyl) acrylic acid uncle monooctyl ester etc., preferred (methyl) isopropyl acrylate wherein, (methyl) isobutyl acrylate, Tert-butyl Methacrylate etc., more preferably isopropyl methacrylate, Tert-butyl Methacrylate etc.
Have as being used for importing the monomer of alicyclic structure in (A) resin synthetic, can list on side chain (methyl) acrylate that carbon number is the alicyclic ring shape alkyl of 5～20.as concrete example, can list (methyl) acrylic acid (two ring [2.2.1] heptan-2-alcohol) ester, (methyl) acrylic acid 1-diamantane ester, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid 3-methyl isophthalic acid-diamantane ester, (methyl) acrylic acid 3,5-dimethyl-1-diamantane ester, (methyl) acrylic acid 3-ethyl diamantane ester, (methyl) acrylic acid 3-methyl-5-ethyl-1-diamantane ester, (methyl) acrylic acid 3,5,8-triethyl-1-diamantane ester, (methyl) acrylic acid 3,5-dimethyl-8-ethyl-1-diamantane ester, (methyl) acrylic acid-2-methyl-2-diamantane ester, (methyl) acrylic acid 2-ethyl-2-diamantane ester, (methyl) acrylic acid 3-hydroxyl-1-diamantane ester, (methyl) acrylic acid octahydro-4,7-menthol indenes (menthanoindene)-5-base ester, (methyl) acrylic acid octahydro-4,7-menthol indenes-1-base methyl esters, (methyl) acrylic acid 1-menthyl ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (methyl) acrylic acid 3-hydroxyl-2,6,6-trimethyl-two ring [3.1.1] heptyl ester, (methyl) acrylic acid 3,7,7-trimethyl-4-hydroxyl-two ring [4.1.0] heptyl ester, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid turnip ester, (methyl) acrylic acid 2,2,5-3-methyl cyclohexanol ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters etc.
in above-mentioned (methyl) acrylate, from making compressive modulus of elasticity by bulky functional group, the viewpoint that elastic recovery becomes good is set out, preferred (methyl) cyclohexyl acrylate, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 1-diamantane ester, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid turnip ester, (methyl) acrylic acid 1-menthyl ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters etc., (methyl) cyclohexyl acrylate particularly preferably, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters.
In addition, as be used for importing the monomer of alicyclic structure on side chain in (A) resin synthetic, can list the compound of following general formula (4) or (5) expression.Here, in general formula (4), (5), X represents the organic concatenating group of divalence, and R represents hydrogen atom or methyl.Y represent 1 or 2, n represent 0～15.In general formula (4), (5), be preferably y=1 or 2, n=0～8.More preferably y=1 or 2, n=0～4 (more preferably n=0～2).Preferred object lesson as the compound of general formula (4) or (5) expression can list following Compound D-1～D-11, T-1～T-12.
Wherein, the viewpoint of the elastic recovery rate that produces from the reactivity at two keys positions, the compound of preferred following general formula (4) expression.
General formula (4)
General formula (5)
In general formula (4)～(5), the organic concatenating group of the divalence that X represents can also can have substituting group without replacing, and the organic concatenating group meaning of divalence that represents with the X of above-mentioned general formula (3) is identical, and preferred form is also identical.
As be used for importing the monomer of alicyclic structure on side chain in (A) resin synthetic, can use the monomer of suitable manufacturing, also can use commercially available product.
As above-mentioned commercially available product, can list FA-511A, FA-512A (S) that Hitachi Chemical Co., Ltd. makes, FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M etc.Wherein, the viewpoint good from developability, that the deformation-recovery rate is good, preferred FA-512A (S), FA-512M.
～～acidic groups～～
(A) resin contains at least a acidic groups on the side chain that links with main chain.Acidic groups can contain a plurality of in side chain.In addition, acidic groups also can and above-mentioned branching and/or alicyclic structure and contain in the side chain of (A) resin together with the substituted alkyl with 2 ethylenic unsaturated links that configures by ester group between main chain.
In addition, above-mentioned acidic groups can only consist of with the direct combination of the main chain of (A) resin the side chain of (A) resin with acidic groups, also can be combined with the main chain of (A) resin by the organic concatenating group of divalence, consist of the side chain of (A) resin as the group with acidic groups.Here, the relevant organic concatenating group of divalence can list the organic concatenating group of the divalence that lists in the explanation of above-mentioned branching and/or alicyclic structure, and preferred scope is also identical.
As above-mentioned acidic groups, be not particularly limited, can suitably select from known acidic groups, can list such as carboxyl, sulfonic group, sulfoamido, phosphate, phenol hydroxyl etc.Wherein, from the viewpoint that has excellent water-resistance of developability and cured film, be preferably carboxyl, phenol hydroxyl.
As the object lesson that is used for importing to (A) resin the monomer of above-mentioned acidic groups, can be from known monomer suitably select, can list addition compound product such as (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, alpha-cyano cinnamic acid, acrylic acid dimer, the monomer with hydroxyl and cyclic acid anhydride, ω-carboxyl-polycaprolactone list (methyl) acrylate etc.They can use the monomer of suitable manufacturing, also can use commercially available product.
The monomer with hydroxyl that uses in addition compound product as the above-mentioned monomer with hydroxyl and cyclic acid anhydride can list such as (methyl) acrylic acid 2-hydroxy methacrylate etc.As above-mentioned cyclic acid anhydride, can list such as maleic anhydride, phthalic anhydride, cyclohexyl dicarboxylic acid's acid anhydride etc.
Commercially available product as monomer, can list ア ロ ニ Star Network ス M-5300, ア ロ ニ Star Network ス M-5400, ア ロ ニ Star Network ス M-5500, ア ロ ニ Star Network ス M-5600 that East Asia synthetic chemical industry Co., Ltd. makes, NK エ ス テ Le CB-1, NK エ ス テ Le CBX-1 that Xin Zhong village chemical industry Co., Ltd. makes, HOA-MP, HOA-MS that oil chemical industry Co., Ltd. of common prosperity society makes, the PVC ス コ one ト #2100 that Osaka Organic Chemical Industry Co., Ltd. makes etc.Wherein,, cheaply viewpoint good from developability, preferred (methyl) acrylic acid etc.
(substituted alkyl with 2 ethylenic unsaturated links)
(A) resin is containing at least a substituted alkyl (following also only be called " substituted alkyl ") with 2 ethylenic unsaturated links on side chain that main chain is combined.Above-mentioned substituted alkyl also can contain a plurality of in the side chain of (A) resin.
In addition, substituted alkyl is included in the form in the structural unit different from above-mentioned branching and/or alicyclic structure and acidic groups in the side chain of (A) resin.
In addition, above-mentioned substituted alkyl can only consist of with the direct combination of the main chain of (A) resin the side chain of (A) resin with substituted alkyl, also can be combined with the main chain of (A) resin by the organic concatenating group of divalence, consist of the side chain of (A) resin as the group with substituted alkyl, in addition, between the ester group with substituted alkyl and main chain, can also further have the organic concatenating group of above-mentioned divalence.
As the organic concatenating group of above-mentioned divalence, identical with the organic concatenating group of divalence of record in the item of the group with branching and/or alicyclic structure, preferred example is also identical.
In above-mentioned, supply with the viewpoints such as property, synthetic adaptability from controlled, the synthesis material of the developability brought by high sensitivity and high polymerisation reactivity and the thickness of patterning body etc., be preferably substituted alkyl at least by the ester group (form of main chain side-COO-) be combined with the main chain of (A) resin.This form is not limited to substituted alkyl, and only (form of main chain side-COO-) be combined with the main chain of (A) resin can also be substituted alkyl by containing the ester group (form that the bivalence linking base of main chain side-COO-) is combined with the main chain of (A) resin by ester group.
That is, (COO-) and/or at substituted alkyl with (A) between the main chain of resin, can also contain other atom or other concatenating group (1～9 alkylidene) at substituted alkyl and ester group.
As above-mentioned substituted alkyl (namely, substituted alkyl with 2 ethylenic unsaturated links), be not particularly limited, but from the viewpoint of the characteristic (curing property, synthetic adaptability etc.) of the film that brings by the high sensitivity of photosensitive polymer combination, high polymerisation reactivity, the group of preferred following general formula (1) expression.
General formula (1)
In general formula (1),
*Expression one side of being combined with the main chain of resin, A1 represents by the carbon number that 2 substituting groups with ethylenic unsaturated link have replaced to be 1～9 alkyl.In addition, A1 is by above-mentioned ester group (main chain side-CO-O-) be combined with main chain.
In general formula (1), as abovementioned alkyl, get final product so long as carbon number is 1～9 alkyl, can list linear chain structure, branched structure, alicyclic structure etc.
As linear chain structure, can list methyl, ethyl, propyl group, butyl, amyl group etc., preferred carbon number is 1～9, more preferably carbon number is 1～6.
As branched structure, can list at the branched structure of above-mentioned branching and/or alicyclic structure record in this etc., preferred carbon number is 3～8, more preferably carbon number is 3～5.
As alicyclic structure, can list at the alicyclic structure of above-mentioned branching and/or alicyclic structure record in this etc., preferred carbon number is 5～20, more preferably carbon number is 5～15.
In general formula (1), B1 and B2 represent independently respectively singly-bound, urethane bond (the main chain side :-O-CO-NHR-), ester bond (the main chain side :-O-CO-), R represents that carbon number is 1～3 alkyl.
As B1, preferred singly-bound, urethane bond (the main chain side :-O-CO-NHR-), more preferably singly-bound.
As B2, preferred singly-bound, urethane bond (the main chain side :-O-CO-NHR-), more preferably singly-bound.
B1 and B2 can be identical, can be also different structures.
In general formula (1), in addition, X1 and X2 represent respectively (main chain side)-O-CO-independently.
In general formula (1), R
1And R
2Represent independently respectively hydrogen atom or methyl, be preferably methyl.R
1And R
2Can be identical, can be also different structures.
In (A) resin synthetic; the method that imports (methyl) acryloyl group on the side chain can suitably be selected from known method, can list method, (3) that the method, (2) that make (methyl) acrylate with epoxy radicals and the repetitive with acidic groups carry out addition such as (1) make (methyl) acrylate with isocyanate group and the repetitive with hydroxyl carry out addition and make (methyl) acrylate with hydroxyl and the repetitive with isocyanate group carry out the method etc. of addition.
Wherein, make method that (methyl) acrylate with epoxy radicals and the repetitive with acidic groups carry out addition the most easily make, be preferred aspect low-cost.
in (A) resin synthetic, as import the method for 2 (methyl) acryloyl groups on side chain, for example above-mentioned (1) can be made (methyl) acrylate with epoxy radicals and the repetitive with acidic groups carry out addition, then the method for using (methyl) acryloyl chloride etc. that hydroxy esterification is obtained, with containing (methyl) acrylate-based isocyanates (カ レ Application ズ MOI of making of Showa Denko K. K for example, MOIEG, known Combination of Methods next the synthesizing of ground such as the method that AOI etc.) hydroxy functional urethane is obtained.
As above-mentioned (methyl) acrylate with epoxy radicals, be not particularly limited the compound of preference such as following structural formula (1) expression and the compound of following structural formula (2) expression.
Structural formula (1)
Wherein, in said structure formula (1), R
1Expression hydrogen atom or methyl.L
1Identical with the B2 meaning with the B1 in general formula (1).
Structural formula (2)
Wherein, in said structure formula (2), R
2Expression hydrogen atom or methyl.L
2Identical with the B2 meaning with the B1 in general formula (1).W represents the aliphatic alkyl of 4～7 rings, and is identical with A1 meaning in above-mentioned general formula (1), and preferred example is also identical.
As the compound of said structure formula (1) expression or the compound of structural formula (2) expression, be not particularly limited, can list following exemplary compounds (1)～(10).
～～other monomer～～
In (A) resin in the present invention, can also import other group with other monomer.
As above-mentioned other monomer, be not particularly limited, can list such as monomer with (methyl) acrylate, styrene, vinyl ether, dibasic acid anhydride base, vinyl ester group, hydrocarbon chain thiazolinyl etc. etc.
As above-mentioned vinyl ether group, be not particularly limited, can list such as butyl vinyl ether etc.
As above-mentioned dibasic acid anhydride base, be not particularly limited, can list such as maleic anhydride base, itaconic anhydride base etc.
As above-mentioned vinyl ester group, be not particularly limited, can list such as vinyl acetate ester group etc.
As above-mentioned hydrocarbon chain thiazolinyl, be not particularly limited, can list such as butadienyl, prenyl etc.
As the containing ratio of other monomer in above-mentioned (A) resin, its ratio of components is preferably 1～40 quality %, more preferably 2～30 quality %.
As the object lesson of (A) resin, can list the compound of for example using following representation (exemplary compounds PD-1～PD-56, PU-1～PU-56), but be not limited to these compounds.
In addition, the x in exemplary compounds, y and z (and St) represent the ratio of components (mass ratio) of each repetitive, are preferably the form that consists of in preferable range described later.In addition, the weight-average molecular weight of each exemplary compounds also is preferably the form that consists of in preferable range described later.
＜synthetic method 〉
(A) resin can be synthesized by the operation of (being total to) polyreaction of monomer and this two-stage operation of operation or three stage procedures that import 2 ethylenic unsaturated groups.
At first, (being total to) polyreaction is undertaken by (being total to) polyreaction of various monomers, can suitably select from known reaction with no particular limitation.For example, the spike of relevant polymerization can suitably be selected free radical polymerization, cationic polymerization, anionic polymerisation, coordination polymerization etc.Wherein, from synthetic easily, viewpoint cheaply, preferred free radical polymerization.In addition, for polymerization, also can suitably select from known method with no particular limitation.Can suitably select such as mass polymerization, suspension polymerization, emulsion polymerization, solution polymerization process etc.Wherein, more preferably solution polymerization process.
＜carbon number 〉
As the total carbon atom number of (A) resin, aspect elasticity coefficient (hardness), be preferably more than 10.Wherein, total carbon atom number more preferably 10～30 is particularly preferably 10～15.
＜molecular weight 〉
As the molecular weight of (A) resin, weight-average molecular weight is preferably 10000～100,000, and more preferably 12000～60000, be particularly preferably 15000～45000.If weight-average molecular weight in above-mentioned scope, is being preferred aspect the manufacturing adaptability of resin (being preferably multipolymer), developability.In addition, aspect being difficult for that decline because of melt viscosity causes that formed shape caves in and be difficult for becoming crosslinked bad aspect, do not have when developing the sept shape residue aspect be preferred.
Weight-average molecular weight is measured with gel permeation chromatography (GPC).Relevant GPC describes in detail in embodiment described later.
＜glass transition temperature 〉
(A) glass transition temperature of resin (Tg) is preferably 40～180 ℃, more preferably 45～140 ℃, is particularly preferably 50～130 ℃.Glass transition temperature (Tg) can obtain having good developability, the sept of mechanical strength if be in above-mentioned preferred scope.
＜acid number 〉
(A) acid number of resin is according to the difference of resulting molecular structure, and its preferred scope can change, but more than generally being preferably 20mgKOH/g, more preferably more than 40mgKOH/g, is particularly preferably 50～130mgKOH/g.If acid number is in above-mentioned preferred scope, can obtain having good developability, the sept of mechanical strength.
Viewpoint from the sept that obtains having good developability, mechanical strength, the glass transition temperature (Tg) of above-mentioned (A) resin is preferably 40～180 ℃, and weight-average molecular weight is preferably 10000～100000, more preferably Tg is 40～140 ℃ (more preferably 50～130 ℃), and weight-average molecular weight is 12000～60000 (more preferably 15000～45000).
And then in the preferred example of above-mentioned (A) resin, each combination of preferred above-mentioned molecular weight, glass transition temperature (Tg) and acid number is preferred.
The viewpoint of the deformation-recovery rate when forming patterning body (for example color filter use sept), development residue, fine wrinkle (reticulation), (A) resin in the present invention preferably with branching and/or alicyclic structure, acidic groups and from main chain between the substituted alkyl that contains 2 ethylenic unsaturated links that configures by ester group contain respectively multipolymer more than ternary polymerization in different repetitive (copolymerization units).
Particularly, above-mentioned (A) resin is preferably the above multipolymer of ternary polymerization that has at least following repetitive: the repetitive X (x % by mole) with branching and/or alicyclic structure; Repetitive Y (y % by mole) with acidic groups; And has a repetitive Z (z % by mole) of " and the substituted alkyl that contains 2 ethylenic unsaturated links that configures by ester group between main chain ".And then, can also have as required other repetitive L (l % by mole).
Above-mentioned multipolymer for example can obtain by making monomer, the monomer with acidic groups with branching and/or alicyclic structure, other monomer generation copolymerization with the monomer of " and the substituted alkyl that contains 2 ethylenic unsaturated links that configures by ester group between main chain " and interpolation as required.Wherein, from the viewpoint that makes compressive modulus of elasticity, elastic recovery become good by bulky functional group, preferred at least as above-mentioned monomer with branching and/or alicyclic structure, make the monomer copolymerization of above-mentioned general formula (4) expression, thereby imported the situation of the multipolymer of the group with branching and/or alicyclic structure.In this situation, (A) resin has the structural unit from the monomer of above-mentioned general formula (4) expression on main chain.
Copolymerization ratio of components when relevant above-mentioned (A) resin is multipolymer can be considered to determine after glass transition temperature and acid number.Although can not without exception, can be set as following ranges.
(A) ratio of components (x) of the repetitive with branching and/or alicyclic structure in resin is preferably 10～70 % by mole, more preferably 15～65 % by mole, is particularly preferably 20～60 % by mole.If ratio of components (x) is in above-mentioned scope, can obtain good developability, the while developer solution patience of image section is also good.
(A) ratio of components (y) of the repetitive with acidic groups in resin is preferably 5～70 % by mole, more preferably 10～60 % by mole, is particularly preferably 20～50 % by mole.If ratio of components (y) is in above-mentioned scope, can obtain good curing, developability.
(A) ratio of components (z) of the repetitive of having in resin " and the substituted alkyl that contains 2 ethylenic unsaturated links that configures by ester group between main chain " is preferably 10～70 % by mole, more preferably 20～70 % by mole, be particularly preferably 30～70 % by mole.If ratio of components (z) is that in above-mentioned scope, pigment-dispersing is good, simultaneously sensitivity and polymerization-curable are good, and the ageing stability when transferring long preservation under fluid preservation after liquid and the dry film state after coating is good.
And then, as (A) resin, preferred following situation: ratio of components (x) is 10～70 % by mole (more preferably 15～65 % by mole, be particularly preferably 20～50 % by mole), ratio of components (y) is 5～70 % by mole (more preferably 10～60 % by mole, be particularly preferably 30～70 % by mole), ratio of components (z) be 10～70 % by mole (more preferably 20～70 % by mole are particularly preferably 30～70 % by mole).
As the content of above-mentioned (A) resin in photosensitive polymer combination, be preferably 5～70 quality % with respect to the total solid composition of composition, more preferably 10～50 quality %.
(A) resin can with other resin described later and use, but only be preferably situation about being consisted of by above-mentioned (A) resin.
～～other resin～～
As can with the resin of above-mentioned (A) resin and use, be preferably the compound that demonstrates swellability for alkaline aqueous solution, more preferably have the compound of solubility for alkaline aqueous solution.
As demonstrate swellability or deliquescent resin for alkaline aqueous solution; can preferably list the resin that for example has acidic groups, preferred particularly: as to have imported ethylenic unsaturated double-bond and acidic groups and have ethylenic copolymer, the epoxy acrylic ester compounds of (methyl) acryloyl group and acidic groups on the compound (epoxy acrylic ester compounds) that obtains, side chain and have potpourri, maleamic acid based copolymer of the ethylenic copolymer of (methyl) acryloyl group and acidic groups etc. on side chain in epoxy compound.
As above-mentioned acidic groups, be not particularly limited, can suitably select according to purpose, can list such as carboxyl, sulfonic group, phosphate etc., wherein, from obtaining the viewpoints such as easiness of raw material, can preferably list carboxyl.
With above-mentioned (A) resin and other resin and used time, as the total content (solid constituent) of (A) resin with the resin that may be used, total solid composition with respect to photo-sensitive resin is preferably 5～70 quality %, more preferably 10～50 quality %.If this content more than 5 quality %, can be kept the film strength of photosensitive resin layer, can keep well the stickability on this photosensitive resin layer surface, and if above-mentioned content below 70 quality %, exposure sensitivity becomes good.
(B) polymerizable compound
Photosensitive polymer combination of the present invention contains at least a polymerizable compound with ethylenic unsaturated link.Be subject to forming cured film from polymerization reaction take place after the effect of the free radical of Photoepolymerizationinitiater initiater described later.
As above-mentioned polymerizable compound, can be from the polymerizable compound that consists of known composition choice for use, can list the composition of record in paragraph [0027]～[0053] of the composition of record in the paragraph of JP 2006-23696 communique [0010]～[0020] for example or JP 2006-64921 communique.
With the relation of above-mentioned (A) resin in, (B) polymerizable compound is preferably 0.5～2.0 with respect to the quality ratio (ratio of (B)/(A)) of (A) resin, more preferably 0.6～1.4, be particularly preferably 0.7～1.2.If ratio (B)/(A) is in above-mentioned scope, can obtain having good developability, the sept of mechanical strength.
(C) Photoepolymerizationinitiater initiater
Photosensitive polymer combination of the present invention contains at least a Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater as in the present invention is not particularly limited, and can use known Photoepolymerizationinitiater initiater.As known Photoepolymerizationinitiater initiater, can list the initiating agent of record in paragraph [0027]～[0053] of the paragraph of JP 2006-23696 communique [0010]～[0020] for example or JP 2006-64921 communique.Example as known Photoepolymerizationinitiater initiater; from the viewpoint of sensitivity, preferably contain glycyl benzene compounds, acylphosphine oxide based compound, the oxime ester based compound beyond above-mentioned and the mixed type initiating agent that six aryl united imidazole/aromatic series sulfhydryl compound/auxiliary combinations are formed.
As the object lesson of glycyl benzene compounds, can list IRGACURE (Irg) 907 (Ciba Specialty Chemicals Co., Ltd. make) etc.As the object lesson of acylphosphine oxide based compound, can list DAROCUR TPO, Irgacure (Irg) 819 (above for Ciba Specialty Chemicals Co., Ltd. make) etc.As the object lesson of oxime ester based compound, can list IRGACURE (Irg) OXE01 or CGI242 etc. (above for Ciba SpecialtyChemicals Co., Ltd. make).As the mixed type initiating agent that six aryl united imidazole/aromatic series sulfhydryl compound/auxiliary combinations are formed, can list 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (B-CIM, Baotugu Chemical Industrial Co., Ltd make)/2-mercaptobenzimidazole/4,4-diethylamino benzophenone.
Following table illustrates the structure of above-mentioned initiating agent.
＜glycyl benzene compounds 〉
＜acylphosphine oxide based compound 〉
＜oxime ester based compound 〉
The total amount of Photoepolymerizationinitiater initiater in photosensitive polymer combination is preferably 0.5～25 quality % with respect to the total solid composition of photosensitive polymer combination, more preferably 1～20 quality %.
Be difficult for distillation under the heating of this Photoepolymerizationinitiater initiater when pattern forms, can suppress the pollution of firing furnace or photomask etc., and by with above-mentioned Resin A and use, can make becoming of polyreaction good, further improve the controlled of shape and thickness.Thus, even if at for example 1500J/m
2Following low exposure zone also can obtain good sensitivity, adhesiveness.For example when forming the sept that color filter uses, can obtain with the good adhesion of substrate and form the sept of desired shape.
In addition, thus in the present invention, said Photoepolymerizationinitiater initiater refers to that the exposure by visible light, ultraviolet ray, far ultraviolet, charge particle ray, X ray etc. produces the composition of the spike that can cause the polymerization of above-mentioned specific aggregation compound.
＜particulate 〉
From the viewpoint of mechanical strength, photosensitive polymer combination of the present invention preferably except resin, polymerizable compound, Photoepolymerizationinitiater initiater, also contains at least a particulate.
As particulate, be not particularly limited, can suitably select according to purpose, but the extender pigment of record in [0035] of preference such as JP 2003-302639 communique～[0041], wherein, from the viewpoint of the light spacer that obtains having good developability, mechanical strength, preferred cataloid.
From forming the viewpoint that can obtain high mechanical strength when light spacer etc. easily is subject to the structure of external force, the mean grain size of above-mentioned particulate is preferably 5～50nm, and more preferably 10～40nm, be particularly preferably 15～30nm.
As the content of above-mentioned particulate in photosensitive polymer combination (being light spacer or the photo-sensitive resin that consists of it when forming light spacer), viewpoint from the light spacer that obtains having high mechanical strength, be preferably 5～50 quality % with respect to the total solid composition (quality) in photosensitive polymer combination, more preferably 10～40 quality %, be particularly preferably 15～30 quality %.
＜other 〉
In photosensitive polymer combination of the present invention, except resin, specific aggregation compound, Photoepolymerizationinitiater initiater and the particulate that contains as required, can also contain as required photopolymerization and cause other compositions such as auxiliary agent.
Photosensitive polymer combination can also and cause auxiliary agent as other adding ingredient with photopolymerization.It is for the polymerization that promotes to have been caused by Photoepolymerizationinitiater initiater the polymerizable compound of polymerization that photopolymerization causes auxiliary agent, can be used in combination with Photoepolymerizationinitiater initiater.Cause auxiliary agent as photopolymerization, preferably use at least a of amine compound.
as above-mentioned amine compound, can list for example triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-ethyl cyclohexyl, N, the N-dimethyl-p-toluidine, 4, 4 '-two (dimethylamino) benzophenone (being commonly called as michler's ketone), 4, 4 '-two (diethylamino) benzophenone, 4, 4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4, 4 '-two (diethylamino) benzophenone.In addition, also the auxiliary combination use can be caused in various kinds of amine system or other photopolymerization.
Cause auxiliary agent as other photopolymerization beyond above-mentioned, can list such as alkoxy anthracene based compound, thioxanthones based compound, coumarin series compounds etc.As above-mentioned alkoxy anthracene based compound, for example can list 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.As above-mentioned thioxanthones based compound, can list for example ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
In addition, cause auxiliary agent as photopolymerization, also can use commercially available product.Cause auxiliary agent as commercially available photopolymerization, can list such as trade name " EAB-F " (Baotugu Chemical Industrial Co., Ltd's manufacturing) etc.
Cause the content of auxiliary agent in photosensitive polymer combination as photopolymerization, with respect to above-mentioned Photoepolymerizationinitiater initiater 1 mass parts, be preferably 0.6 mass parts～20 mass parts, 1 mass parts～15 mass parts more preferably, especially preferred 1.5 mass parts～15 mass parts.
In addition, as other composition, can be from the composition that consists of known composition choice for use, can list the composition of record in paragraph [0027]～[0053] of the paragraph of JP 2006-23696 communique [0010]～[0020] for example or JP 2006-64921 communique.
Photosensitive polymer combination of the present invention except the formation that can be suitable for light spacer described later, colored pattern, diaphragm, can also be suitable for dividing wall (such as black matrix" etc.), orientation control with projection etc. other the patterning body or the formation of tunicle.
" light spacer and forming method thereof "
Light spacer of the present invention is to use above-mentioned photosensitive polymer combination of the present invention to form.For details and the preferred configuration thereof of photosensitive polymer combination, as mentioned above.
Light spacer of the present invention is owing to being to use photosensitive polymer combination of the present invention to form, so even if low exposure also has uniform cross sectional shape, can suppress height tolerance.
And then photosensitive polymer combination of the present invention can obtain having the light spacer as the necessary high compression elastic modulus of light spacer, deformation-recovery.
In the present invention, the state that has " uniformly cross sectional shape " as patterning bodies such as light spacers is preferably in a plurality of positions (being preferably 3 more than the position) in substrate, the cross sectional shape of patterning body becomes the state of the shape that is similar to rectangle.
As the above-mentioned shape that is similar to rectangle, following shape more preferably: when using parallel with the substrate normal direction and vertical with the edge (in the situation that the cylindrical-shaped structure body is the tangent line at edge) from the substrate normal direction is seen of patterning body plane to cut off this patterning body, on section, the line that is equivalent to the patterning body side surface is 80 °～100 ° with the line angulation (following also referred to as " coning angle ") that is equivalent to patterning body lower surface.
Here, the lower surface of above-mentioned patterning body refers to, in the surface of patterning body, with the surface of contact of the substrate contact that has formed this patterning body.In addition, the side of above-mentioned patterning body refers to, in the surface of patterning body, the surface of (face parallel with above-mentioned patterning body lower surface, and be and the discontiguous face of above-mentioned substrate) neither the upper surface that the lower surface of above-mentioned patterning body neither the patterning body.
So long as used the method for photosensitive polymer combination of the present invention, just can form light spacer of the present invention with any method, but by use contain the method (the formation method of light spacer of the present invention) of following operation (i)～(iii) can optimum ground formation.
The formation method of light spacer of the present invention is provided with following operation and consists of: the operation (following also referred to as " tunicle formation operation ") that (i) forms the tunicle of above-mentioned photosensitive polymer combination of the present invention on substrate; The operation of (ii) at least a portion of described tunicle being exposed (following also referred to as " exposure process "); (iii) operation (following also referred to as " developing procedure ") of developing of the described tunicle after exposing, operation (following also referred to as " tunicle heating process ") and other operation that the described tunicle after (iv) can also be set as required develop heats consist of.
(i) tunicle forms operation
It is to form the tunicle of above-mentioned photosensitive polymer combination of the present invention on substrate that tunicle forms operation.Photo-sensitive resin can form tunicle, and this photo-sensitive resin just consists of the sept of holding unit thickness equably through other operations such as exposure process described later and developing procedures.The sept of the application of the invention can effectively solve particularly easily the demonstration that the change because of element thickness produces in the image that shows in uneven display device (particularly liquid crystal indicator) uneven.
Method as form photo-sensitive resin on substrate can preferably list: (a) to containing at least above-mentioned (A) resin, (B) polymerizable compound and (C) rubbing method that is coated with of the photosensitive polymer combination of Photoepolymerizationinitiater initiater; And (b) use the photosensitive transfer printing material with above-mentioned photo-sensitive resin, the transfer printing that photo-sensitive resin is carried out lamination, transfer printing by heating and/or pressurization.
(a) rubbing method
The coating of photosensitive composite can be with carrying out with the extrusion coated method of hopper etc. of putting down in writing in known rubbing method such as spin-coating method, curtain coating method, slot coated method, dip coated method, airblade coating method, rolling method, coiling rod rubbing method, intaglio plate rubbing method or No. 2681294 instructions of United States Patent (USP).Wherein, in JP 2004-89851 communique, JP 2004-17043 communique, JP 2003-170098 communique, JP 2003-164787 communique, JP 2003-10767 communique, JP 2002-79163 communique, JP 2001-310147 communique etc., the method for utilizing gap nozzle or slot coated device of record is preferred.
(b) transfer printing
Transfer printing is to use photosensitive transfer printing material, will form on the temporary supporting body membranaceous photo-sensitive resin use for example heat and/or pressurize after roller or dull and stereotyped by pressure viscosity or or heating pressure viscosity and desired real estate stickup after, by peeling off of temporary supporting body, photo-sensitive resin is transferred on substrate.Can list particularly laminate and the laminating method put down in writing in Unexamined Patent 7-110575 communique, Unexamined Patent 11-77942 communique, JP 2000-334836 communique, JP 2002-148794 communique, from the viewpoint of few foreign, preferably use the method for putting down in writing in Unexamined Patent 7-110575 communique.
When forming photo-sensitive resin, oxygen insulating course (following also referred to as " oxygen partition film " or " middle layer ") can be set further between photo-sensitive resin and temporary supporting body.Can improve exposure sensitivity thus.In addition, in order to improve transfer printing, the thermoplastic resin with resiliency can also be set.
The method for making of temporary supporting body, oxygen insulating course, thermoplastic resin, other layer and this photosensitive transfer printing material of relevant formation photosensitive transfer printing material can be suitable for formation, the method for making put down in writing in paragraph [0024]～[0030] of JP 2006-23696 communique.
When passing through (a) rubbing method and (b) transfer printing forms photo-sensitive resin, all preferred its bed thickness is 0.5～10.0 μ m, more preferably 1～6 μ m.If bed thickness is above-mentioned scope, the generation of the pin hole when in can preventing from making, coating forms need not spend the development that just can carry out unexposed section for a long time and remove.
As the substrate that forms photo-sensitive resin, can list such as transparency carrier (such as glass substrate or plastic base), with the substrate of nesa coating (such as the ITO film), with the substrate (also referred to as filter substrate) of color filter, with the driving substrate of driving element (such as thin film transistor (TFT) (TFT)) etc.As the thickness of substrate, generally be preferably 700～1200 μ m.
(ii) exposure process and (iii) developing procedure
In exposure process, at least a portion of the tunicle that will form in above-mentioned tunicle formation operation is exposed, and forms sub-image.In developing procedure thereafter, the tunicle that will expose in above-mentioned exposure process develops, and can form the spacer patterns of desired shape.
As the object lesson of above-mentioned these operations, can list the formation example of putting down in writing in paragraph [0071]～[0077] of JP 2006-64921 communique, the middle operation of putting down in writing in paragraph [0040]～[0051] of JP 2006-23696 communique etc. as preferred example in the present invention.
(iv) tunicle heating process
In the tunicle heating process, the tunicle after developing in above-mentioned developing procedure heats.By heating the curing of further promotion tunicle, can obtain having the good sept of high strength, compressive modulus of elasticity and elastic recovery.
Can be produced on the base board for display device that possesses light spacer on substrate as described above.Light spacer is preferably forming above the black light shielding parts such as the black matrix" that forms on substrate or on the driving element such as TFT.In addition, also can there be the alignment films such as the transparency conducting layers (transparency electrode) such as ITO or polyimide between the driving elements such as the black light shielding parts such as black matrix" or TFT and light spacer.
For example, when light spacer is arranged on the top of black light shielding part or driving element, can make by the following method base board for display device: after covering the black light shielding part (black matrix" etc.) or driving element that is provided in advance on this substrate, for example the photo-sensitive resin with photosensitive transfer printing material is laminated on support dignity, peel off transfer printing and after forming photo-sensitive resin, it is implemented exposure, development, heat treated etc. to form light spacer.
The colored pixels such as redness (R), blue (B), green (G) three looks can also further be set on base board for display device of the present invention as required.
Light spacer of the present invention forms after can containing in formation the color filter of the painted sections such as the black shielding portion such as black matrix" and colored pixels.
Above-mentioned black shielding portion and painted and light spacer can be by forming rubbing method and transfer printing combination in any, wherein said rubbing method is the method for photosensitive resin coating composition, uses the transfer materials with the photo-sensitive resin that is made of photosensitive polymer combination in described transfer printing.
above-mentioned black shielding portion and painted and above-mentioned light spacer can be formed by photosensitive polymer combination respectively, particularly, for example on substrate directly the above-mentioned photosensitive polymer combination of coating liquid with after forming photo-sensitive resin, expose and develop, above-mentioned black shielding portion and painted section are formed pattern-like, then the above-mentioned photosensitive polymer combination of other liquid is set to form photo-sensitive resin on the other substrate different from aforesaid substrate (temporary supporting body), make thus transfer materials, use the transfer materials of making thus, thereby make this transfer materials and the aforesaid substrate that is formed with above-mentioned black shielding portion and painted section adhere to the transfer printing photo-sensitive resin, then expose and develop, light spacer can be formed pattern-like thus.
Can make the color filter that is provided with light spacer as described above.
" diaphragm "
Diaphragm of the present invention uses above-mentioned photosensitive polymer combination of the present invention to form.
Diaphragm of the present invention is owing to consisting of with photosensitive polymer combination of the present invention, so even in the situation that to form film thickness uniformity with low exposure also good.
So long as used the method for photosensitive polymer combination of the present invention, just can form diaphragm of the present invention with any method, can form with the method identical with the formation method of above-mentioned light spacer of the present invention.Here, when diaphragm not being implemented patterning, namely, when diaphragm is formed as the whole facial mask of what is called, and in above-mentioned (ii) exposure process, the method for preferably tunicle being carried out whole exposure.
" colored pattern "
Colored pattern of the present invention uses above-mentioned photosensitive polymer combination of the present invention to form.Here, photosensitive polymer combination is preferably except each above-mentioned composition, also further contains at least a form of colorant.
As above-mentioned colorant, be not particularly limited, can suitably select from known colorant.As known colorant, can list particularly the middle pigment of putting down in writing in JP 2005-17716 communique [0038]～[0054] and dyestuff, the middle pigment of putting down in writing in JP 2004-361447 communique [0068]～[0072], the middle colorant of putting down in writing in JP 2005-17521 communique [0080]～[0088] etc.
Colored pattern of the present invention is owing to consisting of with photosensitive polymer combination of the present invention, even so in the situation that form with low exposure, also have uniform cross sectional shape, film thickness uniformity is good.
In addition, when colored pattern of the present invention will usually use as of the color filter of the colored pattern with multiple color, as long as the colored pattern of at least a color forms with photosensitive polymer combination of the present invention.
So long as used the method for photosensitive polymer combination of the present invention, just can form colored pattern of the present invention with any method, for example, can form with the method identical with the formation method of above-mentioned light spacer of the present invention.
" base board for display device "
Base board for display device of the present invention possesses at least a in light spacer of the present invention, diaphragm of the present invention and colored pattern of the present invention and consists of.
Base board for display device of the present invention is owing to possessing the structure that uses that photosensitive polymer combination of the present invention forms, cross sectional shape and thickness (highly) to have good uniformity (at least a in light spacer of the present invention, diaphragm of the present invention and colored pattern of the present invention; below identical), so can suppress to show uneven when being used for display device.
Here so-called base board for display device, refer at least one for a pair of supporter that consists of display device.
object lesson as base board for display device, according to the difference of the formation of display element or display device and difference, can list for example the possess colored pattern filter substrate of (following also referred to as " colored pixels "), (for example possesses the band driving means substrate of driving means, the simple matrix substrate, active-matrix substrate etc.), (for example possesses the band dividing wall substrate of dividing wall, possesses the band black matrix substrate of black matrix" etc.), possesses the two color filter array COA (color filter onarray) substrate of colored pattern and driving means, the glass substrate of patterning body or tunicle etc. is not set.
The above-mentioned colored pattern group (colored pixels group) of above-mentioned filter substrate can be made of the pixel of two looks that mutually present different colours, also can be made of the pixel of three looks, pixel more than four looks.For example in the situation that three looks, consisted of by red (R), green (G) and blue (B) these three kinds of tones.In the situation that the pixel groups of configuration RGB three looks, the configuration of preferably inlaying (mosaic) type, triangle type etc., in the situation that the pixel groups more than configuration four looks, which type of configuration can.The making of filter substrate for example can form black matrix" as already described after the pixel groups that forms more than two looks, also can form pixel groups conversely after forming black matrix".The formation of relevant rgb pixel can be with reference to JP 2004-347831 communique etc.
" display element "
Use base board for display device of the present invention can form display element.
A kind of as display element can list the liquid crystal display cells that possesses at least liquid crystal layer and liquid crystal drive means (comprising simple matrix type of drive and driven with active matrix mode) between at least one is a pair of supporter (comprising base board for display device) of transmitance.
In the situation that this liquid crystal display cells, base board for display device can be used as each pixel that has a plurality of rgb pixel groups, consists of this pixel groups and is mutually used by the filter substrate that black matrix" is divided.On this filter substrate, due to the structure that is provided with cross sectional shape and thickness (highly) and has good uniformity, show uneven generation so possess color spot that liquid crystal material skewness that the liquid crystal display cells of this filter substrate can prevent effectively that the change due to the cell gap between filter substrate and counter substrate (element thickness) from causing, low-temp foaming etc. cause etc.Thus, the liquid crystal display cells of made can demonstrate distinct image.
In addition, more detailed form as liquid crystal display cells, can list the form of following formation: possess at least liquid crystal layer and liquid crystal drive means between at least one is a pair of supporter (comprising base plate for liquid crystal display device) of transmitance, above-mentioned liquid crystal drive means have active component (for example TFT), and will be restricted to Rack between a pair of substrate by light spacer.
" display device "
Display device of the present invention possesses above-mentioned base board for display device.
Display device of the present invention is owing to possessing the base board for display device of the present invention that is provided with the structure that cross sectional shape and thickness (highly) have good uniformity, so can suppress to show uneven.
As display device, can list the display device such as liquid crystal indicator, plasm display device, EL display device, CRT display device etc.About the definition of display device and the explanation of each display device, for example be documented in " electronic display unit (assistant
The clear husband of wood work, Co., Ltd.'s census of manufacturing can the nineteen ninety distribution) ", in " display device (she blows along chapter work, the distribution in 1989 of industry books Co., Ltd.) " etc.
In display device, be preferably liquid crystal indicator.
Liquid crystal indicator for example consists of as follows: with being restricted to Rack between a pair of substrate of light spacer with the ground configuration of mutual subtend, enclose liquid crystal material (will enclose the position and be called liquid crystal layer) in the gap of restriction.The thickness of liquid crystal layer (element thickness) is retained as desired uniform thickness.
As the liquid crystal display pattern of liquid crystal indicator, can preferably list STN type, TN type, GH type, ECB type, ferroelectric liquid crystals, anti ferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, other various patterns.Wherein, in liquid crystal indicator of the present invention, from bringing into play most effectively the viewpoint of effect of the present invention, be preferably easily change because of the element thickness of liquid crystal cells and cause and show uneven display mode, preferably constituting component thickness is VA type display mode, IPS type display mode, the OCB type display mode of 2～4 μ m.
In addition, as spendable liquid crystal in the present invention, can list nematic crystal, cholesteric crystal, smectic crystal, ferroelectric liquid crystals.
Basic comprising form as liquid crystal indicator, can list the form of following formation etc.: (a) will arrange the driving side substrate that forms and the counter substrate that possesses opposite electrode (conductive layer) by the driving element such as thin film transistor (TFT) (TFT) and pixel electrode (conductive layer) and clip light spacer and relatively configure, and enclose liquid crystal material in gap section betwixt; (b) will drive substrate and clip light spacer with the counter substrate that possesses opposite electrode (conductive layer) and relatively configuration, enclose liquid crystal material in gap section betwixt.Liquid crystal indicator of the present invention can be suitable for various liquid crystal displays.
Relevant liquid crystal indicator, for example " lcd technology of future generation (Uchida Tatsuo compiles, the meeting of the side census of manufacturing, 1994 the distribution) " on the books.For liquid crystal indicator of the present invention, except possessing liquid crystal display cells of the present invention, be not particularly limited, can constitute for example liquid crystal indicator of the variety of way of above-mentioned " lcd technology of future generation " middle record.Wherein particularly effective for the liquid crystal indicator that consists of colored TFT mode.The liquid crystal indicator of relevant colored TFT mode, on the books in for example " color TFT-LCD shows (altogether vertical publish Co., Ltd., distribution in 1996) ".
Liquid crystal indicator generally can also consist of with various members such as electrode base board, polarization film, phase-contrast film, backlight, light spacer, view angle compensation film, antireflective film, light diffusion film, anti-dazzle films except possessing above-mentioned light spacer, colored pattern, diaphragm, base plate for liquid crystal display device, liquid crystal display cells.Relevant these members are documented in the market of " ' 94 liquid crystal display periphery material chemicals for example (island Itou Kentaro, the MC of Co., Ltd. C, distribution in 1994) ", in " present situation in 2003 liquid crystal related market and prospect (last volume) (show good Ji, the キ メ ラ of Fuji of Co., Ltd. always grind, distribution in 2003) " in the future.The application quotes the full text of Patent 2007-339917 communique of the Japanese patent application on Dec 28th, 2007, requires it as right of priority at this.
Embodiment
Below, be described more specifically the present invention by embodiment, but only otherwise exceed its purport, the present invention just is not limited to following embodiment.In addition, as long as no particularly pointing out, " part " is take quality as benchmark.
In addition, weight-average molecular weight is to use gel permeation chromatography (GPC) to measure.In GPC, use HLC-8020GPC (TOSOH Co., Ltd. make), as pillar, (TOSOH Co., Ltd. makes, 4.6mmID * 15cm), use THF (tetrahydrofuran) as eluent to use 3 TSKgel, Super Multipore HZ-H.In addition, as condition, sample solution concentration is set as 4.5 quality %, and flow velocity is set as 0.35ml/min, and the sample injection rate IR is set as 10 μ l, and measuring Temperature Setting is 40 ℃, uses the IR detecting device to measure.In addition, " standard sample TSK standard, the polystyrene " that calibration curve is made by TOSOH Co., Ltd.: " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 ", " n-proplbenzene " these 8 samples are made.
＜(A) resin is synthetic 〉
At first, as the resin in photosensitive polymer combination, carry out the synthetic of (A) resin (exemplary compounds PD-52, PU-52, PD-51, PD-53, PD-46, PD-47, PU-53).
(synthesis example 1)
(exemplary compounds PD-52's is synthetic)
Add in advance 7.48 parts of 1-methoxy-2-propanols (MFG, Japanese emulsifying agent Co., Ltd. make) in reaction vessel, be warming up to 90 ℃, under nitrogen atmosphere with dripping in the reaction vessel of 2 hours to 90 ℃ by 3.1 parts of styrene (St), the methacrylic acid three cyclopentene esters (TCPD-M that Hitachi Chemical Co., Ltd. makes; X) 4.28 parts, methacrylic acid (MAA; Y) 11.7 parts, azo are the mixed solution of 2.08 parts of polymerization initiators (make with the pure medicine of light Co., Ltd., V-601) and 55.2 parts of formations of 1-methoxy-2-propanol.After dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide in aforesaid propylene acid resin solution, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd make); Z).After dropping, make its reaction 4 hours while injecting air at 90 ℃, then modulate by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. make), make solid component concentration reach 45%, obtain having the compounds X of a unsaturated group.
And then, make methacrylic chloride (Tokyo changes into Co., Ltd. and makes) carry out addition reaction with above-claimed cpd X, obtain resin solution (45% solution of solid constituent acid number: 76.0mgKOH/g, Mw:25000,1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester) (x: y: z: St=30mol%: 27mol%: 37mol%: 6mol%) of exemplary compounds PD-52 ((A) resin).
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on methacrylic acid and obtain.
In addition, the molecular weight Mw of exemplary compounds PD-52 represents weight-average molecular weight, and the mensuration of weight-average molecular weight is (following identical) of using gel permeation chromatography (GPC method) to carry out.
(synthesis example 2)
(exemplary compounds PU-52's is synthetic)
Add in advance 7.48 parts of 1-methoxy-2-propanols (MFG, Japanese emulsifying agent Co., Ltd. make) in reaction vessel, be warming up to 90 ℃, under nitrogen atmosphere with dripping in the reaction vessel of 2 hours to 90 ℃ by 3.1 parts of styrene (St), the methacrylic acid three cyclopentene esters (TCPD-M that Hitachi Chemical Co., Ltd. makes; X) 4.28 parts, methacrylic acid (MAA; Y) 11.7 parts, azo are the mixed solution of 2.08 parts of polymerization initiators (make with the pure medicine of light Co., Ltd., V-601) and 55.2 parts of formations of 1-methoxy-2-propanol.After dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide in aforesaid propylene acid resin solution, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd make); Z).After dropping, make its reaction 4 hours while injecting air at 90 ℃, then modulate by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. make), make solid component concentration reach 45%, obtain having the compound of a unsaturated group.
And then, make カ レ Application ズ MOI (Showa Denko K. K's manufacturing) and above-claimed cpd carry out addition reaction, obtain resin solution (45% solution of solid constituent acid number: 76.0mgKOH/g, Mw:25000,1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester) (x: y: z: St=30mol%: 27mol%: 37mol%: 6mol%) of exemplary compounds PU-52 ((A) resin).
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on methacrylic acid and obtain.
In addition, the molecular weight Mw of exemplary compounds PU-52 represents weight-average molecular weight, and the mensuration of weight-average molecular weight is to use gel permeation chromatography (GPC method) to carry out (following identical).
(synthesis example 3)
(exemplary compounds PD-51's is synthetic)
except in above-mentioned exemplary compounds PD-52 synthetic, do not use styrene, change TCPD-M (x), the addition of methacrylic acid (y) and GLM-MAA (z) makes the x in exemplary compounds PD-51: y: z is 34mol%: 27mol%: beyond 39mol%, with synthetic with the synthetic same method of above-mentioned exemplary compounds PD-52, obtain having resin solution (the solid constituent acid number: 72.5mgKOH/g of the exemplary compounds PD-51 ((A) resin) of unsaturated group, Mw:22000,45% solution of 1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester).
(synthesis example 4)
(exemplary compounds PD-53's is synthetic)
except in above-mentioned exemplary compounds PD-52 synthetic, do not use styrene, methacrylic acid three cyclopentene esters are replaced with acrylic acid dicyclopentenyl 2-ethoxyethyl acetate (the Off ア Application Network リ Le FA-512M that Hitachi Chemical Co., Ltd. makes), change FA-512M (x), the addition of methacrylic acid (y) and GLM-MAA (z) makes the x in exemplary compounds PD-53: y: z is 46.2mol%: 24.3mol%: beyond 29.5mol%, with synthetic with the synthetic same method of above-mentioned exemplary compounds PD-52, obtain having resin solution (the solid constituent acid number: 71.2mgKOH/g of the exemplary compounds PD-53 ((A) resin) of unsaturated group, Mw:25500, 45% solution of 1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester).
(synthesis example 5)
(exemplary compounds PD-46's is synthetic)
except in above-mentioned exemplary compounds PD-52 synthetic, methacrylic acid three cyclopentene esters are replaced with ADMA (Idemitsu Kosen Co., Ltd.'s manufacturing), change ADMA (x), methacrylic acid (y), GLM-MAA (z) and cinnamic addition, make the composition x that has added in compound PD-1 from after cinnamic structural unit: y: z: St is 30mol%: 24mol%: 38mol%: beyond 8mol%, with synthetic with the synthetic same method of above-mentioned exemplary compounds PD-52, obtain resin solution (the solid constituent acid number: 74.1mgKOH/g of exemplary compounds PD-46 ((A) resin), Mw:29000, 45% solution of 1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester).
(synthesis example 6)
(exemplary compounds PD-47's is synthetic)
except in above-mentioned exemplary compounds PD-52 synthetic, methacrylic acid three cyclopentene esters are replaced with methacrylic acid norborneol ester, change methacrylic acid norborneol ester (x), methacrylic acid (y), it is 34mol%: 24mol%: 36mol% that GLM-MAA (z) and cinnamic addition make composition x: y: z: St: beyond 6mol%, with synthetic with the synthetic same method of above-mentioned exemplary compounds PD-52, obtain resin solution (the solid constituent acid number: 72.9mgKOH/g of exemplary compounds PD-47 ((A) resin), Mw:29000, 45% solution of 1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester).
(synthesis example 7)
(exemplary compounds PU-53's is synthetic)
except in the exemplary compounds PU-52 of synthesis example 2 synthetic, change to acrylic acid dicyclopentenyl 2-ethoxyethyl acetate (the Off ア Application Network リ Le FA-512M that Hitachi Chemical Co., Ltd. makes), do not use styrene, change acrylic acid dicyclopentenyl 2-ethoxyethyl acetate (x), methacrylic acid (y), it is 46.2mol%: 24.3mol% that the addition of GLM-MAA (z) makes composition x: y: z: beyond 29.5mol%, with synthetic with the synthetic same method of exemplary compounds PU-52, obtain resin solution (the solid constituent acid number: 76.0mgKOH/g of exemplary compounds PU-53 ((A) resin), Mw:25500, 45% solution of 1-methoxy-2-propanol/acetic acid 1-methoxyl-2-propyl ester).
(synthesis example 8) (comparative example is used)
Add 2 in the flask that possesses cooling tube, stirring machine, 200 parts of 7 parts of 2 '-azos two (2,4-methyl pentane nitrile) and propylene glycol monomethyl ether.Then, add 5 parts of styrene, 20 parts of methacrylates, methacrylic acid three ring [5.2.1.02,6] 20 parts, 25 parts, decane-8-base, 3-(methacryloxypropyl methyl)-25 parts of 3-Ethyloxetanes, methacrylic acid tetrahydrofurfuryl alcohol ester and 1,5 parts of 3-butadiene, after nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept 5 hours at this temperature, obtain containing the polymer solution of copolymer 1.
The solid component concentration of the polymer solution that obtains is 45.0%, and the weight-average molecular weight of polymkeric substance is 18000.
[embodiment 1]: rubbing method
The making of＜filter substrate 〉
Make color filter with black matrix", R (redness) pixel, G (green) pixel, B (blueness) pixel (following it is called filter substrate) with the method for record in paragraph [0084]～[0095] of JP 2005-3861 communique.Here, the substrate size of filter substrate is 550mm * 650mm.
Then, further form the transparency electrode of ITO (tin indium oxide) by sputter on the R of the filter substrate that obtains pixel, G pixel, B pixel and black matrix".
The formation of＜light spacer 〉
On the ito transparent electrode of the filter substrate that has formed ito transparent electrode by sputter of above-mentioned making, use spinner to carry out slot coated with coating fluid by the photo-sensitive resin that formula shown in following table 1 (being formula 1 in embodiment 1) consists of.Then, use vacuum drier VCD (manufacturing of Tokyo Ying Hua company) to make the part of solvent dry within 30 seconds, after coated film was lost flowability, prebake conditions was 3 minutes on the hot plate of 90 ℃, and forming thickness is the photo-sensitive resin (tunicle formation operation) of 5.2 μ m.
Then, use has the proximity type exposure machine (the Ha イ テ of Hitachi Network Electricity エ Application ジ ニ ア リ Application グ Co., Ltd. make) of extra-high-pressure mercury vapour lamp, make mask (having diameter is the quartzy exposed mask of the circular pattern of 15 μ m) with so that the filter substrate almost parallel that this mask mode relative with photo-sensitive resin configures under the state that stands vertically, distance between the surface of mask face and photo-sensitive resin is set as 100 μ m, across 10 seconds of this mask irradiation ultraviolet radiation, described ultraviolet ray is with 250W/m at 365nm
2Intensity see through the ultraviolet ray of ultraviolet transmission filtrator (UV-35, glass Co., Ltd. of Toshiba make) (exposure process, exposure be 250mJ/cm
2).
Then, using sodium carbonate is that developer solution (contains the sodium bicarbonate of 0.38 mol/L, the sodium carbonate of 0.47 mol/L, 5% nekal, anionic surfactant, defoamer and stabilizing agent, the product of commodity T-CD1 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 10 times and the solution that obtains with pure water), be to carry out drip washing under the condition of 0.15MPa to develop for 30 seconds at 29 ℃, conical nozzle pressure, form pattern image (developing procedure).Then, use (contains phosphate, silicate, non-ionic surfactant, defoamer, stabilizing agent with washing agent, trade name: T-SD3 (Fuji Photo Film Co., Ltd.'s manufacturing)) be diluted to 10 times and the solution that obtains with pure water, be to spray for 20 seconds with shower under the condition of 0.02MPa at 33 ℃, conical nozzle pressure, remove the residue of formed pattern image periphery, form columned spacer patterns in the mode of 1 sept in interval on 300 μ m * 300 μ m.
Then, the filter substrate that is provided with spacer patterns in 230 ℃ of lower heat treated 30 minutes (tunicle heating process), is made light spacer thus on filter substrate.Here, for 1000 of resulting light spacers, use three-dimensional surface structure analysis microscope (manufacturer: ZYGO company, model: New View 5022) form from ito transparent electrode the extreme higher position (n=20) that the face side is measured the highest sept, the mean value after average is made as height (average height).In addition, the measurement of the floorage of resulting light spacer utilizes the SEM photo to carry out.Consequently diameter is 15.1 μ m, and average height is the cylindrical shape of 4.7 μ m.Measured value is shown in following table 2.
Table 1
| The photo-sensitive resin coating fluid | Formula 1 (embodiment 1,3 embodiment 5～9) | Formula 2 (comparative examples 1,3) | Formula 3 (embodiment 2,4) | Formula 4 (comparative examples 2) |
| Acetic acid 1-methoxyl-2-propyl ester | 26 | 26 | 26 | 35 |
| MEK | 28 | 28 | 28 | 30 |
| Cataloid dispersion (cataloid: 30 parts, methyl isobutyl ketone: 70 parts, the MIBKst processed of Nissan Chemical Ind Ltd) | 0 | 0 | 14.1 | 0 |
| ソ Le ス パ one ス 20000 | 0.42 | 0.42 | 0.42 | 0.42 |
| DPHA liquid (dipentaerythritol acrylate: 76 parts, acetic acid 1-methoxyl-2-propyl ester: 24 parts) | 18.2 | 18.2 | 18.2 | 18.2 |
| The solution of resin (wherein resin is the compound of record in following table 2) | 20.5 | 0 | 20.5 | 0 |
| The solution of resin (wherein, synthesis example 8-comparative example compound (weight-average molecular weight=1.8 ten thousand)) | 0 | 20.5 | 0 | 0 |
| CGI242 (Ciba Specialty Chemicals Co., Ltd. system, Photoepolymerizationinitiater initiater) | 0.227 | 0.227 | 0.227 | 0.23 |
| Hydroquinone monomethylether | 0.0036 | 0.0036 | 0.0036 | 0.0036 |
| Surfactant 1 (メ ガ Off ア Star Network F-780-F, Dainippon Ink. ﹠ Chemicals Inc's system) | 0.032 | 0.032 | 0.032 | 0.032 |
| 5% methanol solution of Victoria ethereal blue-NAPS (Baotugu Chemical Industrial Co., Ltd's system) | 0 | 0 | 2.05 | 0 |
Unit: part
The making of＜liquid crystal indicator 〉
In addition, prepare glass substrate as counter substrate, implementing respectively the Butut that the PVA pattern is used on the transparency electrode of filter substrate obtained above and on counter substrate, the alignment films that is made of polyimide further is set thereon.
Then, on the position of the black matrix" housing around the mode of the pixel groups that is equivalent to surround color filter is arranged at, be coated with the sealant of ultraviolet curable resin by the divider mode, drip PVA pattern liquid crystal, after pasting with counter substrate, the substrate of pasting is carried out the UV irradiation, and then thermal treatment makes sealant cures.Paste the polaroid HLC2-2518 of サ Application リ Star Star Co., Ltd. system on the two sides of the liquid crystal cells that obtains like this.
Then, use FR1112H (Stanley electric Co., Ltd. make chip-type LED) to consist of side lamp mode backlight as green (G) LED, DB1112H (Stanley electric Co., Ltd. make chip-type LED) as blue (B) LED as red (R) LED, DG1112H (Stanley electric Co., Ltd. make chip-type LED), be disposed at the above-mentioned back side one side that is provided with the liquid crystal cells of polaroid, make liquid crystal indicator.
＜estimate
With coating fluid and light spacer, carry out following mensuration and evaluation for resulting photo-sensitive resin.The results are shown in following table 2 of evaluation of measuring.
-deformation-recovery rate-
Resulting light spacer with following mensuration of micro-hardness tester (DUH-W201, Shimadzu Scisakusho Ltd make), and is estimated.In mensuration, adopt the frustum of a cone pressure head of 50 μ m φ, peak load is made as 50mN, retention time and is made as 5 seconds, with load-removing the lotus test method(s) carries out.Obtain deformation-recovery rate (%) by this measured value by following formula, estimate according to following metewand.Be determined under 22 ± 1 ℃, the environment of 50%RH and carry out.
Deformation-recovery rate (%)=(reply volume (μ m) after load discharges/when applying load deflection (μ m)) * 100
(metewand)
5: the deformation-recovery rate is more than 90%.
4: the deformation-recovery rate is more than 87% but lower than 90%.
3: the deformation-recovery rate is more than 85% but lower than 87%.
2: the deformation-recovery rate is more than 80% but lower than 85%.
1: the deformation-recovery rate is more than 75% but lower than 80%.
0: the deformation-recovery rate is lower than 75%.
-sensitivity-
For resulting photo-sensitive resin coating fluid, observe whether can form spacer patterns when making exposure that various variation occur, estimate according to following metewand.
(metewand)
AA: exposure is lower than 60mJ/cm
2The time can form pattern.
A: exposure is 60mJ/cm
2Above but lower than 100mJ/cm
2The time can form pattern.
B: exposure is 100～200mJ/cm
2The time can form pattern.
C: for pattern forms, need to surpass 200mJ/cm
2Exposure.
-keeping quality-
(1) fluid preservation
Photo-sensitive resin obtained above is covered tightly with coating fluid, use respectively after covering tightly (25 ℃) through nature after 180 days and photo-sensitive resin is put into coating fluid after the baking oven of 60 ℃ through the coating fluid after 2 weeks, with operation in the evaluation of above-mentioned " sensitivity " similarly, estimate according to following metewand.
(metewand)
A: exposure is lower than 60mJ/cm
2The time can form pattern.
B: exposure is 60mJ/cm
2Above but lower than 150mJ/cm
2The time can form pattern.
C: for pattern forms, need 150mJ/cm
2Above but lower than 300mJ/cm
2Exposure.
D: for pattern forms, need 300mJ/cm
2Above exposure.
(2) ageing stability of photo-sensitive resin
Photo-sensitive resin after prebake conditions (being formed with the filter substrate of photo-sensitive resin) is put into the baking oven 14 days of 60 ℃, with operation in the evaluation of above-mentioned " sensitivity " similarly, estimate according to following metewand.
(metewand)
A: exposure is lower than 60mJ/cm
2The time can form pattern.
B: exposure is 60mJ/cm
2Above but lower than 150mJ/cm
2The time can form pattern.
C: for pattern forms, need 150mJ/cm
2Above but lower than 300mJ/cm
2Exposure.
D: for pattern forms, need 300mJ/cm
2Above exposure.
(embodiment 3 and embodiment 5～9, comparative example 1～3): rubbing method
In embodiment 1, except the formula of photo-sensitive resin with coating fluid changed as shown in Table 1 above, beyond simultaneously compound PD-52 ((A) resin), particulate and the initiating agent that uses in the modulation of photo-sensitive resin with coating fluid being changed as described in Table 2, make similarly to Example 1 light spacer and liquid crystal indicator.Resulting light spacer is made cylindrical shape.
(embodiment 2,4): transfer printing
In embodiment 1, except replacing the coating of photo-sensitive resin coating fluid (formula 1), form beyond photo-sensitive resin but carry out transfer printing with sept shown below with photosensitive transfer film, make similarly to Example 1 light spacer and liquid crystal indicator.Resulting light spacer is cylindrical shape.
The making of-sept use photosensitive transfer film-
Be on the pet film temporary supporting body (PET temporary supporting body) of 75 μ m at thickness, the thermoplastic resin that coating is made of following formula A is with coating fluid and make its drying, and forming dry thickness is the thermoplastic resin of 15.0 μ m.
[the thermoplastic resin formula A of coating fluid]
Methyl methacrylate/acrylic acid 2-Octyl Nitrite/benzyl methacrylate/
25.0 parts of methacrylic acid copolymers
(=55/11.7/4.5/28.8 (mol ratio), weight-average molecular weight are 90000)
58.4 parts of styrene/acrylic acid co-polymer
(=63/37 (mol ratio), weight-average molecular weight are 8000)
39.0 parts, two [4-(methacryloxy polyethoxy) phenyl] propane of 2,2-
1 10.0 parts, following surfactant
90.0 parts of methyl alcohol
51.0 parts of 1-methoxy-2-propanols
700 parts of MEKs
*Surfactant 1
Following structure 1 30%
MEK 70%
Structure 1
(n＝6、x＝55、y＝5、
Mw＝33940、Mw/Mn＝2.55
PO: epoxypropane, EO: oxirane
Then, the middle layer that coating is made of following formula B on the thermoplastic resin that forms is with coating fluid and make its drying, thereby stacked dry bed thickness is the middle layer of 1.5 μ m.
[the middle layer formula B of coating fluid]
3.22 parts of polyvinyl alcohol (PVA)
(PVA-205 (saponification rate 80%), the Network ラ レ of Co., Ltd. make)
1.49 parts of polyvinyl pyrrolidones
(PVP K-30, ISP JAPAN Co., Ltd. make)
42.3 parts of methyl alcohol
524 parts of distilled water
Then, on the middle layer that forms further the photo-sensitive resin that consisted of by the formula 3 shown in above-mentioned table 1 of coating with coating fluid ((A) resin is the compound in table 2) and make its drying, thereby stacked dry bed thickness is the photo-sensitive resin of 5.0 μ m.
Consist of as described above lit-par-lit structure (total bed thickness of 3 layers: 21.5 μ m) of PET temporary supporting body/thermoplastic resin/middle layer/photo-sensitive resin, on the surface of photo-sensitive resin further by heating pressurize to paste thickness be the polypropylene made membrane of 12 μ m as cover film, obtain the sept photosensitive transfer film.
The making of-light spacer-
Peel off the resulting sept cover film of photosensitive transfer film, the surface of the photo-sensitive resin that will expose overlaps similarly to Example 1 on the ito transparent electrode of filter substrate that the sputter of making is formed with ito transparent electrode, use laminating machine LamicII type (イ of Co., Ltd. Hitachi Application ダ ス ト リ イ ズ manufacturing), the travelling speed with 2m/ minute under line pressure 100N/cm, the pressurized, heated condition of 130 ℃ is pasted together them.Then, PET temporary supporting body is being removed with peeling off at the interface of thermoplastic resin, thereby with photo-sensitive resin transfer printing together with thermoplastic resin and middle layer (tunicle formation operation).
Then, use has the proximity type exposure machine (the Ha イ テ of Hitachi Network Electricity エ Application ジ ニ ア リ Application グ Co., Ltd. make) of extra-high-pressure mercury vapour lamp, make mask (the quartzy exposed mask with picture pattern) with so that this mask mode relative with photo-sensitive resin and the filter substrate almost parallel that configures under the state that stands vertically, mask face and the distance that contacts with the middle layer of photo-sensitive resin between the surface of a side are set as 100 μ m, across this mask from the thermoplastic resin side with 90mJ/cm
2Exposure approach exposure (exposure process).
Then, with 50 seconds of triethanolamine to be developer solution (contain 30% triethanolamine, the product of commodity T-PD2 (Fuji Photo Film Co., Ltd.'s manufacturings) by name be diluted to 12 times (ratio take 1 part of T-PD2 and 11 parts of pure water is mixed) with pure water and the solution that obtains) carry out under the condition of 0.04MPa at 30 ℃, flat burner pressure drip washing development, remove thermoplastic resin and middle layer.Then, the upper surface of this glass substrate is blowed air with after removing liquid, spray 10 seconds of pure water with shower, carry out pure water drip washing, blow air is accumulated with the liquid that reduces on substrate.Then, using sodium carbonate is that developer solution (contains the sodium bicarbonate of 0.38 mol/L, the sodium carbonate of 0.47 mol/L, 5% nekal, anionic surfactant, defoamer and stabilizing agent, the product of commodity T-CD1 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 10 times and the solution that obtains with pure water), be to carry out drip washing under the condition of 0.15MPa to develop for 30 seconds at 29 ℃, conical nozzle pressure, form pattern image (developing procedure).
Then, use (contains phosphate, silicate, non-ionic surfactant, defoamer, stabilizing agent with washing agent, trade name: T-SD3 (Fuji Photo Film Co., Ltd.'s manufacturing)) be diluted to 10 times and the solution that obtains with pure water, be to spray for 20 seconds with shower under the condition of 0.02MPa at 33 ℃, conical nozzle pressure, remove the residue of formed pattern image periphery, form columned spacer patterns in the mode of 1 sept in interval on 300 μ m * 300 μ m.
Then, the filter substrate that is provided with spacer patterns in 230 ℃ of lower heat treated 30 minutes (tunicle heating process), is made light spacer thus on filter substrate.Resulting light spacer is that diameter is that 15.1 μ m, average height are the cylindrical shape of 4.7 μ m.
Then, use the filter substrate of light spacer, make similarly to Example 1 the PVA mode LCD.
Table 2
Mw: weight-average molecular weight
The detailed compound that uses in embodiment, comparative example is as described below.
CGI-242: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(O acetyl oxime) (Ciba Specialty Chemicals Co., Ltd. make)
As shown in Table 2 above, embodiment compares with comparative example, can obtain higher sensitivity, and the ageing stability of the photo-sensitive resin when keeping with the dry film state after the fluid preservation of the photo-sensitive resin use coating fluid of modulating and coating is also good.
For resulting sept, embodiment compares with comparative example, also can obtain higher homogeneity and good deformation-recovery rate.
[embodiment 10]
The formation of＜diaphragm 〉
In embodiment 1; in the making of filter substrate; after forming black matrix", R pixel, G pixel and B pixel; further be coated with the photosensitive polymer combination that is consisted of by above-mentioned formula 1 on black matrix" and each pixel; expose (whole exposure) in the situation that stay out of mask, form diaphragm after heat treated.Here, the condition of coating, exposure, heat treated is, and is except in the situation that stay out of mask exposes, identical with the condition of coating during the light spacer of embodiment 1 forms, exposure, heat treated.
Then, further form the transparency electrode of ITO (tin indium oxide) by sputter on resulting protective seam.
The formation of＜light spacer 〉
On the ito transparent electrode of above-mentioned formation, except use the photosensitive polymer combination that uses in embodiment 1 as photosensitive polymer combination, with method formation light spacer similarly to Example 1.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 1.
To resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.Evaluation result is shown in Table 3.
[embodiment 11]
The formation of＜colored pattern 〉
Except forming the R pixel with following method, make similarly to Example 1 filter substrate in the making of the filter substrate of embodiment 1.
That is, further add paratonere 254 (19.4 parts) and paratonere 177 (4.83 parts) in above-mentioned formula 1, modulation R pixel photosensitive polymer combination.
Except using the R pixel modulate to use the R pixel with photomask with photosensitive polymer combination and as photomask, use with the same method of the formation method of the light spacer of embodiment 1 and form the R pixel.
After R pixel, G pixel and the B pixel of the filter substrate of made form, further form the transparency electrode of ITO (tin indium oxide) by sputter on each pixel.
The formation of＜light spacer 〉
On the ito transparent electrode of above-mentioned formation, except use the photosensitive polymer combination that uses in embodiment 1 as photosensitive polymer combination, with method formation light spacer similarly to Example 1.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 1.
To resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.Evaluation result is shown in Table 3.
[comparative example 4,5]
Use except the structure PD-52 of (A) resin of replacing embodiment 10 in comparative example 4 copolymer 1; in addition; use except the structure PD-52 of (A) resin of replacing embodiment 11 in comparative example 5 copolymer 1; similarly carry out with embodiment 10 and 11 respectively; thereby make respectively diaphragm and coloured material, and similarly estimate.
Table 3
As shown in table 3, when forming diaphragm and colored pattern with photosensitive polymer combination of the present invention, also can obtain result same good when forming light spacer.
According to the present invention, can provide the good patterning body of a kind of ageing stability that can form the photosensitive film after the good and film forming of keeping quality under highly sensitive, liquid and mechanical characteristic or the photosensitive polymer combination of diaphragm.
In addition, according to the present invention, even can provide a kind of in the situation that form with low sensitivity, also have light spacer and the manufacture method thereof of good high homogeneity and uniform cross sectional shape.
In addition, according to the present invention, even can provide a kind of in the situation that form with low sensitivity, also have diaphragm or the colored pattern of good film thickness uniformity and uniform cross sectional shape.
In addition, according to the present invention, can provide a kind of and can suppress to show uneven base board for display device and show the uneven display device that suppresses that obtained when being used for display device.
The foregoing description of concrete form of the present invention provides for the purpose of describing and illustrate.Do not wish the present invention is defined in disclosed form itself, neither comprehensively enumerate.This form is selected for concept of the present invention and practical application thereof are described the most fully, make thus other those skilled in the art understand the present invention, thereby make other those skilled in the art in order to make its special-purpose that is suitable for wanting, can make various forms or carry out various distortion.
The detailed content of the preferred implementation of relevant the invention described above certainly can be wished the form that is suitable for and freely change to various application forms according to those skilled in the art.Scope of the present invention wishes to decide according to the scope of following claims and equivalent thereof.
Claims (14)
1. photosensitive polymer combination, it contains:
(A) resin, it has branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has 2 ethylenic unsaturated links,
(B) have the polymerizable compound of ethylenic unsaturated link,
(C) Photoepolymerizationinitiater initiater;
Wherein, described substituted alkyl is the group with following general formula (1) expression,
General formula (1)
In general formula (1), * represents the side of being combined with the main chain of resin; A1 represents that carbon number is dibasic alkyl of 1～9; B1 and B2 represent respectively singly-bound independently, be the urethane bond of-O-CO-NHR-from the main chain side; R represents that carbon number is 1～3 alkyl; In addition, X1 and X2 represent respectively from the main chain side the ester bond for-O-CO-independently; R
1And R
2Represent independently respectively hydrogen atom or methyl.
2. photosensitive polymer combination according to claim 1, wherein, the substituting group of described substituted alkyl be (methyl) acryloxy and should (methyl) acryloxy Direct Bonding on described alkyl.
3. photosensitive polymer combination according to claim 1, wherein, described group with branching and/or alicyclic structure has the group of following general formula (3) expression and consists of,
General formula (3)
In general formula (3), X represents not have substituting group or the organic concatenating group of substituent divalence is arranged; Y represents 1 or 2; N represents 0～15 integer.
4. photosensitive polymer combination according to claim 1, wherein, the weight-average molecular weight of described (A) resin is 12000～60000 scope, described (A) resin has branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has 2 ethylenic unsaturated links.
5. photosensitive polymer combination according to claim 1, wherein, the glass transition temperature Tg of described (A) resin is 40～180 ℃, described (A) resin has branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has 2 ethylenic unsaturated links.
6. photosensitive polymer combination according to claim 1, wherein, the acid number of described (A) resin is more than 20mgKOH/g, described (A) resin has branching and/or alicyclic structure, acidic groups and substituted alkyl on side chain, and described substituted alkyl has 2 ethylenic unsaturated links.
7. photosensitive polymer combination according to claim 1, wherein, described (B) polymerizable compound with respect to the quality ratio of described (A) resin namely the ratio of (B)/(A) be 0.5～2.0.
8. photosensitive polymer combination according to claim 1, it further contains the extender pigment that mean grain size is 5～50nm.
9. light spacer, it is that right to use requires in 1～8 the described photosensitive polymer combination of any one and forms.
10. the formation method of a light spacer, it contains following operation (i)～(iii) at least:
(i) form the operation of the tunicle of the described photosensitive polymer combination of any one in claim 1～8 on substrate;
The operation of (ii) at least a portion of described tunicle being exposed;
The operation that described tunicle after (iii) exposing develops;
The operation that described tunicle after (iv) developing heats.
11. a diaphragm, it is that right to use requires the described photosensitive polymer combination of any one in 1～8 and forms.
12. a colored pattern, it is that right to use requires the described photosensitive polymer combination of any one in 1～8 and forms.
13. a base board for display device, it possesses that right to use requires the described photosensitive polymer combination of any one in 1～8 and at least a in the light spacer that forms, diaphragm, colored pattern.
14. a display device, it possesses the described base board for display device of claim 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP339917/2007 | 2007-12-28 | ||
| JP2007339917 | 2007-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101470350A CN101470350A (en) | 2009-07-01 |
| CN101470350B true CN101470350B (en) | 2013-06-12 |
Family
ID=40827936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101852446A Expired - Fee Related CN101470350B (en) | 2007-12-28 | 2008-12-24 | Photo sensitive resin compositon, optical spacer, protective film, coloring pattern, display device and substrate thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5361373B2 (en) |
| KR (1) | KR101622991B1 (en) |
| CN (1) | CN101470350B (en) |
| TW (1) | TWI476513B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5218750B2 (en) * | 2008-07-25 | 2013-06-26 | Ｊｓｒ株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
| JP6190650B2 (en) * | 2013-07-19 | 2017-08-30 | 昭和電工株式会社 | Resin composition for overcoat layer of color filter, overcoat layer using the same, image display element, and method for producing image display element |
| JP2016080803A (en) * | 2014-10-14 | 2016-05-16 | 太陽インキ製造株式会社 | Dry film and flexible printed wiring board |
| KR20170028016A (en) * | 2015-09-03 | 2017-03-13 | 동우 화인켐 주식회사 | Negative-type photosensitive resin comopsition and photocurable pattern forming by the same |
| DE102015119939A1 (en) | 2015-11-18 | 2017-05-18 | ALTANA Aktiengesellschaft | Crosslinkable polymeric materials for dielectric layers in electronic components |
| JP6499568B2 (en) * | 2015-11-30 | 2019-04-10 | 富士フイルム株式会社 | Photosensitive composition, method for producing cured film, cured film, touch panel, and display device |
| JP7210091B2 (en) * | 2017-03-28 | 2023-01-23 | 株式会社レゾナック | Transfer type photosensitive film, method for forming cured film pattern, cured film and touch panel |
| CN114236887A (en) * | 2021-12-14 | 2022-03-25 | 广州华星光电半导体显示技术有限公司 | Spacer manufacturing device and display panel |
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| CN1147868A (en) * | 1995-03-13 | 1997-04-16 | 互応化学工业株式会社 | Photosensitive resin composition, and coating film, resist ink, resist protective film solder protective resist film and substrate of printed circuit |
| JP2006276847A (en) * | 2005-03-02 | 2006-10-12 | Jsr Corp | Radiation sensitive resin composition and spacer for liquid crystal display element |
| JP2007148366A (en) * | 2005-10-25 | 2007-06-14 | Hitachi Chem Co Ltd | Liquid crystal spacer and method for manufacturing the same |
| CN1991584A (en) * | 2005-12-28 | 2007-07-04 | 富士胶片电子材料有限公司 | Light solidification pigmentation composition and color filter, and liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000204130A (en) * | 1998-11-09 | 2000-07-25 | Toray Ind Inc | Photo-sensitive paste and production of display material using the same |
| JP2002014468A (en) | 2000-06-28 | 2002-01-18 | Mitsubishi Chemicals Corp | Photopolymerizable composition, photopolymerizable colored composition and color filter |
| JP4503821B2 (en) * | 2000-12-12 | 2010-07-14 | コダック株式会社 | Photopolymerizable composition and photopolymerizable lithographic printing plate |
| JP2002293837A (en) * | 2001-03-30 | 2002-10-09 | Dainippon Printing Co Ltd | Hardenable resin and its production method |
| JP4181436B2 (en) * | 2003-03-31 | 2008-11-12 | 富士フイルム株式会社 | Planographic printing plate precursor |
| JP2006184521A (en) * | 2004-12-27 | 2006-07-13 | Sekisui Chem Co Ltd | Photocurable resin composition |
| JP2007093793A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Photosensitive film, permanent pattern forming method and pattern |
| JP2007114604A (en) | 2005-10-21 | 2007-05-10 | Fujifilm Electronic Materials Co Ltd | Photosensitive composition and color filter |
-
2008
- 2008-12-23 KR KR1020080132576A patent/KR101622991B1/en active IP Right Grant
- 2008-12-23 TW TW097150161A patent/TWI476513B/en not_active IP Right Cessation
- 2008-12-24 CN CN2008101852446A patent/CN101470350B/en not_active Expired - Fee Related
- 2008-12-26 JP JP2008334172A patent/JP5361373B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147868A (en) * | 1995-03-13 | 1997-04-16 | 互応化学工业株式会社 | Photosensitive resin composition, and coating film, resist ink, resist protective film solder protective resist film and substrate of printed circuit |
| JP2006276847A (en) * | 2005-03-02 | 2006-10-12 | Jsr Corp | Radiation sensitive resin composition and spacer for liquid crystal display element |
| JP2007148366A (en) * | 2005-10-25 | 2007-06-14 | Hitachi Chem Co Ltd | Liquid crystal spacer and method for manufacturing the same |
| CN1991584A (en) * | 2005-12-28 | 2007-07-04 | 富士胶片电子材料有限公司 | Light solidification pigmentation composition and color filter, and liquid crystal display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101470350A (en) | 2009-07-01 |
| JP5361373B2 (en) | 2013-12-04 |
| TW200935173A (en) | 2009-08-16 |
| JP2009175730A (en) | 2009-08-06 |
| KR20090072995A (en) | 2009-07-02 |
| TWI476513B (en) | 2015-03-11 |
| KR101622991B1 (en) | 2016-05-20 |
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