CN101470350A - 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
- Publication number
- CN101470350A CN101470350A CNA2008101852446A CN200810185244A CN101470350A CN 101470350 A CN101470350 A CN 101470350A CN A2008101852446 A CNA2008101852446 A CN A2008101852446A CN 200810185244 A CN200810185244 A CN 200810185244A CN 101470350 A CN101470350 A CN 101470350A
- Authority
- CN
- China
- Prior art keywords
- resin
- photosensitive polymer
- polymer combination
- mentioned
- substituted alkyl
- 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.)
- Granted
Links
- 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 93
- -1 (methyl) acryloxy Chemical group 0.000 claims description 67
- 230000015572 biosynthetic process Effects 0.000 claims description 47
- 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 12
- 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 7
- 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 55
- 239000010408 film Substances 0.000 description 40
- 238000005755 formation reaction Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 30
- 238000000059 patterning Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 28
- 239000000178 monomer Substances 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 24
- 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
- 239000000463 material 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
- 238000011161 development Methods 0.000 description 17
- 230000018109 developmental process Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 15
- 230000003252 repetitive effect Effects 0.000 description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 11
- 150000002148 esters Chemical group 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
- 238000010438 heat treatment 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000011521 glass 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000006866 deterioration 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- SURWYRGVICLUBJ-UHFFFAOYSA-N 2-ethyl-9,10-dimethoxyanthracene Chemical compound C1=CC=CC2=C(OC)C3=CC(CC)=CC=C3C(OC)=C21 SURWYRGVICLUBJ-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
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 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
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-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
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-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
- 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
- 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
- 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
- 238000002156 mixing Methods 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
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-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
- 239000011342 resin composition Substances 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
- 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
- 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)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Optical Filters (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (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, because the large tracts of landization of liquid crystal indicator and the raising of throughput rate etc., the maximization of plain glass (MotherGlass) substrate advances.With regard to substrate size (about 680 * 880mm) in the past, because substrate size is less than mask size, so utilize the mode of exposure in the lump corresponding with regard to energy.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, utilize 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, on a substrate, carrying out multiexposure, multiple exposure, 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
2About 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, it is more and more stricter that the controlled required value of the shape of relevant sept, thickness becomes in recent years, the shape that produces for the process variations when forming sept, the change of thickness, follow composition solution through the time shape, the stability of thickness that change, 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, employed photosensitive resin combination is during preservation or in using in the manufacturing of display panels, composition generation crystallizations in the composition etc. and the problems such as foreign matter, polluting device that produce become seriously are so hope has 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 constitutes, 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, opening the 2002-296775 communique) that the structural unit of free-radical polymerised base links with reference to the spy.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, opening the 2002-293837 communique) that the structural unit of free-radical polymerised base links with reference to the spy.
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.First form of the present invention provides 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 the patterning body or the diaphragm of exhibiting excellent stability with time of photosensitive film.Second form of the present invention provides a kind of formation method of light spacer, and it contains following operation: use the photosensitive polymer combination of above-mentioned 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 the exposure; And the operation that heats of the above-mentioned tunicle after will developing.The 3rd form of the present invention provides light spacer, diaphragm or the colored pattern of the photosensitive polymer combination formation of using above-mentioned first form.The display device that the 4th form of the present invention provides 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 on substrate, (for example to form the patterning body; light spacer, colored pattern etc.; below identical) or during diaphragm; may not necessarily obtain being used to obtain the sensitivity and the polymerisation reactivity of 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 finishes, and is problem to realize following purpose.
Promptly 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 ofly under situation about forming, also have good high homogeneity and the uniformly light spacer and the manufacture method thereof of cross sectional shape with low sensitivity.
In addition, even the purpose of this invention is to provide a kind ofly under situation about forming, also have good film thickness uniformity and the uniformly diaphragm or the colored pattern of cross sectional shape with low sensitivity.
In addition, the purpose of this invention is to provide a kind of when being used for display device, can suppress to show uneven base board for display device and the uneven display device that suppresses that obtained of demonstration.
The means that the present invention is used to solve above-mentioned problem are:
＜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) has 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 the general formula (1), * represents the side that combines with the main chain of resin, and 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 hydrogen atom or methyl respectively independently.)
＜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 in each described photosensitive polymer combination, wherein, described group with branching and/or alicyclic structure has the group of following general formula (3) expression,
General formula (3)
In the general formula (3), X represents the organic concatenating group of divalence, can also substituting group can be arranged by unsubstituted.Y represents 1 or 2, and n represents 0～15 integer.
＜5〉according to above-mentioned＜1 〉～＜4 in each described photosensitive polymer combination, 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 in each described photosensitive polymer combination, 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 in each described photosensitive polymer combination, wherein, described (A) is more than the 20mgKOH/g having the acid number that branching and/or alicyclic structure, acidic groups and substituted alkyl and described substituted alkyl have a resin of 2 ethylenic unsaturated links on the side chain.
＜8〉according to above-mentioned＜1 〉～＜7 in each described photosensitive polymer combination, 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 in each described photosensitive polymer combination, it further contains the extender pigment that mean grain size is 5～50nm.
＜10〉a kind of light spacer, it is to use above-mentioned＜1 〉～＜9 in each described photosensitive polymer combination form.
＜11〉a kind of formation method of light spacer, it contains following operation (i)～(iii) at least:
(i) on substrate, form above-mentioned＜1 〉～＜9 in the operation of tunicle of each described photosensitive polymer combination;
The (ii) operation that at least a portion of described tunicle is exposed;
The operation that described tunicle after (iii) will exposing develops;
The operation that described tunicle after (iv) will developing heats.
＜12〉a kind of diaphragm, it is to use above-mentioned＜1 〉～＜9 in each described photosensitive polymer combination form.
＜13〉a kind of colored pattern, it is to use above-mentioned＜1 〉～＜9 in each described photosensitive polymer combination form.
＜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 the 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) has the polymerizable compound of ethylenic unsaturated link, (C) Photoepolymerizationinitiater initiater.
General when the usability photosensitive resin composition on substrate, forms the patterning body (for example, light spacer, colored pattern etc., below identical) or during diaphragm, if only with exposing, then polymerizing curable is insufficient.In addition, the ageing stability of keeping quality under the liquid state and the photosensitive film after the film forming also may not be abundant.
And then; when carrying out high-temperature heating treatment in exposure with after developing, might make the patterning body or the diaphragm deterioration that will form or make the patterning body that is formed on the substrate or the phenomenon of diaphragm deterioration in order to ensure the ageing stability of the photosensitive film after the above-mentioned film forming.For example, when on having the filter substrate of colored pattern, forming light spacer, might make the light spacer deterioration that will form or make the phenomenon of the colored pattern deterioration that is formed on the substrate.
Therefore; by photosensitive polymer combination being set for the formation of the invention described above, that photosensitive polymer combination then of the present invention can form is highly sensitive, be difficult for taking place that viscosity rises, the polymerization-curable during exposure improves, the keeping quality under liquid is good and film forming after the 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 development, simultaneously owing to have 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 the 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 have branching and/or alicyclic structure, so the compressive modulus of elasticity can improve formed patterning body and be subjected to external force time the, from the elastic recovery of compression deformation.Thus, when the patterning bodies such as light spacer that configuration example such as display device are used, be useful.
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 is represented acryloyl group or methacryl; (methyl) acrylate is represented acrylate or methacrylate; (methyl) propenyl is represented propenyl or methylpropenyl; (methyl) acrylamide is represented acrylamide or Methacrylamide, and (methyl) acrylanilide is represented acrylanilide or metering system anilid.
(branching and/or alicyclic structure)
(A) resin with side chain that the main chain of resin combines on contain at least a branching and/or alicyclic structure.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 contain in the side chain of (A) resin with acidic groups and/or the substituted alkyl with 2 ethylenic unsaturated links.
In addition, branching and/or alicyclic structure can directly combine with the main chain of (A) resin and only constitute the side chain of (A) resin with branching and/or alicyclic structure, also can combine with the main chain of (A) resin, constitute the side chain of (A) resin as group with branching and/or alicyclic structure by the organic concatenating group of divalence.
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 the 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 methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl etc. particularly, 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 development and elastic recovery rate, branching and/or alicyclic structure are preferably at least by the ester group (form of main chain side-COO-) combine 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-) combine with the main chain of (A) resin can also be that branching and/or alicyclic structure are by containing the ester group (form that main chain side-bivalence linking base COO-) combines with the main chain of (A) resin by ester group.That is, between branching and/or alicyclic structure and the 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 3～12 branch-like alkyl, 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., preferred especially isopropyl, sec-butyl, the tert-butyl group etc.
As above-mentioned alicyclic structure, can list carbon number and be 5～20 alicyclic ring shape alkyl, preference such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, adamantyl, three ring decyls, dicyclopentenyl, two cyclopentyl, three cyclopentenyls, three cyclopentyl etc. and 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., preferred especially dicyclopentenyl, three cyclopentenyls.
And then, as group, preferably have the group of following general formula (3) expression and the form that constitutes with branching and/or alicyclic structure.
General formula (3)
In the general formula (3), X represents the organic concatenating group of divalence, can also substituting group can be arranged by unsubstituted.Y represents 1 or 2, and n represents 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 the 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 groups such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl particularly, 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 the monomer that in (A) resin synthetic, is used on side chain, importing branching and/or alicyclic structure, 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 the concrete monomer that in (A) resin synthetic, is used on side chain, importing branched structure, 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., wherein preferred (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, metering system tert-butyl acrylate etc., more preferably isopropyl methacrylate, metering system tert-butyl acrylate etc.
As the monomer that in (A) resin synthetic, is used on side chain, importing alicyclic structure, can list and have (methyl) acrylate that carbon number is 5～20 an alicyclic ring shape alkyl.As concrete example, can list (methyl) acrylic acid (two the 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., preferred especially (methyl) cyclohexyl acrylate, (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 the monomer that in (A) resin synthetic, is used on side chain, importing alicyclic structure, 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 represents 1 or 2, and n represents 0～15.In general formula (4), (5), be preferably y=1 or 2, n=0～8.Y=1 or 2 more preferably, 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, from the viewpoint of the elastic recovery rate that reactivity produced at two keys position, 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 not have replacement also can have substituting group, and with the organic concatenating group same meaning of divalence that the X of above-mentioned general formula (3) represents, preferred form is also identical.
As the monomer that in (A) resin synthetic, is used on side chain, importing alicyclic structure, 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 development, 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 the substituted alkyl that between main chain, disposes with 2 ethylenic unsaturated links by ester group contain in the side chain of (A) resin.
In addition, above-mentioned acidic groups can directly combine with the main chain of (A) resin and only constitute the side chain of (A) resin with acidic groups, also can combine with the main chain of (A) resin, constitute the side chain of (A) resin as group with acidic groups by the organic concatenating group of divalence.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 range is also identical.
As above-mentioned acidic groups, be not particularly limited, can from known acidic groups, suitably select, can list for example carboxyl, sulfonic group, sulfoamido, phosphate, phenol hydroxyl etc.Wherein, from the viewpoint that has excellent water-resistance of development and cured film, be preferably carboxyl, phenol hydroxyl.
As the object lesson that is used for importing the monomer of above-mentioned acidic groups to (A) resin, can be from known monomer suitably select, for example can list the addition compound product, ω-carboxyl-polycaprolactone list (methyl) acrylate of (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, monomer and cyclic acid anhydride etc. with hydroxyl.They can use the monomer of suitable manufacturing, also can use commercially available product.
The monomer with hydroxyl that uses in the addition compound product as above-mentioned monomer with hydroxyl and cyclic acid anhydride for example can list (methyl) acrylic acid 2-hydroxy methacrylate etc.As above-mentioned cyclic acid anhydride, can list for example maleic anhydride, phthalic anhydride, cyclohexyl dicarboxylic acid's acid anhydride etc.
Commercially available product as monomer, can list ァ ロ ニ Star Network ス M-5300, ァ ロ ニ Star Network ス M-5400, ァ ロ ニ Star Network ス M-5500, ァ 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 chemistry Industrial Co., Ltd of common prosperity society makes, PVC ス コ-ト #2100 that Osaka Organic Chemical Industry Co., Ltd. makes etc.Wherein,, cheaply viewpoint good, preferred (methyl) acrylic acid etc. from development.
(substituted alkyl) with 2 ethylenic unsaturated links
(A) resin with side chain that main chain combines on contain at least a substituted alkyl (following also only be called " substituted alkyl ") with 2 ethylenic unsaturated links.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 with above-mentioned branching and/or alicyclic structure and acidic groups in the side chain of (A) resin.
In addition, above-mentioned substituted alkyl can directly combine with the main chain of (A) resin and only constitute the side chain of (A) resin with substituted alkyl, also can combine with the main chain of (A) resin by the organic concatenating group of divalence, constitute the side chain of (A) resin as group with substituted alkyl, in addition, between 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 viewpoints such as property, synthetic adaptability from controlled, the synthesis material of the development that brings 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-) combine with the main chain of (A) resin.This form is not limited to substituted alkyl, and only (form of main chain side-COO-) combine with the main chain of (A) resin can also be that substituted alkyl is by containing the ester group (form that main chain side-bivalence linking base COO-) combines 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 (promptly, substituted alkyl with 2 ethylenic unsaturated links), be not particularly limited, but from the viewpoint of the characteristic (curable, 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 the general formula (1),
*The side that combines with the main chain of resin of expression, 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-) combine with main chain.
In the general formula (1),, get final product, can list linear chain structure, branched structure, alicyclic structure etc. so long as carbon number is 1～9 alkyl as abovementioned alkyl.
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 the 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, also can be different structures.
In the general formula (1), in addition, X1 and X2 represent (main chain side)-O-CO-respectively independently.
In the general formula (1), R
1And R
2Represent hydrogen atom or methyl respectively independently, be preferably methyl.R
1And R
2Can be identical, also can be different structures.
In (A) resin synthetic; the method that imports (methyl) acryloyl group on side chain can suitably be selected from known method, for example can list method, (3) that method, (2) that (1) make (methyl) acrylate with epoxy radicals and the repetitive with acidic groups carry out addition 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, making method that (methyl) acrylate with epoxy radicals and the repetitive with acidic groups carry out addition is preferred in the easiest manufacturing, aspect low-cost.
In (A) resin synthetic; as the method that on side chain, imports 2 (methyl) acryloyl groups; for example above-mentioned (1) can be made (methyl) acrylate with epoxy radicals and repetitive carry out addition, use method that (methyl) acryloyl chloride etc. obtains hydroxy esterification then, the known method such as method that hydroxy functional urethaneization obtains to synthesize in combination with containing (methyl) acrylate-based isocyanates (for example Showa Denko K. K make カ レ Application ズ MOI, MOIEG, AOI etc.) with acidic groups.
As above-mentioned (methyl) acrylate, be not particularly limited the compound of preference such as following structural formula (1) expression and the compound of following structural formula (2) expression with epoxy radicals.
Structural formula (1)
Wherein, in the said structure formula (1), R
1Expression hydrogen atom or methyl.L
1With B1 and the B2 same meaning in the general formula (1).
Structural formula (2)
Wherein, in the said structure formula (2), R
2Expression hydrogen atom or methyl.L
2With B1 and the B2 same meaning in the general formula (1).W represents the aliphatic alkyl of 4～7 yuan of rings, and with the A1 same meaning in the above-mentioned general formula (1), 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 among the present invention, can also use other monomer to import other group.
As above-mentioned other monomer, be not particularly limited, can for example list 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 for example butyl vinyl ether etc.
As above-mentioned dibasic acid anhydride base, be not particularly limited, can list for example maleic anhydride base, itaconic anhydride base etc.
As above-mentioned vinyl ester group, be not particularly limited, can list for example vinyl acetate ester group etc.
As above-mentioned hydrocarbon chain thiazolinyl, be not particularly limited, can list for example 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 for example represented (exemplary compounds PD-1～PD-56, PU-1～PU-56), but be not limited to these compounds with following structure.
In addition, the x in the exemplary compounds, y and z (and St) represent the ratio of components (mass ratio) of each repetitive, are preferably the form that constitutes in preferable range described later.In addition, the weight-average molecular weight of each exemplary compounds also is preferably the form that constitutes 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 not have especially restrictedly and suitably selects from known reaction.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, can not have especially restrictedly yet and from known method, suitably select.Can suitably select for example 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 preferably 10～15 especially.
＜molecular weight 〉
As the molecular weight of (A) resin, weight-average molecular weight is preferably 10000～100,000, and more preferably 12000～60000, be preferably 15000～45000 especially.If weight-average molecular weight in above-mentioned scope, is being preferred aspect the manufacturing adaptability of resin (being preferably multipolymer), the development then.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, when developing, do not have the sept shape residue aspect be preferred.
Weight-average molecular weight is measured with gel permeation chromatography (GPC).Relevant GPC describes in detail among the embodiment described later.
＜glass transition temperature 〉
(A) glass transition temperature of resin (Tg) is preferably 40～180 ℃, more preferably 45～140 ℃, is preferably 50～130 ℃ especially.Glass transition temperature (Tg) is if be in the above-mentioned preferred range, then can obtain having good development, the sept of mechanical strength.
＜acid number 〉
(A) acid number of resin is according to the difference of resulting molecular structure, and its preferred range can change, but generally is preferably more than the 20mgKOH/g, more preferably more than the 40mgKOH/g, is preferably 50～130mgKOH/g especially.If acid number is in the above-mentioned preferred range, then can obtain having good development, the sept of mechanical strength.
Viewpoint from the sept that obtains having good development, 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 among the present invention preferably with branching and/or alicyclic structure, acidic groups and with main chain between the substituted alkyl that contains 2 ethylenic unsaturated links by the ester group configuration contain multipolymer more than the ternary polymerization in different repetitive (copolymerization units) respectively.
Particularly, above-mentioned (A) resin is preferably the above multipolymer of ternary polymerization that has following repetitive at least: the repetitive X (x mole %) with branching and/or alicyclic structure; Repetitive Y (y mole %) with acidic groups; And repetitive Z (z mole %) with " and between the main chain substituted alkyl that contains 2 ethylenic unsaturated links by ester group configuration ".And then, can also have other repetitive L (1 mole of %) as required.
Above-mentioned multipolymer for example can obtain by other monomer generation copolymerization that makes monomer, the monomer with acidic groups with branching and/or alicyclic structure, the monomer with " and the substituted alkyl that contains 2 ethylenic unsaturated links that disposes by ester group between the 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 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 behind glass transition temperature and the acid number.Though can not can be set at following ranges without exception.
(A) ratio of components (x) of the repetitive with branching and/or alicyclic structure in the resin is preferably 10～70 moles of %, and more preferably 15～65 moles of % are preferably 20～60 moles of % especially.If ratio of components (x) is in the above-mentioned scope, then can obtain good development, the developer solution patience of image portion is also good simultaneously.
(A) ratio of components (y) of the repetitive with acidic groups in the resin is preferably 5～70 moles of %, and more preferably 10～60 moles of % are preferably 20～50 moles of % especially.If ratio of components (y) is in the above-mentioned scope, then can obtain good curable, development.
(A) ratio of components (z) of the repetitive of having in the resin " and the substituted alkyl that contains 2 ethylenic unsaturated links that disposes by ester group between the main chain " is preferably 10～70 moles of %, more preferably 20～70 moles of % are preferably 30～70 moles of % especially.If ratio of components (z) is that then pigment-dispersing is good in the above-mentioned scope, sensitivity simultaneously and polymerization-curable are good, and the ageing stability when transferring long preservation under fluid preservation behind the 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 moles of % (15～65 moles of % more preferably, be preferably 20～50 moles of % especially), ratio of components (y) is 5～70 moles of % (10～60 moles of % more preferably, be preferably 30～70 moles of % especially), ratio of components (z) is 10～70 moles of % (more preferably 20～70 moles of % are preferably 30～70 moles of % especially).
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 usefulness, but only be preferably situation about constituting by above-mentioned (A) resin.
～～other resin～～
As can with the resin of above-mentioned (A) resin and usefulness, 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 in epoxy compound, 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 on side chain, have potpourri, maleamic acid based copolymer of the ethylenic copolymer of (methyl) acryloyl group and acidic groups etc.
As above-mentioned acidic groups, be not particularly limited, can suitably select according to purpose, can list for example carboxyl, sulfonic group, phosphate etc., wherein,, can preferably list carboxyl from obtaining the viewpoints such as easiness of raw material.
With above-mentioned (A) resin and other resin and time spent, as (A) resin and can and the total content (solid constituent) of the resin of usefulness, be preferably 5～70 quality % with respect to the total solid composition of photo-sensitive resin, more preferably 10～50 quality %.If this content more than 5 quality %, then can be kept the film strength of photosensitive resin layer, can keep the stickability of this photosensitive resin laminar surface well, and if above-mentioned content below 70 quality %, then 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 subjected 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 select to use from the polymerizable compound that constitutes known composition, for example can listing, the spy opens composition or the special composition of putting down in writing in paragraph [0010]～[0020] of 2006-23696 communique of putting down in writing in paragraph [0027]～[0053] of 2006-64921 communique of opening.
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 preferably 0.7～1.2 especially.If ratio (B)/(A) is in the above-mentioned scope, then can obtain having good development, the sept of mechanical strength.
(C) Photoepolymerizationinitiater initiater
Photosensitive polymer combination of the present invention contains at least a Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater as among the present invention is not particularly limited, and can use known Photoepolymerizationinitiater initiater.As known Photoepolymerizationinitiater initiater, can list for example special paragraph [0010]～[0020] or the special initiating agent of putting down in writing in paragraph [0027]～[0053] of 2006-64921 communique of opening of opening the 2006-23696 communique.Example as known Photoepolymerizationinitiater initiater; from the viewpoint of sensitivity, preferably contain glycyl benzene compounds, acylphosphine oxide based compound, oxime ester based compound beyond above-mentioned and the mixed type initiating agent that six aryl united imidazole/aromatic series sulfhydryl compound/auxiliary agent is combined.
As the object lesson of glycyl benzene compounds, can list IRGACURE (Irg) 907 (manufacturing of Ciba Specialty Chemicals Co., Ltd.) etc.As the object lesson of acylphosphine oxide based compound, can list DAROCUR TPO, Irgacure (Irg) 819 (above is that Ciba Specialty Chemicals Co., Ltd. makes) etc.As the object lesson of oxime ester based compound, can list IRGACURE (Irg) OXE01 or CGI242 etc. (above is that Ciba SpecialtyChemicals Co., Ltd. makes).As the mixed type initiating agent that six aryl united imidazole/aromatic series sulfhydryl compound/auxiliary agent is combined, 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 〉
lrg?907
＜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 usefulness, 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 formed the sept of desired shape.
In addition, thus said Photoepolymerizationinitiater initiater is meant 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 above-mentioned specific aggregation compound polymerization among the present invention.
＜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 preference such as spy open the extender pigment of record in 2003-302639 communique [0035]～[0041], wherein, from the viewpoint of the light spacer that obtains having good development, mechanical strength, preferred cataloid.
From forming the viewpoint that can obtain high mechanical strength when light spacer etc. is subjected to the structure of external force easily, the mean grain size of above-mentioned particulate is preferably 5～50nm, and more preferably 10～40nm is preferably 15～30nm especially.
As the content of above-mentioned particulate in photosensitive polymer combination (when forming light spacer is light spacer or the photo-sensitive resin that constitutes it), 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 the photosensitive polymer combination, more preferably 10～40 quality % are preferably 15～30 quality % especially.
＜other 〉
In the photosensitive polymer combination of the present invention, except resin, specific aggregation compound, Photoepolymerizationinitiater initiater and the particulate that contains as required, can also contain photopolymerization as required 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 the polymerization that is used to promote 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, 4-dimethylaminobenzoic acid ethyl ester, 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 various kinds of amine system or other photopolymerization initiation auxiliary agent can be used in combination.
Cause auxiliary agent as other photopolymerization beyond above-mentioned, can list for example 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, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.As above-mentioned thioxanthones based compound, can list for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
In addition, cause auxiliary agent, also can use commercially available product as photopolymerization.Cause auxiliary agent as commercially available photopolymerization, for example can list trade name " EAB-F " (Baotugu Chemical Industrial Co., Ltd's manufacturing) etc.
Cause the content of auxiliary agent in photosensitive polymer combination as photopolymerization,, 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 with respect to above-mentioned Photoepolymerizationinitiater initiater 1 mass parts.
In addition, as other composition, can from the composition that constitutes known composition, select to use, can list for example special paragraph [0010]～[0020] or the special composition of putting down in writing in paragraph [0027]～[0053] of 2006-64921 communique of opening of opening the 2006-23696 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 (for example 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 the details and the preferred configuration thereof of photosensitive polymer combination, as mentioned above.
Light spacer of the present invention so also have uniform cross sectional shape even if hang down exposure, can suppress height tolerance owing to be to use photosensitive polymer combination of the present invention to form.
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.
Among the present invention, have the state of " uniformly cross sectional shape " as patterning bodies such as light spacers, be 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, more preferably following shape: when using parallel with the substrate normal direction and vertical plane to cut off this patterning body with the edge (being the tangent line at edge under the situation of cylindrical-shaped structure body) from the substrate normal direction is seen of patterning body, on section, the line that is equivalent to the patterning body side surface and the line angulation that is equivalent to patterning body lower surface (below be also referred to as " coning angle ") are 80 °～100 °.
Here, the lower surface of above-mentioned patterning body is meant, in the surface of patterning body, and the surface of contact that contacts with the substrate that has formed this patterning body.In addition, the side of above-mentioned patterning body is meant, in the surface of patterning body, neither the surface of the upper surface (, and being and the discontiguous face of above-mentioned substrate) that the lower surface of above-mentioned patterning body neither the patterning body with the parallel face of above-mentioned patterning body lower surface.
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 constitutes: (i) the operation of the tunicle that forms above-mentioned photosensitive polymer combination of the present invention on the substrate (below be also referred to as " tunicle form worker [preface "); The (ii) operation that at least a portion of described tunicle is exposed (below be also referred to as " exposure process "); The operation that described tunicle after (iii) will exposing develops (below be also referred to as " developing procedure ") can also be provided with the operation that the described tunicle after (iv) will developing heats (below be also referred to as " tunicle heating process ") and other operation as required and constitute.
(i) tunicle forms operation
It is the tunicle that forms 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 constitutes 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 change because of element thickness and produce demonstration inequality in the image that shows in the uneven display device (particularly liquid crystal indicator).
Method as form photo-sensitive resin on substrate can preferably list: (a) to containing above-mentioned (A) resin, (B) polymerizable compound and (C) rubbing method that is coated with of the photosensitive polymer combination of Photoepolymerizationinitiater initiater at least; And (b) use photosensitive transfer printing material, the transfer printing that photo-sensitive resin is carried out lamination, transfer printing by heating and/or pressurization with above-mentioned photo-sensitive resin.
(a) rubbing method
The coating of photosensitive composite can be used the extrusion coated method of the use hopper that known rubbing method for example puts down in writing in 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) to wait to carry out.Wherein, the spy opens 2004-89851 communique, spy and opens 2004-17043 communique, spy and open 2003-170098 communique, spy and open 2003-164787 communique, spy and open 2003-10767 communique, spy and open 2002-79163 communique, spy to open the method for utilizing gap nozzle or slot coated device of record in the 2001-310147 communique etc. be preferred.
(b) transfer printing
Transfer printing is to use photosensitive transfer printing material, will form on the interim supporter membranaceous photo-sensitive resin use for example heat and/or pressurize after roller or dull and stereotyped by press sticking or or add thermocompression bonded and desired real estate stickup after, by peeling off of interim supporter photo-sensitive resin is transferred on the substrate.Can list the spy particularly opens flat 7-110575 communique, spy and opens that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens laminate and the laminating method of putting down in writing in the 2002-148794 communique, from the viewpoint of few foreign, the special method of putting down in writing in the flat 7-110575 communique of opening of preferred use.
When forming photo-sensitive resin, can oxygen insulating course (below be also referred to as " oxygen partition film " or " middle layer ") be set further between photo-sensitive resin and the interim supporter.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 interim supporter, oxygen insulating course, thermoplastic resin, other layer and this photosensitive transfer printing material of relevant formation photosensitive transfer printing material can be suitable for middle formation, the method for making of putting down in writing in paragraph [0024]～[0030] that the spy opens the 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 coating forms in then can preventing to make need not spend the development that just can carry out unexposed portion for a long time and remove.
As the substrate that forms photo-sensitive resin, can list transparency carrier (for example glass substrate or plastic base) for example, have nesa coating (for example ITO film) substrate, have color filter substrate (being also referred to as filter substrate), have the driving substrate of driving element (for example 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, formation example, the spy that can list record in paragraph [0071]～[0077] that the spy opens the 2006-64921 communique opens the operation of record in paragraph [0040]～[0051] of 2006-23696 communique etc. as preferred example among the present invention.
(iv) tunicle heating process
In the tunicle heating process, the tunicle after will 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 the substrate as described above.Light spacer is preferably forming above the black light shielding parts such as the black matrix" that forms on the substrate or on the driving element such as TFT.In addition, between driving elements such as black light shielding parts such as black matrix" or TFT and light spacer, also can there be alignment films such as transparency conducting layers (transparency electrode) such as ITO or polyimide.
For example, when light spacer is arranged on the top of black light shielding part or driving element, can make base board for display device by the following method: 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 the support dignity, peel off transfer printing and after forming photo-sensitive resin, it is implemented exposure, development, heat treated etc. to form light spacer.
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 the color filter of painted portions such as black shielding portion such as black matrix" and colored pixels in formation.
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 photosensitive resin coating method for compositions, uses the transfer materials with the photo-sensitive resin that is made of photosensitive polymer combination in the 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 the 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 portion are formed pattern-like, the above-mentioned photosensitive polymer combination of other liquid is set then to form photo-sensitive resin on the other substrate different with aforesaid substrate (interim supporter), make transfer materials thus, 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 portion adhere to the transfer printing photo-sensitive resin, expose then 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 is to use above-mentioned photosensitive polymer combination of the present invention to form.
Diaphragm of the present invention is owing to using photosensitive polymer combination of the present invention to constitute, so even film thickness uniformity is also good under situation about forming with low exposure.
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, promptly, when diaphragm is formed as the whole facial mask of what is called, in above-mentioned (ii) exposure process, preferably tunicle is carried out the method for whole exposure.
" colored pattern "
Colored pattern of the present invention is to use 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 from known colorant, suitably select.As known colorant, can list the spy particularly and open colorant that pigment, spy that the pigment of record in 2005-17716 communique [0038]～[0054] and dyestuff, spy open record in 2004-361447 communique [0068]～[0072] open record in 2005-17521 communique [0080]～[0088] etc.
Colored pattern of the present invention is owing to using photosensitive polymer combination of the present invention to constitute, so even under situation about forming 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 uses photosensitive polymer combination of the present invention to form.
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 the colored pattern of the present invention and constitutes.
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 the colored pattern of the present invention; below identical), so can suppress when being used for display device to show uneven.
Here so-called base board for display device is meant at least one of a pair of supporter that is used for constituting 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 and for example possess colored pattern the filter substrate of (below be also referred to as " colored pixels "), the band driving means substrate that possesses driving means (for example, the simple matrix substrate, active-matrix substrate etc.), the band dividing wall substrate (the band black matrix substrate etc. that for example, possesses black matrix") that possesses dividing wall, 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 present different colours mutually, also can be made of the pixel of three looks, pixel more than four looks.For example under the situation of three looks, constitute by red (R), green (G) and blue (B) these three kinds of tones.Under the situation of the pixel groups that disposes RGB three looks, the configuration of preferably inlaying (mosaic) type, triangle type etc., under the situation of 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 opened 2004-347831 communique etc. with reference to the spy.
" 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 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 at least.
Under the situation of this liquid crystal display cells, base board for display device can be used as each pixel that has a plurality of rgb pixel groups, constitutes this pixel groups and is used by the filter substrate that black matrix" is divided mutually.On this filter substrate, owing to be provided with the structure that cross sectional shape and thickness (highly) have good uniformity, so possess that the liquid crystal display cells of this filter substrate can effectively prevent because the color spot that the liquid crystal material skewness that the change of the cell gap between filter substrate and the counter substrate (element thickness) causes, low-temp foaming etc. cause etc. show the generation of inequality.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: between at least one is a pair of supporter (comprising base plate for liquid crystal display device) of transmitance, possess liquid crystal layer and liquid crystal drive means at least, 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 owing to possess is provided with the base board for display device of the present invention of the structure that cross sectional shape and thickness (highly) have good uniformity, so can suppress to show uneven.
As display device, can list 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 (helping wooden clear husband's work, Co., Ltd.'s census of manufacturing meeting nineteen ninety distribution) ", " 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 constitutes 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 the viewpoint of effect of the present invention most effectively, be preferably easily change because of the element thickness of liquid crystal cells and cause and show uneven display mode that 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 among 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 driving side substrate that forms and the counter substrate that possesses opposite electrode (conductive layer) and clip light spacer and configuration relatively, and enclose liquid crystal material betwixt in the portion of crack by thin film transistor (TFT) driving elements such as (TFT) and pixel electrode (conductive layer); (b) driving substrate and the counter substrate that possesses opposite electrode (conductive layer) are clipped light spacer and configuration relatively, enclose liquid crystal material in the portion of crack 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 the liquid crystal indicator of the variety of way of record in for example above-mentioned " lcd technology of future generation ".Wherein particularly effective for the liquid crystal indicator that constitutes colored TFT mode.The liquid crystal indicator of relevant colored TFT mode, on the books in for example " colored TFT liquid crystal display (altogether upright publish Co., Ltd., distribution in 1996) ".
Liquid crystal indicator generally can also use 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 film to constitute 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) ", " present situation in the related market of 2003 liquid crystal and in the future prospect (last volume) (table good lucky, the キ メ ラ of Fuji of Co., Ltd. always grinds, distribution in 2003) " in.The spy that the application quotes the Japanese patent application on Dec 28th, 2007 is willing to the full text of 2007-339917 communique, 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, short of particularly pointing out, then " part " is to be benchmark with the quality.
In addition, weight-average molecular weight is to use gel permeation chromatography (GPC) to measure.Among the GPC, use HLC-8020GPC (manufacturing of TOSOH Co., Ltd.), 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 at 4.5 quality %, and flow velocity is set at 0.35ml/min, and the sample injection rate IR is set at 10 μ l, measures temperature and is set at 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 the 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)
In reaction vessel, add 7.48 parts of 1-methoxyl-2-propyl alcohol (MFG, Japanese emulsifying agent Co., Ltd. make) in advance, be warming up to 90 ℃, under nitrogen atmosphere, in 90 ℃ reaction vessel, dripped by 3.1 parts of styrene (St), the methacrylic acid three cyclopentene esters (TCPD-M that Hitachi Chemical Co., Ltd. makes with 2 hours; 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 1-methoxyl-55.2 parts of formations of 2-propyl alcohol.After the dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, in aforesaid propylene acid resin solution, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd make); Z).After the dropping, make its reaction 4 hours while injecting air at 90 ℃, modulate by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. make) then, 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, obtain resin solution (45% solution of solid constituent acid number: 76.0mgKOH/g, Mw:25000,1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) (x: y:z:St=30mol%:27mol%:37mol%:6mol%) of exemplary compounds PD-52 ((A) resin) with above-claimed cpd X.
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on the methacrylic acid and obtain.
In addition, the molecular weight Mw of exemplary compounds PD-52 represents weight-average molecular weight, (following identical) that the mensuration of weight-average molecular weight is to use gel permeation chromatography (GPC method) to carry out.
(synthesis example 2)
(exemplary compounds PU-52's is synthetic)
In reaction vessel, add 7.48 parts of 1-methoxyl-2-propyl alcohol (MFG, Japanese emulsifying agent Co., Ltd. make) in advance, be warming up to 90 ℃, under nitrogen atmosphere, in 90 ℃ reaction vessel, dripped by 3.1 parts of styrene (St), the methacrylic acid three cyclopentene esters (TCPD-M that Hitachi Chemical Co., Ltd. makes with 2 hours; 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 1-methoxyl-55.2 parts of formations of 2-propyl alcohol.After the dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, in aforesaid propylene acid resin solution, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd make); Z).After the dropping, make its reaction 4 hours while injecting air at 90 ℃, modulate by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. make) then, 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, the resin solution (45% solution of solid constituent acid number: 76.0mgKOH/g, Mw:25000,1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) that obtains exemplary compounds PU-52 ((A) resin) (x:y:z:St=30mol%:27mol%:37mol%:6mol%).
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on the 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 that the x:y:z among the exemplary compounds PD-51 is beyond the 34mol%:27mol%:39mol%, with synthetic, obtain having resin solution (the solid constituent acid number: 72.5mgKOH/g of the exemplary compounds PD-51 ((A) resin) of unsaturated group with the synthetic same method of above-mentioned exemplary compounds PD-52, Mw:22000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 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 ァ 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 that the x:y:z among the exemplary compounds PD-53 is beyond the 46.2mol%:24.3mol%:29.5mol%, with synthetic, obtain having resin solution (the solid constituent acid number: 71.2mgKOH/g of the exemplary compounds PD-53 ((A) resin) of unsaturated group with the synthetic same method of above-mentioned exemplary compounds PD-52, Mw:25500,45% solution of 1-methoxyl-2-propyl alcohol/acetate 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 that the composition x:y:z:St that has added from behind the cinnamic structural unit is 30mol% in Compound P D-1: beyond the 24mol%:38mol%:8mol%, with synthetic, obtain resin solution (the solid constituent acid number: 74.1mgKOH/g of exemplary compounds PD-46 ((A) resin) with the synthetic same method of above-mentioned exemplary compounds PD-52, Mw:29000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 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), GLM-MAA (z) and cinnamic addition make that forming x:y:z:St is beyond the 34mol%:24mol%:36mol%:6mol%, with synthetic, obtain resin solution (the solid constituent acid number: 72.9mgKOH/g of exemplary compounds PD-47 ((A) resin) with the synthetic same method of above-mentioned exemplary compounds PD-52, Mw:29000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 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 7 ァ 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), the addition of GLM-MAA (z) makes that forming x:y:z is beyond the 46.2mol%:24.3mol%:29.5mol%, with synthetic, obtain resin solution (the solid constituent acid number: 76.0mgKOH/g of exemplary compounds PU-53 ((A) resin) with the synthetic same method of exemplary compounds PU-52, Mw:25500,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(synthesis example 8) (comparative example is used)
In the flask that possesses cooling tube, stirring machine, add 2,200 parts of 7 parts of 2 '-azos two (2, the 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 in 25 parts in decane-8-base, 3-(methacryloxypropyl methyl)-25 parts of 3-ethyl oxetanes, methacrylic acid tetrahydrofurfuryl alcohol ester and 1,5 parts of 3-butadiene, behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, under this temperature, kept 5 hours, 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 〉
The method of opening record in paragraph [0084]～[0095] of 2005-3861 communique with the spy is made color filter with black matrix", R (redness) pixel, G (green) pixel, B (blueness) pixel (following it is called filter substrate).Here, the substrate size of filter substrate is 550mm * 650mm.
Then, on the R of the filter substrate that obtains pixel, G pixel, B pixel and black matrix", further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Above-mentioned making pass through use spinner to carry out slot coated with coating fluid on the ito transparent electrode of filter substrate that sputter formed ito transparent electrode by the photo-sensitive resin that prescription shown in the following table 1 (being prescription 1 among the embodiment 1) constitutes.Then, use vacuum drier VCD (manufacturing of Tokyo Ying Hua company) in 30 seconds, to make the part of solvent dry, after coated film was lost flowability, prebake conditions was 3 minutes on 90 ℃ hot plate, and forming thickness is the photo-sensitive resin (tunicle formation operation) of 5.2 μ m.
Then, use have extra-high-pressure mercury vapour lamp near type exposure machine (manufacturing of the Ha イ テ of Hitachi Network Electricity エ Application ジ two ァ リ Application グ Co., Ltd.), 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 disposes under the state that stands vertically, with the distance setting between the surface of mask face and photo-sensitive resin is 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, the sodium carbonate of 0.47 mol, 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)) is 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, with on 300 μ m * 300 μ m at interval the mode of 1 sept form columned spacer patterns.
Then, the filter substrate that is provided with spacer patterns in 230 ℃ of following 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 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) from ito transparent electrode.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 the following table 2.
Table 1
| The photo-sensitive resin coating fluid | Prescription 1 (embodiment 1,3 embodiment 5～9) | Prescription 2 (comparative examples 1,3) | Prescription 3 (embodiment 2,4) | Prescription 4 (comparative examples 2) |
| Acetate 1-methoxyl-2-propyl ester | 26 | 26 | 26 | 35 |
| MEK | 28 | 28 | 28 | 30 |
| Cataloid disperses thing (cataloid: 30 parts, methyl isobutyl ketone: 70 parts, the system MIBKst of Nissan Chemical Ind Ltd) | 0 | 0 | 14.1 | 0 |
| ソルスパ—ス20000 | 0.42 | 0.42 | 0.42 | 0.42 |
| DPHA liquid (dipentaerythritol acrylate: 76 parts, acetate 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 the 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 ァ 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, implementing the Butut that the PVA pattern is used on the transparency electrode of the above-mentioned filter substrate that obtains and on the counter substrate respectively, the alignment films that is made of polyimide further is set thereon as counter substrate.
Then, on the position of the black matrix" housing around the mode with the pixel groups of surrounding color filter of being equivalent to is arranged at, be coated with the sealant of ultraviolet curable resin by the divider mode, drip PVA pattern liquid crystal, after the counter substrate stickup, the substrate of pasting is carried out the UV irradiation, and thermal treatment makes sealant cures then.On the two sides of the liquid crystal cells that obtains like this, paste the polaroid HLC2-2518 of サ Application リ Star Star Co., Ltd. system.
Then, use FR1112H (chip-type LED that Stanley electric Co., Ltd. makes) to constitute the backlight of side lamp mode as green (G) LED, DB1112H (chip-type LED that Stanley electric Co., Ltd. makes) as blue (B) LED as red (R) LED, DG1112H (chip-type LED that Stanley electric Co., Ltd. makes), 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 the 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 the mensuration, adopt the frustum of a cone pressure head of 50 μ m φ, peak load is made as 50mN, retention time and was 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 is lower than 90%.
3: the deformation-recovery rate is more than 85% but is lower than 87%.
2: the deformation-recovery rate is more than 80% but is lower than 85%.
1: the deformation-recovery rate is more than 75% but is lower than 80%.
0: the deformation-recovery rate is lower than 75%.
-sensitivity-
For resulting photo-sensitive resin coating fluid, whether observation can form spacer patterns when making exposure that various variations take place, and estimates according to following metewand.
(metewand)
AA: exposure is lower than 60mJ/cm
2The time can form pattern.
A: exposure is 60mJ/cm
2More than but be lower than 100mJ/cm
2The time can form pattern.
B: exposure is 100～200mJ/cm
2The time can form pattern.
C:, need to surpass 200mJ/cm for pattern forms
2Exposure.
-keeping quality-
(1) fluid preservation
The above-mentioned photo-sensitive resin that obtains is covered completely with coating fluid, use respectively after covering completely (25 ℃) through nature after 180 days and photo-sensitive resin put into coating fluid behind 60 ℃ the baking oven 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
2More than but be lower than 150mJ/cm
2The time can form pattern.
C:, need 150mJ/cm for pattern forms
2More than but be lower than 300mJ/cm
2Exposure.
D:, need 300mJ/cm for pattern forms
2Above exposure.
(2) ageing stability of photo-sensitive resin
Photo-sensitive resin after the prebake conditions (being formed with the filter substrate of photo-sensitive resin) is put into 60 ℃ baking oven 14 days, with operation in the evaluation of above-mentioned " sensitivity " similarly, estimate according to following metewand.
(metewand)
A: can form pattern when exposure is lower than 60mJ/cm2.
B: exposure is 60mJ/cm
2More than but be lower than 150mJ/cm
2The time can form pattern.
C:, need 150mJ/cm for pattern forms
2More than but be lower than 300mJ/cm
2Exposure.
D:, need 300mJ/cm for pattern forms
2Above exposure.
(embodiment 3 and embodiment 5～9, comparative example 1～3): rubbing method
In embodiment 1, except the prescription of photo-sensitive resin with coating fluid changed shown in above-mentioned table 1, beyond simultaneously Compound P D-52 ((A) resin), particulate and the initiating agent that uses in the modulation of photo-sensitive resin with coating fluid being changed, make light spacer and liquid crystal indicator similarly to Example 1 shown in following table 2.Resulting light spacer is made cylindrical shape.
(embodiment 2,4): transfer printing
In embodiment 1, except replacing the coating of photo-sensitive resin with coating fluid (prescription 1), form beyond the photo-sensitive resin and be to use sept shown below to carry out transfer printing, make light spacer and liquid crystal indicator similarly to Example 1 with photosensitive transfer film.Resulting light spacer is a cylindrical shape.
The making of-sept usefulness photosensitive transfer film-
At thickness is on the interim supporter of pet film (the interim supporter of PET) of 75 μ m, and the thermoplastic resin that coating is made of following prescription 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 prescription A of coating fluid]
Methyl methacrylate/2-EHA/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)
2,39.0 parts in two [4-(methacryloxy polyethoxy) phenyl] propane of 2-
1 10.0 parts in following surfactant
90.0 parts of methyl alcohol
51.0 parts of 1-methoxyls-2-propyl alcohol
700 parts of MEKs
* surfactant 1
Following structure 1 30%
MEK 70%
Structure 1
(n＝6、X＝55、Y＝5
Mw＝3394D、Mw/Mn＝2.55
PO: epoxypropane, EO: oxirane
Then, the middle layer that coating is made of following prescription 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 prescription 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 constitutes by the prescription 3 shown in the above-mentioned table 1 of coating with coating fluid ((A) resin is the compound in the table 2) and make its drying, thereby stacked dry bed thickness is the photo-sensitive resin of 5.0 μ m.
Constitute lit-par-lit structure (total bed thickness of 3 layers: 21.5 μ m) of the interim supporter/thermoplastic resin of PET/middle layer/photo-sensitive resin as described above, on the surface of photo-sensitive resin further by heating and pressurizing 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 cover film of resulting sept with 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, 130 ℃ pressurized, heated condition is pasted together them.Then, the interim supporter of PET is being removed with peeling off at the interface of thermoplastic resin, thus with photo-sensitive resin with thermoplastic resin and middle layer transfer printing (tunicle formation operation).
Then, use have extra-high-pressure mercury vapour lamp near type exposure machine (manufacturing of the Ha イ テ of Hitachi Network Electricity エ Application ジ ニ ァ リ Application グ Co., Ltd.), make mask (quartzy exposed mask) with picture pattern with so that this mask mode relative and the filter substrate almost parallel that disposes with photo-sensitive resin under the state that stands vertically, with mask face and the distance setting that contacts with the middle layer of photo-sensitive resin between the surface of a side is 100 μ m, across this mask from the thermoplastic resin side with 90mJ/cm
2Exposure carry out near the exposure (exposure process).
Then, 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 (with ratio mixing of 1 part of T-PD2 and 11 parts of pure water) with pure water and the solution that obtains) carry out drip washing under 30 ℃, flat burner pressure are the condition of 0.04MPa developed for 50 seconds with triethanolamine, removes 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 the substrate.Then, using sodium carbonate is that developer solution (contains the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 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)) is 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, with on 300 μ m * 300 μ m at interval the mode of 1 sept form columned spacer patterns.
Then, the filter substrate that is provided with spacer patterns in 230 ℃ of following 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 the PVA mode LCD similarly to Example 1.
Table 2
Mw: weight-average molecular weight
Employed detailed compound is as described below in embodiment, the comparative example.
CGI-242: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(O acetyl oxime) (manufacturing of Ciba Specialty Chemicals Co., Ltd.)
Shown in above-mentioned table 2, embodiment compares with comparative example, can obtain higher sensitivity, and the ageing stability of the photo-sensitive resin the when fluid preservation of the photo-sensitive resin of being modulated usefulness coating fluid and coating back keep with the dry film state 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 〉
Among the embodiment 1; in the making of filter substrate; after forming black matrix", R pixel, G pixel and B pixel; on black matrix" and each pixel, further be coated with the photosensitive polymer combination that constitutes by above-mentioned prescription 1; staying out of under the situation of mask expose (whole exposure), form diaphragm after the heat treated.Here, the condition of coating, exposure, heat treated is, except stay out of expose under the situation of mask, identical with the condition of coating during the light spacer of embodiment 1 forms, exposure, heat treated.
Then, on resulting protective seam, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
On the ito transparent electrode of above-mentioned formation, except use the photosensitive polymer combination that uses among the 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 in the making of the filter substrate of embodiment 1, forming the R pixel, make filter substrate similarly to Example 1 with following method.
That is, in above-mentioned prescription 1, further add paratonere 254 (19.4 parts) and paratonere 177 (4.83 parts), modulation R pixel photosensitive polymer combination.
Except using the R pixel modulated to use the R pixel with the photomask, use with the same method of the formation method of the light spacer of embodiment 1 and form the R pixel with photosensitive polymer combination and as photomask.
After R pixel, G pixel and the B pixel of the filter substrate of made form, on each pixel, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
On the ito transparent electrode of above-mentioned formation, except use the photosensitive polymer combination that uses among the 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 in comparative example 4, replacing embodiment 10 copolymer 1; in addition; use except the structure PD-52 of (A) resin of in comparative example 5, replacing embodiment 11 copolymer 1; similarly carry out with embodiment 10 and 11 respectively; thereby make diaphragm and coloured material respectively, and similarly estimate.
Table 3
As shown in table 3, when using photosensitive polymer combination of the present invention to form diaphragm and colored pattern, also can obtain and same good result 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,, also have the light spacer and the manufacture method thereof of good high homogeneity and uniform cross sectional shape even can provide a kind of under situation about forming with low sensitivity.
In addition, according to the present invention,, also have the diaphragm or the colored pattern of good film thickness uniformity and uniform cross sectional shape even can provide a kind of under situation about forming with low sensitivity.
In addition, according to the present invention, can provide a kind of and when being used for display device, can suppress to show uneven base board for display device and show the uneven display device that suppresses that obtained.
The foregoing description of concrete form of the present invention provides in order to describe with illustrative purposes.Do not wish the present invention is defined in disclosed form itself, neither comprehensively enumerate.This form is for fullest ground explanation notion of the present invention and practical application thereof and selected, make other those skilled in the art understand the present invention thus, thereby the those skilled in the art that make other can make various forms or carry out various distortion in order to make its special-purpose that is suitable for wanting.
The detailed content of the preferred implementation of relevant the invention described above is certainly wished the form that is suitable for and is freely changed 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 (15)
1, a kind of 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.
2, photosensitive polymer combination according to claim 1, wherein, described substituted alkyl is the group with following general formula (1) expression,
General formula (1)
In the general formula (1), * represents the side that combines with the main chain of resin; A1 represents that carbon number is dibasic alkyl of 1～9; B1 and B2 represent singly-bound respectively independently, from the main chain side for the urethane bond of-O-CO-NHR-, from the ester bond of main chain side for-CO-O-; R represents that carbon number is 1～3 alkyl; In addition, X1 and X2 represent respectively independently from the ester bond of main chain side for-O-CO-; R
1And R
2Represent hydrogen atom or methyl respectively independently.
3, photosensitive polymer combination according to claim 1, wherein, the substituting group of described substituted alkyl is (methyl) acryloxy.
4, 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 constitutes,
General formula (3)
In the 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.
5, 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.
6, 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.
7, photosensitive polymer combination according to claim 1, wherein, the acid number of described (A) resin is more than the 20mgKOH/g, and 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.
8, photosensitive polymer combination according to claim 1, wherein, described (B) polymerizable compound with respect to the quality ratio of described (A) resin promptly the ratio of (B)/(A) be 0.5～2.0.
9, photosensitive polymer combination according to claim 1, it further contains the extender pigment that mean grain size is 5～50nm.
10, a kind of light spacer, it is to use, and each described photosensitive polymer combination forms in the claim 1～9.
11, a kind of formation method of light spacer, it contains following operation (i)～(iii) at least:
(i) on substrate, form the operation of the tunicle of each described photosensitive polymer combination in the claim 1～9;
The (ii) operation that at least a portion of described tunicle is exposed;
The operation that described tunicle after (iii) will exposing develops;
The operation that described tunicle after (iv) will developing heats.
12, a kind of diaphragm, it is to use, and each described photosensitive polymer combination forms in the claim 1～9.
13, a kind of colored pattern, it is to use, and each described photosensitive polymer combination forms in the claim 1～9.
14, a kind of base board for display device, it possesses at least a in the light spacer that uses each described photosensitive polymer combination in the claim 1～9 and form, diaphragm, the colored pattern.
15, a kind of display device, it possesses the described base board for display device of claim 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP339917/2007 | 2007-12-28 | ||
| JP2007339917 | 2007-12-28 |
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| CN101470350A true CN101470350A (en) | 2009-07-01 |
| CN101470350B CN101470350B (en) | 2013-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| 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) |
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| CN106502051A (en) * | 2015-09-03 | 2017-03-15 | 东友精细化工有限公司 | Negative light-sensitive resin combination and the photo-curable pattern formed by which |
| CN106796395A (en) * | 2014-10-14 | 2017-05-31 | 太阳油墨制造株式会社 | Dry film and flexible printed circuit board |
| CN106933031A (en) * | 2015-11-30 | 2017-07-07 | 富士胶片株式会社 | Photosensitive composite, cured film preparation method, cured film, Trackpad and display device |
| CN108352450A (en) * | 2015-11-18 | 2018-07-31 | 阿尔塔纳股份公司 | Crosslinkable polymeric material for the dielectric layer in electronic device |
| TWI656160B (en) * | 2013-07-19 | 2019-04-11 | 昭和電工股份有限公司 | Resin composition for protective film layer of color filter, protective film layer using the same, image display element and method for manufacturing image display element |
| 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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| 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 |
| CN110462560B (en) * | 2017-03-28 | 2023-07-28 | 株式会社力森诺科 | Transfer photosensitive film |
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| TWI656160B (en) * | 2013-07-19 | 2019-04-11 | 昭和電工股份有限公司 | Resin composition for protective film layer of color filter, protective film layer using the same, image display element and method for manufacturing image display element |
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| CN106933031A (en) * | 2015-11-30 | 2017-07-07 | 富士胶片株式会社 | Photosensitive composite, cured film preparation method, cured film, Trackpad and display device |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101470350B (en) | 2013-06-12 |
| JP2009175730A (en) | 2009-08-06 |
| JP5361373B2 (en) | 2013-12-04 |
| TWI476513B (en) | 2015-03-11 |
| KR20090072995A (en) | 2009-07-02 |
| TW200935173A (en) | 2009-08-16 |
| KR101622991B1 (en) | 2016-05-20 |
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