CN106465508B - Refuse ink agent, negative light-sensitive resin combination, partition wall and optical element - Google Patents
Refuse ink agent, negative light-sensitive resin combination, partition wall and optical element Download PDFInfo
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- CN106465508B CN106465508B CN201580031150.1A CN201580031150A CN106465508B CN 106465508 B CN106465508 B CN 106465508B CN 201580031150 A CN201580031150 A CN 201580031150A CN 106465508 B CN106465508 B CN 106465508B
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- partition wall
- polymer
- compound
- refuse ink
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- 238000005192 partition Methods 0.000 title claims abstract description 153
- 229920005989 resin Polymers 0.000 title claims abstract description 112
- 239000011347 resin Substances 0.000 title claims abstract description 112
- 230000003287 optical effect Effects 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 189
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 104
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 77
- 239000012948 isocyanate Substances 0.000 claims abstract description 49
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 48
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims description 140
- -1 silanes compound Chemical class 0.000 claims description 117
- 239000000203 mixture Substances 0.000 claims description 71
- 239000002585 base Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 25
- 239000003086 colorant Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 230000009257 reactivity Effects 0.000 claims description 15
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 230000036961 partial effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 11
- 150000002923 oximes Chemical class 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 150000003951 lactams Chemical class 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 2
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- 239000010408 film Substances 0.000 description 68
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
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- 125000004429 atom Chemical group 0.000 description 9
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- 239000003431 cross linking reagent Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
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- 239000012860 organic pigment Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
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- 239000002270 dispersing agent Substances 0.000 description 7
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- 125000000962 organic group Chemical group 0.000 description 7
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- TXHZNLCKXHJYNX-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C TXHZNLCKXHJYNX-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
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- 229910052581 Si3N4 Inorganic materials 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- 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 2
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 1
- AMQCWFKKFGSNNA-UHFFFAOYSA-N 2-butylcyclohexa-2,5-diene-1,4-dione Chemical group CCCCC1=CC(=O)C=CC1=O AMQCWFKKFGSNNA-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical class C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- BKDCQCZRMNHVCR-UHFFFAOYSA-N 3-[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl]phthalic acid Chemical class OC(=O)C1=CC=CC(CC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)=C1C(O)=O BKDCQCZRMNHVCR-UHFFFAOYSA-N 0.000 description 1
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical class CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 1
- NMILGIZTAZXMTM-UHFFFAOYSA-N 4-propylmorpholine Chemical compound CCCN1CCOCC1 NMILGIZTAZXMTM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910020487 SiO3/2 Inorganic materials 0.000 description 1
- 229910020485 SiO4/2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000037429 base substitution Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 1
- 229960003132 halothane Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
Abstract
There is provided the partition wall of refuse ink agent, the negative light-sensitive resin combination containing it, upper surface with good good refuse ink, with by the divider walls into opening portion even spread is black and the optical element of point that is precisely formed, wherein, the storage-stable of photosensitive polymer combination containing the refuse ink agent is abundant, and the refuse ink agent can make the photosensitive polymer combination that can form partition wall and ink affinity good opening portion of the upper surface with good good refuse ink.A kind of refuse ink agent is the refuse ink agent that good refuse ink is assigned to the upper surface of partition wall, and the partition wall is formed as substrate surface being separated into the shape of multiple subregions for formation point, and the refuse ink agent includes：With fluorine-containing atomic unit and containing can be by heating to unseal the unit of the blocked isocyanate base for generating isocyanate group, and the polymer that the containing ratio of fluorine atom is 1~40 mass %.
Description
Technical field
The present invention relates to refuse ink agent, negative light-sensitive resin combination, partition wall and optical elements.
Background technology
In organic EL (Electro-Luminescence；Electroluminescent) in the manufacture of optical elements such as element, make sometimes
By the use of using organic layers such as luminescent layers as point, the method for carrying out pattern printing with ink-jet (IJ) method.In the above-mentioned methods, along desired
The profile of the point of formation sets partition wall, the injection in the subregion (hereinafter also referred to as " opening portion ") surrounded by the partition wall
The ink of material comprising organic layer is dried it, heats, and is consequently formed the point of desired pattern.
In the above method, the mixing of the ink between adjacent point and the even spread ink in formation, need in order to prevent
Want partition wall upper surface that there is good refuse ink, and the opening portion that the point surrounded by partition wall including partition wall side is formed has
There is ink affinity.
Then, in order to obtain upper surface have good refuse ink partition wall, it is known that following method：Using containing refuse ink agent
Photosensitive polymer combination forms the corresponding partition wall of pattern with putting using photoetching process.For example, patent document 1, patent are literary
Offer the minus sense for being disclosed in 2 and including the silicon-type refuse ink agent being made of the hydrolytic condensate of fluorine-containing hydrolysable silanes compound
Photosensitive resin composition.
When forming partition wall using the negative light-sensitive resin combination containing this refuse ink agent, by the film of said composition
Be equivalent to the Partial exposure of partition wall after, by developing, removal is equivalent to the composition of opening portion.At this time, it is difficult to by minus sense
Photosensitive resin composition removes completely from opening portion, it will usually which in opening portion, there are some residues.Due to the negative-type photosensitive tree
The presence of the residue of oil/fat composition, the ink affinity of opening portion reduce, the even spread of ink are caused to hinder, this is a problem.
Prior art literature
Patent document
Patent document 1：International Publication No. 2010/013816
Patent document 2：International Publication No. 2014/046209
The content of the invention
Problems to be solved by the invention
To the residue of the negative light-sensitive resin combination of above-mentioned opening portion, the inventors of the present invention confirm, the parent of opening portion
The degree of ink can because of the species of used negative light-sensitive resin combination, more specifically negative photosensitive resin combine
The species of refuse ink agent contained by object and it is different, more be more than it is different due to the amount of residue.
Then, from make above-mentioned opening portion ink affinity it is good from the perspective of select negative light-sensitive resin combination in match somebody with somebody
During mixed refuse ink agent, the negative light-sensitive resin combination containing the refuse ink agent there are storage-stable it is insufficient the problem of.Separately
Outside, the problem of similary in the case of positive type photosensitive organic compound there is also.
Storage-stable it is an object of the invention to provide the photosensitive polymer combination containing it is abundant and can make
Work can form the photosensitive polymer combination of partition wall and ink affinity good opening portion of the upper surface with good good refuse ink
Refuse ink agent.
It is an object of the invention to provide storage-stable it is good, can be formed the good partition wall of good refuse ink of upper surface and
The negative light-sensitive resin combination of the good opening portion of ink affinity.
It is an object of the invention to provide the partition walls that upper surface has good good refuse ink.
The present invention also aims to provide have by divider walls into opening portion even spread ink and precision is good
The optical element of the point formed well.
The solution to the problem
The present invention provides the refuse ink agent with following composition, negative light-sensitive resin combination, partition wall and optics member
Part.
[1] a kind of refuse ink agent, is the refuse ink agent that good refuse ink is assigned to the upper surface of partition wall, and the partition wall is formed as
Substrate surface is separated into the shape of multiple subregions for formation point,
The refuse ink agent includes：With fluorine-containing atomic unit and containing can be by heating to unseal to generate isocyanates
The unit of the blocked isocyanate base of base, and the polymer that the containing ratio of fluorine atom is 1~40 mass %.
[2] according to the refuse ink agent of [1], wherein, foregoing blocked isocyanate base deblocking and it is 10 as isocyanate group small
When half life temperature be 60~180 DEG C.
[3] according to the refuse ink agent of [1] or [2], wherein, foregoing blocked isocyanate base is represented with following formula (1).
- NHC (=O)-B ... (1)
(in formula (1), B is by unary alcohol, phenols, lactams, oximes, Acetacetic acid alkyl ester class, malonic acid alkyl
1 in esters, phthalimide class, imidazoles or reactive hydrogen possessed by pyrazoles removes the group formed；Chlorine is former
Son or itrile group；Or the group for forming the hydrogen removing of sodium hydrogensulfite.)
[4] according to the refuse ink agent of [3], wherein, B is the group that forms the hydrogen atom removing of the hydroxyl of oximes or by structure
The group that the reactive hydrogen removing being bonded on into the nitrogen-atoms of the ring of pyrazoles forms.
[5] according to the refuse ink agent of any one of [1]~[4], wherein, aforementioned polymer is and the matter using hydrocarbon chain as main chain
Average molecular weight is in 5 × 103~1 × 105Scope polymer, foregoing fluorine-containing atomic unit be with optionally contain ethereal oxygen
The fluorine alkylidene of atom and/or the optionally unit of the fluoroalkyl containing etheric oxygen atom.
[6] according to the refuse ink agent of [5], wherein, aforementioned polymer also have be selected from by the unit with acidic-group, with
At least one kind of unit in the group of the unit of olefinic double bond, the unit with hydroxyl and the composition of the unit with polyoxyalkylene chain.
[7] according to the refuse ink agent of any one of [1]~[4], wherein, aforementioned polymer is the portion of hydrolysable silanes compound
Divide hydrolytic condensate, foregoing fluorine-containing atomic unit is to be bonded with the fluorine alkylene with optionally containing etheric oxygen atom on the silicon atoms
Base and/or the optionally siloxane unit of the group of the fluoroalkyl containing etheric oxygen atom.
[8] according to the refuse ink agent of [7], wherein, preceding sections hydrolytic condensate is comprising the water with fluorine-containing atomic radical
Solution property silane compound and with blocked isocyanate base hydrolysable silanes compound homogeney of hydrolysable silanes compound mixture
Partial hydrolysis condensate, the homogeney of hydrolysable silanes compound mixture optionally include in the group being made of following compounds
At least one hydrolysable silanes compound：The hydrolysable silanes compound of 4 hydrolization groups is bonded on the silicon atoms, is had
Group containing olefinic double bond and the hydrolysable silanes compound without fluorine atom, the hydrolysis only with the alkyl for being bonded to silicon atom
Property silane compound and with sulfydryl and without fluorine atom hydrolysable silanes compound.
[9] according to the refuse ink agent of any one of [1]~[8], wherein, aforesaid base plate will at least form foregoing partition wall
One side surface possesses the functional group with the reactivity of isocyanate group reaction.
[10] a kind of negative light-sensitive resin combination, which is characterized in that contain the alkali soluble resins with photo-curable
Or the alkaline soluble monomers with photo-curable, and contain the refuse ink agent of any one of Photoepolymerizationinitiater initiater and [1]~[8].
[11] according to the negative light-sensitive resin combination of [10], black colorant is also contained.
[12] a kind of partition wall is formed as substrate surface being separated into the shape of multiple subregions for formation point, institute
Partition wall is stated to be formed by the solidfied material of [10] or the negative light-sensitive resin combination of [11].
[13] according to the partition wall of [12], wherein, foregoing partition wall, which is formed in, to be possessed and isocyanate group reaction
On the substrate of the functional group of reactivity.
[14] a kind of optical element, which is characterized in that it has multiple points and between adjacent point in substrate surface
Partition wall, foregoing partition wall formed by the partition wall of [12] or [13].
[15] according to the optical element of [14], wherein, the point is formed using ink-jet method.
The effect of invention
In accordance with the invention it is possible to it provides the storage-stable of the photosensitive polymer combination containing it fully and can make
Refusing for the photosensitive polymer combination of partition wall and ink affinity good opening portion of the upper surface with good good refuse ink can be formed
Black agent.
The storage-stable of the negative light-sensitive resin combination of the present invention is good, using can form upper surface at that time
The good partition wall of good refuse ink and the good opening portion of ink affinity.
The partition wall of the present invention has good good refuse ink in upper surface.
The optical element of the present invention be with by divider walls into opening portion even spread ink and precisely
The optical element of the point of formation.
Description of the drawings
Figure 1A is the process chart of the manufacturing method for the partition wall for schematically showing embodiments of the present invention.
Figure 1B is the process chart of the manufacturing method for the partition wall for schematically showing embodiments of the present invention.
Fig. 1 C are the process chart of the manufacturing method for the partition wall for schematically showing embodiments of the present invention.
Fig. 1 D are the process chart of the manufacturing method for the partition wall for schematically showing embodiments of the present invention.
Fig. 2A is the process chart of the manufacturing method for the optical element for schematically showing embodiments of the present invention.
Fig. 2 B are the process chart of the manufacturing method for the optical element for schematically showing embodiments of the present invention.
Specific embodiment
In this specification, " (methyl) acryloyl group " is the general designation of " methylacryloyl " and " acryloyl group ".(methyl)
Acryloxy, (methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide and (methyl) acrylic resin also with
Subject to this.
In this specification, the group shown in formula (x) is abbreviated as group (x) sometimes.
In this specification, formula (y) compound represented is abbreviated as compound (y) sometimes.
Herein, formula (x), formula (y) represent arbitrary formula.
" side chain " in this specification refers to, is formed in the polymer for forming main chain in the repetitive unit formed by carbon atom
The group in addition to hydrogen atom and halogen atom being bonded on the carbon atom of main chain.Fluorine-containing atomic unit etc. " unit " represents poly-
Close unit.
In this specification, number-average molecular weight (Mn) and matter average molecular weight (Mw) refer to lead in case of no particular description
Cross what gel permeation chromatography was measured using polystyrene as standard substance.
" all solids ingredient of photosensitive polymer combination " in this specification refers to, contained by photosensitive polymer combination
The ingredient of aftermentioned cured film is formed among some ingredients, by photosensitive polymer combination is heated at 140 DEG C 24 it is small when make a return journey
Except residue is obtained obtained from solvent.It should be noted that all solids component amount can also be calculated by inventory.
In this specification, the film formed by the solidfied material using resin as the composition of principal component is known as " resin solidification
Film ".
In this specification, film obtained from photosensitive resin coating composition is known as " film ", it will be dried
Film be known as " desciccator diaphragm ".It is " resin cured film " to make film obtained from " desciccator diaphragm " curing.In addition, in this specification,
Sometimes " resin cured film " is referred to as " cured film ".
" partition wall " is created as predetermined region being separated into a form of the resin cured film of the shape of multiple subregions.
By divider walls into subregion, the opening portion that is surrounded by partition wall injects for example following " ink " and formed " point ".
" ink " in this specification is to be referred to as the liquid after drying, curing etc. with optical function and/or Electricity Functional
Term.
In organic EL element, the colour filter of liquid crystal cell and TFT (thin film transistor (TFT)s；Thin Film Transistor) battle array
In the optical elements such as row, sometimes for the point as various inscapes, using for forming the ink of the point, pass through ink-jet (IJ)
Method carries out pattern printing." ink " in this specification includes the ink used in such use.
" good refuse ink " in this specification is to repel the property of above-mentioned ink, has both water repellency and oil repellent.Good refuse ink
Such as contact angle when can be fallen by making ink droplet is evaluated." ink affinity " is the property opposite with good refuse ink, same with good refuse ink
Contact angle when can be fallen by making ink droplet is evaluated sample.Alternatively, can be by falling ink droplet with defined benchmark evaluation when
The degree (black wetting autgmentability) of wetting extension of ink evaluate ink affinity.
" point " in this specification represents the Minimum Area that can carry out light modulation in optical element.Organic EL element,
In the optical elements such as the colour filter and organic tft array of liquid crystal cell, in white and black displays, 1 point=1 pixel is shown in colour
When, such as 3 points of pixels of (R (red), G (green), B (indigo plant) etc.)=1.
Illustrate embodiments of the present invention below.It should be noted that in situation about being not particularly illustrated in this specification
Under, % represents quality %.
[refuse ink agent]
The refuse ink agent of the present invention is that the refuse ink agent of good refuse ink is assigned to the upper surface of partition wall, the partition wall be formed as by
Substrate surface is separated into the shape of multiple subregions for formation point, and the refuse ink agent includes：With fluorine-containing atomic unit and contain
Having can be by heating to unseal the unit of the blocked isocyanate base for generating isocyanate group, and the containing ratio of fluorine atom is
The polymer of 1~40 mass %.
It should be noted that in this specification, the refuse ink agent of the present invention is also known as refuse ink agent (C).In addition, it will act as refusing
The polymer with above-mentioned characteristic of black agent (C) is known as polymer (C).
The partition wall of refuse ink agent (C) can be applied to be not particularly limited.Refuse ink agent (C) uses preferably in the form of following：Bag
It is contained in photosensitive polymer combination, after said composition is coated on substrate, during partition wall is formed as described later
It migrates to the upper surface of composition layer, it is intensive to form refuse ink agent (C) in the upper layer part including upper surface of obtained partition wall
Existing layer (is also sometimes referred to as " refusing layer of ink " below.), so as to assign good refuse ink to partition wall upper surface.Above-mentioned photoresist
Composition can be eurymeric, or minus.
Polymer (C) contains fluorine atom with the ratio of 1~40 mass %, thus has and migrates to the upper surface of composition layer
Property (upper surface migration) and good refuse ink, good good refuse ink can be assigned to the upper surface of the partition wall of gained.Polymerization
The containing ratio of fluorine atom in object (C) is preferably 5~35 mass %, particularly preferably 10~30 mass %.The fluorine of polymer (C)
When the containing ratio of atom is more than the lower limiting value of above range, good good refuse ink can be assigned to partition wall upper surface, to be upper
When below limit value, become good with the compatibility of other ingredients in photosensitive polymer combination.
In addition, polymer (C) have can be by heating to unseal the blocked isocyanate base for generating isocyanate group
(hereinafter also referred to as " blocked isocyanate base ".), reactivity thus is can inhibit when less than the temperature that above-mentioned deblocking occurs, because
This, as refuse ink agent or containing in photosensitive polymer combination storage-stable can be improved when storing.And then during use
By heating its deblocking is made to form isocyanate group, so as to the reactivity raising of polymer (C), with other ingredients, Qi Tacai
Associativity, the adaptation of material improve.Thereby, it is possible to inhibit the residual of photosensitive polymer combination in the opening portion surrounded by partition wall
The wetting autgmentability of slag damage ink, makes ink affinity good.
From this point of view, as the photosensitive polymer combination containing refuse ink agent (C) is used to be formed in substrate surface
Substrate during partition wall, the side surface that preferably at least form partition wall possess the reactivity reacted with isocyanate group
Functional group, such as hydroxyl, amino, carboxyl, sulfydryl etc..That is, refuse ink agent (C) is for example containing in photosensitive polymer combination
In use, possessing the reactive function reacted with isocyanate group at least to form a side surface of partition wall
During the substrate of group, it is particular enable to play effect.It is thought that because, by having the substrate surface of one side of partition wall to be formed
Have the functional group possessed with the reactivity of isocyanate group reaction, so as in opening portion substrate surface and refuse ink agent (C) it is close
Conjunction property improves, even if having the residue of photosensitive polymer combination in opening portion, also ensures that the ink affinity of opening portion.
Can be to make isocyanic acid by heating to unseal the blocked isocyanate base for generating isocyanate group specifically
The functional group that ester group is reacted with the compound (end-capping reagent) containing reactive hydrogen and inactivated at normal temperatures, with when being heated to it
End-capping reagent dissociates and regenerates property as isocyanate group.
It should be noted that the blocked isocyanate base deblocking and as isocyanate group 10 it is small when half life temperature it is excellent
Elect 60~180 DEG C, more preferably 80~150 DEG C as.The 10 of the blocked isocyanate base it is small when half life temperature be above range
When, ink affinity is good.
As this blocked isocyanate base, specifically, the group shown in following formula (1) can be included.
- NHC (=O)-B ... (1)
(in formula (1), B is by unary alcohol, phenols, lactams, oximes, Acetacetic acid alkyl ester class, malonic acid alkyl
1 in esters, phthalimide class, imidazoles or reactive hydrogen possessed by pyrazoles removes the group formed；Chlorine is former
Son or itrile group；Or the group for forming the hydrogen removing of sodium hydrogensulfite.)
In above-mentioned, for unary alcohol, phenols, oximes, the hydrogen of hydroxyl possessed by them is reactive hydrogen.Acetyl second
Dialkylaminobenzoic acid esters, malonates class are the compound with methylene reactive hydrogen.Lactams, phthalimide
Class, imidazoles, pyrazoles are the compound with amino reactive hydrogen.
As unary alcohol, the straight-chain of carbon number 1~10 or the monohydric alcohol of branched, preferably methanol, ethyl alcohol can be included
Deng.As phenols, the phenolate that can include 1 in the hydrogen being bonded on aromatic rings carbon number being optionally substituted by a hydroxyl group 6~15 is closed
Object, preferably phenol, cresols etc..
As lactams, the lactams that first number is 3~6 can be included.As oximes, can include has>C=N-OH
The aldoxime of the carbon number 1~6 of base or the ketoxime of carbon number 3~9, preferably Rk1Rk2C=N-OH (Rk1And Rk2Each independently represent carbon number 1
~4 alkyl.) shown in carbon number 3~7 ketoxime.
The moieties of Acetacetic acid alkyl ester class and malonates class are respectively preferably the straight-chain of carbon number 1~4
Or the alkyl of branched.
As phthalimide class, the carbon that can include phthalimide and phthalimide ring is former
The phthalimide that the hydrogen atom being bonded on son is substituted by the alkyl of the straight-chain of carbon number 1~6 or branched derives
Object etc..As imidazoles, the hydrogen atom being bonded on the carbon atom of imidazoles and imidazole ring can be included by the straight chain of carbon number 1~6
Imdazole derivatives that shape or the substitution of the alkyl of branched form etc..As pyrazoles, the carbon of pyrazoles and pyrazole ring can be included
Pyrazole derivatives that the hydrogen atom being bonded on atom is substituted by the alkyl of the straight-chain of carbon number 1~6 or branched etc..
It is preferably oximes, pyrazoles, particularly preferably pyrazoles among these.In the case of oximes ,-B is to remove oximes
Hydroxyl the group that forms of hydrogen atom, in the case of pyrazoles ,-B is to be bonded on the nitrogen-atoms for remove the ring for forming pyrazoles
The group that forms of hydrogen atom.As particularly preferred-B, the group and following formula (b2) shown in following formula (b1) can be included
Shown group etc..
Herein, for example, among group (1) ,-NHC (=O)-(b1) ,-NHC that-B is group (b2) that-B is group (b1)
(=O)-(b2) 10 it is small when half life temperature be respectively 110 DEG C and 140 DEG C.
Polymer (C) contains above-mentioned fluorine atom, to contain blocked isocyanate base list in the form of fluorine-containing atomic unit respectively
The form of member contains blocked isocyanate base.In polymer (C), fluorine-containing atomic unit and the unit of base containing blocked isocyanate can be with
For same unit, i.e., there is fluorine atom and blocked isocyanate base in same unit, but usually fluorine-containing atomic unit is with containing envelope
Terminal isocyanate group unit is different units.
As this polymer (C), such as can include：It is condensed by the partial hydrolysis of homogeney of hydrolysable silanes compound mixture
Object formed polymer (hereinafter referred to as polymer (C1)), main chain for hydrocarbon chain and possess with the side chain containing fluorine atom unit and
Polymer (hereinafter referred to as polymer (C2)) of unit with blocked isocyanate base etc., the hydrolysable silanes compound is mixed
Close the hydrolysable silanes chemical combination that object includes the hydrolysable silanes compound with fluorine-containing atomic radical and the base containing blocked isocyanate
Object.
It should be noted that the content on the blocked isocyanate base in polymer (C), no matter polymer (C1) and poly-
Close object (C2), it is preferably to for 0.2mmol/g~4mmol/g, more preferably 0.3mmolol/g~4mmol/g.
<Polymer (C1)>
Polymer (C1) is homogeney of hydrolysable silanes compound mixture (hereinafter also referred to " mixture (M) ".) partial hydrolysis
Condensation product.The mixture (M) includes the hydrolysable silanes compound with fluorine-containing atomic radical, for example with optionally containing ethereal
The fluorine alkylidene of oxygen atom and/or the optionally fluoroalkyl containing etheric oxygen atom and the hydrolysable silanes with hydrolization group
Close object (hereinafter also referred to " compound (s1) ".) and there is the hydrolysable silanes compound of blocked isocyanate base (below
Referred to as " compound (s2) ".) as required ingredient, and optionally comprising the hydrolysable silanes in addition to compound (s1), (s2)
Compound.As the hydrolysable silanes compound that mixture (M) optionally contains, following hydrolysable silanes compound can be included
(s3)~(s6) (is also referred to as " compound (s3) ", " compound (s4) ", " compound (s5) ", " compound individually below
(s6)”.).As the hydrolysable silanes compound that mixture (M) optionally contains, preferred compound (s3).
Hydrolysable silanes compound (s3)；The hydrolysable silanes compound of 4 hydrolization groups is bonded on silicon atom.
Hydrolysable silanes compound (s4)；Possess group and hydrolization group with olefinic double bond, and without fluorine atom
Hydrolysable silanes compound.
Hydrolysable silanes compound (s5)；As the group for being bonded to silicon atom, only with alkyl and hydrolization group
Hydrolysable silanes compound (wherein, is included in except the substance in hydrolysable silanes compound (s4)).
Hydrolysable silanes compound (s6)；With sulfydryl and hydrolization group, and the hydrolysable silanes without fluorine atom
Close object.
Hereinafter, compound (s1)~(s6) is illustrated.
<1>Compound (s1)
By using compound (s1), polymer (C1) is with the fluorine alkylidene optionally containing etheric oxygen atom and/or optionally
The form of fluoroalkyl containing etheric oxygen atom has fluorine atom, has excellent upper surface migration and good refuse ink.
In order to which these properties possessed by compound (s1) is made to be higher level, compound (s1) more preferably have be selected from by
It is at least one kind of in the group of fluoroalkyl, perfluorinated alkylidene and perfluoroalkyl composition, particularly preferably with perfluoroalkyl.It needs to illustrate
, these fluorine-containing alkyl can also contain etheric oxygen atom, and the perfluoroalkyl containing etheric oxygen atom is also preferred.That is,
It is the chemical combination for having perfluoroalkyl and/or perfluoroalkyl comprising etheric oxygen atom as the most preferred compound of compound (s1)
Object.
As hydrolization group, alkoxy, halogen atom, acyl group, isocyanate group, amino, amino can be included extremely
Group that few 1 hydrogen is substituted by alkyl etc..Become hydroxyl (silanol group) from by hydrolysis, and then intermolecular
Condensation reaction occurs and formed Si-O-Si keys reaction be easily smoothed out from the perspective of, the preferred alkane of carbon number 1~4
Oxygroup or halogen atom, more preferably methoxyl group, ethyoxyl or chlorine atom, particularly preferably methoxy or ethoxy.
Compound (s1) can be used singly or in combination of two or more.
As compound (s1), preferably following formula (cx-1) compound represented.
(A-RF11)a-Si(RH11)bX11 (4-a-b)…(cx-1)
In formula (cx-1), each symbol is as described below.
RF11It is organic for divalent comprising at least one fluorine alkylidene, the optionally carbon number 1~16 with etheric oxygen atom
Group.Wherein, RF11The terminal atom being bonded with A and the terminal atom being bonded with Si be carbon atom.
RH11For the alkyl of carbon number 1~6.
A is 1 or 2, b are 0 or 1, a+b are 1 or 2.
A is the group shown in fluorine atom or following formula (Ia).
-Si(RH12)cX12 (3-c)…(Ia)
RH12For the alkyl of carbon number 1~6.
C is 0 or 1.
X11And X12For hydrolization group.
X11There are it is multiple when, they can it is different from each other can also be identical.
X12There are it is multiple when, they can it is different from each other can also be identical.
A-RF11There are it is multiple when, they can it is different from each other can also be identical.
Compound (cx-1) is the fluorine-containing hydrolysis with 1 or the hydrolyzable silyl group of 22 functionalities or 3 functionalities
Property silane compound.
RH11And RH12The preferably alkyl of carbon number 1~3, particularly preferably methyl.
In formula (cx-1), particularly preferred a is 1, b is 0 or 1.
X11And X12Concrete example and preferred mode it is as described above.
As compound (s1), particularly preferably following formula (cx-1a) compound represented.
T-RF12-Q11-SiX11 3…(cx-1a)
In formula (cx-1a), each symbol is as described below.
RF12For the perfluorinated alkylidene for optionally including etheric oxygen atom of carbon number 2~15.
T is the group shown in fluorine atom or following formula (Ib).
-Q12-SiX12 3…(Ib)
X11And X12For hydrolization group.
3 X11Can it is different from each other can also be identical.
3 X12Can it is different from each other can also be identical.
Q11And Q12Represent the divalent organic group without fluorine atom of carbon number 1~10.
In formula (cx-1a), when T is fluorine atom, RF12The preferably perfluorinated alkylidene of carbon number 4~8 or carbon number 4
The perfluorinated alkylidene of~10 perfluorinated alkylidene containing etheric oxygen atom, more preferably carbon number 4~8, particularly preferably carbon
The perfluorinated alkylidene of atomicity 6.
In addition, in formula (cx-1a), when T is group (Ib), RF12Preferably the perfluorinated alkylidene of carbon number 3~15 or
The perfluorinated alkylidene of the perfluorinated alkylidene containing etheric oxygen atom of carbon number 3~15, particularly preferably carbon number 4~6.
RF12For foregoing illustrative group when, polymer (C1) has good good refuse ink, and compound (cx-1a) exists
Dissolubility in solvent is excellent.
As RF12Structure, linear chain structure, branched structure, ring structure, partially annulose structure etc. can be included, it is excellent
Select linear chain structure.
As RF12Concrete example, No. 2014/046209 (hereinafter referred to as WO2014/ of International Publication No. can be included
046209) such as the substance described in paragraph [0043].
Q11And Q12Associative key, the R on right side are bonded to SiF12The form of the associative key in left side is bonded to when representing, to have
For body, preferably-(CH2)i1- (i1 is 1~5 integer.)、-CH2O(CH2)i2- (i2 is 1~4 integer.)、-SO2NR1-
(CH2)i3-(R1For hydrogen atom, methyl or ethyl, i3 is 1~4 integer, R1With (CH2)i3Carbon number add up to 4 with
Under integer.) or-(C=O)-NR1-(CH2)i4-(R1As described above, i4 be 1~4 integer, R1With (CH2)i4Carbon it is former
The integer for adding up to less than 4 of subnumber.) shown in group.As Q11And Q12, more preferable i1 be 2~4 integer-
(CH2)i1-, particularly preferably-(CH2)2-。
It should be noted that RF12During to be free of the perfluorinated alkylidene of etheric oxygen atom, as Q11And Q12, preferably-
(CH2)i1- shown group.The integer that more preferable i1 is 2~4, particularly preferred i1 are 2.
RF12For perfluoroalkyl containing etheric oxygen atom when, as Q11And Q12, preferably-(CH2)i1-、-CH2O(CH2)i2-、-
SO2NR1-(CH2)i3- or-(C=O)-NR1-(CH2)i4- shown group.At this time also more preferably-(CH2)i1-, further preferably
I1 is 2~4 integer, and particularly preferred i1 is 2.
When T is fluorine atom, as the concrete example of compound (cx-1a), such as paragraph of WO2014/046209 can be included
[0046] substance described in etc..
When T is group (Ib), as the concrete example of compound (cx-1a), such as section of WO2014/046209 can be included
Fall substance described in [0047] etc..
In the present invention, as compound (cx-1a), wherein particularly preferred F (CF2)6CH2CH2Si(OCH3)3With F (CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3。
The containing ratio of compound (s1) in mixture (M) is preferably, and the partial hydrolysis obtained by the mixture is contracted
The containing ratio of the fluorine atom in object is closed as 1~40 mass %, more preferably 5~35 mass %, particularly preferably 10~30 matter
Measure %.When the containing ratio of compound (s1) is more than the lower limiting value of above range, the upper surface of cured film can be assigned good
Good good refuse ink when being below upper limit value, becomes good with the compatibility of other hydrolysable silanes compounds in the mixture.
<2>Compound (s2)
By making containing compound (s2) in the mixture (M) in the present invention, as refuse ink agent or containing in photonasty tree
When storing, storage-stable can be improved in oil/fat composition.And then isocyanates is formed to unseal by heating when in use
Base so as to the reactivity raising of polymer (C), is improved with other ingredients, the associativity of other materials, adaptation.As a result, in quilt
The opening portion that partition wall surrounds inhibits the wetting autgmentability of the residue damage ink of photosensitive polymer combination, makes ink affinity good.
Compound (s2) can be used singly or in combination of two or more.
As hydrolization group, the same group of hydrolization group with compound (s1) can be used.
Compound (s2) can be represented by following formula (cx-2).
(BI-Q2)d-Si(RH2)eX2 (4-d-e)…(cx-2)
Symbol in formula (cx-2) is as described below.
BI is blocked isocyanate base.
Q2For the divalent organic group without fluorine atom of carbon number 1~6.Wherein, Q2The terminal atom for being bonded to Si
For carbon atom.
RH2For the alkyl of carbon number 1~6.
X2For hydrolization group.
D is 1 or 2, e are 0 or 1, d+e are 1 or 2.
BI-Q2There are it is multiple when, they can it is different from each other can also be identical.
X2There are it is multiple when, they can it is different from each other can also be identical.
As RH2, can be used and foregoing RH11And RH12Same group.
As X2, can be used and foregoing X11And X12Same group.
As BI, above-mentioned group (1) can be included, preferred mode is also similary with group (1).
It is preferred that d is 1, e is 0 or 1.
Compound (cx-2) can be used singly or in combination of two or more.
As the concrete example of compound (cx-2), following compound can be included.
The content ratio of compound (s2) in mixture (M) preferably 0.5~6 is rubbed for 1 mole compared with compound (s1)
That is particularly preferably 0.5~5 mole.And then the content ratio of the compound (s2) in mixture (M) is preferably to make to be mixed by this
Closing the content of the blocked isocyanate base in the partial hydrolysis condensate i.e. polymer (C1) that object obtains becomes the ratio of above range
Example.When content ratio is more than the lower limiting value of above range, the ink affinity of storage-stable and opening portion is good.For upper limit value with
When lower, the containing ratio of the fluorine atom in polymer (C1) is high, can assign good good refuse ink.
<3>Compound (s3)
Comprising compound (s3) in mixture (M) by making the present invention, such as polymer (C1) is included for using
For partition wall obtained from photosensitive polymer combination, polymer (C1) can be improved, the film forming after the migration of upper surface occurs
Property.That is, it is considered that since the quantity of the hydrolization group in compound (s3) is more, post-consumer polymer is migrated in upper surface
(C1) it is condensed well each other, thin film is integrally formed in upper surface, becomes and refuses layer of ink.
In addition, by making to become easily to be dissolved in the molten of hydrocarbon system comprising compound (s3), polymer (C1) in mixture (M)
Agent.
Compound (s3) can be used singly or in combination of two or more.
As hydrolization group, the same group of hydrolization group with compound (s1) can be used.
Compound (s3) can be represented by following formula (cx-3).
SiX3 4…(cx-3)
In formula (cx-3), X3Represent hydrolization group, 4 X3Can it is different from each other can also be identical.As X3, can make
With with foregoing X11And X12Same group.
As the concrete example of compound (cx-3), following compound can be included.In addition, as compound (cx-3),
It can also use as needed in advance by partial hydrolysis condensate obtained from its multiple progress partial hydrolysis condensation.
Si(OCH3)4、Si(OC2H5)4、Si(OCH3)4Partial hydrolysis condensate, Si (OC2H5)4Partial hydrolysis condensation
Object.
When mixture (M) includes compound (s3), the content ratio of the compound (s3) in mixture (M) is compared with chemical combination
1 mole of object (s1) is preferably 0.01~5 mole, particularly preferably 0.05~3 mole.Content ratio is the lower limiting value of above range
More than when, the film forming of polymer (C1) is good, be upper limit value below when, the good refuse ink of polymer (C1) is good.
<4>Compound (s4)
Comprising compound (s4) in mixture (M) by making the present invention, can make by the group with olefinic double bond
Polymer (C1) is polymerized together or makes the olefinic double bond that has contained by polymer (C1) and such as photosensitive polymer combination
Other ingredient copolymerization, are preferred.As a result, as described above, polymer (C1) can be improved in layer of ink is refused
Fixed effect.
Compound (s4) can be used singly or in combination of two or more.
As hydrolization group, the same group of hydrolization group with compound (s1) can be used.
As the group with olefinic double bond, preferably (methyl) acryloxy, ethenylphenyl, pi-allyl, vinyl,
Norborny, particularly preferred (methyl) acryloxy.
As compound (s4), preferably following formula (cx-4) compound represented.
(Y-Q4)g-Si(RH4)hX4 (4-g-h)…(cx-4)
Symbol in formula (cx-4) is as described below.
Y is the group with olefinic double bond.
Q4For the divalent organic group without fluorine atom of carbon number 1~6.Wherein, Q4The terminal atom for being bonded to Si
For carbon atom.
RH4For the alkyl of carbon number 1~6.
X4For hydrolization group.
G is 1 or 2, h are 0 or 1, g+h are 1 or 2.
Y-Q4There are it is multiple when, they can it is different from each other can also be identical.
X4There are it is multiple when, they can it is different from each other can also be identical.
As RH4, can be used and foregoing RH11And RH12Same group.
As X4, can be used and foregoing X11And X12Same group.
As Y, preferably (methyl) acryloxy or ethenylphenyl, particularly preferred (methyl) acryloxy.
As Q4Concrete example, alkylidene, phenylene of carbon number 2~6 etc. can be included.Wherein, preferably-
(CH2)3-。
It is preferred that g is 1, h is 0 or 1.
Compound (cx-4) can be used singly or in combination of two or more.
As the concrete example of compound (cx-4), can include described in such as paragraph [0057] of WO2014/046209
Substance etc..
When mixture (M) includes compound (s4), the content ratio of the compound (s4) in mixture (M) is compared with chemical combination
1 mole of object (s1) is preferably 0.1~5 mole, particularly preferably 0.5~4 mole.Content ratio for above range lower limiting value with
When upper, the upper surface migration of polymer (C1) is good, in addition, refusing layer of ink including upper surface after the migration of upper surface, gathers
It is good to close the stationarity of object (C1), and then the storage-stable of refuse ink agent (C1) is good.During for below upper limit value, polymer (C1)
Good refuse ink it is good.
<5>Compound (s5)
When in the mixture (M) of the present invention using compound (s3), such as cure by photosensitive polymer combination
Partition wall in, sometimes on it surface end formed protuberance.It is that can be observed with scanning electron microscope (SEM) etc.
Horizontal tump.The content that the present inventor confirms F and/or Si in the protuberance is more than other parts.
Above-mentioned protuberance will not be counteracted especially for partition wall etc., but the inventors discovered that, by by compound
(s3) a part is substituted for the few compound (s5) of quantity of hydrolization group, can inhibit the generation of above-mentioned protuberance.
The mutual reaction of silanol group generated by the compound (s3) more than the quantity by hydrolization group, polymer
(C1) film forming increases.However, it is believed that above-mentioned protuberance can occur due to its high response.Accordingly, it is believed that pass through by
A part for compound (s3) is substituted for the few compound (s5) of quantity of hydrolization group, mutual so as to inhibit silanol group
Reaction, can inhibit the generation of above-mentioned protuberance.
Compound (s5) can be used singly or in combination of two or more.
As hydrolization group, the same group of hydrolization group with compound (s1) can be used.
As compound (s5), preferably following formula (cx-5) compound represented.
(RH5)j-SiX5 (4-j)…(cx-5)
In formula (cx-5), each symbol is as described below.
RH5For the alkyl of carbon number 1~20.
X5For hydrolization group.
J be 1~3 integer, be preferably 2 or 3.
RH5There are it is multiple when, they can it is different from each other can also be identical.
X5There are it is multiple when, they can it is different from each other can also be identical.
As RH5, when j is 1, the aliphatic alkyl of carbon number 1~20 or the fragrance of carbon number 6~10 can be included
Race's alkyl is preferably alkyl, phenyl of carbon number 1~10 etc..When j is 2 or 3, RH5Preferably the alkyl of carbon number 1~6,
The more preferably alkyl of carbon number 1~3.
As X5, can use and foregoing X11And X12Same group.
As the concrete example of compound (cx-5), can include described in such as paragraph [0063] of WO2014/046209
Substance etc..
When mixture (M) includes compound (s5), the content ratio of the compound (s5) in mixture (M) is compared with chemical combination
1 mole of object (s1) is preferably 0.05~5 mole, particularly preferably 0.3~3 mole.Content ratio is the lower limiting value of above range
More than when, the protuberance of the end of partition wall upper surface can be inhibited.During for below upper limit value, the good refuse ink of polymer (C1) is good
It is good.
<6>Compound (s6)
By using compound (s6), such as photosensitive polymer combination can be made to be cured with lower light exposure.
It is thought that because the sulfydryl in compound (s6) has chain transfer, above-mentioned alkali soluble resins or alkaline soluble monomers, polymer
(C1) when there is olefinic double bond, easily with polymer (C1) itself possessed by olefinic double bond etc. be connected, promote photocuring.
In addition, the pKa of the compound (s6) comprising sulfydryl is 10 or so, easily deprotonation, i.e. dissociation in aqueous slkali.
Herein, pKa=-log is used10Ka is represented, in formula, Ka represents acid ionization constant.It is therefore contemplated that sulfydryl improves photosensitive resin composition
The alkali solubility during development of object.
Compound (s6) can be used singly or in combination of two or more.
As hydrolization group, the same group of hydrolization group with compound (s1) can be used.
As compound (s6), preferably following formula (cx-6) compound represented.
(HS-Q6)p-Si(RH6)qX6 (4-p-q)…(cx-6)
In formula (cx-6), each symbol is as described below.
Q6For the divalent organic group without fluorine atom of carbon number 1~10.Wherein, Q6The terminal atom for being bonded to Si
For carbon atom.
RH6For the alkyl of carbon number 1~6.
X6For hydrolization group.
P is 1 or 2, q are 0 or 1, p+q are 1 or 2.
HS-Q6There are it is multiple when, they can it is different from each other can also be identical.
X6There are it is multiple when, they can it is different from each other can also be identical.
As X6, can use and foregoing X11And X12Same group.
As Q6, be preferably carbon number 1~10 alkylidene, more preferably carbon number 1~5 alkylidene, especially
The preferably alkylidene of carbon number 1~3.
As RH6, can use and foregoing RH11And RH12Same group.
As the concrete example of compound (cx-6), HS- (CH can be included2)3-Si(OCH3)3、HS-(CH2)3-Si(CH3)
(OCH3)2Deng.
When mixture (M) includes compound (s6), the content ratio of the compound (s6) in mixture (M) is compared with chemical combination
1 mole of object (s1) is preferably 0.125~18 mole, particularly preferably 0.125~8 mole.Content ratio is under above range
When more than limit value, such as photosensitive polymer combination can be made to be cured with lower light exposure.In addition, alkali solubility can be improved,
Developability is good.During for below upper limit value, the good refuse ink of polymer (C1) is good.
<7>Other hydrolysable silanes compounds
Mixture (M) can optionally include the one kind or two or more hydrolysable silanes in addition to compound (s1)~(s6)
Close object.
As other hydrolysable silanes compounds, can include with oxyalkylene and hydrolization group and without fluorine atom
Hydrolysable silanes compound.Specifically, such as CH can be included3O(C2H4O)kC3H6Si(OCH3)3(containing polyoxyethylene groups
Trimethoxy silane) (herein, k e.g., about 10.) etc..
<8>Polymer (C1)
Polymer (C1) is the partial hydrolysis condensate of mixture (M).
As an example of polymer (C1), the average composition formula of polymer (C11) is shown in lower formula (II), the polymer
(C11) it is as required ingredient, optionally comprising compound (cx-3)~(cx- comprising compound (cx-1a) and compound (cx-2)
6), the group T in compound (cx-1a) is the partial hydrolysis condensate of the mixture (M) of fluorine atom.
[T-RF12-Q11-SiO3/2]n1·[(BI-Q2)d-Si(RH2)eSiO(4-d-e)/2]n2·[SiO4/2]n3·[(Y-Q4)g-
Si(RH4)hSiO(4-g-h)/2]n4·[(RH5)j-SiO(4-j)/2]n5·[(HS-Q6)p-Si(RH6)qO(4-p-q)/2]n6…(II)
In formula (II), n1~n6 represents mole fraction of each structural unit compared with the integral molar quantity of structural unit.n1>0、
n2>0th, n3 >=0, n4 >=0, n5 >=0, n6 >=0, n1+n2+n3+n4+n5+n6=1.Other each symbols are as described above.Wherein, T is
Fluorine atom.
It should be noted that polymer (C11) is the product (part for actually remaining hydrolization group or silanol group
Hydrolytic condensate), therefore, it is difficult to the product is represented by the chemical formula.
Average composition formula shown in formula (II) assumes that hydrolization group or silanol group whole shape in polymer (C11)
Chemical formula during into siloxanes key.
In addition, thus it is speculated that in formula (II), be originated from compound (cx-1a), (cx-2)~(cx-6) unit randomly
Arrangement.
The n1 in average composition formula shown in formula (II)：n2：n3：n4：n5：The n6 and compound (cx- in mixture (M)
It is 1a) consistent with the composition that feeds intake of (cx-2)~(cx-6).
The molar ratio of each ingredient can be designed according to the balance of the effect of each ingredient.
The containing ratio of fluorine atoms of the n1 in polymer (C11) become above-mentioned preferred scope amount in be preferably 0.02~
0.4th, it is particularly preferably 0.02~0.3.
N2 is preferably 0.05~0.6, particularly preferably 0.1~0.5.
N3 is preferably 0~0.98, particularly preferably 0.05~0.6.
N4 is preferably 0~0.8, particularly preferably 0~0.5.
N5 is preferably 0~0.5, particularly preferably 0.05~0.3.
N6 is preferably 0~0.9, more preferably 0~0.8, particularly preferred 0~0.4.
It should be noted that when T of the preferred molar ratio of above-mentioned each ingredient in compound (cx-1a) is group (Ib)
Similarly.
In addition, the preferred molar ratio of above-mentioned each ingredient mixture (M) containing compound (s1) and compound (s2) and
It also can similarly be applied when optionally including compound (s3)~(s6).That is, for obtaining in the mixture of polymer (C1) (M)
The preferred inventory of compound (s1)~(s6) is respectively equivalent to the preferred scope of above-mentioned n1~n6.
The matter average molecular weight (Mw) of polymer (C1) is preferably 5 × 102Above, preferably less than 1 × 106, particularly preferably deficiency
1×104。
When matter average molecular weight (Mw) is more than lower limiting value, when forming partition wall using photosensitive polymer combination, refuse ink agent
(C1) upper surface migration easily occurs.During insufficient upper limit value, the dissolubility of polymer (C1) in a solvent becomes good.
The matter average molecular weight (Mw) of polymer (C1) can be adjusted by manufacturing condition.
Polymer (C1) is hydrolyzed by using well known method said mixture (M) to make with condensation reaction
It makes.
In the reaction it is preferable to use the inorganic acids such as commonly used hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid, oxalic acid,
The organic acids such as maleic acid are as catalyst.Furthermore it is possible to as needed using sodium hydroxide, tetramethylammonium hydroxide (TMAH) etc.
Base catalyst.
Well known solvent can be used in above-mentioned reaction.
The polymer (C1) obtained in above-mentioned reaction can be compounded into photoresist together with solvent with the character of solution
In composition.
<Polymer (C2)>
The main chain of polymer (C2) is hydrocarbon chain, and possesses unit with the side chain containing fluorine atom and with blocking isocyanide
The unit of perester radical.The matter average molecular weight (Mw) of polymer (C2) is preferably 1 × 102~1 × 106, particularly preferably 5 × 103~
1×105.When matter average molecular weight (Mw) is more than lower limiting value, when forming partition wall using photosensitive polymer combination, polymer
(C2) upper surface migration is easily carried out.During insufficient upper limit value, the dissolubility of polymer (C2) in a solvent becomes good.
On polymer (C2), as the above-mentioned unit with the side chain containing fluorine atom, it is preferably provided with having and optionally contains
The fluorine alkylidene of etheric oxygen atom and/or the optionally unit of the fluoroalkyl containing etheric oxygen atom.
Fluoroalkyl can be straight-chain, or branched.
As the concrete example of the fluoroalkyl without etheric oxygen atom, such as paragraph of WO2014/046209 can be included
[0082] group described in etc..
As the concrete example of the fluoroalkyl containing etheric oxygen atom, such as paragraph of WO2014/046209 can be included
[0083] group described in etc..
As fluoroalkyl, from good refuse ink it is good from the perspective of be preferably perfluoroalkyl.
The carbon number of fluoroalkyl is preferably 4~15, more preferably 4~12.When the carbon number of fluoroalkyl is 4~15,
Good refuse ink is excellent, in addition, when manufacturing polymer (C2), has the monomer of fluoroalkyl and the aftermentioned monomer in addition to the monomer
Compatibility becomes good.
Polymer (C2) is preferably as the above-mentioned unit with the side chain containing fluorine atom comprising the unit with fluoroalkyl
Polymer.Unit with fluoroalkyl is preferably by making the polymerizable monomer with fluoroalkyl polymerize to imported into polymer
In.In addition, the various method of modifying reacted by the polymer for making there is reactive site with appropriate compound, it can also be by fluothane
Base is imported into polymer.
As the hydrocarbon chain for the main chain for forming polymer (C2), specifically, can include by the monomer with olefinic double bond
Polymerization obtained from main chain, by-Ph-CH2- (wherein, " Ph " represents benzene skeleton.) repetitive unit formed phenolic varnish type
Main chain etc..
It, will be with olefinic double bond and with fluorine by the polymerization of the monomer with olefinic double bond and when obtaining polymer (C2)
The monomer of alkyl is with the monomer with olefinic double bond and with blocked isocyanate base or as needed with other with olefinic pair
The monomer of key is polymerize.
Hereinafter, it is the main chain as obtained from the polymerization of the monomer with olefinic double bond for the main chain of polymer (C2)
Situation illustrates.
As the monomer with olefinic double bond and with fluoroalkyl, CH can be included2=CR4COOR5Rf、CH2=
CR4COOR6NR4SO2Rf、CH2=CR4COOR6NR4CORf、CH2=CR4COOCH2CH(OH)R5Rf、CH2=CR4CR4=CFRfDeng.
In above-mentioned formula, RfRepresent fluoroalkyl, R4Represent hydrogen atom, halogen atom or methyl in addition to fluorine atom, R5It represents
The divalent organic group of singly-bound or carbon number 1~6, R6Represent the divalent organic group of carbon number 1~6.
As Rf, be preferably carbon number 4~8 perfluoroalkyl or carbon number 4~10 containing the complete of etheric oxygen atom
The perfluoroalkyl of the perfluoroalkyl of fluoroalkyl, more preferably carbon number 4~8, particularly preferably carbon number 6.
As R4The halogen atom of expression is preferably chlorine atom.
As R5And R6, it is preferably to it is alkylidene.As R5、R6Concrete example ,-CH can be included2-、-CH2CH2-、-CH
(CH3)-、-CH2CH2CH2-、-C(CH3)2-、-CH(CH2CH3)-、-CH2CH2CH2CH2-、-CH(CH2CH2CH3)-、-CH2(CH2)3CH2-、CH(CH2CH(CH3)2)-etc..
Above-mentioned polymerizable monomer can be used singly or in combination of two or more.
Polymer (C2) includes the above-mentioned unit with the side chain containing fluorine atom and the unit with blocked isocyanate base.
Polymer (C2) is by with blocked isocyanate base, so as to as refuse ink agent or containing being store in photosensitive polymer combination
During Tibetan, storage-stable can be improved.And then by heating to unseal it and forming isocyanate group during use, so as to poly-
The reactivity raising of object (C2) is closed, is improved with other ingredients, the associativity of other materials, adaptation.As a result, by partition wall bag
The opening portion enclosed inhibits the wetting autgmentability of the residue damage ink of photosensitive polymer combination, makes ink affinity good.
As blocked isocyanate base, the group (1) shown in above-mentioned formula (1) can be included.It is as described above, wherein preferably different
Cyanic acid ester group and blocked isocyanate base obtained from pyrazoles or oximes reaction, obtained from particularly preferably being reacted with pyrazoles
Blocked isocyanate base.
As with olefinic double bond and with the monomer of blocked isocyanate base, CH can be included2=CR4COOR5-NHC
(=O)-B etc..In the formula, R4And R5For with R during monomer with fluoroalkyl4And R5Identical meaning, B be in formula (1)
Meaning identical B.
As CH2=CR4COOR5- NHC (=O)-B specifically, can include the monomer shown in following formula (m1) under
State the monomer shown in formula (m2).
Polymer (C2) in addition to fluorine-containing atomic unit and the unit of base containing blocked isocyanate, can also possess selected from by
Unit with acidic-group, the unit with olefinic double bond, the unit with hydroxyl and the unit group with polyoxyalkylene chain
Into group at least one kind of unit.
From the perspective of alkali solubility is good, polymer (C2) is preferably the polymer with acidic-group.
As acidic-group, at least one kind of acidic groups being preferably selected from the group being made of carboxyl, phenolic hydroxyl group and sulfo group
Group or its salt.
From with photocrosslinking reaction, curing in the manufacturing process for the cured film for forming photosensitive polymer combination curing
The upper layer part of film bonds together or is bonded with other ingredients with olefinic double bond contained by photosensitive polymer combination, so as to
From the perspective of the stationarity that polymer (C2) can be improved, polymer (C2) is preferably the polymer with olefinic double bond.
It is preferably (methyl) acryloxy, ethenylphenyl, pi-allyl, ethylene as the group with olefinic double bond
Base, norborny, particularly preferably (methyl) acryloxy.
Preferably, olefinic double bond imports after polymer is formed and polymer (C2) is made.Olefinic double bond is in monomer
It reacts during polymerization, therefore usually can not the polymer with olefinic double bond only be manufactured by the polymerization of monomer.It is at this point, logical
The polymerization for crossing monomer manufactures the polymer with reactive sites such as hydroxyls, then makes to have an olefinic double bond and can be with polymer
The compound of reactive site bonding is reacted, so as to manufacture the polymer with olefinic double bond.Specifically, such as manufacture is wrapped
Polymer containing the unit with the side chain containing fluorine atom, the unit with blocked isocyanate base and the unit with hydroxyl,
Then react isocyanates (methyl) alkyl acrylate, the polymer (C2) with olefinic double bond can be manufactured.
Polymer (C2) can also have hydroxyl, polyoxy alkylidene.
Polyoxy alkylidene, hydroxyl do not have photocrosslinking reaction, but with polyoxy alkylidene, hydroxyl polymer (C2) and with
It is similary during olefinic double bond, in the manufacturing process of cured film upper layer part bond together or with photosensitive polymer combination contained by
Other ingredients bonding, so as to improve the stationarity of polymer (C2).In addition, hydroxyl can also be as described above as polymerization
The reactive site of object functions.Among polyoxy alkylidene, polyoxyethylene groups have hydrophily, therefore are also improved to developer solution
Wetability effect.
Polymer (C2) can include one or more of acidic-group, olefinic double bond, hydroxyl and polyoxy alkylidene.Also may be used
To include two or more in these groups in 1 side chain of polymer.For example, it is also possible in the end key of polyoxy alkylidene
Conjunction has hydroxyl.
As the introduction method of above-mentioned group, preferably make the monomer with fluoroalkyl, the list with blocked isocyanate base
Body and the method that there is the monomer of above-mentioned group to be copolymerized.In addition, by make to have the polymer of reactive site with it is appropriate
Above-mentioned group, can also imported into polymer by the various method of modifying of compound reaction.
As the concrete example of the monomer with carboxyl, the monomer with phenolic hydroxyl group and the monomer with sulfo group, can enumerate
Go out WO2014/046209 such as the substance described in paragraph [0092], [0093] and [0094].
As importing the method for carboxyl to the polymer with reactive site, such as (1) can be included make that there is hydroxyl
The method of polymer and anhydride reaction, (2) make the polymer of the unit with the acid anhydrides comprising olefinic double bond and with hydroxyls
Method of compound reaction etc..
As the concrete example of the monomer with hydroxyl, note in such as paragraph [0096] of WO2014/046209 can be included
Substance of load etc..
Monomer with hydroxyl can also be the monomer with polyoxyalkylene chain that end is hydroxyl.
For example, can include WO2014/046209 such as the substance described in paragraph [0097].
As acid anhydrides, can include WO2014/046209 such as the substance described in paragraph [0098].
As the compound with hydroxyl, to have the compound of 1 or more hydroxyl, such as can include
WO2014/046209 such as the substance described in paragraph [0099].
Can also use not hydroxyl and acidic-group and with polyoxy alkylidene monomer, such as following formula (POA-1) or
(POA-2) monomer shown in.
CH2=CR71-COO-W-(R72-O)K4-R73…(POA-1)
CH2=CR71-O-W-(R72-O)K4-R73…(POA-2)
(R71For hydrogen atom, chlorine atom, bromine atoms, iodine atom, cyano, the alkyl of carbon number 1~20, the virtue by carbon number 7~20
Alkyl, the aryl of carbon number 6~20 or the cycloalkyl of carbon number 3~20 of base substitution.
R72For the alkylidene of carbon number 1~5.R73For the alkyl of carbon number 1~4.W is singly-bound or carbon number is 1~10
The divalent organic group without fluorine atom.K4 is 6~30 integer.)
In addition, monomer and reaction according to well known to desired composition come appropriate select, so as to obtain possessing with fluorine
The side chain of atom and blocked isocyanate base, and there is acidic-group, olefinic double bond, hydroxyl and polyoxy alkylidene as needed
Polymer (C2).
It should be noted that the at this point, it is preferred that so that content of the fluorine atom and blocked isocyanate base in polymer (C2)
Carry out the compounding ratio of monomer used in appropriate adjust as the mode of above-mentioned preferred scope.
The main chain of polymer (C2) is served as reasons-Ph-CH2- repetitive unit formed phenolic varnish type main chain when, usually may be used
So that possess in the benzene skeleton (Ph) for forming main chain the side chain with fluorine atom and the side chain with blocked isocyanate base,
Optionally the polymer of the group with acidic-group, the group with olefinic double bond, oxyalkylene etc. is bonded with as polymer
(C2).The above-mentioned side chain with fluorine atom is preferably the optional fluoroalkyl containing etheric oxygen atom and/or with optionally containing ether
The side chain of the fluoroalkyl of property oxygen atom.On acidic-group, there is group, the oxyalkylene etc. of olefinic double bond, can include with
It is described above there is the main chain as obtained from the polymerization of the monomer comprising olefinic double bond polymer (C2) it is similary
Group.
It should be noted that at this time it is also preferred that so that the content of the fluorine atom and blocked isocyanate base in polymer (C2)
MOLECULE DESIGN is carried out to polymer (C2) as the mode of above-mentioned preferred scope.
This polymer (C2) can be by the way that the monomer polymerization for being imported with above-mentioned each group in benzene skeleton in advance be made
It makes, it can also be by obtaining with reactive site, specifically hydroxyl, amino, sulfydryl, sulfonic group, carboxylic acid group, carbonyl, alkene
After the polymer for belonging to double bond etc., make the reactive site and the method for modifying of appropriate compound reaction, by above-mentioned each group
It imported into polymer.
[negative light-sensitive resin combination]
The negative light-sensitive resin combination of the present invention, which contains the alkali soluble resins with photo-curable, (hereinafter also referred to be set
Fat (AP)) or alkaline soluble monomers (hereinafter also referred to monomer (AM)) with photo-curable, and contain Photoepolymerizationinitiater initiater and upper
State refuse ink agent (C).The negative light-sensitive resin combination of the present invention is used as refuse ink agent by containing refuse ink agent (C), so as to store
When having good stability, and manufacturing partition wall using it, partition wall upper surface has excellent good refuse ink, and opening portion has good
Ink affinity.
The negative light-sensitive resin combination of the present invention is further as needed containing black colorant, crosslinking agent, solvent
And other optional members.
Hereinafter, illustrated for each ingredient contained by the negative light-sensitive resin combination of the present invention.
It is preferably the photoresist in 1 molecule with acidic-group and olefinic double bond as resin (AP).Pass through resin
(AP) there is olefinic double bond in the molecule, so that the exposure portion of negative light-sensitive resin combination by Photoepolymerizationinitiater initiater by being produced
Raw free radical is polymerize and is cured.
Such cured exposure portion will not be removed by alkaline developer.In addition, there is acidity in the molecule by resin (AP)
Group can be optionally removed the non-exposed portion of uncured negative light-sensitive resin combination with alkaline developer.As a result,
Cured film can be made to become the form of partition wall for the shape that predetermined region is separated into multiple subregions.
As acidic-group, carboxyl, phenolic hydroxyl group, sulfo group and phosphate etc. can be included, they can be used alone 1
Kind, two or more can also be applied in combination.
As olefinic double bond, (methyl) acryloyl group, pi-allyl, vinyl, ethyleneoxy and ethyleneoxy can be included
Alkyl etc. has the double bond of polyaddition.They can be used singly or in combination of two or more.Need what is illustrated
It is that part or all of hydrogen atom possessed by olefinic double bond can be substituted by alkyl such as methyl.
As resin (AP), the resin for possessing the side chain with acidic-group and the side chain with olefinic double bond can be included
(AP-1) and on epoxy resin resin (AP-2) of acidic-group and olefinic double bond etc. has been imported.They can be used alone 1
Kind, two or more can also be applied in combination.
As resin (AP-1), the second for possessing the side chain with acidic-group and the side chain with olefinic double bond can be included
Ene based resins etc..
As resin (AP-2), epoxy resin of sening as an envoy to can be enumerated with making after the compound reaction with carboxyl and olefinic double bond
Resin etc. obtained from polybasic carboxylic acid or its anhydride reactant.It as used epoxy resin, is not particularly limited, can use and make
The conventionally known epoxy resin that is used for the main chain of negative photosensitive resin, such as International Publication No. 2010/013816
Epoxy resin Deng described in.
In addition, as resin (AP), preferred acid number is 10~300mgKOH/g, particularly preferably 30~150mgKOH/g.
In addition, number-average molecular weight (Mn) is preferably 5 × 102~2 × 104, particularly preferably 2 × 103~1.5 × 104.In addition, matter is divided equally
Son amount (Mw) is preferably 1 × 103~4 × 104, particularly preferably 3 × 103~2 × 104。
As resin (AP), from the stripping of cured film when can inhibit development and the pattern of high-resolution point is obtained
The good viewpoint of linearity of pattern when viewpoint, point are linear is easy to get from the perspective of smooth curing film surface,
It is preferable to use resin (AP-2).
As monomer (AM), such as it is preferable to use the monomers (AM-1) with acidic-group and olefinic double bond.Acidic-group
It is similary with olefinic double bond and resin (AP).The acid value of monomer (AM) is preferably also and resin (AP) same scope.
As monomer (AM-1), 2,2,2- tri- acryloyloxymethyl ethyl phthalic acids etc. can be included.
Contained resin (AP) and monomer (AM) can be used alone respectively in negative light-sensitive resin combination,
Two or more can be applied in combination.
The content ratio of resin (AP) in all solids ingredient in negative light-sensitive resin combination and monomer (AM)
Content ratio be respectively preferably 5~80 mass %.It, should when negative light-sensitive resin combination does not contain aftermentioned black colorant
Content is particularly preferably 30~70 mass %.When negative light-sensitive resin combination contains aftermentioned black colorant, the content is special
It You Xuanwei not 10~60 mass %.When content ratio is above range, the photo-curable of negative light-sensitive resin combination and aobvious
Shadow is good.
(Photoepolymerizationinitiater initiater)
Photoepolymerizationinitiater initiater in the present invention does not have as long as having the function of as the compound of Photoepolymerizationinitiater initiater
Especially limitation, the compound preferably generated free radicals by light.
As Photoepolymerizationinitiater initiater, it can include and be classified as α-diones, acyloin class, acyloin ethers, thioxanthene ketone class, two
The various compounds of Benzophenone class, acetophenones, quinones, aminobenzoic acids, peroxide, oxime esters, aliphatic amine etc..
Among Photoepolymerizationinitiater initiater, benzophenone, aminobenzoic acids and aliphatic amine trigger with other free radicals
When agent is used together, sensitization effect is shown sometimes, is preferred.
As Photoepolymerizationinitiater initiater, preferably it is classified as 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- of acetophenones
Morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butane -1- ketone, it is classified as oxime esters
1,2- acetyl caproyls 1- [4- (thiophenyl) -2- (O- benzoyls oxime)], ethyl ketone 1- [9- ethyls -6- (2- methyl benzoyls) -
9H- carbazole -3- bases] -1- (O- acetyl oxime), it is classified as the 2,4- diethyl thioxanthones of thioxanthene ketone class.And then particularly preferably it
Combination with benzophenone such as 4,4 '-bis- (diethylaminos) benzophenone.
Photoepolymerizationinitiater initiater can be used singly or in combination of two or more.
The content ratio of the Photoepolymerizationinitiater initiater in all solids ingredient in negative light-sensitive resin combination is preferably
0.1~50 mass %, more preferably 0.5~30 mass %.Negative light-sensitive resin combination does not contain aftermentioned black colorant
When, which is particularly preferably 5~15 mass %.When negative light-sensitive resin combination contains aftermentioned black colorant, this contains
Amount is particularly preferably 2~12 mass %.Content ratio be above range when, the photo-curable of negative light-sensitive resin combination and
Developability is good.
(refuse ink agent (C))
The refuse ink agent (C) of the present invention has fully to be migrated during photosensitive polymer combination is used to form partition wall
To upper surface, to the function of the good good refuse ink of upper surface imparting of the partition wall of gained.In addition, refuse ink agent (C) is included in sense
When being stored in photosensitive resin composition, storage-stable can be improved.And then when in use by heating to unseal and be formed different
Cyanic acid ester group so as to the reactivity raising of refuse ink agent (C), is improved with other ingredients, the associativity of other materials, adaptation.By
This, the residue for inhibiting photosensitive polymer combination in the opening portion surrounded by partition wall interferes the wetting autgmentability of ink, makes ink-receptive
Property is good.
The content ratio of refuse ink agent (C) in all solids ingredient in negative light-sensitive resin combination is preferably 0.01
~15 mass %, more preferably 0.01~5 mass %, particularly preferably 0.03~1.5 mass %.Content ratio is above range
Lower limiting value more than when, the upper surface of the cured film formed by negative light-sensitive resin combination has excellent good refuse ink.For
When below the upper limit value of above range, the adaptation of cured film and substrate becomes good.
(black colorant)
The minus photosensitive composite of the present invention contains black colorant according to purposes when assigning light-proofness to partition wall
Agent.When colorant is compounded in the minus photosensitive composite containing existing refuse ink agent, the good refuse ink of partition wall upper surface becomes
Insufficient or opening portion ink affinity is obtained to become inadequate.By using the refuse ink agent (C) of the present invention, even if having in compounding
During toner, the above problem will not occur, the good good refuse ink of partition wall upper surface and the ink affinity of opening portion can be taken into account.
Particularly using main chain for hydrocarbon chain and the polymer with the side chain containing fluorine atom is as during refuse ink agent, using containing having
When the minus of toner makes partition wall with photosensitive composite, often the ink affinity of opening portion is difficult to deserve to be called abundant.Using poly-
Object (C2) is closed as the refuse ink agent (C) of the present invention when preparing minus photosensitive composite, the parent of the opening portion can be solved
The problem of ink, obtains the partition wall of opening portion and upper surface with abundant good refuse ink with abundant ink affinity.
As black colorant, can include carbon black, nigrosine, anthraquinone system black pigment, be black pigment, it is specific and
Say C.I. pigment blacks 1,6,7,12,20,31 etc..As black colorant, red pigment, blue pigment, green can also be used
The mixture of the organic pigments such as pigment, yellow uitramarine, inorganic pigment.As the concrete example of organic pigment, C.I. face can be included
Material basket 15：6th, paratonere 254, pigment green 36, pigment yellow 150, azomethine series pigments etc..As black colorant, from electric spy
Preferred organic pigment from the perspective of property, from price and the preferred carbon black of light-proofness viewpoint.Carbon black is preferably carried out with resin etc.
Surface treatment, in addition, in order to adjust tone, can be applied in combination blue pigment, violet pigment.
As organic pigment, from the perspective of the shape of black matrix", the specific surface area preferably measured by BET method is 50
~200m2/g.Specific surface area is 50m2During/more than g, black matrix" shape is not easily deteriorated.For 200m2During/below g, dispersing aid
Organic pigment will not be exceedingly adsorbed in, a large amount of dispersing aiies need not be compounded in order to show each physical property.
In addition, average 1 grain size observed by transmission electron microscope of organic pigment be preferably 20~
150nm.When average 1 grain size is more than 20nm, it can be scattered in minus photosensitive composite, be easy to get with high concentration
The good minus photosensitive composite of ageing stability.For below 150nm when, partition wall shape is not easily deteriorated.In addition, by saturating
Average 2 grain sizes that emitting electron microscope observation obtains are preferably 80~200nm.
Minus with the content ratio of the black colorant in all solids ingredient in photosensitive composite be preferably 20~
65 mass %, more preferably 25~60 mass %, particularly preferably 30~60 mass %.Content ratio is the lower limit of above range
When more than value, value, that is, optical concentration for representing the light-proofness of the light of the partition wall of gained becomes abundant.For above range
When below upper limit value, the curability of minus photosensitive composite becomes good, can obtain the cured film of good appearance, refuses ink
Property also becomes good.
In order to improve dispersiveness of the black colorant in minus photosensitive composite, alkaline macromolecule point is preferably comprised
Powder or acid macromolecule dispersing agent.The amine value of the alkalescence macromolecule dispersing agent be preferably 10~100mgKOH/g, particularly preferably
For 30~70mgKOH/g.The acid value of the acidity macromolecule dispersing agent be preferably 30~150mgKOH/g, particularly preferably 50~
100mgKOH/g.The macromolecule dispersing agent is preferably to have basic functionality from the perspective of the compatibility to black colorant
Compound.As the basic functionality, when having primary amino radical, secondary amino group or tertiary amino, dispersiveness is especially excellent.
As macromolecule dispersing agent, carbamate system, polyimides system, alkyd system, epoxy, unsaturation can be included
Polyester, melamine series, phenol system, acrylic compounds, vinyl chloride, Chlorovinyl-acetate vinyl based copolymer system, polyamide
The compound of system, polycarbonate-based etc..Wherein particularly preferred carbamate system, the compound of Polyester.
The dosage of macromolecule dispersing agent is preferably 5~30 weight %, particularly preferably 10~25 compared with black colorant
Weight %.When dosage is more than the lower limiting value of above range, the scattered of black colorant becomes good, is the upper limit of above range
When value is following, developability becomes good.
(crosslinking agent)
The crosslinking agent optionally contained in the negative light-sensitive resin combination of the present invention is to have 2 or more alkene in 1 molecule
Belong to double bond and the compound without acidic-group.Crosslinking agent is included by negative light-sensitive resin combination, during so as to expose
Negative light-sensitive resin combination curability improve, can also form cured film even if with low light exposure.
As crosslinking agent, can include WO2014/046209 such as the substance described in paragraph [0137].
From the perspective of photoreactivity, multiple olefinic double bonds are preferably had.For example, it is preferable to pentaerythrite four (methyl) third
Olefin(e) acid ester, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol
Five (methyl) acrylate, (methyl) acrylate of ethoxylation isocyanuric acid three and urethane acrylate etc..
Crosslinking agent can be used singly or in combination of two or more.
The content ratio of the crosslinking agent in all solids ingredient in negative light-sensitive resin combination is preferably 10~60
Quality %.When negative light-sensitive resin combination is free of black colorant, which is particularly preferably 20~55 mass %.Minus
When photosensitive polymer combination contains black colorant, which is particularly preferably 5~50 mass %.
(solvent)
The negative light-sensitive resin combination of the present invention reduces viscosity by containing solvent, so as to negative photosensitive resin
Coating of the composition on substrate surface becomes easy.As a result, it is possible to form the combination of the negative photosensitive resin of uniform film thickness
The film of object.
As solvent (F), well known solvent can be used.Solvent can be used alone, and can also be applied in combination 2 kinds
More than.
As solvent, aklylene glycol alkyl ether, aklylene glycol alkylether acetates class, alcohols, molten can be included
Agent naphthas etc..Wherein, it is preferably selected from by aklylene glycol alkyl ether, aklylene glycol alkylether acetates class and alcohols
At least one kind of solvent in the group of composition is further preferably selected from by propylene glycol methyl ether acetate, propylene glycol monomethyl ether, diethyl
At least one kind of solvent in the group of alcohol ethyl methyl ether and 2- propyl alcohol composition.
The content ratio of solvent in negative light-sensitive resin combination is preferably 50~99 matter compared with total composition
Measure %, more preferably 60~95 mass %, particularly preferably 65~90 mass %.
(other ingredients)
The present invention negative light-sensitive resin combination can also contain as needed one kind or two or more thermal cross-linking agent,
Dispersing aid, silane coupling agent, particle (filler), phosphate cpd, curing accelerator, thickener, plasticizer, antifoaming agent, stream
Other additives such as flat agent, antishrinking agent and ultra-violet absorber.
Above-mentioned each ingredient of specified amount can be obtained by mixing by the negative light-sensitive resin combination of the present invention.
The negative light-sensitive resin combination of the present invention improves the refuse ink agent (C) of storage-stable due to containing,
With good storage-stable.During using negative light-sensitive resin combination of the invention, obtained partition wall is in upper table
Face has good good refuse ink, and the opening portion surrounded by partition wall has good ink affinity.
[partition wall]
The present invention partition wall be created as by substrate surface be separated into it is multiple for formed point subregions it is shape, by
The partition wall that the solidfied material of the negative light-sensitive resin combination of the invention described above is formed.Partition wall can for example obtain as follows：
In the negative light-sensitive resin combination of the surface of the substrates such as the substrate coating present invention, it is dried to remove solvent as needed
Deng after, implement masking to becoming to be formed the part of subregion of point, develop after exposure, then heated, so as to
It arrives.
It is removed, is formed together with partition wall and the subregion for formation point and non-exposed part by masked by developing
Corresponding opening portion.When forming partition wall, the refuse ink agent (C) contained by negative light-sensitive resin combination occurs upper surface and moves
It moves, becomes the layer of ink of refusing on the upper strata of partition wall and exist with high concentration.And then pass through heating, the sealing end isocyanic acid of refuse ink agent (C)
Ester group is unsealed as isocyanate group, is firmly fixed at and is refused layer of ink.And then even if non-exposed part is not complete by developing
It removes and locally lies in when opening portion, refuse ink agent (C) can also be fixed on substrate surface, it is ensured that the ink affinity of opening portion.
Therefore, the substrate as the partition wall for forming the present invention, it is preferred that at least to form a side surface of partition wall
With the functional group possessed with the reactivity of isocyanate group reaction, such as hydroxyl, amino, carboxyl, sulfydryl etc..This is because
Possess the functional group for the reactivity reacted with isocyanate group by the substrate surface for the one side for making partition wall to be formed,
Substrate surface and the adaptation of refuse ink agent (C) improve in opening portion, even if having the residual of photosensitive polymer combination in opening portion
During slag, the ink affinity of opening portion is also ensured that.
As the above-mentioned material possessed with the surface of the functional group of the reactivity of isocyanate group reaction is formed, specifically
For, glass, metal oxide, organic film etc. can be included.As metal oxide, can include tin-doped indium oxide (ITO),
Antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO), gallium-doped zinc oxide (GZO) etc..In addition, for example have
Have in the case that surface of metal electrode etc. is formed with the surface of metal oxide, can be included in and above-mentioned possess and isocyanide
In the surface of the functional group of the reactivity of perester radical reaction.
Hereinafter, an example of the manufacturing method of the partition wall of embodiments of the present invention is illustrated using Figure 1A~1D, but is divided
The manufacturing method in next door is not limited to following.It should be noted that following manufacturing method is with negative light-sensitive resin combination
Form containing solvent (F) illustrates.
As shown in Figure 1A, negative light-sensitive resin combination is coated in a main surface whole face of substrate 1, forms film
21.At this point, refuse ink agent (C) is integrally dissolved and is evenly dispersed in film 21.It should be noted that in Figure 1A schematically
Refuse ink agent (C) is shown, is actually not existed with this grain shape.
Then, as shown in Figure 1B, dry film 21, desciccator diaphragm 22 is made.As drying means, it is dry that heating can be included
It is dry, be dried under reduced pressure with vacuum drying under reduced pressure etc..Although also different due to the species of solvent, in the case of heat drying, heating temperature
Degree is preferably 50~120 DEG C.Warm-up time is preferably 30 seconds~5 minutes or so.
In the drying process, refuse ink agent (C) is migrated to the upper layer part of desciccator diaphragm.It should be noted that in negative photosensitive
Property resin combination be free of solvent when, similarly reach in film refuse ink agent (C) upper surface migration.
Then, as shown in Figure 1 C, across the shelter 31 with the comparable shape in opening portion with being surrounded by partition wall
Photomask 30 is exposed 22 irradiation light of desciccator diaphragm.Film after being exposed to desciccator diaphragm 22 is known as exposed film 23.It exposes
In light film 23, photocuring has occurred in exposure portion 23A, and non-exposed portion 23B is and 22 same state of desciccator diaphragm.
As the light of irradiation, visible ray can be included；Ultraviolet light；Far ultraviolet；KrF excimer laser, ArF quasi-molecules swash
Light, F2Excimer laser, Kr2Excimer laser, KrAr excimer laser and Ar2The excimer laser such as excimer laser；X-ray；
Electron beam etc..
As the light irradiated, the light of the light of 100~600nm of optimal wavelength, more preferably 300~500nm, particularly preferably
Include the light of i rays (365nm), h rays (405nm) or g rays (436nm).Alternatively, it is also possible to clip 330nm as needed
Following light.
As Exposure mode, can include whole face expose together, scan exposure etc..Same position can be performed in multiple times
Exposure.At this point, multiple conditions of exposure can be the same or different.Light exposure is both preferably in above-mentioned arbitrary Exposure mode
Such as 5~1000mJ/cm2, more preferably 5~500mJ/cm2, further preferably 5~300mJ/cm2.It should be noted that
Light exposure is appropriate excellent according to thickness of the wavelength of the light irradiated, the composition of negative light-sensitive resin combination and film etc.
Change.
The time for exposure of per unit area is not particularly limited, according to the exposure power of used exposure device and required
Light exposure etc. design.It should be noted that in the case of scan exposure, the time for exposure is obtained by the sweep speed of light.Often
The time for exposure of unit area is usually 1~60 second or so.
Then, as shown in figure iD, the development using alkaline developer is carried out, is formed only by the exposure portion 23A with exposed film 23
The partition wall 4 that corresponding position is formed.The opening portion 5 surrounded by partition wall 4 is that once there are non-exposed portions in exposed film 23
The position of 23B will be shown in Fig. 1 D by the state after the removal non-exposed portion 23B that develops.Non-exposed portion 23B is as described above
It is migrated in refuse ink agent (C) to upper layer part, it is more molten with alkaline developer in the state of refuse ink agent (C) than there's almost no in its layer on the lower
It solves and removes, therefore the upper surface of obtained partition wall has good good refuse ink.
It should be noted that in the partition wall 4 shown in Fig. 1 D, the top layer including its upper surface is to refuse layer of ink 4A.It refuses
When black agent (C) possesses the side chain of olefinic double bond, in exposure, refuse ink agent (C) is directly present in top layer with high concentration
And it is formed and refuses layer of ink.More specifically, during exposure, the resin (AP) or monomer (AM) that are present in around refuse ink agent (C) and appoint
The photocuring ingredient in addition contained photocuring securely is selected, layer of ink is refused so as to which refuse ink agent (C) is fixed on.
Refuse ink agent (C) have olefinic double bond when, refuse ink agent (C) occur each other photocuring and/or with resin (AP) or monomer
(AM), photocuring occurs together for other photocuring ingredients, formed be securely joined with refuse ink agent (C) refuse layer of ink 4A.
In the case of any of the above-described kind, mainly contain by resin (AP) or monomer (AM) and optionally refusing the downside of layer of ink 4A
The distribution third contact of a total solar or lunar eclipse that is light-cured into of some in addition cures, so as to form the layer 4B for being practically free of refuse ink agent (C).
After development, partition wall 4 is further heated.Heating temperature be set to refuse ink agent (C) blocked isocyanate base deblocking and
It is more than the temperature for generating isocyanate group.Although also different due to the species of blocked isocyanate base possessed by refuse ink agent (C),
Heating temperature can be set to about 150~250 DEG C, preferably 200~250 DEG C.Warm-up time is preferably 20~70 minutes or so.
By heating, the blocked isocyanate base of refuse ink agent (C) unseals and forms isocyanate group, and refuse ink agent (C) is more firm
Admittedly be fixed on and refuse in layer of ink 4A.In addition, by heating, the curing of partition wall 4 becomes more securely.
And then non-exposed part is not removed completely sometimes through above-mentioned development, it is micro in opening portion and local with residue
Form there are non-exposed portion 23B.Even in this case, ink will be refused also by the effect of the isocyanate group unsealed
Agent (C) is fixed on substrate surface, it is ensured that the ink affinity of opening portion.
Even if the partition wall 4 of the so obtained present invention, when being exposed with low light exposure, upper surface also has good
Good refuse ink.In addition, in partition wall 4, after development, heating, the hydrophily of opening portion 5 is good, can substantially ensure Mo Xiangkai
The uniform coating of oral area 5.
It should be noted that for the purpose for the ink affinity for more reliably obtaining opening portion 5, in order to be gone after above-mentioned heating
Development residue except the negative light-sensitive resin combination for being likely to be present in opening portion 5 etc., can be to the substrate 1 with partition wall 4
Implement ultraviolet light/ozone treatment.
The partition wall such as preferable width formed by the negative light-sensitive resin combination of the present invention is less than 100 μm, spy
It You Xuanwei not be less than 20 μm.In addition, the distance between adjacent partition wall (width of pattern) is preferably less than 300 μm, especially
Preferably less than 100 μm.The highly preferred of partition wall is 0.05~50 μm, particularly preferably 0.2~10 μm.
The partition wall of the present invention may be used as regarding its opening portion as black injection region when carrying out pattern printing by IJ methods
The partition wall in domain.When carrying out pattern printing by IJ methods, if the partition wall of the present invention noted with its opening portion and desired ink
Enter the consistent mode in region to be formed and used, then since partition wall upper surface has good good refuse ink, ink can be inhibited
It crosses partition wall and is injected into undesirable opening portion i.e. ink injection zone.In addition, by partition wall surround opening portion by
It is good in the wetting autgmentability of ink, therefore ink can be equably printed to desired region without blank etc. occurs.
During using partition wall of the invention, as described above, the printing of the pattern based on IJ methods can be carried out fine.Therefore,
The partition wall of the present invention as to be formed by IJ methods point, in substrate surface with multiple points and between adjacent point
The partition wall of the optical element of partition wall is useful.
[optical element]
The optical element of the present invention is that have multiple points and the invention described above between adjacent point in substrate surface
Partition wall optical element.In the optical element of the present invention, point is preferably formed by IJ methods.
Hereinafter, to be illustrated in case of the optical element of embodiments of the present invention is made by IJ legal systems.It needs
Illustrate, the manufacturing method of optical element of the invention is not limited to following.
Fig. 2A~2B schematically shows using the partition wall 4 formed on the substrate 1 shown in above-mentioned Fig. 1 D to manufacture
The method of optical element.Herein, the partition wall 4 on substrate 1 is the pattern with opening portion 5 and the point for the optical element for wanting manufacture
What consistent mode was formed.
As shown in Figure 2 A, in the opening portion 5 surrounded by partition wall 4, ink 10 is added dropwise from ink gun 9, injects and advises to opening portion 5
Quantitative ink 10.As ink, well known ink in optical element purposes is correspondingly suitably selected with the function of point.
Then, according to used black 10 species, for example, removal, curing for solvent and implement dry and/or add
The processing such as heat as shown in Figure 2 B, obtain the optical element 12 that desired point 11 is formed in the form of being adjacent to partition wall 4.
The optical element of the present invention is by using the partition wall of the present invention, and in the fabrication process, ink can be by partition wall
The opening portion being separated into equably soaks extension, uneven without occurring, and thus has the point precisely formed.
As optical element, organic EL element, the colour filter of liquid crystal cell and tft array element, quantum dot can be included
Display, thin-film solar cells etc..
Tft array element refers to following element：Multiple points are configured to overlook rectangular, and each point is provided with pixel electrode
With as driving the TFT of its switch element.
Tft array element can be provided in as tft array substrate in organic EL element or liquid crystal cell etc..
Tft array can for example manufacture as follows, but be not limited to this.
Using sputtering method etc. the grids such as aluminium, its alloy is made to form a film on the light-transmitting substrates such as glass.The grid is as needed
And it is patterned.
Then, the gate insulating films such as silicon nitride are formed using plasma CVD method etc..Can also on gate insulating film shape
Into source electrode, drain electrode.Source electrode and drain electrode by vacuum evaporation, sputtering such as can form aluminium, gold, silver, copper, their alloy
Metallic film make.As the method for making source electrode and drain pattern, there is following method：After forming metallic film, apply
Dress resist layer is simultaneously exposed, develops, and is wanting to form the part of electrode residual resist layer, then, dew removing is being gone with phosphoric acid, chloroazotic acid etc.
The metal gone out, finally removes resist layer.In addition, formed gold when metallic film when, also have following method：Advance application resists
Erosion layer is simultaneously exposed, develops, and resist layer is remained in the part for being not desired to be formed electrode, after then forming metallic film, by metal
Film removes together with photoresist layer.Metal nano colloid alternatively, it is also possible to use silver, copper etc. etc. passes through the side such as ink-jet
Method forms source electrode and drain electrode.
Then, using the present invention composition, using including coating, exposed and developed photoetching process, along the wheel of each point
Exterior feature forms partition wall to overlook clathrate.
Then, solution is dried, is consequently formed semiconductor layer using IJ method coating semiconductor solution in point.As this
Semiconductor solution can also use solutions of organic semiconductors, inorganic application type oxide semiconductor solution.Source electrode, drain electrode
Can after the semiconductor layer is formed use ink-jet the methods of and formed.
Finally, using sputtering method etc. the optically transparent electrodes such as ITO is made to form a film, the protective films such as silicon nitride is made to form a film, are consequently formed.
Organic EL element can for example manufacture as follows.
The optically transparent electrode for making tin-doped indium oxide (ITO) etc. using sputtering method etc. on the light-transmitting substrates such as glass forms a film.
The optically transparent electrode is patterned as needed.
Then, using the negative light-sensitive resin combination of the present invention, using including coating, exposed and developed photoetching
Method forms partition wall along the profile of each point to overlook clathrate.
Then, be respectively coated using IJ methods in point hole injection layer, hole transporting layer, luminescent layer, hole trapping layer and
The material of electron injecting layer and drying stack gradually these layers.The type and quantity for being formed at the organic layer in a little can be appropriate
Design.
Finally, the reflecting electrodes such as aluminium are formed using vapour deposition method etc..
In addition, quantum dot displays can for example manufacture as follows, but it is not limited to this.
The optically transparent electrode for making tin-doped indium oxide (ITO) etc. using sputtering method etc. on the light-transmitting substrates such as glass forms a film.
The optically transparent electrode is patterned as needed.
Then, using the negative light-sensitive resin combination of the present invention, using including coating, exposed and developed photoetching
Method forms partition wall along the profile of each point to overlook clathrate.
Then, hole injection layer, hole transporting layer, quantum dot layer, hole trapping layer are respectively coated in point using IJ methods
Material and drying with electron injecting layer, these layers are stacked gradually.The type and quantity for the organic layer being formed in a little can fit
Work as design.
Finally, the reflecting electrodes such as aluminium are formed using vapour deposition method etc..
And then the optical element of embodiments of the present invention can also be applied to for example following blue light manufactured like that and turn
The quantum dot displays remodeled.
Using the composition of the present invention on the light-transmitting substrates such as glass, formed along the profile of each point with overlooking clathrate
Partition wall.
Then, it is coated with to be converted to blue light the nanoparticles solution of green light in point by IJ methods, for will
Blue light is converted to the nanoparticles solution of red light, the color ink of blueness as needed and drying, makes component.Using aobvious
Color for blueness light source as backlight, colour filter is replaced using aforementioned components, so as to obtain the excellent liquid crystal of color reproducibility
Display.
Embodiment
Hereinafter, the present invention is illustrated based on embodiment, but the present invention is from their restriction.Example 1,2,5~8, example 10~16
For embodiment, example 3,4,9, example 17~19 are comparative example.
Each measure is carried out by the following method.
[number-average molecular weight (Mn), matter average molecular weight (Mw)]
By gel permeation chromatography, using polystyrene as standard substance, measure number-average molecular weight (Mn) and matter is divided equally
Son amount (Mw).As gel permeation chromatography, use HPLC-8220GPC (TOSOH Co., Ltd's manufacture).As column, using by 3
Column obtained from shodex LF-604 connections.As detector, RI detectors are used.As standard substance, EasiCal is used
PS1 (manufacture of Polymer Laboratories companies).And then when measuring number-average molecular weight and matter average molecular weight, column is kept
At 37 DEG C, tetrahydrofuran is used as eluent, flow velocity is set to 0.2mL/ minutes, injects 0.5% tetrahydrochysene furan of determination sample
Mutter 40 μ L of solution.
[containing ratio of fluorine atom]
The containing ratio (quality %) of fluorine atom passes through using Isosorbide-5-Nitrae-bis- (trifluoromethyl) benzene as standard substance19F NMR are measured
To calculate.
[content of blocked isocyanate base]
The content of blocked isocyanate base is calculated by the compounding ratio of raw material.
[content of olefinic double bond (C=C)]
The content of olefinic double bond is calculated by the compounding ratio of raw material.
[acid value]
Acid value by raw material compounding ratio theoretical property calculate.
The abbreviation of the compound used in following each example is shown in following.
(alkali soluble resins (AP))
Alkali soluble resins (AP1) composition；Cresol novolak type epoxy resin and acrylic acid are reacted, then with 1,2,
3,6- tetrabydrophthalic anhydrides react, tree obtained from the resin for so having imported acryloyl group and carboxyl is purified with hexane
The composition (70 mass %, PGMEA30 mass % of solid constituent) of fat (alkali soluble resins (A1), acid value 60mgKOH/g).
(Photoepolymerizationinitiater initiater)
IR907；IRGACURE907, trade name, BASF AG's manufacture, 2- methyl-1s-[4- (methyl mercapto) phenyl] -2-
Quinoline is for propane -1- ketone.
OXE02；Trade name；IRGACURE OXE 02, ethyl ketone 1- [9- ethyls -6- (2- methyl benzoyls) -9H- clicks
Azoles -3- bases] -1- (O- acetyl group oxime) (BASF AG's manufacture).
EAB；4,4 '-bis- (diethylamino) benzophenone.
(raw material of polymer (C1))
It is equivalent to the compound (cx-11) of compound (cx-1)；F(CF2)6CH2CH2Si(OCH3)3。
It is equivalent to the compound (cx-21) of compound (cx-2)；By 3- isocyanates propyl-triethoxysilicanes 3,5-
The 50 mass % solution of toluene of compound obtained from dimethylpyrazole (is manufactured by well known method.).
It is equivalent to the compound (cx-31) of compound (cx-3)；Si(OC2H5)4。
It is equivalent to the compound (cx-41) of compound (cx-4)；CH2=CHCOO (CH2)3Si(OCH3)3。
It is equivalent to the compound (cx-51) of compound (cx-5)；(CH3)3-Si-OCH3。
It is equivalent to the compound (cx-61) of compound (cx-6)；HS-(CH2)3-Si(OCH3)3。
(raw material of polymer (C2))
C6FMA；CH2=C (CH3)COOCH2CH2(CF2)6F
MAA；Methacrylic acid
2-HEMA；2-hydroxyethyl methacrylate
PME400；CH2=C (CH3)COO(C2H4O)9CH3
MOI-BP；(trade name, Showa Denko K. K manufacture Karenz MOI-BP, the chemical combination shown in above-mentioned formula (m1)
Object)
MOI-BM；(trade name, Showa Denko K. K manufacture Karenz MOI-BM, the chemical combination shown in above-mentioned formula (m2)
Object)
V-65；(2,2 '-azo is double (2,4- methyl pentane nitriles))
AOI；Karenz AOI (trade name, Showa Denko K. K's manufacture, 2- acryloyloxyethyl isocyanates)
DBTDL；Dibutyl tin laurate
TBQ；Tertiary butyl 1,4-benzoquinone
MEK；2- butanone
(black colorant)
Black colorant (D-1)：PGMEA dispersion liquids (the azomethine system black organic pigment of black organic pigment：12 matter
Measure %, macromolecule dispersing agent：7.2 mass %, PGMEA：80.8 mass %, solid constituent acid value：7.2mgKOH/g).
(crosslinking agent)
DPHA；Dipentaerythritol hexaacrylate
(solvent)
PGMEA；Propylene glycol methyl ether acetate
PGME；Propylene glycol monomethyl ether
[synthesis of polymer (C)]
Such synthetic polymer (C1) and polymer (C2) as described below.In addition, the polymer (Cf) of synthesis comparative example.
(example 1；The synthesis of polymer (C1-1))
Possessing the 300cm of mixer3Three-necked flask in add in compound (cx-11) 3.87g, compound (cx-21)
13.30g, compound (cx-31) 4.16g, compound (cx-51) 1.28g, obtain homogeney of hydrolysable silanes compound mixture.Then,
PGME 71.1g are added in the mixture, and material solution is made.
1% aqueous solution of nitric acid 6.30g is added dropwise in obtained material solution.After completion of dropwise addition, 12 are stirred at 40 DEG C
Hour, obtain PGME solution (polymer (C1-1) concentration of polymer (C1-1)：10 mass %, hereinafter also referred to " polymer
(C1-1) solution ".).
It should be noted that after reaction, the ingredient of reaction solution is measured using gas chromatography, is confirmed as raw material
Each compound to reach detection limit following.
Inventory of raw material hydrolysable silanes compound used in the manufacture of obtained polymer (C1-1) etc. is shown
In table 1.In table 1, silane compound means hydrolysable silanes compound.In addition, the number by obtained polymer (C1-1)
Average molecular weight (Mn), matter average molecular weight (Mw), the containing ratio of fluorine atom, the measurement result of content of C=C are shown in table 1 together.
(example 2~4：Polymer (C1-2) and (Cf-1), the synthesis of (Cf-2))
In addition to being set to shown in table 1 by raw material composition, equally operated with example 1, i.e. in each silane chemical combination shown in table 1
PGME is added in the mixture of object and makes material solution, the aqueous acid shown in dropwise addition table 1 and is stirred thereto in the same manner as example 1
It mixes, it (is compound concentration to obtain polymer (C1-2) and (Cf-1), the solution of (Cf-2)：10 mass %, below also will be each molten
Liquid is known as " polymer (C1-2), (Cf-1), (Cf-2) solution ".).
By polymer obtained above (C1-2) and (Cf-1), (Cf-2) manufacture in the water-disintegrable silanization of raw material that uses
Inventory, the molar ratio for closing object are shown in table 1.In table 1, silane compound means hydrolysable silanes compound.In addition, by gained
The number-average molecular weight (Mn) of the polymer arrived, matter average molecular weight (Mw), the containing ratio of fluorine atom, C=C content measurement result
Table 1 is shown in together.
[table 1]
(example 5；The synthesis of polymer (C2-1))
MEK (466.7g), C6FMA (94.0g), MOI-BP are put into the autoclave for the internal volume 1L for possessing mixer
(66.0g), PME-400 (40.0g) and polymerization initiator V-65 (0.91g) are stirred, in a nitrogen atmosphere on one side while at 50 DEG C
Under make its polymerization 24 it is small when, obtain the solution of polymer (C2-1).The solution of obtained polymer (C2-1) is added in into hexane
Middle progress reprecipitation is dried in vacuo after purification, obtains polymer (C2-1) (169.2g).The number of polymer (C2-1) is divided equally
Son amount is 35900, matter average molecular weight 71600.
(example 6：The synthesis of polymer (C2-2))
In addition to MOI-BP is changed to MOI-BP, is equally operated with synthesis example 5, obtain polymer (C2-2).Polymerization
The number-average molecular weight of object (C2-2) is 34500, matter average molecular weight 72300.
(example 7：The synthesis of polymer (C2-3))
MEK (466.7g), C6FMA (94.0g), 2-HEMA are put into the autoclave for the internal volume 1L for possessing mixer
(46.0), MOI-BP (20.0g), PME-400 (40.0g) and polymerization initiator V-65 (1.2g) are stirred in a nitrogen atmosphere on one side
Mix, while make its polymerize at 50 DEG C 24 it is small when, obtain the solution of polymer (C2-3) precursor.
The solution of above-mentioned polymer (C2-3) precursor is put into the autoclave for the internal volume 1L for possessing mixer
(500.0g), AOI (37.5g), DBTDL (0.15g), TBQ (1.87g) are stirred while that it is made to react 24 at 40 DEG C is small
When, obtain the solution of polymer (C2-3).It is pure that the solution of obtained polymer (C2-3) is added in into progress reprecipitation in hexane
It is dried in vacuo after change, obtains polymer (C2-3) (143.1g).The number-average molecular weight of polymer (C2-3) is 41200, matter
Average molecular weight is 85700.
(example 8 and example 9：The synthesis of polymer (C2-4) and (Cf-3))
In polymer (C2-3), in addition to the proportioning of raw material is changed as shown in table 2, by same anti-
It should come synthetic polymer (C2-4) and (Cf-3).
By the number-average molecular weight (Mn) of the polymer obtained in example 1~4, matter average molecular weight (Mw), fluorine atom containing ratio,
The content of blocked isocyanate base, the content of olefinic double bond, acid value are shown in table 2.
[table 2]
[manufacture of negative light-sensitive resin combination and the manufacture of partition wall]
(example 10；The manufacture of negative light-sensitive resin combination)
By alkali soluble resins (AP1) composition of 12.66g, the polymer of EAB, 1.61g of IR907,1.00g of 1.12g
(C1-1) solution, the PGMEA of A9530,74.7g of 8.96g are put into 200cm3Stirring container in, stirring 3 it is small when, manufacture
Negative light-sensitive resin combination 1.
(manufacture of partition wall)
The glass substrate of 10cm square is subjected to 30 seconds ultrasonic cleanings with ethyl alcohol, then carries out the UV/O of 5 minutes3Place
Reason.UV/O3In processing UV/O is used as using PL2001N-58 (Sen Engineering Co., Ltd. manufacture)3Generating means.
The luminous power (light output) of 254nm conversions is 10mW/cm2。
Glass baseplate surface after above-mentioned cleaning is coated with negative photosensitive resin obtained above using spinner and combines
Object 1, it is then 2 minutes dry on hot plate at 100 DEG C, form the desciccator diaphragm of 2.4 μm of film thickness.For obtained desciccator diaphragm,
Across the photomask that shelter (non-exposed portion) is 2.5cm × 5cm, whole face irradiates the exposure power (exposure of 365nm conversions together
Output) it is 25mW/cm2Ultrahigh pressure mercury lamp UV light (light exposure 250mJ/cm2).During exposure, the light of below 330nm is clipped.
In addition, the spacing distance of desciccator diaphragm and photomask is set to 50 μm.
Then, the glass substrate after above-mentioned exposure-processed is impregnated 40 seconds in 2.38% tetramethylammonium hydroxide aqueous solution
Clock develops, be rinsed with water non-exposed portion and make its drying.Then, it is heated 60 minutes on hot plate with 230 DEG C, by
This obtains partition wall in the form of having the cured film of opening portion corresponding with the shelter of photomask.
Following evaluation is implemented to obtained negative light-sensitive resin combination 1 and partition wall.Evaluation result is shown in
Table 3.
(evaluation)
<The film thickness of partition wall>
Using laser microscope, (Keyence companies manufacture, device name：VK-8500) measure.
<The good refuse ink of partition wall>
The PGMEA contact angles of partition wall upper surface obtained above, the evaluation as good refuse ink are measured by following methods.
By sessile drop method, according to JIS R3257 " base plate glass wettability of the surface test method ", in cured film upper surface
3 at load PGMEA drops, each PGMEA drops are measured.Drop is set to 2 μ L/ drops, measures and is carried out at 20 DEG C.Contact angle by
The average value of 3 measured values is obtained.
<The ink affinity of opening portion>
Opening by partition wall encirclement obtained above is measured by method same with the evaluation method of above-mentioned good refuse ink
The PGMEA contact angles of oral area, the evaluation as ink affinity.
It should be noted that when PGMEA contact angles are 40 degree or more, it may be said that good refuse ink is good.In addition, PGMEA is contacted
When angle is less than 5 degree, it may be said that ink affinity is good.
<The storage-stable of negative light-sensitive resin combination>
Negative light-sensitive resin combination 1 is taken care of 20 days under room temperature (20~25 DEG C).Then, visually to observe minus
The state (transparent or gonorrhoea) of photosensitive polymer combination 1, then operates as described above, manufactures partition wall and cured film (its
In, the size of glass substrate is set to 7.5cm square).It should be noted that in the fabrication process, in the state of film with mesh
Depending on having foreign with laser capture microdissection sem observation film surface.
There is foreign with visual and appearance, the film surface of the obtained partition wall of laser capture microdissection sem observation and cured film, with
The partition wall and cured film formed as described above by the negative light-sensitive resin combination 1 before keeping is (wherein, by glass base
The dimension modifying of plate is 7.5cm square) it is compared, and evaluated according to following benchmark.
◎：Even if with laser microscope and visually observation film, also do not find foreign matter, be with by the negative photosensitive before keeping
Property resin combination formed partition wall and the same appearance of cured film.
○：Can confirm that granular foreign matter during laser capture microdissection sem observation film.
△：Granular foreign matter is can confirm that during film visually to observe.
×：Gonorrhoea occurs for the negative light-sensitive resin combination after keeping.
(example 11~19)
It according to the composition shown in table 3, is operated in the same manner as example 10, the negative photosensitive resin combination of 11~example of Production Example 19
Object.It using obtained negative light-sensitive resin combination, is operated in the same manner as example 10, manufactures partition wall.For obtained
Negative light-sensitive resin combination, partition wall, opening portion operate to be evaluated in the same manner as example 10.Show the result in table 3.
[table 3]
Industrial availability
The refuse ink agent of the present invention such as containing in photosensitive polymer combination in use, in organic EL element, liquid crystal
In the optical elements such as the colour filter and tft array of element, partition wall when carrying out the printing of the pattern based on IJ methods is suitable for forming.
The negative light-sensitive resin combination of the present invention is in organic EL element, the colour filter of liquid crystal cell and tft array etc.
Optical element in, partition wall when can suitably be used as carrying out the pattern printing based on IJ methods forms the combination of purposes etc.
Object.
The partition wall of the present invention may be used as being used to carry out the organic layers such as luminescent layer by IJ methods in organic EL element
The partition wall (dike) or may be used as being used to carry out pattern printing to colour filter by IJ methods in liquid crystal cell that pattern prints
Partition wall (partition wall can double as black matrix" (BM).) etc..
The partition wall of the present invention can also be used as being used for through IJ methods in tft array to conductive pattern or semiconductor pattern
Carry out partition wall of pattern printing etc..
The partition wall of the present invention for example may be used as the organic semiconductor by IJ methods for the channel layer of formation TFT
Layer, grid, source electrode, drain electrode, grid wiring and source wiring etc. carry out partition wall of pattern printing etc..
It should be noted that by the specification of Japanese patent application filed in 9 days June in 2014 2014-118475, power
The full content of sharp claim, summary and attached drawing is quoted so far, is incorporated as a disclosure of the specification of the present invention.
Reference sign
1 ... substrate, 21 ... films, 22 ... desciccator diaphragms, 23 ... exposed films, 23A ... exposure portions, 23B ... non-exposed portions, 4 ...
Partition wall, 4A ... refuse layer of ink, 5 ... opening portions, 31 ... shelters, 30 ... photomasks, 9 ... ink guns, 10 ... ink, 11 ... points,
12 ... optical elements.
Claims (15)
1. a kind of refuse ink agent, is the refuse ink agent that good refuse ink is assigned to the upper surface of partition wall, the partition wall is formed as base
Plate surface is separated into the shape of multiple subregions for formation point, and the point represents that light modulation can be carried out most in optical element
Zonule,
The refuse ink agent is：With fluorine-containing atomic unit, containing can be by heating to unseal the envelope for generating isocyanate group
The unit of terminal isocyanate group and the unit with olefinic double bond, and the polymer that the containing ratio of fluorine atom is 1~40 mass %.
2. refuse ink agent according to claim 1, wherein, the blocked isocyanate base unseals and becomes isocyanate group
10 it is small when half life temperature be 60~180 DEG C.
3. refuse ink agent according to claim 1 or 2, wherein, the blocked isocyanate base is represented with following formula (1),
- NHC (=O)-B ... (1)
In formula (1), B be by unary alcohol, phenols, lactams, oximes, Acetacetic acid alkyl ester class, malonates class,
1 in phthalimide class, imidazoles or reactive hydrogen possessed by pyrazoles removes the group formed；Chlorine atom or nitrile
Base；Or the group for forming the hydrogen removing of sodium hydrogensulfite.
4. refuse ink agent according to claim 3, wherein, B be the group that forms the hydrogen atom removing of the hydroxyl of oximes or
The group that the reactive hydrogen removing being bonded on the nitrogen-atoms that the ring of pyrazoles will be formed forms.
5. refuse ink agent according to claim 1 or 2, wherein, the polymer is and the equal molecule of matter using hydrocarbon chain as main chain
Amount is in 5 × 103~1 × 105Scope polymer, the fluorine-containing atomic unit be with optionally containing etheric oxygen atom
Fluorine alkylidene and/or the optionally unit of the fluoroalkyl containing etheric oxygen atom.
6. refuse ink agent according to claim 5, wherein, the polymer is also with selected from by the list with acidic-group
At least one kind of unit in the group of member, the unit with hydroxyl and the composition of the unit with polyoxyalkylene chain.
7. refuse ink agent according to claim 1 or 2, wherein, the polymer is the part water of hydrolysable silanes compound
Condensation product is solved, the fluorine-containing atomic unit is to be bonded with the fluorine alkylidene with optionally containing etheric oxygen atom on the silicon atoms
And/or the optional siloxane unit of the group of the fluoroalkyl containing etheric oxygen atom.
8. refuse ink agent according to claim 7, wherein, the partial hydrolysis condensate is to include to have fluorine-containing atomic radical
Hydrolysable silanes compound and hydrolysable silanes compound with blocked isocyanate base and with the base containing olefinic double bond
Group and the partial hydrolysis condensate for being free of the homogeney of hydrolysable silanes compound mixture of the hydrolysable silanes compound of fluorine atom, the water
Solution property silane compound mixture optionally includes at least one of the group for being selected from and being made of following compounds hydrolysable silanes
Close object：The hydrolysable silanes compound of 4 hydrolization groups is bonded on the silicon atoms, only there is the alkyl for being bonded to silicon atom
Hydrolysable silanes compound and with sulfydryl and without fluorine atom hydrolysable silanes compound.
9. refuse ink agent according to claim 1 or 2, wherein, the one side that at least form the partition wall of the substrate
Surface possesses the functional group with the reactivity of isocyanate group reaction.
10. a kind of negative light-sensitive resin combination, which is characterized in that containing the alkali soluble resins with photo-curable or with
The alkaline soluble monomers of photo-curable, and contain Photoepolymerizationinitiater initiater and refuse ink agent according to any one of claims 1 to 8.
11. negative light-sensitive resin combination according to claim 10, also contains black colorant.
12. a kind of partition wall is formed as substrate surface being separated into the shape of multiple subregions for formation point, the separation
Wall is formed as the solidfied material of the negative light-sensitive resin combination described in claim 10 or 11, and the point is represented in optical element
The Minimum Area that can carry out light modulation.
13. partition wall according to claim 12, wherein, the partition wall be formed in possess it is anti-with isocyanate group
On the substrate of the functional group for the reactivity answered.
14. a kind of optical element, which is characterized in that it has multiple points and the separation between adjacent point in substrate surface
Wall, the partition wall are formed as the partition wall described in claim 12 or 13, and the point represents that in optical element light can be carried out
The Minimum Area of modulation.
15. optical element according to claim 14, wherein, the point is formed using ink-jet method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014118475 | 2014-06-09 | ||
| JP2014-118475 | 2014-06-09 | ||
| PCT/JP2015/065239 WO2015190294A1 (en) | 2014-06-09 | 2015-05-27 | Ink repellent, negative photosensitive resin composition, partitioning walls, and light emitting element |
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| CN106465508A CN106465508A (en) | 2017-02-22 |
| CN106465508B true CN106465508B (en) | 2018-05-25 |
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| JP (1) | JP6593331B2 (en) |
| KR (1) | KR102372955B1 (en) |
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| JP6838876B2 (en) * | 2016-07-08 | 2021-03-03 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, resin pattern manufacturing method, cured film and display device |
| JP2018205605A (en) * | 2017-06-07 | 2018-12-27 | 三菱ケミカル株式会社 | Coloring photosensitive resin composition, cured product, organic electroluminescent element, image display device and illumination |
| KR102467651B1 (en) * | 2017-07-27 | 2022-11-16 | 삼성디스플레이 주식회사 | Display device and manufacturing method of the same |
| KR20190094731A (en) * | 2018-02-05 | 2019-08-14 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color pixel and display device produced using the same |
| WO2019182041A1 (en) * | 2018-03-23 | 2019-09-26 | 東レ株式会社 | Method for manufacturing cured film and method for manufacturing organic el display |
| CN112689799A (en) * | 2018-09-20 | 2021-04-20 | 富士胶片株式会社 | Photosensitive resin composition, cured film, laminate, transfer film, and method for producing touch panel |
| KR20210023720A (en) * | 2019-08-21 | 2021-03-04 | 시앤양 차이훙 옵토일렉트로닉스 테크놀로지 컴퍼니 리미티드 | Manufacturing method of display panel, and display panel and display apparatus |
| WO2022138173A1 (en) * | 2020-12-24 | 2022-06-30 | 昭和電工株式会社 | Copolymer, and method for producing said copolymer |
| JPWO2022181350A1 (en) * | 2021-02-24 | 2022-09-01 |
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| JPWO2015190294A1 (en) | 2017-05-25 |
| TWI666235B (en) | 2019-07-21 |
| WO2015190294A1 (en) | 2015-12-17 |
| KR102372955B1 (en) | 2022-03-10 |
| CN106465508A (en) | 2017-02-22 |
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