WO2017208771A1 - Composition, cured film, color filter, light blocking film, solid-state imaging device and image display device - Google Patents
Composition, cured film, color filter, light blocking film, solid-state imaging device and image display device Download PDFInfo
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- WO2017208771A1 WO2017208771A1 PCT/JP2017/017856 JP2017017856W WO2017208771A1 WO 2017208771 A1 WO2017208771 A1 WO 2017208771A1 JP 2017017856 W JP2017017856 W JP 2017017856W WO 2017208771 A1 WO2017208771 A1 WO 2017208771A1
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- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- UZZFFIUHUDOYPS-UHFFFAOYSA-L disodium 4-amino-3,6-bis[[4-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]-5-oxido-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccc(cc4)N=Nc4ccc(N)cc4N)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 UZZFFIUHUDOYPS-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- YDMWUMUNUXUYKT-UHFFFAOYSA-N ethyl [(1-oxo-1-phenylpropan-2-ylidene)amino] carbonate Chemical compound CCOC(=O)ON=C(C)C(=O)C1=CC=CC=C1 YDMWUMUNUXUYKT-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- 125000002092 orthoester group Chemical group 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- KHJHBFLMOSTPIC-UHFFFAOYSA-N prop-2-enylidenechromium Chemical compound C(=C)C=[Cr] KHJHBFLMOSTPIC-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229940030966 pyrrole Drugs 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QYJYJTDXBIYRHH-UHFFFAOYSA-N trimethoxy-[8-(oxiran-2-ylmethoxy)octyl]silane Chemical compound C(C1CO1)OCCCCCCCC[Si](OC)(OC)OC QYJYJTDXBIYRHH-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- RSJKGSCJYJTIGS-BJUDXGSMSA-N undecane Chemical group CCCCCCCCCC[11CH3] RSJKGSCJYJTIGS-BJUDXGSMSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
Definitions
- the present invention relates to a composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.
- the black light shielding film is used for various applications.
- the light shielding film is used in a solid-state imaging device.
- a solid-state imaging device includes a photographing lens and a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor, complementary metal oxide semiconductor) disposed behind the photographing lens.
- An element hereinafter, the solid-state image sensor is also referred to as an “image sensor”) and a circuit board on which the solid-state image sensor is mounted.
- noise due to reflection of visible light may occur. Therefore, there is a case where a predetermined light shielding film is provided in the solid-state imaging device for the purpose of suppressing the generation of noise.
- Another application of the light shielding film is a so-called black matrix.
- Patent Document 1 states that “a black resin composition for a resin black matrix containing at least a light shielding material, a resin and a solvent, and containing at least titanium nitride particles as a light shielding material, and using CuK ⁇ rays as an X-ray source.
- a black resin composition for a resin black matrix having a diffraction angle 2 ⁇ of a peak derived from the (200) plane of the titanium nitride particles of 42.5 ° or more and 42.8 ° or less is disclosed. 1).
- the present inventor made a light-shielding film of a color filter disposed in a solid-state imaging device, a liquid crystal image device or the like using a black composition prepared based on Patent Document 1, and examined various performances thereof. It came to know that the light-shielding performance in a specific wavelength region is low (in other words, the optical density is low).
- a dispersant is often used from the viewpoint of improving the dispersibility of the pigment.
- the content of the dispersant in the composition is relatively increased, resulting in the light shielding performance of the resulting light shielding film. May decrease. Therefore, it is desirable to improve the light shielding performance of the light shielding film by means other than increasing the pigment concentration.
- An object of this invention is to provide the composition which can form the light shielding film excellent in light-shielding performance in view of the said situation.
- Another object of the present invention is to provide a cured film having excellent light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device.
- an inorganic pigment preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride
- the present invention has been completed by finding that the above-mentioned problems can be solved by using a composition containing. That is, it has been found that the above object can be achieved by the following configuration.
- a composition comprising an inorganic pigment and a black dye.
- the inorganic pigment is a pigment containing nitride or oxynitride.
- the black dye has a polymerizable group.
- the polymerizable group is an acryloyl group or a methacryloyl group.
- the black dye is a xanthene dye or an azo dye.
- compositions as described in (7) whose acid value of the said dispersing agent is 50 mgKOH / g or more.
- (11) The composition according to any one of (1) to (10), further comprising an organic solvent.
- the composition which can form the light shielding film excellent in light shielding performance can be provided.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- Actinic light or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. .
- light means actinic rays or radiation.
- exposure in the present specification is not limited to exposure with a deep ultraviolet ray, an X-ray, EUV light or the like represented by a mercury lamp or an excimer laser, but also a particle beam such as an electron beam and an ion beam. Include drawing in exposure.
- (meth) acrylate represents acrylate and methacrylate
- (meth) acryl represents acrylic and methacryl
- (meth) acryloyl represents acryloyl and methacryloyl.
- monomer and “monomer” are synonymous.
- the monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less.
- the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer.
- the polymerizable group refers to a group that participates in a polymerization reaction.
- the composition of the present invention contains an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride) and a black dye.
- an inorganic pigment preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride
- a black dye preferably a pigment containing nitride or oxynitride
- a light shielding film having excellent light shielding performance can be formed. That is, according to the composition of the present invention, there is no reduction in the light shielding performance in a specific wavelength region, and the minimum optical density (hereinafter also referred to as “minimum OD value”) in a predetermined region (eg, visible light region to 1200 nm). It is possible to form a light shielding film in a range where sufficient light shielding ability can be provided.
- the composition of the present invention is characterized in that it contains a black dye.
- the content of the dispersant used for the purpose of improving the dispersibility of the inorganic pigment in the composition is relatively increased, resulting in this.
- the light shielding performance of the resulting light shielding film may deteriorate.
- the composition of the present invention does not require a dispersant and contains a black dye having absorption over almost the entire wavelength region of visible light, the minimum of the light-shielding film without increasing other components such as a dispersant.
- the optical density can be improved.
- the present inventor has recently found out that the above-described black dye preferably has a polymerizable group.
- the black dye when the black dye has a polymerizable group, the dye is incorporated into the matrix constituting the film via the polymerizable group. It is known that dyes are generally inferior in heat resistance to pigments. When a dye is used as a constituent component of a light shielding film, the light shielding film may be inferior in heat resistance due to the dye.
- the matrix constituting the film and the black dye are chemically bonded to each other by a polymerizable group, thereby improving heat resistance.
- reworkability is required.
- a color filter (cured film) produced using a composition containing an inorganic pigment, a black dye having a polymerizable group, an alkali-soluble resin, or the like is used, such as TMAH (tetramethylammonium hydroxide).
- the black dye In the case of removing with an alkaline aqueous solution, since the black dye is chemically bonded to a film including an alkali-soluble resin, the dye can be removed (peeled) together with the matrix.
- the black dye does not have a polymerizable group, that is, when the black dye is not chemically bonded to the matrix, the dye generally does not dissolve in an alkaline aqueous solution, so that the residue alone on the solid-state image sensor It becomes difficult to remove. That is, it is inferior to reworkability.
- the black dye has an acryloyl group or a methacryloyl group as a polymerizable group
- the patterning property (hereinafter also referred to as “resolution”) of the coating film formed by the composition of the present invention is further improved. I have also confirmed that.
- the black dye is preferably a dye multimer. Heat resistance improves more because black dye is a dye multimer.
- the black dye is preferably a dye multimer having a polymerizable group.
- the composition of the present invention contains an inorganic pigment.
- the inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
- examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( 1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink.
- a black inorganic pigment and as the inorganic pigment, carbon black, titanium black, and at least a content capable of forming a cured film having a high optical density is obtained.
- Metal pigments are preferred. Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Products, metal nitrides, and metal oxynitrides.
- inorganic pigments metal pigments containing titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, silver, It is preferably at least one selected from the group consisting of a metal pigment containing tin and a metal pigment containing silver and tin. Especially, it is more preferable that an inorganic pigment is at least 1 sort (s) selected from the pigment containing the nitride or oxynitride mentioned later. In addition, an inorganic pigment may be used individually by 1 type, or may use 2 or more types together.
- the content of the inorganic pigment is preferably 30 to 70% by mass with respect to the total solid content of the composition.
- the content of the inorganic pigment is 30% by mass or more based on the solid content, the light shielding performance of the obtained light shielding film is further improved, and the heat resistance is also improved.
- the content of the inorganic pigment is 70% by mass or less with respect to the solid content, reworkability and patterning property are further improved.
- the content of the inorganic pigment is more preferably 35 to 70% by mass, and still more preferably 40 to 70% by mass with respect to the total solid content of the composition.
- the inorganic pigment preferably has an average primary particle size in the range of 10 to 80 nm, and more preferably in the range of 10 to 50 nm.
- the average primary particle diameter can be measured, for example, by the following method.
- the average primary particle diameter of the inorganic pigment can be measured using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
- Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length)
- Dmax maximum length at two points on the contour of the particle image
- DV-max maximum vertical length
- the shortest length connecting two straight lines perpendicularly) was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the particle diameter.
- the particle diameter of 100 particles is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
- the inorganic pigment is preferably a pigment containing nitride or oxynitride.
- the pigment containing nitride or oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. It is done. Among them, those having absorption in the wavelength region of 400 to 1200 nm are preferable.
- the absorption wavelength and optical density of the inorganic pigment and black dye described later can be measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). From the viewpoint of realizing a high optical density in a small amount, for example, titanium nitride, titanium oxynitride, niobium nitride, or vanadium nitride is preferable, and titanium nitride or titanium oxynitride is more preferable. Although it does not specifically limit as titanium nitride or titanium oxynitride, The titanium nitride as described in international publication 2008/123097 gazette, international publication 2010/147098 gazette, and patent 5777659 gazette can be used.
- the content of nitride or oxynitride is the total mass of the pigment.
- the content is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.
- Titanium black Titanium black particles that are titanium oxynitride pigments will be described below.
- the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility or suppressing aggregation. It is possible to coat titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a surface treatment of titanium black is possible with a water repellent material as disclosed in JP-A-2007-302836. Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small. Specifically, an average primary particle diameter in the range of 10 nm to 80 nm is preferable. The average primary particle diameter can be measured, for example, by the above method.
- the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance It is preferably 5 m 2 / g or more and 150 m 2 / g or less, and more preferably 20 m 2 / g or more and 120 m 2 / g or less.
- Examples of commercially available products of titanium black include titanium black 10S, 12S, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), and Tilac. ) D (trade name: manufactured by Ako Kasei Co., Ltd.).
- titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
- the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles). In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
- a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed.
- a dispersed material containing Si and Ti as components can be obtained.
- the reduction treatment is performed in an atmosphere of a reducing gas such as ammonia.
- titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). Titanium oxide is not limited to this, but preferably has a primary particle size of 5 nm or more and 70 nm or less, more preferably 7 nm or more and 50 nm or less. These mixed crystals may be used.
- silica particles examples include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).
- a dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
- the dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. can do.
- composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more).
- a suitable range for example, 0.05 or more.
- the above-described dispersion tends to have a small particle size (for example, a particle size of 30 nm or less), and the component containing Si atoms in the dispersion It is estimated that this increases the adsorptivity with the base of the entire film, which contributes to the improvement of the development removability of the uncured composition (particularly titanium black) in the formation of the light-shielding film.
- titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light.
- the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is in terms of mass)
- the light-shielding film formed by using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
- the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
- the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the light-shielding film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
- the above-described titanium black can be used. In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black. Moreover, in this to-be-dispersed body, as long as the effect of this invention is not impaired, other colorants (an organic pigment, dye, etc.) may be used together as desired, as long as the effect of the present invention is not impaired. Good.
- materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
- silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used. Furthermore, if the particle size of the silica particles is smaller than the film thickness when the light shielding film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
- a titanium nitride containing particle can also be used, for example.
- a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
- the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
- the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable.
- titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles.
- the thermal plasma method is not limited to the above.
- the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a peak diffraction angle 2 ⁇ (details will be described later) derived from the (200) plane when CuK ⁇ rays are used as an X-ray source, It becomes easy to adjust to the range of 42.8 ° or more and 43.5 ° or less.
- the content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, and preferably 55 to 85% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 55 to 80% by mass.
- the content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectroscopy.
- the content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 15 to 50% by mass and preferably 15 to 45% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 40% by mass.
- the nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
- the titanium nitride-containing particles may have a diffraction angle 2 ⁇ of a peak derived from the (200) plane of 42.8 ° or more and 43.5 ° or less when an X-ray diffraction spectrum is measured using CuK ⁇ ray as an X-ray source.
- a light-shielding film obtained using a composition containing titanium nitride-containing particles having such characteristics has an appropriate OD value and is excellent in patterning properties (resolution).
- the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8 ° and not more than 43.5 ° as described above, and is 42.85 to 43.3 °. Is more preferably 42.9 to 43.2 °.
- Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed during the synthesis and when the particle diameter is small. Some may contain oxygen atoms. However, a smaller amount of oxygen contained in the titanium nitride-containing particles is preferable because a higher OD value (optical density) can be obtained.
- the titanium nitride-containing particles preferably contains no TiO 2 as an auxiliary component.
- TiO 2 is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.
- the crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
- the crystallite size is preferably 20 nm or more, more preferably 20 to 50 nm.
- the specific surface area of the titanium nitride-containing particles can be determined by the BET method and is preferably 40 to 60 m 2 / g, more preferably 40 to 58 m 2 / g, and 42 to 55 m 2 / g. More preferably.
- the specific surface area of the titanium nitride-containing particles By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m 2 / g, the obtained light-shielding film has an OD (optical density) value in an appropriate range, and is excellent in patternability (resolution).
- the average primary particle diameter of the titanium nitride-containing particles is preferably 10 to 30 nm, and more preferably 10 to 25 nm.
- the obtained light shielding film has an OD (optical density) value in an appropriate range, and is excellent in patterning properties (resolution).
- the average primary particle diameter can be measured, for example, by the above method.
- the composition of the present invention may also contain inorganic pigments other than those listed above as the inorganic pigment.
- examples of other pigments include tungsten compounds and metal borides. Tungsten compounds and metal borides have a feature of high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) with respect to infrared rays). Note that the tungsten compound and the metal boride have a low absorption with respect to visible light as compared with a light shielding property against infrared rays. In addition, the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image formation.
- tungsten compound examples include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
- composition formula) (I) M x W y O z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001 ⁇ x / y ⁇ 1.1 2.2 ⁇ z / y ⁇ 3.0
- alkali metal for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.
- M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.
- infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
- z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
- tungsten oxide compound represented by the general formula (I) examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
- the tungsten compound is preferably fine particles.
- the average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. For reasons such as ease of handling during production, the average particle diameter of tungsten fine particles is usually 1 nm or more.
- two or more tungsten compounds can be used.
- Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205). Further, the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
- lanthanum boride LaB 6
- PrB 6 praseodymium boride
- NdB 6 cerium boride
- CeB 6 cerium boride
- YB 6 yttrium boride
- boride Titanium TiB 2
- zirconium boride ZrB 2
- hafnium boride HfB 2
- vanadium boride VB 2
- tantalum boride TaB 2
- CrB 2 chromium boride
- boride One or more of molybdenum (MoB 2 , Mo 2 B 5 , MoB) and tungsten boride (W 2 B 5 ) can be used, and lanthanum boride (LaB 6 ) is preferable. .
- the metal boride is preferably fine particles.
- the average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more preferably 100 nm or less.
- the average particle size of the metal boride fine particles is usually 1 nm or more.
- two or more metal borides can be used.
- the metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.
- the inorganic pigment may be an extender pigment.
- extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite.
- the extender is preferably used in combination with a color pigment (for example, a black inorganic pigment).
- a color pigment for example, a black inorganic pigment.
- extender pigments can be used alone or in admixture of two or more.
- the amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant.
- the colorant and extender pigment can be used with their surface modified with a polymer.
- the composition of the present invention comprises a black dye.
- the black dye those having absorption over the entire wavelength region of visible light (380 nm to 780 nm) are preferable.
- the black dye include C.I. I.
- the black dye include xanthene dyes, azo dyes, and aniline dyes.
- the black dye preferably has an optical density of 2 or more, more preferably 4 or more in the entire wavelength region of 400 to 500 nm.
- the black dye preferably has a polymerizable group.
- the polymerizable group is a functional group that can form a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group.
- a radical polymerizable group is preferable from the viewpoint of more excellent reactivity.
- radical polymerizable group examples include acryloyl group, methacryloyl group, acrylic acid ester group (acryloyloxy group), methacrylic acid ester group (methacryloyloxy group), itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group,
- unsaturated carboxylic acid ester groups such as maleic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups are exemplified.
- a methacryloyl group or an acryloyl group is more preferable.
- Two or more polymerizable groups may be contained in the black dye.
- the number of polymerizable groups contained in the black dye is not particularly limited, and may be one or two or more.
- the black dye may be either a dye monomer or a dye multimer, but is preferably a dye multimer from the viewpoint of further improving heat resistance. Especially, it is preferable that it is a dye multimer which has a structural unit represented by the following general formula (1), has a polymeric group, and has the structural unit represented by the following general formula (1) More preferred is a multimer.
- R A to R C each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
- L represents a single bond or a divalent linking group
- Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye.
- R A to R C each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Of these, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is preferable.
- L represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —S—, —NR 1 —, —CO—, a vinylene group, an ethynylene group, and an alkylene group (which may be cyclic, branched, or linear). Or an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof.
- R 1 is, for example, a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, an I atom ) And aryl groups (preferably aryl groups having 6 to 20 carbon atoms).
- a hydrogen atom or an alkyl group is preferable.
- Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye. Although it does not specifically limit as black dye, The black dye mentioned above is mentioned. Of these, xanthene dyes or azo dyes are preferred from the viewpoint of forming a light-shielding film having better light-shielding performance.
- the position of the polymerizable group in the dye multimer is not particularly limited. As the position of the polymerizable group in the dye multimer, for example, Dye may have a polymerizable group or may have a structural unit having a polymerizable group.
- Dye having a polymerizable group intends that the dye residue represented by Dye, which is obtained by removing one arbitrary hydrogen atom from a black dye, has a polymerizable group.
- the content of the structural unit represented by the general formula (1) in the dye multimer is preferably 80% by mass or more based on the total structural unit, and 85 More preferably, it is 90 mass% or more, and 95 mass% or more is especially preferable.
- the dye multimer having the structural unit represented by the general formula (1) can be produced by a known method.
- the black dye is a dye multimer
- its molecular weight is not particularly defined, but as a polystyrene equivalent value by GPC (gel permeation chromatography) method
- the weight average molecular weight (Mw) is preferably 1000 or more and 20000 or less. More preferably, it is 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.
- the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
- Examples of commercially available black dyes having a polymerizable group include RDW series manufactured by Wako Pure Chemical Industries, Ltd., and specific examples include RDW-K01.
- the content of the black dye is preferably 0.3 or less in terms of mass ratio (black dye / inorganic pigment) to the content of the inorganic pigment from the viewpoint of further improving reworkability, and is 0.25 or less. Is more preferable, and it is still more preferable that it is 0.2 or less. In addition, although the minimum of content of black dye is not specifically limited, It is preferable that it is 0.01 or more by mass ratio with respect to an inorganic pigment.
- the content of the black dye is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, with respect to the total solid content of the composition. More preferably, it is mass%.
- the black dye may be used alone or in combination of two or more.
- the composition of the present invention preferably contains a dispersant.
- a dispersing agent contributes to the improvement of the dispersibility of pigment components, such as the inorganic pigment mentioned above.
- a dispersing agent and the binder resin mentioned later are different components.
- the dispersant for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
- dispersant examples include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalene sulfonic acid formalin condensate and the like], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
- the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- the polymer compound is adsorbed on the surface of a dispersion such as an inorganic pigment and a pigment used in combination as desired, and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are preferable. On the other hand, by modifying the surface of the inorganic pigment, the adsorptivity of the polymer compound can be promoted.
- the polymer compound preferably has a structural unit having a graft chain.
- structural unit is synonymous with “repeating unit”. Since the polymer compound having a structural unit having such a graft chain has an affinity with a solvent by the graft chain, the dispersibility of the color pigment such as the above-mentioned inorganic pigment and the dispersion stability after aging are improved. It is excellent. Further, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
- the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as the above-mentioned inorganic pigments is lowered, and the dispersibility of the pigments and the like tends to be lowered.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
- the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
- the graft chain preferably has a polymer structure.
- a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
- the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure.
- the graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
- the macromonomer having such a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.
- AA-6 trade name, Toa Gosei Co., Ltd.
- AA-10 Product name, manufactured by Toa Gosei Co., Ltd.
- AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
- AS-6 trade name, produced by Toa Gosei Co., Ltd.
- AN-6 trade name, manufactured by Toa Gosei Co., Ltd.
- Co., Ltd. AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.
- AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is done.
- the dispersant preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. Among them, it is preferable to have at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester, and polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethacrylic acid. More preferably, it has at least one structure selected from the group consisting of methyl.
- the dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
- the polycaprolactone structure means a structure having a ring-opened structure of ⁇ -caprolactone as a repeating unit.
- the polyvalerolactone structure means a structure having a ring-opened structure of ⁇ -valerolactone as a repeating unit.
- Specific examples of the dispersant having a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
- Specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
- dispersant having a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant having a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
- the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
- X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
- Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
- a and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.
- (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
- Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
- the structure of the organic group is not particularly limited. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, and the like Is mentioned.
- the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
- alkyl groups or alkoxy groups are preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms, respectively. Is preferred.
- the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
- n, m, p, and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of dispersion stability and developability of the composition.
- R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
- R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
- R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
- the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
- a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
- the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
- the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.
- X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
- X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
- the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of dispersion stability and developability of the composition. .
- X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
- the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
- the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a range of 5 to 30%.
- the structural unit having a graft chain is contained within this range, the above-described inorganic pigment has high dispersibility and good developability when a light-shielding film is formed.
- the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
- the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
- the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
- ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
- logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
- logP log (Coil / Cwater)
- Coil represents the molar concentration of the compound in the oil phase
- Cwater represents the molar concentration of the compound in the aqueous phase.
- the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.
- R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- R 2 and R 3 are more preferably a hydrogen atom.
- X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- L is a single bond or a divalent linking group.
- a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
- divalent aromatic group for example, arylene group
- Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched chain structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
- L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
- the aliphatic group may have a cyclic structure or a branched chain structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
- bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon rings such as tricyclo [4.3.1.1 2,5 ] undecane ring, and , Tetracyclo [4.4.0.1 2,5 .
- the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
- a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
- the carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
- the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
- R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms.
- a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
- an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.
- Z or LZ.
- L and Z are as defined above.
- R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure.
- a compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
- R 1 is a hydrogen atom or a methyl group
- L is an alkylene group
- Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
- R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
- Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
- Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Embedded in.
- the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
- the polymer compound can introduce a functional group capable of forming an interaction with the above-described colored pigment such as the inorganic pigment.
- the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the above-described colored pigment such as the inorganic pigment.
- the functional group capable of forming an interaction with the color pigment such as the above-described inorganic pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
- the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively.
- the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, it is possible to impart developability for pattern formation by alkali development to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention is such that the polymer compound as a dispersant that contributes to the dispersion of the color pigment such as the inorganic pigment has alkali solubility. .
- a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
- a high molecular compound has a structural unit which has an acid group
- the acid group in the structural unit having an acid group easily interacts with the above-described colored pigment such as the inorganic pigment, and the polymer compound stably disperses the above-described inorganic pigment or the like, and the above-described inorganic pigment.
- the viscosity of the polymer compound that disperses colored pigments such as pigments is low and the polymer compound itself is easily dispersed stably.
- the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
- Examples of the acid group that is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment described above include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. It is at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and more preferable is an adsorbing power to a coloring pigment such as the above-mentioned inorganic pigment, and the dispersibility of the coloring pigment In a high point, it is a carboxylic acid group.
- the polymer compound When the polymer compound has an acid group, the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- the polymer compound may have one or more structural units having an acid group.
- the polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is calculated in terms of mass with respect to the total mass of the polymer compound. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
- Examples of the basic group that is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment described above include a primary amino group, a secondary amino group, a tertiary amino group, and a hetero group including an N atom.
- a primary amino group a secondary amino group, a tertiary amino group, and a hetero group including an N atom.
- the polymer compound can have one or more of these basic groups.
- the polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppression of developability inhibition.
- Examples of the coordinating group which is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride And acid chlorides.
- Preferable one is an acetylacetoxy group in that the adsorbing power to the color pigment such as the above-mentioned inorganic pigment is good and the dispersibility of the color pigment is high.
- the polymer compound may have one or more of these groups.
- the polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
- the polymer compound in the present invention has a functional group capable of forming an interaction with a colored pigment such as the above-mentioned inorganic pigment in addition to the graft chain
- a colored pigment such as the above-mentioned inorganic pigment in addition to the graft chain
- the above-described various colored pigments such as the above-mentioned inorganic pigments and the like
- the polymer compounds are represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from the monomer represented by:
- R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
- R 12 and R 13 are each particularly preferably a hydrogen atom.
- X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- Y in the general formula (v) represents a methine group or a nitrogen atom.
- L 1 represents a single bond or a divalent linking group.
- the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
- R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched chain structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 1 may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z 1 represents a functional group capable of forming an interaction with the above-described pigment such as the inorganic pigment in addition to the graft chain, and includes a carboxylic acid group and a tertiary group An amino group is preferable, and a carboxylic acid group is more preferable.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - Z 1, or an L 1 -Z 1.
- L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
- R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
- a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
- R 11 is a hydrogen atom or a methyl group
- L 1 is an alkylene group
- Z 1 is a carboxylic acid group
- Y is methine. Compounds that are groups are preferred.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and L 1 is a single bond or an alkylene group, A compound in which Z 1 is a carboxylic acid group is preferred.
- monomers represented by general formula (iv) to general formula (vi).
- monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
- a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxy Phenyl methacrylamide, and the like.
- the content of the structural unit having a functional group capable of forming an interaction with the colored pigment such as the above-described inorganic pigment, the interaction with the colored pigment such as the above-described inorganic pigment, the dispersion stability, and the permeability to the developer is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass with respect to the total mass of the polymer compound.
- the polymer compound is a coloring unit such as a structural unit having a graft chain, a hydrophobic structural unit, and the above-described inorganic pigment, as long as the effects of the present invention are not impaired.
- a coloring unit such as a structural unit having a graft chain, a hydrophobic structural unit, and the above-described inorganic pigment
- other structural unit having various functions for example, a structural unit having a functional group having affinity with the dispersion medium used in the dispersion
- examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
- the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
- the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g.
- the lower limit is more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. If the acid value of the polymer compound is 50 mgKOH / g or more, precipitation of colored pigments such as the above-mentioned inorganic pigments can be further suppressed, and the number of coarse particles is reduced (in other words, the amount of particles in the liquid is reduced) And the stability over time of the composition can be further improved. Further, from the viewpoint of more effectively suppressing pattern peeling during development when forming a light shielding film, the upper limit is preferably 140 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
- the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
- the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
- the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
- the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
- the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
- Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
- Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
- Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
- Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd. These polymer compounds may be used alone or in combination of two or more.
- polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
- graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to columns 0075 to 0133 in US2011 / 0124824.
- it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group.
- Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
- the content of the dispersant is preferably in the range of 0.1 to 1 in terms of mass ratio with respect to the above-described inorganic pigment, A range is more preferable.
- the content of the dispersant is in the range of 0.1 to 0.4 by mass ratio with respect to the above-mentioned inorganic pigment, so that the amount of coarse particles in the composition can be further reduced, and the obtained light-shielding film Excellent shading performance.
- the content of the dispersant is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the total solid content of the composition. More preferably, the content is 5 to 10% by mass.
- a dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention preferably contains a binder resin.
- a binder resin a linear organic polymer is preferably used.
- a linear organic polymer a well-known thing can be used arbitrarily.
- a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development.
- an alkali-soluble resin a resin having a group that promotes alkali-solubility
- the binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used.
- polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferred, and developability From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acryl / (meth) acrylamide copolymer resins are preferred.
- the group that promotes alkali solubility hereinafter also referred to as an acid group
- examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group.
- an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable.
- These acid groups may be used alone or in combination of two or more.
- binder resin examples include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group Resins in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated by homopolymerizing a monomer having an acid, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride Can be mentioned.
- radical polymers having a carboxylic acid group in the side chain such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-
- Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
- Examples of the monomer having an acid anhydride include And maleic anhydride.
- an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
- a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.
- 2001-318463 has a film strength and developability. It is excellent in balance and is suitable.
- polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
- alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
- a known radical polymerization method can be applied.
- Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, the type and amount of the radical initiator, the type of solvent, and the like when producing the alkali-soluble resin by the radical polymerization method.
- a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
- the definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable range is also the same.
- the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. More preferred is a carboxylic acid group.
- the structural unit having an acid group preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).
- R 21 , R 22 , and R 23 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 21 , R 22 , and R 23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Each independently represents a hydrogen atom or a methyl group.
- R 21 and R 23 are each particularly preferably a hydrogen atom.
- X 2 in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- Y in the general formula (viii) represents a methine group or a nitrogen atom.
- L 2 represents a single bond or a divalent linking group.
- the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR 41 ′ —
- R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched chain structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 42 , where R 42 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- L 2 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 2 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z 2 is an acid group, preferably a carboxylic acid group.
- R 24 , R 25 , and R 26 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms. (e.g., methyl group, ethyl group, propyl group, etc.), - represents a Z 2, or L 2 -Z 2.
- L 2 and Z 2 has the same meaning as L 2 and Z 2 in the above, and preferred examples are also the same.
- R 24 , R 25 and R 26 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or an oxyalkylene structure.
- a compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
- R 21 is a hydrogen atom or a methyl group
- L 2 is an alkylene group
- Z 2 is a carboxylic acid group
- Y is methine.
- Compounds that are groups are preferred.
- a compound in which R 24 , R 25 , and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
- the binder resin can be synthesized by the same method as the dispersant having a structural unit having a graft chain described above, and the preferred acid value and weight average molecular weight are the same.
- the binder resin may have one or more structural units having an acid group.
- the content of the structural unit having an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder resin, and more preferably, from the viewpoint of suppressing damage to image strength due to alkali development. 10 to 90%.
- the content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
- Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, still more preferably 3 or more, and particularly preferably 5 or more.
- the upper limit is 15 or less, for example.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. Monomers are preferred.
- the molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
- monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, amides, and multimers thereof.
- esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
- a dehydration condensation reaction product of a carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
- reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups or tosyloxy groups
- a reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
- the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.
- the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
- compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.
- the polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.).
- Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
- A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred.
- oligomer types can also be used.
- NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- Preferred embodiments of the polymerizable compound are shown below.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
- an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
- a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
- the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
- the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution property is good, and when it is 40 mgKOH / g or less, it is advantageous in production or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
- compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.
- R 1 represents a hydrogen atom or a methyl group
- m represents a number of 1 or 2
- “*” Indicates a bond.
- R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
- polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
- each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —.
- Each represents independently an integer of 0 to 10
- each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
- the total of (meth) acryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40 .
- the total number of (meth) acryloyl groups is 5 or 6
- each n independently represents an integer of 0 to 10
- the total of each n is an integer of 0 to 60 .
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
- — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom
- a form in which the terminal on the side is bonded to X is preferred.
- the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
- a form in which all six Xs are acryloyl groups in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
- the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
- the compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
- a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
- Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a), (B), (e) and (f) are preferred.
- Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
- Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, or Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, or JP-B-62-39418 are also suitable. . Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
- urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
- the polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and preferably 10.60 or more. Further preferred.
- the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 .
- the composition also preferably has a polymerizable compound having a cardo skeleton from the viewpoint of improving development residue.
- a polymerizable compound having a cardo skeleton a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
- Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line.
- X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
- a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4.
- R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively.
- the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.
- X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
- the substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group having a polymerizable group.
- the aliphatic group having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is still more preferable.
- aliphatic group having a polymerizable group represented by X 1 to X 4 when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom.
- R is a substituent
- the non-adjacent —CH 2 — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is More preferably, it is substituted with an oxygen atom.
- the aliphatic group having a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar 11 to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line 14 is substituted with a heteroatom.
- a polymerizable group capable of radical polymerization or cationic polymerization hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively
- radical polymerizable group a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one.
- a vinyl group, a (meth) acryloyloxy group, etc. are mentioned. Of these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
- cationic polymerizable group generally known cationic polymerizable groups can be used.
- alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
- the polymerizable group contained in the substituent contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.
- Two or more of Ar 1 ⁇ Ar 4 includes a substituent having a polymerizable group, preferably contains a substituent 2-4 of Ar 1 ⁇ Ar 4 has a polymerizable group, Ar 1 ⁇ Ar More preferably, 2 or 3 out of 4 contain a substituent having a polymerizable group, and more preferably 2 out of Ar 1 to Ar 4 contain a substituent having a polymerizable group.
- X 1 to X 4 are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
- a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
- c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
- R 1 to R 4 each independently represents a substituent.
- the substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups An aryl group, an alicyclic group, etc. are mentioned.
- the substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group.
- R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
- e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar 11 to Ar 14 can have.
- the value obtained by subtracting a, b, c, or d from the number of. e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
- Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.
- Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
- Examples of the polymerizable compound having a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
- Examples of such a polymerizable compound having a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
- the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
- One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention preferably contains a polymerization initiator.
- a polymerization initiator There is no restriction
- the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the above-described inorganic pigment and black dye, it is cured by irradiation with actinic rays or radiation. Sometimes called a "composition".
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like.
- Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
- trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
- a compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable.
- trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones
- examples thereof include at least one compound selected from the group consisting of a compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
- composition of the present invention when used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is important that From such a viewpoint, it is preferable to use an oxime compound as the photopolymerization initiator.
- stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low.
- an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
- the photopolymerization initiator for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
- acylphosphine-based initiator commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.
- the photopolymerization initiator include oxime compounds (oxime initiators).
- an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
- Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
- Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M.
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
- N-1919 carboxyl ether skeleton-containing photoinitiator
- oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
- the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
- a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.
- R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
- R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
- R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
- halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms
- X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
- R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- X is preferably a direct bond.
- Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
- oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
- the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is more preferable.
- a known method can be used for the molar extinction coefficient of the compound.
- an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
- the content of the polymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content in the composition, and is preferably 1 to 25% by mass. %, More preferably 1 to 10% by mass.
- the composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
- the composition of the present invention preferably contains an organic solvent.
- organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Ter, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether,
- composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but the inorganic pigment particles described above are prepared when the composition of the invention is prepared. It is preferable to contain two or more organic solvents from the viewpoint that the diameter variation can be suppressed.
- the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
- the content of the organic solvent is preferably 10 to 90% by mass and more preferably 60 to 90% by mass with respect to the total mass of the composition. preferable.
- the total amount is preferably within the above range.
- the composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
- the water content is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and more preferably 0.1 to 0.00% by mass with respect to 100% by mass of the composition. More preferably, it is 7 mass%.
- the water content is within the above range, the generation of pinholes when the light shielding film is produced can be suppressed, or the moisture resistance of the light shielding film can be improved.
- silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
- a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
- the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
- the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), Silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms are It is desirable not to include.
- the silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
- R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
- the silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
- the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
- a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
- the molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.
- silane coupling agent X represented by the formula (W).
- R z1 represents a hydrolyzable group, and the definition is as described above.
- R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
- Lz represents a single bond or a divalent linking group.
- Lz represents a divalent linking group
- the divalent As the linking group an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
- a group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
- R 12 represents a hydrogen atom or a methyl group.
- N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
- a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
- the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
- Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group and the like.
- substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
- at least one hydrolyzable group is bonded to the silicon atom.
- the definition of the hydrolyzable group is as described above.
- the silane coupling agent Y may contain a group represented by the formula (Z).
- the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group.
- the amino group structure may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
- examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent.
- substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
- the nitrogen atom is couple
- Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
- the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
- the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
- the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).
- the content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the composition. More preferably, it is 0 to 6% by mass.
- composition of the present invention may contain one silane coupling agent or two or more silane coupling agents.
- silane coupling agents When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
- the composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
- various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
- the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness or liquid-saving property is further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film or liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc.
- the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
- a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
- the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
- Specific examples include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, or RS- 72-K and the like.
- nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-10
- cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
- silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
- the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.
- the composition preferably contains a polymerization inhibitor.
- the composition has better temporal stability.
- the content of the polymerization inhibitor is preferably from 0.00055 to 0.055 mass%, more preferably from 0.0015 to 0.01 mass%, based on the total solid content of the composition.
- the polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used.
- the compound used as the polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
- the said compound may be used individually by 1 type, or may use 2 or more types together.
- phenol compound examples include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol.
- phenolic compound a phenolic compound represented by the formula (IH-1) is preferable.
- R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
- R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
- R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group
- R 2 and R 4 are more preferably a hydrogen atom
- R 3 is a hydrogen atom
- an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
- Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
- Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
- R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
- R 7 to R 10 each independently represents a hydrogen atom or an alkyl group.
- the alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
- each of the above compounds may be used alone, in combination of two or in combination of three or more.
- the polymerization inhibitor preferably contains a phenolic compound.
- a polymerization inhibitor contains a 2 or more types of phenol type compound from a viewpoint of temporal stability.
- the said polymerization inhibitor contains a phenol type compound and a hindered amine type compound from a viewpoint of temporal stability.
- the composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
- an ultraviolet absorber salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used.
- compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
- a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
- the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
- the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the composition.
- each said compound may be used individually by 1 type, or may use 2 or more types together.
- the composition may contain an organic pigment.
- organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24. , 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 Etc.
- CI Color Index
- a pigment may be used individually by 1 type, or may use 2 or more types together.
- ⁇ Chromatic dye> examples include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501.
- dye currently disclosed by 194828 gazette etc. can be used.
- pyrazole azo compounds When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
- a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the chromatic dye polymeric dye which has superposition
- the colorant may further contain an infrared absorber.
- the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm).
- the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
- Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
- Examples include compounds, dithiol metal complex compounds, and croconium compounds.
- the phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound
- the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated into.
- the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
- the content of the colorant is preferably 1 to 10% by mass with respect to the total solid content of the composition. More preferably, it is ⁇ 7% by mass.
- the following components may be further added to the composition of the present invention.
- Examples include sensitizers, pigment dispersants other than those described above, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers.
- Adhesion promoters to the substrate surface and other auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, perfumes, surface tension modifiers, and , Chain transfer agents and the like
- These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No.
- JP2008-250074A Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .
- the solid content of the composition of the present invention is preferably 10 to 40% by mass.
- the light shielding performance of a light shielding film improves more because the solid content of a composition is 10 mass% or more.
- the solid content of the composition is 40% by mass or less, the amount of particles in the composition can be further reduced, and the temporal stability is improved.
- the solid content is preferably 12% by mass or more.
- the composition of the present invention can be produced by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
- a known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser.
- various components constituting the composition may be combined at once, or may be sequentially mixed after the various components are dissolved or dispersed in an organic solvent.
- the charging order and working conditions when blending are not particularly limited.
- the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
- materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
- the composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
- Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
- a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
- fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like
- PP polypropylene
- nylon are preferable.
- the filter has a pore diameter of about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment while suppressing filtration clogging of the pigment.
- different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
- the second filter a filter formed of the same material as the first filter described above can be used.
- the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
- the cured film of this invention is obtained using the composition mentioned above.
- the cured film of the present invention mainly contains the above-described inorganic pigment (preferably a black inorganic pigment, more preferably a pigment containing a nitride or oxynitride) and a black dye.
- the cured film of the present invention is suitably used as a light-shielding film, and specifically, suitably used as a light-shielding film (frame light-shielding film) around an image sensor such as a CCD image sensor or a CMOS image sensor.
- the image sensor peripheral light shielding film obtained by using the composition of the present invention is excellent in light shielding performance. That is, the light shielding performance does not deteriorate in a specific wavelength region, and the minimum optical density is within a range where sufficient light shielding ability can be provided in a predetermined region (for example, visible light region to 1200 nm).
- the film thickness of the cured film of the present invention can be appropriately selected depending on the application, and is not particularly limited.
- the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less, and 0.2 ⁇ m. It is more preferably 30 ⁇ m or less, further preferably 0.2 ⁇ m or more and 25 ⁇ m or less, particularly preferably 0.2 ⁇ m or more and 20 ⁇ m or less, and most preferably 0.2 ⁇ m or more and 10 ⁇ m or less.
- the size (length of one side) of the light shielding film is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, and further preferably 0.1 mm or more and 3.5 mm or less.
- the manufacturing method of the cured film (light-shielding film) of the present invention is not particularly limited, and a known method can be adopted.
- a method for producing a patterned cured film will be described in detail.
- the method for producing a patterned cured film of the present invention is a process of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter abbreviated as “composition layer forming process” as appropriate). And a step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing the exposed composition layer to form a patterned cured film. (Hereinafter, abbreviated as “development step” as appropriate).
- composition layer forming step a composition layer
- exposure process irradiated with light
- development process developing with a developer
- composition layer forming step In the composition layer forming step, the composition of the present invention is applied on a substrate to form a composition layer (coating film).
- the substrate examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and a transparent conductive film attached to these, photoelectric devices used in solid-state imaging devices, and the like.
- Examples include a conversion element substrate (for example, a silicon substrate), a CCD substrate, and a CMOS substrate.
- an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
- composition of the present invention As a method for applying the composition of the present invention on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, or screen printing method can be applied.
- the coating thickness of the composition is preferably 0.35 ⁇ m or more and 1.5 ⁇ m or less, more preferably 0.40 ⁇ m or more and 1.0 ⁇ m or less from the viewpoint of resolution and developability. preferable.
- composition coated on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for 2 minutes or longer and 4 minutes or shorter. Thereby, a composition layer can be formed.
- the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
- the exposure is preferably performed by irradiation with actinic rays or radiation, and more preferably ultraviolet rays such as g-line, h-line, or i-line.
- the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
- an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
- the developer an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable.
- the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
- Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
- the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metaoxalate having a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
- the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.
- An alkaline aqueous solution in which an alkaline compound such as 0.001 to 10% by mass, preferably 0.01 to 1% by mass is dissolved.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution.
- a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
- the developing method for example, a paddle developing method or a shower developing method can be used.
- the formed cured film of this invention after performing the composition layer formation process, the exposure process, and the image development process which were mentioned above, the formed cured film is hardened
- a curing step may be included.
- the cured film formed using the composition of the present invention can be preferably used as a pixel black matrix of a color filter or a light-shielding film applied to various members in an image display device or sensor module described later.
- the color filter can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels.
- the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
- the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the partition in this case preferably has a low refractive index for each color pixel.
- Examples of the image pickup device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A. If the color filter of this invention has the said cured film, the form will not be specifically limited.
- the cured film can be suitably used as, for example, a pixel black matrix of a color filter.
- the light shielding film is formed on various members in the image display device or the sensor module (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of the wafer level lens, or the back surface of the solid-state imaging device). Can be used. Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
- the thickness of the light shielding film is not particularly limited, but is preferably 0.2 to 25 ⁇ m, and more preferably 0.2 to 10 ⁇ m.
- the thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light shielding film and arithmetically averaging them.
- the reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less.
- the reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. .
- the solid-state imaging device of the present invention includes the solid-state imaging element as described above, and includes the cured film (color filter, light-shielding film, etc.) on the outer peripheral portion or the back surface of the solid-state imaging element.
- the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the cured film and the solid-state imaging device, and examples thereof include the following configurations.
- the substrate has a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and a transfer electrode made of polysilicon, and the photodiodes receive light on the photodiodes and the transfer electrodes.
- a light-shielding film having an opening only in the part, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, and a color filter on the device protective film It is the composition which has.
- the light source has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and below the color filter (on the side close to the substrate), and a constitution having a light condensing means on the color filter. May be.
- a condensing means for example, a microlens, etc., the same shall apply hereinafter
- the cured film (such as a color filter or a light-shielding film) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- the display device For the definition of the display device or details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., issued in 1990)”, “Display Device (Junsho Ibuki, Industrial Book Co., Ltd.) Issued in the first year).
- the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
- the form is not particularly limited.
- the color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device.
- the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
- the color filter of the present invention is a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), or an STN ( Also applicable to Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), or R-OCB (Reflective Bench).
- the color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.
- the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above.
- the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
- a resin film may be provided on the color filter layer.
- the liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
- the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
- these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
- backlights SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. It is described in.
- the cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an office automation (OA) device such as a printer multifunction device or a scanner; a monitoring camera, a barcode reader, and an automatic cash deposit Industrial equipment such as personal identification using payer (ATM) or high-speed camera or face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope or catheter; biosensor , Optical sensors used in space equipment such as biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological or oceanographic observation cameras, land resource exploration cameras, or exploration cameras for space astronomy or deep space targets Or a light shielding member or a light shielding layer of the module; It can be used for anti-reflective member or anti-reflective layer.
- ATM personal identification using payer
- ATM high-speed camera or face image authentication
- in-vehicle camera equipment medical camera equipment such as endoscope, capsule endo
- the cured film of this invention can be used also for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode).
- micro LED Light Emitting Diode
- micro OLED Organic Light Emitting Diode
- it does not specifically limit,
- the optical filter or optical film used for micro LED or micro OLED it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
- the micro LED or micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
- curing the composition of this invention can be used also for uses, such as a quantum dot display.
- a quantum dot display In addition to the optical or optical film used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
- quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
- composition ⁇ Composition ⁇
- each component contained in the composition will be described first.
- TiN-1 manufactured by Nissin Engineering Co., Ltd.
- TiN-2 titanium nitride-containing particles, BET specific surface area 55 m 2 / g, average primary particle size 24.2 nm
- TiN-3 Product name “TiN 20 nm” manufactured by Hefei (titanium nitride-containing particles, average primary particle size 41.7 nm)
- TiN-3 Product name “13M-T” manufactured by Mitsubishi Materials Corporation (titanium oxynitride-containing particles, average primary particle size 75 nm)
- Dye A was synthesized based on the following procedure.
- Binder resin As binder resin, the following resin A which is alkali-soluble resin was used.
- Resin A ACRYCURE RD-F8 made by Nippon Shokubai, see the following formula
- Dispersants A to E having the following structures were used as the dispersants.
- the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
- the numerical values (a to e) described in each structural unit are intended to be the molar ratio of each structural unit relative to all structural units, and x and y are intended to be the number of linkages.
- the numerical value described in the coupling group linked to Z intends the number of linkages linked to Z.
- Polymerizable compound M1 (Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”, see formula below)
- oxime initiators were used as polymerization initiators.
- OXE-02 Irgacure OXE02 (trade name, manufactured by BASF Japan)
- Organic solvent The following organic solvents were used as the organic solvent.
- PGMEA Propylene glycol monomethyl ether acetate
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of various resins used were calculated by GPC (Gel Permeation Chromatography) measurement.
- the ratio (mass ratio) of the dispersant to the pigment containing nitride or oxynitride (hereinafter also referred to as “D / P”) is the ratio shown in each example and comparative example in Table 1. Added to.
- a coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 ⁇ m, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film. The obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the minimum OD at a wavelength of 400 to 1200 nm, the spectroscopic (light shielding property) was evaluated according to the following criteria.
- each composition of an Example and a comparative example is a negative photosensitive resin composition which an exposure part hardens
- the silicon wafer substrate on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd.
- the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center from a jet nozzle.
- the wafer was rinsed and then spray-dried to form a wafer having a frame-like pattern.
- the obtained wafer having a frame-like pattern is immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85 ° C. for 5 hours, and immersed in a 2 L DIW (pure water) bath at room temperature for 2 minutes.
- TMAH tetramethylammonium hydroxide
- DIW pure water
- A no pattern is observed
- B particulate removal residue is observed in 5% or less of the pattern formation region
- C particulate removal residue is present in more than 5% and 10% or less of the pattern formation area
- D particulate removal residue is observed in more than 10% of the pattern formation area, or a pattern or a part of the pattern is observed
- a coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 ⁇ m, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film.
- the obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the lowest OD at a wavelength of 400 to 1200 nm, the spectral (light-shielding property) was evaluated and set as the lowest OD before the heat resistance test.
- the dried film was heat-treated on a hot plate at 265 ° C.
- a coating film was formed on an image sensor device substrate by a spin coater. Next, the obtained coating film was pre-baked at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film that has been subjected to the pre-baking process is exposed using an i-line exposure apparatus (FPA, manufactured by Canon Inc.), and further developed to cover the outer periphery of the light receiving part on the substrate except for the dicing line and the electrode part. Simultaneously with the formation of the light shielding film, 20 alignment marks having a line width of 20 ⁇ m were formed on the substrate. The resolution was evaluated by observing the number of alignment marks formed using an optical microscope. “A”: 20 marks were formed. “B”: 19 marks were formed. “C”: 18 marks were formed. “D”: 17 or less marks were formed.
- FPA i-line exposure apparatus
- the content of the black dye is 0.3 or less (preferably 0.25 or less, more preferably) with respect to the pigment containing nitride or oxynitride. Is 0.2 or less), it was shown that reworkability is further improved.
- Example 1 When Examples 1, 4 and 5 were compared, it was shown that the reworkability, heat resistance and patterning properties were further improved due to the black dye having a polymerizable group. In Example 5 using an azo dye, it was confirmed that the heat resistance was excellent.
- Comparison of Examples 1 and 9 to 12 shows that the amount of particles in the liquid can be further reduced by setting the acid value of the dispersant to 50 mgKOH / g or more.
- the amount of particles in the liquid is smaller and the patterning property is also excellent.
- Examples 1, 20 and 21 are compared, it is shown that when the pigment content is 30% by mass or more based on the solid content, the light shielding performance of the obtained light shielding film is further improved and the heat resistance is also improved. It was done. On the other hand, it was shown that when the pigment content is 70% by mass or less with respect to the solid content, reworkability and patterning properties are further improved.
- Example 22 A composition was prepared and evaluated in the same manner except that the polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of using the dye A in Example 1. It was found to have the same performance as in Example 1.
- the polymerizable black dye “RDW-K01” manufactured by Wako Pure Chemical Industries, Ltd.
- Example 23 The same as Example 1 except that Dye A and polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye A, and the mass ratio was 1: 1. When the composition was prepared and evaluated, it was found that it had the same performance as Example 1.
- Example 24 The same as Example 4 except that Dye B and polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye B, and the weight ratio was 1: 1.
- Dye B and polymerizable black dye "RDW-K01" manufactured by Wako Pure Chemical Industries, Ltd.
- the weight ratio was 1: 1.
- evaluation superior to that of Example 4 was obtained. Specifically, the reworkability evaluation, the heat resistance evaluation, and the patterning evaluation were all “B”. I understood.
- Example 25 In Example 1, instead of using TiN-1, TiN-1 and carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, gas black method When the composition was prepared and evaluated in the same manner except that it was used at a mass ratio of 7: 3, it was found that it had the same performance as in Example 1.
- TiN-1 and carbon black trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, gas black method
- Example 26 In Example 1, TiN-1 and Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) were used instead of TiN-1, and the mass ratio was 9: 1.
- the composition was prepared and evaluated in the same manner except that it was used as a light-shielding film, it was found that the composition had the same performance as that of Example 1, and a darker light-shielding film was obtained. From this result, it is presumed that the desired effect of the present application can be obtained even in combination with other organic pigments or chromatic dyes.
Abstract
Description
また、遮光膜の他の用途としては、いわゆるブラックマトリクスも挙げられる。 The black light shielding film is used for various applications. For example, the light shielding film is used in a solid-state imaging device. Usually, a solid-state imaging device includes a photographing lens and a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor, complementary metal oxide semiconductor) disposed behind the photographing lens. An element (hereinafter, the solid-state image sensor is also referred to as an “image sensor”) and a circuit board on which the solid-state image sensor is mounted. In this solid-state imaging device, noise due to reflection of visible light may occur. Therefore, there is a case where a predetermined light shielding film is provided in the solid-state imaging device for the purpose of suppressing the generation of noise.
Another application of the light shielding film is a so-called black matrix.
一般的にチタン窒化物含有粒子等の顔料を用いる場合には、顔料の分散性を向上させる観点から分散剤が用いられる場合が多い。しかし、遮光性能を向上させるために組成物中の顔料濃度を高くした場合、組成物中の分散剤の含有量が相対的に多くなり、これに起因して、得られる遮光膜の遮光性能が低下する場合がある。
したがって、顔料濃度を増やす以外の手段により、遮光膜の遮光性能を改善させることが望まれるところである。 The present inventor made a light-shielding film of a color filter disposed in a solid-state imaging device, a liquid crystal image device or the like using a black composition prepared based on Patent Document 1, and examined various performances thereof. It came to know that the light-shielding performance in a specific wavelength region is low (in other words, the optical density is low).
In general, when a pigment such as titanium nitride-containing particles is used, a dispersant is often used from the viewpoint of improving the dispersibility of the pigment. However, when the pigment concentration in the composition is increased in order to improve the light shielding performance, the content of the dispersant in the composition is relatively increased, resulting in the light shielding performance of the resulting light shielding film. May decrease.
Therefore, it is desirable to improve the light shielding performance of the light shielding film by means other than increasing the pigment concentration.
また、本発明は、遮光性能に優れた硬化膜、上記硬化膜を備えるカラーフィルタ、遮光膜、固体撮像装置及び画像表示装置を提供することも目的とする。 An object of this invention is to provide the composition which can form the light shielding film excellent in light-shielding performance in view of the said situation.
Another object of the present invention is to provide a cured film having excellent light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device.
すなわち、以下の構成により上記目的を達成することができることを見出した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride), a black dye, The present invention has been completed by finding that the above-mentioned problems can be solved by using a composition containing.
That is, it has been found that the above object can be achieved by the following configuration.
(2) 上記無機顔料が、窒化物又は酸窒化物を含有する顔料である(1)に記載の組成物。
(3) 上記黒色染料が重合性基を有する、(1)又は(2)に記載の組成物。
(4) 上記重合性基がアクリロイル基又はメタクリロイル基である、(3)に記載の組成物。
(5) 上記黒色染料がキサンテン系染料又はアゾ系染料である、(1)~(4)のいずれかに記載の組成物。
(6) 上記黒色染料が染料多量体である、(1)~(5)のいずれかに記載の組成物。
(7) 更に、分散剤を含む、(1)~(6)のいずれかに記載の組成物。
(8) 上記分散剤の酸価が50mgKOH/g以上である、(7)に記載の組成物。
(9) 上記分散剤が、ポリカプロラクトン、ポリバレロラクトン、ポリアクリル酸メチル及びポリメタクリル酸メチルからなる群より選択される少なくとも1種の構造を有する、(7)又は(8)に記載の組成物。
(10) 更に、重合性化合物と、重合開始剤と、を含む、(1)~(9)のいずれかに記載の組成物。
(11) 更に、有機溶剤を含む、(1)~(10)のいずれかに記載の組成物。
(12) 更に、アルカリ可溶性樹脂を含む、(1)~(11)のいずれかに記載の組成物。
(13) 上記黒色染料の含有量が、上記無機顔料の含有量に対して質量比で0.3以下である、(1)~(12)のいずれかに記載の組成物。
(14) 組成物全質量に対する固形分量が10~40質量%である、(1)~(13)のいずれかに記載の組成物。
(15) 上記無機顔料の含有量が、固形分量に対して30~70質量%である、(1)~(14)のいずれかに記載の組成物。
(16) (1)~(15)のいずれかに記載の組成物を用いて得られる、硬化膜。
(17) (16)に記載の硬化膜を有する、カラーフィルタ。
(18) (16)に記載の硬化膜を有する、遮光膜。
(19) (16)に記載の硬化膜を有する、固体撮像装置。
(20) (16)に記載の硬化膜を有する、画像表示装置。 (1) A composition comprising an inorganic pigment and a black dye.
(2) The composition according to (1), wherein the inorganic pigment is a pigment containing nitride or oxynitride.
(3) The composition according to (1) or (2), wherein the black dye has a polymerizable group.
(4) The composition according to (3), wherein the polymerizable group is an acryloyl group or a methacryloyl group.
(5) The composition according to any one of (1) to (4), wherein the black dye is a xanthene dye or an azo dye.
(6) The composition according to any one of (1) to (5), wherein the black dye is a dye multimer.
(7) The composition according to any one of (1) to (6), further comprising a dispersant.
(8) The composition as described in (7) whose acid value of the said dispersing agent is 50 mgKOH / g or more.
(9) The composition according to (7) or (8), wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate. object.
(10) The composition according to any one of (1) to (9), further comprising a polymerizable compound and a polymerization initiator.
(11) The composition according to any one of (1) to (10), further comprising an organic solvent.
(12) The composition according to any one of (1) to (11), further comprising an alkali-soluble resin.
(13) The composition according to any one of (1) to (12), wherein the content of the black dye is 0.3 or less by mass ratio with respect to the content of the inorganic pigment.
(14) The composition according to any one of (1) to (13), wherein the solid content is 10 to 40% by mass relative to the total mass of the composition.
(15) The composition according to any one of (1) to (14), wherein the content of the inorganic pigment is 30 to 70% by mass with respect to the solid content.
(16) A cured film obtained using the composition according to any one of (1) to (15).
(17) A color filter having the cured film according to (16).
(18) A light shielding film having the cured film according to (16).
(19) A solid-state imaging device having the cured film according to (16).
(20) An image display device having the cured film according to (16).
また、本発明によれば、遮光性能に優れた硬化膜、上記硬化膜を備えるカラーフィルタ、遮光膜、固体撮像装置及び画像表示装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the light shielding film excellent in light shielding performance can be provided.
In addition, according to the present invention, it is possible to provide a cured film having excellent light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device.
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、及び、電子線等を意味する。また本発明において光とは、活性光線又は放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、X線、及び、EUV光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も露光に含める。
本明細書において、“(メタ)アクリレート”はアクリレート及びメタアクリレートを表し、“(メタ)アクリル”はアクリル及びメタアクリルを表し、“(メタ)アクリロイル”は、アクリロイル及びメタクリロイルを表す。また、本明細書中において、“単量体”と“モノマー”とは同義である。本発明における単量体は、オリゴマー及びポリマーと区別され、重量平均分子量が2,000以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基をいう。 The present invention will be described below.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in the present specification is not limited to exposure with a deep ultraviolet ray, an X-ray, EUV light or the like represented by a mercury lamp or an excimer laser, but also a particle beam such as an electron beam and an ion beam. Include drawing in exposure.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
本発明の組成物は、無機顔料(好ましくは後述する黒色の無機顔料であり、より好ましくは窒化物又は酸窒化物を含有する顔料)と、黒色染料とを含む。
本発明の組成物によれば、遮光性能に優れた遮光膜を形成することができる。つまり、本発明の組成物によれば、特定の波長領域における遮光性能の低下がなく、所定領域(例えば、可視光領域~1200nm)において最低光学濃度(以下「最低OD値」ともいう。)が充分な遮光能を与え得る範囲にある遮光膜を形成することができる。
本発明の組成物の特徴としては、黒色染料を含有している点にある。最低光学濃度を向上させるために無機顔料濃度を高くした場合、組成物中において、無機顔料の分散性を向上させる目的で使用される分散剤の含有量が相対的に多くなり、これに起因して、得られる遮光膜の遮光性能が低下する場合がある。しかし、本発明の組成物は、分散剤を必要とせず且つ可視光の略全波長領域にわたって吸収を有する黒色染料を含有するため、分散剤等の他の成分を増加させることなく遮光膜の最低光学濃度を向上させることが可能となる。
特に、後述するようなキサンテン系染料又はアゾ系染料を用いた場合、遮光性能により優れ、かつ、解像性に優れた遮光膜を形成できることを知見している。 〔Composition〕
The composition of the present invention contains an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride) and a black dye.
According to the composition of the present invention, a light shielding film having excellent light shielding performance can be formed. That is, according to the composition of the present invention, there is no reduction in the light shielding performance in a specific wavelength region, and the minimum optical density (hereinafter also referred to as “minimum OD value”) in a predetermined region (eg, visible light region to 1200 nm). It is possible to form a light shielding film in a range where sufficient light shielding ability can be provided.
The composition of the present invention is characterized in that it contains a black dye. When the inorganic pigment concentration is increased in order to improve the minimum optical density, the content of the dispersant used for the purpose of improving the dispersibility of the inorganic pigment in the composition is relatively increased, resulting in this. As a result, the light shielding performance of the resulting light shielding film may deteriorate. However, since the composition of the present invention does not require a dispersant and contains a black dye having absorption over almost the entire wavelength region of visible light, the minimum of the light-shielding film without increasing other components such as a dispersant. The optical density can be improved.
In particular, it has been found that when a xanthene dye or azo dye as will be described later is used, a light-shielding film excellent in light-shielding performance and excellent in resolution can be formed.
また、昨今、遮光膜を所定の基板上に形成した後、遮光膜の形成位置のズレ等のために、遮光膜を基板上から剥離することが求められる場合がある。いわゆるリワーク性が求められる。
本発明者は、上記のように、膜を構成するマトリックスと黒色染料とが重合性基により化学的に結合することで、リワーク性も向上することも知見した。つまり、例えば、無機顔料と、重合性基を有する黒色染料と、アルカリ可溶性樹脂等を含有する組成物を用いて作製したカラーフィルタ(硬化膜)を、例えばTMAH(水酸化テトラメチルアンモニウム)等のアルカリ水溶液で除去する場合には、黒色染料がアルカリ可溶性樹脂を含んで構成される膜と化学的に結合しているため、染料をマトリックスごと除去(剥離)することが可能となる。一方、黒色染料が重合性基を有さず、つまり黒色染料がマトリックスと化学的に結合してない場合には、染料は一般的にアルカリ水溶液に溶けないため、固体撮像素子上に単独で残渣として付着し除去が困難となる。すなわちリワーク性に劣る。 The present inventor has recently found out that the above-described black dye preferably has a polymerizable group. When the light-shielding film is formed using the composition of the present invention, when the black dye has a polymerizable group, the dye is incorporated into the matrix constituting the film via the polymerizable group. It is known that dyes are generally inferior in heat resistance to pigments. When a dye is used as a constituent component of a light shielding film, the light shielding film may be inferior in heat resistance due to the dye. On the other hand, as described above, it has been confirmed that the matrix constituting the film and the black dye are chemically bonded to each other by a polymerizable group, thereby improving heat resistance.
In addition, recently, after forming a light shielding film on a predetermined substrate, there is a case where it is required to peel the light shielding film from the substrate in order to shift the formation position of the light shielding film. So-called reworkability is required.
As described above, the present inventor has also found that the reworkability is improved by chemically bonding the matrix constituting the film and the black dye by the polymerizable group. In other words, for example, a color filter (cured film) produced using a composition containing an inorganic pigment, a black dye having a polymerizable group, an alkali-soluble resin, or the like is used, such as TMAH (tetramethylammonium hydroxide). In the case of removing with an alkaline aqueous solution, since the black dye is chemically bonded to a film including an alkali-soluble resin, the dye can be removed (peeled) together with the matrix. On the other hand, when the black dye does not have a polymerizable group, that is, when the black dye is not chemically bonded to the matrix, the dye generally does not dissolve in an alkaline aqueous solution, so that the residue alone on the solid-state image sensor It becomes difficult to remove. That is, it is inferior to reworkability.
本発明の組成物は、無機顔料を含有する。
上記無機顔料としては、特に制限されず、公知の無機顔料を用いることができる。
無機顔料としては、例えば、カーボンブラック、シリカ、亜鉛華、鉛白、リトポン、酸化チタン、酸化クロム、酸化鉄、沈降性硫酸バリウム及びバライト粉、鉛丹、酸化鉄赤、黄鉛、亜鉛黄(亜鉛黄1種、亜鉛黄2種)、ウルトラマリン青、プロシア青(フェロシアン化鉄カリ)ジルコングレー、プラセオジムイエロー、クロムチタンイエロー、クロムグリーン、ピーコック、ビクトリアグリーン、紺青(プルシアンブルーとは無関係)、バナジウムジルコニウム青、クロム錫ピンク、陶試紅、並びに、サーモンピンク等が挙げられる。また、黒色の無機顔料であることが好ましく、無機顔料としては、含有量が少なくとも、高い光学濃度を有する硬化膜を形成することができる組成物が得られる点で、カーボンブラック、チタンブラック、及び金属顔料等が好ましい。金属顔料としては、例えば、Nb、V、Co、Cr、Cu、Mn、Ru、Fe、Ni、Sn、Ti、及びAgからなる群より選ばれる1種又は2種以上の金属元素を含む金属酸化物、金属窒素物、及び金属酸窒化物が挙げられる。
無機顔料としては、窒化チタン、酸窒化チタン、窒化ニオブ、酸窒化ニオブ、窒化バナジウム、酸窒化バナジウム、酸化クロム、窒化クロム、酸窒化クロム、酸化鉄、酸窒化鉄、銀を含有する金属顔料、錫を含有する金属顔料、並びに銀及び錫を含有する金属顔料からなる群から選択される少なくとも1種であることが好ましい。
なかでも、無機顔料は、後述する窒化物又は酸窒化物を含有する顔料から選択される少なくとも1種であることがより好ましい。
なお、無機顔料は1種を単独で用いても、2種以上を併用してもよい。 <Inorganic pigment>
The composition of the present invention contains an inorganic pigment.
The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
Examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( 1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink. Further, it is preferably a black inorganic pigment, and as the inorganic pigment, carbon black, titanium black, and at least a content capable of forming a cured film having a high optical density is obtained. Metal pigments are preferred. Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Products, metal nitrides, and metal oxynitrides.
As inorganic pigments, metal pigments containing titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, silver, It is preferably at least one selected from the group consisting of a metal pigment containing tin and a metal pigment containing silver and tin.
Especially, it is more preferable that an inorganic pigment is at least 1 sort (s) selected from the pigment containing the nitride or oxynitride mentioned later.
In addition, an inorganic pigment may be used individually by 1 type, or may use 2 or more types together.
透過型電子顕微鏡を用いて得た粒子像の最大長(Dmax:粒子画像の輪郭上の2点における最大長さ)、及び最大長垂直長(DV-max:最大長に平行な2本の直線で画像を挟んだ時、2直線間を垂直に結ぶ最短の長さ)を測長し、その相乗平均値(Dmax×DV-max)1/2を粒子径とした。この方法で100個の粒子の粒子径を測定し、その算術平均値を平均粒子径として、顔料の平均一次粒子径とする。 The average primary particle diameter of the inorganic pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length) The shortest length connecting two straight lines perpendicularly) was measured, and the geometric mean value (Dmax × DV-max) 1/2 was taken as the particle diameter. The particle diameter of 100 particles is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
上述のとおり、無機顔料は、窒化物又は酸窒化物を含有する顔料であることが好ましい。
窒化物又は酸窒化物を含有する顔料としては、例えば、窒化チタン、酸窒化チタン、窒化ニオブ、酸窒化ニオブ、窒化バナジウム、酸窒化バナジウム、酸窒化鉄、及び、酸窒化タングステン等の顔料が挙げられる。なかでも、波長400~1200nmの領域に吸収を有するものが好ましい。なお、無機顔料及び後述する黒色染料の吸収波長及び光学濃度は、分光光度計U-4100(日立ハイテクノロジーズ社製)等を用いて測定することができる。
少量で高い光学濃度を実現できる観点からは、例えば、窒化チタン、酸窒化チタン、窒化ニオブ又は窒化バナジウムが好ましく、窒化チタン又は酸窒化チタンがより好ましい。窒化チタン又は酸窒化チタンとしては、特に限定されないが、国際公開第2008/123097号公報、国際公開第2010/147098号公報、特許第5577659号公報に記載の窒化チタンを使用することができる。
また、窒化物又は酸窒化物を含有する顔料において、窒化物又は酸窒化物の含有量(例えば顔料がチタン窒化物を含有する場合には、チタン窒化物の含有量)は、顔料全質量に対して10~100質量%であることが好ましく、20~100質量%であることがより好ましい。 (Pigment containing nitride or oxynitride)
As described above, the inorganic pigment is preferably a pigment containing nitride or oxynitride.
Examples of the pigment containing nitride or oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. It is done. Among them, those having absorption in the wavelength region of 400 to 1200 nm are preferable. The absorption wavelength and optical density of the inorganic pigment and black dye described later can be measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).
From the viewpoint of realizing a high optical density in a small amount, for example, titanium nitride, titanium oxynitride, niobium nitride, or vanadium nitride is preferable, and titanium nitride or titanium oxynitride is more preferable. Although it does not specifically limit as titanium nitride or titanium oxynitride, The titanium nitride as described in international publication 2008/123097 gazette, international publication 2010/147098 gazette, and patent 5777659 gazette can be used.
Further, in the pigment containing nitride or oxynitride, the content of nitride or oxynitride (for example, the content of titanium nitride when the pigment contains titanium nitride) is the total mass of the pigment. The content is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.
以下、酸窒化チタン顔料であるチタンブラック粒子について説明する。
チタンブラック粒子は、分散性向上又は凝集性抑制等の目的で必要に応じ、表面を修飾することが可能である。酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックを被覆することが可能である。また、特開2007-302836号公報に表されるような撥水性物質で、チタンブラックの表面処理も可能である。
チタンブラックは、典型的には、チタンブラック粒子であり、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいものであることが好ましい。
具体的には、平均一次粒子径で10nm~80nmの範囲のものが好ましい。平均一次粒子径は、例えば上記の方法により測定できる。 Titanium black Titanium black particles that are titanium oxynitride pigments will be described below.
The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility or suppressing aggregation. It is possible to coat titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a surface treatment of titanium black is possible with a water repellent material as disclosed in JP-A-2007-302836.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small.
Specifically, an average primary particle diameter in the range of 10 nm to 80 nm is preferable. The average primary particle diameter can be measured, for example, by the above method.
チタンブラックの市販品の例としては、チタンブラック10S、12S、13M、13M-C、13R、13R-N、及び13M-T(商品名:三菱マテリアル(株)製)、並びに、ティラック(Tilack)D(商品名:赤穂化成(株)製)等が挙げられる。 The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance It is preferably 5 m 2 / g or more and 150 m 2 / g or less, and more preferably 20 m 2 / g or more and 120 m 2 / g or less.
Examples of commercially available products of titanium black include titanium black 10S, 12S, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), and Tilac. ) D (trade name: manufactured by Ako Kasei Co., Ltd.).
この形態において、チタンブラックは、組成物中において被分散体として含有されるものであり、被分散体中のSi原子とTi原子との含有比(Si/Ti)が質量換算で0.05以上が好ましく、0.05~0.5がより好ましく、0.07~0.4が更に好ましい。
ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体(二次粒子)の状態であるものの双方を包含する。
被分散体のSi/Tiを変更する(例えば、0.05以上とする)ためには、以下のような手段を用いることができる。
先ず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この分散物を高温(例えば、850~1000℃)にて還元処理することにより、チタンブラック粒子を主成分とし、SiとTiとを含有する被分散体を得ることができる。上記還元処理は、アンモニア等の還元性ガスの雰囲気下で行う。
酸化チタンとしては、TTO-51N(商品名:石原産業製)等が挙げられる。酸化チタンはこれに限定されないが一次粒径が5nm以上70nm以下のものが好ましく、7nm以上50nm以下のものがより好ましく、結晶系としてはルチル、アナタースであればどちらでも好適に用いることができ、これらの混晶であってもよい。
シリカ粒子の市販品としては、AEROSIL(登録商標)90、130、150、200、255、300、及び、380(商品名:エボニック製)等が挙げられる。
酸化チタンとシリカ粒子との分散は、分散剤を用いてもよい。分散剤としては、後述する分散剤の欄で説明するものが挙げられる。
上記の分散は溶剤中で行ってもよい。溶剤としては、水又は有機溶剤が挙げられる。後述する有機溶剤の欄で説明するものが挙げられる。
Si/Tiが、例えば、0.05以上等に調整されたチタンブラックは、例えば、特開2008-266045公報の段落番号〔0005〕及び段落番号〔0016〕~〔0021〕に記載の方法により作製することができる。 Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment is performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). Titanium oxide is not limited to this, but preferably has a primary particle size of 5 nm or more and 70 nm or less, more preferably 7 nm or more and 50 nm or less. These mixed crystals may be used.
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).
A dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned.
Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. can do.
残渣物が低減される理由は不明だが、上記のような被分散体は小粒径となる傾向があり(例えば、粒径が30nm以下)、更に、この被分散体のSi原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減され、これが、遮光膜の形成における未硬化の組成物(特に、チタンブラック)の現像除去性の向上に寄与すると推測している。
また、チタンブラックは、紫外光から赤外光までの広範囲に亘る波長領域の光に対する遮光性に優れることから、上記したチタンブラック及びSi原子を含む被分散体(好ましくはSi/Tiが質量換算で0.05以上であるもの)を用いて形成された遮光膜は優れた遮光性を発揮する。
なお、被分散体中のSi原子とTi原子との含有比(Si/Ti)は、例えば、特開2013-249417号公報の段落0033に記載の方法(1-1)又は方法(1-2)を用いて測定できる。
また、組成物を硬化して得られた遮光膜に含有される被分散体について、その被分散体中のSi原子とTi原子との含有比(Si/Ti)が0.05以上か否かを判断するには、特開2013-249417号公報の段落0035に記載の方法(2)を用いる。 The composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a light shielding film is formed using an object, the residue derived from the composition outside the region where the light shielding film is formed is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle and a resin component.
The reason why the residue is reduced is unknown, but the above-described dispersion tends to have a small particle size (for example, a particle size of 30 nm or less), and the component containing Si atoms in the dispersion It is estimated that this increases the adsorptivity with the base of the entire film, which contributes to the improvement of the development removability of the uncured composition (particularly titanium black) in the formation of the light-shielding film.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is in terms of mass) The light-shielding film formed by using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the light-shielding film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
この場合、全被分散体中の50質量%以上をチタンブラックからなる被分散体が占めることが好ましい。
また、この被分散体においては、遮光性の調整等を目的として、本発明の効果を損なわない限りにおいて、チタンブラックと共に、他の着色剤(有機顔料及び染料等)を所望により併用してもよい。
以下、被分散体にSi原子を導入する際に用いられる材料について述べる。被分散体にSi原子を導入する際には、シリカ等のSi含有物質を用いればよい。
用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、及び、合成シリカ等を挙げることができ、これらを適宜選択して使用すればよい。
更に、シリカ粒子の粒径が遮光膜を形成した際に膜厚よりも小さい粒径であると遮光性がより優れるため、シリカ粒子として微粒子タイプのシリカを用いることが好ましい。なお、微粒子タイプのシリカの例としては、例えば、特開2013-249417号公報の段落0039に記載のシリカが挙げられ、これらの内容は本明細書に組み込まれる。 In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
Moreover, in this to-be-dispersed body, as long as the effect of this invention is not impaired, other colorants (an organic pigment, dye, etc.) may be used together as desired, as long as the effect of the present invention is not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Furthermore, if the particle size of the silica particles is smaller than the film thickness when the light shielding film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
また、窒化物又は酸窒化物を含有する顔料としては、例えば、チタン窒化物含有粒子も用いることができる。
チタン窒化物含有粒子の製造には、通常、気相反応法が用いられ、具体的には電気炉法及び熱プラズマ法等が挙げられる。これらの製法のなかでも、不純物の混入が少ない点、粒子径が揃いやすい点、及び、生産性が高い点等の理由から、熱プラズマ法が好ましい。
熱プラズマの発生方法としては、直流アーク放電、多相アーク放電、高周波(RF)プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマが好ましい。熱プラズマ法によるチタン窒化物含有粒子の具体的な製造方法としては、例えば、チタン粉末を高周波熱プラズマにより蒸発させ、窒素をキャリアガスとして装置内に導入し、冷却過程にてチタン粉末を窒化させ、チタン窒化物含有粒子を合成する方法等が挙げられる。なお、熱プラズマ法は、上記に限定されるものではない。
また、チタン窒化物含有粒子は、熱プラズマ法を用いて得られることにより、CuKα線をX線源とした場合の(200)面に由来するピークの回折角2θ(詳細は後述する)を、42.8°超43.5°以下の範囲に調整することが容易になる。 -Titanium nitride containing particle Moreover, as a pigment containing a nitride or an oxynitride, a titanium nitride containing particle can also be used, for example.
For production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable. As a specific method for producing titanium nitride-containing particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles. The thermal plasma method is not limited to the above.
Further, the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a peak diffraction angle 2θ (details will be described later) derived from the (200) plane when CuKα rays are used as an X-ray source, It becomes easy to adjust to the range of 42.8 ° or more and 43.5 ° or less.
チタン窒化物含有粒子中の窒素原子(N原子)の含有量は、チタン窒化物含有粒子の全質量に対して、15~50質量%であることが好ましく、15~45質量%であることがより好ましく、20~40質量%であることが更に好ましい。窒素原子の含有量は不活性ガス融解-熱伝導度法により分析することができる。 The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, and preferably 55 to 85% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 55 to 80% by mass. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 15 to 50% by mass and preferably 15 to 45% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 40% by mass. The nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
チタン窒化物含有粒子は主成分としてチタン窒化物(TiN)を含み、通常、その合成時に酸素が混入する場合、及び、粒子径が小さい場合等に顕著になるが、粒子表面の酸化等により、一部酸素原子を含有している場合がある。
ただし、チタン窒化物含有粒子に含まれる酸素量が少ない方がより高いOD値(光学濃度)が得られるため好ましい。また、チタン窒化物含有粒子は、副成分としてTiO2を含有しないことが好ましい。副成分として酸化チタンTiO2をチタン窒化物含有粒子が含有する場合、最も強度の強いピークとしてアナターゼ型TiO2(101)に由来するピークが2θ=25.3°近傍に、ルチル型TiO2(110)に由来するピークが2θ=27.4°近傍に見られる。しかし、TiO2は白色でありブラックマトリクスの遮光性を低下させる要因となるため、ピークとして観察されない程度に低減されていることが好ましい。 The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8 ° and not more than 43.5 ° as described above, and is 42.85 to 43.3 °. Is more preferably 42.9 to 43.2 °.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed during the synthesis and when the particle diameter is small. Some may contain oxygen atoms.
However, a smaller amount of oxygen contained in the titanium nitride-containing particles is preferable because a higher OD value (optical density) can be obtained. Further, the titanium nitride-containing particles, preferably contains no TiO 2 as an auxiliary component. When the titanium nitride-containing particles contain titanium oxide TiO 2 as an accessory component, the peak derived from anatase TiO 2 (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, the rutile TiO 2 ( 110) is observed in the vicinity of 2θ = 27.4 °. However, since TiO 2 is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.
本発明の組成物は、無機顔料として、上記で挙げたもの以外の無機顔料も含有してもよい。他の顔料としては、例えば、タングステン化合物及び金属ホウ化物が挙げられる。
タングステン化合物、及び金属ホウ化物は、赤外線(波長が約800~1200nmの光)に対しては吸収が高い(すなわち、赤外線に対する遮光性(遮蔽性)が高く)特徴を有する。なお、タングステン化合物及び金属ホウ化物は、赤外線に対する遮光性に比べると可視光に対しては吸収が低い。また、タングステン化合物及び金属ホウ化物は、画像形成に用いられる、高圧水銀灯、KrF及びArF等の露光に用いられる可視域より短波の光に対しても吸収が小さい。 (Other pigments)
The composition of the present invention may also contain inorganic pigments other than those listed above as the inorganic pigment. Examples of other pigments include tungsten compounds and metal borides.
Tungsten compounds and metal borides have a feature of high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) with respect to infrared rays). Note that the tungsten compound and the metal boride have a low absorption with respect to visible light as compared with a light shielding property against infrared rays. In addition, the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image formation.
MxWyOz・・・(I)
Mは金属、Wはタングステン、Oは酸素を表す。
0.001≦x/y≦1.1
2.2≦z/y≦3.0 Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
M x W y O z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
z/yが2.2以上であることにより、材料としての化学的安定性をより向上させることができ、3.0以下であることにより赤外線を十分に遮蔽することができる。 When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
また、酸化タングステン系化合物は、例えば、住友金属鉱山株式会社製のYMF-02等のタングステン微粒子の分散物としても、入手可能である。 Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205).
Further, the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
無機顔料として体質顔料を用いる場合は、体質顔料を着色顔料(例えば、黒色の無機顔料)と併用することが好ましい。これらの体質顔料は、単独で又は2種以上を混合して使用することができる。体質顔料の使用量は、着色剤100質量部に対して、通常、0~100質量部、好ましくは5~50質量部、より好ましくは10~40質量部である。着色剤及び体質顔料は、場合により、それらの表面をポリマーで改質して使用することができる。 The inorganic pigment may be an extender pigment. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite.
When an extender is used as the inorganic pigment, the extender is preferably used in combination with a color pigment (for example, a black inorganic pigment). These extender pigments can be used alone or in admixture of two or more. The amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant. In some cases, the colorant and extender pigment can be used with their surface modified with a polymer.
本発明の組成物は、黒色染料を含む。
黒色染料としては、可視光(380nm以上780nm)の全波長領域にわたって吸収を有するものが好ましい。
黒色染料としては、例えば、C.I.ダイレクトブラック19、22、32、38、51、56、71、74、75、77、154、168及び171等のほか、公知の黒色を呈する染料が挙げられる。また、黒色染料としては、キサンテン系染料、アゾ系染料、及びアニリン系染料も挙げられる。
黒色染料は、特に、400~500nmの全波長領域において、光学濃度2以上が好ましく、4以上がより好ましい。 <Black dye>
The composition of the present invention comprises a black dye.
As the black dye, those having absorption over the entire wavelength region of visible light (380 nm to 780 nm) are preferable.
Examples of the black dye include C.I. I. In addition to direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like, dyes exhibiting a known black color can be used. Further, examples of the black dye include xanthene dyes, azo dyes, and aniline dyes.
In particular, the black dye preferably has an optical density of 2 or more, more preferably 4 or more in the entire wavelength region of 400 to 500 nm.
重合性基は、エネルギー付与により、化学結合を形成しうる官能基であり、例えば、ラジカル重合性基及びカチオン重合性基等が挙げられる。なかでも、反応性がより優れる点から、ラジカル重合性基が好ましい。ラジカル重合性基としては、例えば、アクリロイル基、メタクリロイル基、アクリル酸エステル基(アクリロイルオキシ基)、メタクリル酸エステル基(メタクリロイルオキシ基)、イタコン酸エステル基、クロトン酸エステル基、イソクロトン酸エステル基、及び、マレイン酸エステル基等の不飽和カルボン酸エステル基のほか、スチリル基、ビニル基、アクリルアミド基、及び、メタクリルアミド基等が挙げられる。なかでも、塗膜の解像性がより向上する観点から、メタクリロイル基又はアクリロイル基がより好ましい。
黒色染料中には、重合性基は2種以上含まれていてもよい。また、黒色染料中に含まれる重合性基の数は特に制限されず、1つでも、2つ以上でもよい。 The black dye preferably has a polymerizable group. When the black dye has a polymerizable group, heat resistance and reworkability can be improved.
The polymerizable group is a functional group that can form a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among these, a radical polymerizable group is preferable from the viewpoint of more excellent reactivity. Examples of the radical polymerizable group include acryloyl group, methacryloyl group, acrylic acid ester group (acryloyloxy group), methacrylic acid ester group (methacryloyloxy group), itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group, In addition to unsaturated carboxylic acid ester groups such as maleic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups are exemplified. Among these, from the viewpoint of further improving the resolution of the coating film, a methacryloyl group or an acryloyl group is more preferable.
Two or more polymerizable groups may be contained in the black dye. In addition, the number of polymerizable groups contained in the black dye is not particularly limited, and may be one or two or more.
なかでも、下記一般式(1)で表される構造単位を有する染料多量体であることが好ましく、重合性基を有し、且つ、下記一般式(1)で表される構造単位を有する染料多量体であることがより好ましい。 The black dye may be either a dye monomer or a dye multimer, but is preferably a dye multimer from the viewpoint of further improving heat resistance.
Especially, it is preferable that it is a dye multimer which has a structural unit represented by the following general formula (1), has a polymeric group, and has the structural unit represented by the following general formula (1) More preferred is a multimer.
Lは、単結合又は2価の連結基を表す。
2価の連結基としては、例えば、-O-、-S-、-NR1-、-CO-、ビニレン基、エチニレン基、アルキレン基(環状、分岐鎖状、直鎖状のいずれであってもよい)、アリーレン基、ヘテロアリーレン基、又は、これらを組み合わせてなる2価の基が挙げられる。
R1は、例えば、水素原子、アルキル基(好ましくは、炭素数1~10の直鎖状又は分岐鎖状のアルキル基)、ハロゲン原子(好ましくは、F原子、Cl原子、Br原子、I原子)、アリール基(好ましくは炭素数6~20のアリール基)が挙げられる。これらのなかでも、水素原子又はアルキル基であることが好ましい。 R A to R C each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Of these, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is preferable.
L represents a single bond or a divalent linking group.
Examples of the divalent linking group include —O—, —S—, —NR 1 —, —CO—, a vinylene group, an ethynylene group, and an alkylene group (which may be cyclic, branched, or linear). Or an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof.
R 1 is, for example, a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, an I atom ) And aryl groups (preferably aryl groups having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.
黒色染料としては、特に限定されないが、上述した黒色染料が挙げられる。なかでも、遮光性能により優れた遮光膜を形成できる観点から、キサンテン系染料又はアゾ系染料が好ましい。
なお、上記一般式(1)で表される構造単位を有する染料多量体が重合性基を有する場合、染料多量体中における重合性基の位置は特に制限されない。染料多量体中における重合性基の位置としては、例えば、Dyeが重合性基を有していてもよいし、重合性基を有する構造単位を有していてもよい。なお、Dyeが重合性基を有するとは、Dyeで表される、黒色染料から任意の水素原子を1個取り除いた染料残基が重合性基を有することを意図する。 Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye.
Although it does not specifically limit as black dye, The black dye mentioned above is mentioned. Of these, xanthene dyes or azo dyes are preferred from the viewpoint of forming a light-shielding film having better light-shielding performance.
When the dye multimer having the structural unit represented by the general formula (1) has a polymerizable group, the position of the polymerizable group in the dye multimer is not particularly limited. As the position of the polymerizable group in the dye multimer, for example, Dye may have a polymerizable group or may have a structural unit having a polymerizable group. In addition, Dye having a polymerizable group intends that the dye residue represented by Dye, which is obtained by removing one arbitrary hydrogen atom from a black dye, has a polymerizable group.
上記一般式(1)で表わされる構造単位を有する染料多量体は、公知の方法により製造することができる。 When the black dye is a dye multimer, the content of the structural unit represented by the general formula (1) in the dye multimer is preferably 80% by mass or more based on the total structural unit, and 85 More preferably, it is 90 mass% or more, and 95 mass% or more is especially preferable.
The dye multimer having the structural unit represented by the general formula (1) can be produced by a known method.
GPC法は、HLC-8020GPC(東ソー(株)製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー(株)製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。 When the black dye is a dye multimer, its molecular weight is not particularly defined, but as a polystyrene equivalent value by GPC (gel permeation chromatography) method, the weight average molecular weight (Mw) is preferably 1000 or more and 20000 or less. More preferably, it is 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
本発明の組成物において、黒色染料は1種を単独で用いても、2種以上を併用してもよい。 In the composition of the present invention, the content of the black dye is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, with respect to the total solid content of the composition. More preferably, it is mass%.
In the composition of the present invention, the black dye may be used alone or in combination of two or more.
本発明の組成物は、分散剤を含有することが好ましい。分散剤は、上述した無機顔料等の顔料成分の分散性向上に寄与する。本発明において、分散剤と、後述するバインダー樹脂とは、異なる成分である。
分散剤としては、例えば、公知の顔料分散剤を適宜選択して用いることができる。なかでも、高分子化合物が好ましい。
分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、及びナフタレンスルホン酸ホルマリン縮合物等〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等が挙げられる。
高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及びブロック型高分子に分類することができる。 <Dispersant>
The composition of the present invention preferably contains a dispersant. A dispersing agent contributes to the improvement of the dispersibility of pigment components, such as the inorganic pigment mentioned above. In this invention, a dispersing agent and the binder resin mentioned later are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalene sulfonic acid formalin condensate and the like], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
一方で、無機顔料の表面を改質することにより、これに対する高分子化合物の吸着性を促進させることもできる。 The polymer compound is adsorbed on the surface of a dispersion such as an inorganic pigment and a pigment used in combination as desired, and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are preferable.
On the other hand, by modifying the surface of the inorganic pigment, the adsorptivity of the polymer compound can be promoted.
このようなグラフト鎖を有する構造単位を有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、上述の無機顔料等の着色顔料の分散性、及び、経時後の分散安定性に優れるものである。また、グラフト鎖の存在により、グラフト鎖を有する構造単位を有する高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
グラフト鎖が長くなると立体反発効果が高くなり顔料等の分散性は向上する。一方、グラフト鎖が長すぎると上述の無機顔料等の着色顔料への吸着力が低下して、顔料等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が40~10000であるものが好ましく、水素原子を除いた原子数が50~2000であるものがより好ましく、水素原子を除いた原子数が60~500であるものが更に好ましい。
ここで、グラフト鎖とは、共重合体の主鎖の根元(主鎖から枝分かれしている基において主鎖に結合する原子)から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound having a structural unit having such a graft chain has an affinity with a solvent by the graft chain, the dispersibility of the color pigment such as the above-mentioned inorganic pigment and the dispersion stability after aging are improved. It is excellent. Further, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as the above-mentioned inorganic pigments is lowered, and the dispersibility of the pigments and the like tends to be lowered. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
グラフト鎖と溶剤との相互作用性を向上させ、それにより分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造及びポリ(メタ)アクリレート構造からなる群から選ばれた少なくとも1種を有するグラフト鎖であることが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを有するグラフト鎖であることがより好ましい。 The graft chain preferably has a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility, the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. The graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
ここで、ポリカプロラクトン構造とは、ε-カプロラクトンを開環した構造を繰り返し単位として有するものをいう。ポリバレロラクトン構造とは、δ-バレロラクトンを開環した構造を繰り返し単位として有するものをいう。
ポリカプロラクトン構造を有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが5であるものが挙げられる。また、ポリバレロラクトン構造を有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが4であるものが挙げられる。
ポリアクリル酸メチル構造を有する分散剤の具体例としては、下記式(4)におけるX5が水素原子であり、R4がメチル基であるものが挙げられる。また、ポリメタクリル酸メチル構造を有する分散剤の具体例としては、下記式(4)におけるX5がメチル基であり、R4がメチル基であるものが挙げられる。 The dispersant preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. Among them, it is preferable to have at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester, and polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethacrylic acid. More preferably, it has at least one structure selected from the group consisting of methyl. The dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
Here, the polycaprolactone structure means a structure having a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure having a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant having a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2). Specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
Specific examples of the dispersant having a polymethyl acrylate structure include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant having a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
式(1)~式(4)において、X1、X2、X3、X4、及びX5は、それぞれ独立に、水素原子又は1価の有機基を表す。X1、X2、X3、X4、及びX5としては、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数1~12のアルキル基であることが好ましく、それぞれ独立に、水素原子又はメチル基であることがより好ましく、メチル基であることが更に好ましい。 In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.
また、式(1)及び式(2)において、j及びkは、それぞれ独立に、2~8の整数を表す。式(1)及び式(2)におけるj及びkは、組成物の分散安定性及び現像性の観点から、4~6の整数が好ましく、5が最も好ましい。 In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of dispersion stability and developability of the composition.
式(4)中、R4は水素原子又は1価の有機基を表し、この1価の有機基としては特に構造上限定はされない。R4として好ましくは、水素原子、アルキル基、アリール基、及びヘテロアリール基が挙げられ、より好ましくは、水素原子、又はアルキル基である。R4がアルキル基である場合、アルキル基としては、炭素数1~20の直鎖状アルキル基、炭素数3~20の分岐鎖状アルキル基、又は炭素数5~20の環状アルキル基が好ましく、炭素数1~20の直鎖状アルキル基がより好ましく、炭素数1~6の直鎖状アルキル基が更に好ましい。式(4)において、qが2~500のとき、グラフト共重合体中に複数存在するX5及びR4は互いに同じであっても異なっていてもよい。 In the formula (3), R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
また、式(2)で表される構造単位としては、組成物の分散安定性及び現像性の観点から、下記式(2A)で表される構造単位であることがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993. ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.
logP=log(Coil/Cwater)
式中、Coilは油相中の化合物のモル濃度を、Cwaterは水相中の化合物のモル濃度を表す。
logPの値が0をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
R1、R2、及びR3は、好ましくは水素原子、又は炭素数が1~3のアルキル基であり、より好ましくは水素原子又はメチル基である。R2及びR3は、水素原子であることが更に好ましい。
Xは、酸素原子(-O-)又はイミノ基(-NH-)を表し、酸素原子であることが好ましい。 In the above formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched chain structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon rings such as tricyclo [4.3.1.1 2,5 ] undecane ring, and , Tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
また、上記一般式(ii)で表される単量体として、R1が水素原子又はメチル基であって、Lがアルキレン基であって、Zが脂肪族基、複素環基又は芳香族基である化合物が好ましい。また、上記一般式(iii)で表される単量体として、R4、R5、及びR6が水素原子又はメチル基であって、Zが脂肪族基、複素環基又は芳香族基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred. Further, as the monomer represented by the general formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
なお、式(i)~(iii)で表される代表的な化合物の例としては、特開2013-249417号公報の段落0089~0093に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Embedded in.
この上述の無機顔料等の着色顔料と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。
高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を有する場合、それぞれ、酸基を有する構造単位、塩基性基を有する構造単位、配位性基を有する構造単位、又は、反応性を有する構造単位を有することが好ましい。
特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与することができる。
すなわち、高分子化合物にアルカリ可溶性基を導入することで、本発明の組成物は、上述の無機顔料等の着色顔料の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を有することになる。このような高分子化合物を含有する組成物は、露光部の遮光性に優れたものとなり、且つ、未露光部のアルカリ現像性が向上される。
また、高分子化合物が酸基を有する構造単位を有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
これは、酸基を有する構造単位における酸基が上述の無機顔料等の着色顔料と相互作用しやすく、高分子化合物が上述の無機顔料等の着色顔料を安定的に分散すると共に、上述の無機顔料等の着色顔料を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。 The polymer compound can introduce a functional group capable of forming an interaction with the above-described colored pigment such as the inorganic pigment. Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the above-described colored pigment such as the inorganic pigment.
Examples of the functional group capable of forming an interaction with the color pigment such as the above-described inorganic pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. It is preferable to have a structural unit having or a structural unit having reactivity.
In particular, since the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, it is possible to impart developability for pattern formation by alkali development to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention is such that the polymer compound as a dispersant that contributes to the dispersion of the color pigment such as the inorganic pigment has alkali solubility. . A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
This is because the acid group in the structural unit having an acid group easily interacts with the above-described colored pigment such as the inorganic pigment, and the polymer compound stably disperses the above-described inorganic pigment or the like, and the above-described inorganic pigment. This is presumably because the viscosity of the polymer compound that disperses colored pigments such as pigments is low and the polymer compound itself is easily dispersed stably.
高分子化合物は、酸基を有する構造単位を1種又は2種以上有してもよい。
高分子化合物は、酸基を有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは5~80%であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、10~60%である。 When the polymer compound has an acid group, the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
The polymer compound may have one or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is calculated in terms of mass with respect to the total mass of the polymer compound. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
高分子化合物は、塩基性基を有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0.01%以上50%以下であり、より好ましくは、現像性阻害抑制という観点から、0.01%以上30%以下である。 Examples of the basic group that is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment described above include a primary amino group, a secondary amino group, a tertiary amino group, and a hetero group including an N atom. There are a ring, an amide group and the like, and a preferable one is a tertiary amino group from the viewpoint of good adsorbing power to the above-mentioned inorganic pigment and other colored pigments and high dispersibility of the colored pigments. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppression of developability inhibition.
高分子化合物は、配位性基を有する構造単位、又は、反応性を有する官能基を有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは10%以上80%以下であり、より好ましくは、現像性阻害抑制という観点から、20%以上60%以下である。 Examples of the coordinating group, which is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride And acid chlorides. Preferable one is an acetylacetoxy group in that the adsorbing power to the color pigment such as the above-mentioned inorganic pigment is good and the dispersibility of the color pigment is high. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
一般式(iv)~一般式(vi)中、R11、R12、及びR13は、好ましくは、それぞれ独立に水素原子、又は炭素数が1~3のアルキル基であり、より好ましくは、それぞれ独立に水素原子又はメチル基である。一般式(iv)中、R12及びR13は、それぞれ水素原子であることが特に好ましい。 In general formula (iv) to general formula (vi), R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (iv) to general formula (vi), R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are each particularly preferably a hydrogen atom.
また、一般式(v)中のYは、メチン基又は窒素原子を表す。 X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.
また、一般式(v)で表される単量体として、R11が水素原子又はメチル基であって、L1がアルキレン基であって、Z1がカルボン酸基であって、Yがメチン基である化合物が好ましい。
更に、一般式(vi)で表される単量体として、R14、R15、及びR16がそれぞれ独立に水素原子又はメチル基であって、L1が単結合又はアルキレン基であって、Z1がカルボン酸基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure. A compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and L 1 is a single bond or an alkylene group, A compound in which Z 1 is a carboxylic acid group is preferred.
単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合及び水酸基を有する化合物(例えば、メタクリル酸2-ヒドロキシエチル)とコハク酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合及び水酸基を有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、4-ビニル安息香酸、ビニルフェノール、及び、4-ヒドロキシフェニルメタクリルアミド等が挙げられる。 The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxy Phenyl methacrylamide, and the like.
このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
高分子化合物は、これらの他の構造単位を1種或いは2種以上用いることができ、その含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0%以上80%以下であり、特に好ましくは、10%以上60%以下である。含有量が上記範囲において、十分なパターン形成性が維持される。 Furthermore, for the purpose of improving various performances such as image strength, the polymer compound is a coloring unit such as a structural unit having a graft chain, a hydrophobic structural unit, and the above-described inorganic pigment, as long as the effects of the present invention are not impaired. Different from the structural unit having a functional group capable of interacting with the pigment, other structural unit having various functions (for example, a structural unit having a functional group having affinity with the dispersion medium used in the dispersion) ) May be further included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
また、遮光膜を形成する際の現像時におけるパターン剥離をより効果的に抑制する観点からは、その上限値は、140mgKOH/g以下が好ましく、120mgKOH/g以下が更に好ましい。 The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g. From the viewpoint of improving the alkali developability, the lower limit is more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. If the acid value of the polymer compound is 50 mgKOH / g or more, precipitation of colored pigments such as the above-mentioned inorganic pigments can be further suppressed, and the number of coarse particles is reduced (in other words, the amount of particles in the liquid is reduced) And the stability over time of the composition can be further improved.
Further, from the viewpoint of more effectively suppressing pattern peeling during development when forming a light shielding film, the upper limit is preferably 140 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
GPC法は、HLC-8020GPC(東ソー(株)製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー(株)製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。 The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
また、両性樹脂の市販品としては、例えば、ビックケミー社製のDISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、味の素ファインテクノ社製のアジスパーPB821、アジスパーPB822、及び、アジスパーPB881等が挙げられる。
これらの高分子化合物は、単独で使用してもよく、2種以上を組み合わせて使用してもよい。 Specific examples of the polymer compound that can be used in the present invention include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (acid group). ), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA Amide), 5765 (high molecular weight polycarboxylate), 622 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester)” manufactured by Enomoto Kasei Co., Ltd. , DA-703-50, DA-705, DA-725 ”,“ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) manufactured by Kao Corporation ) "," Homogenol L-18 (polymeric polycarboxylic acid) ", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)" manufactured by Nippon Lubrizol Co., Ltd. 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (Nikko Chemical Co., Ltd.) Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organoshiro Sunpolymer KP341, “W001: cationic surfactant” manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA manufactured by Morishita Sangyo Co., Ltd.” -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by Sannopco" Disperse Aid 6, Dis Polymer dispersants such as Perth Aid 8, Disperse Aid 15, Disperse Aid 9100, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 manufactured by ADEKA Corporation F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd.
These polymer compounds may be used alone or in combination of two or more.
また、上記以外にも、特開2011-153283号公報の段落0028~0084(対応するUS2011/0279759の段落0075~0133欄)の酸性基が連結基を介して結合してなる側鎖構造を有する構成成分を含む高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。 As the dispersant, in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to columns 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
分散剤は、1種単独で用いてもよいし、2種以上併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。 When the composition contains a dispersant, the content of the dispersant is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the total solid content of the composition. More preferably, the content is 5 to 10% by mass.
A dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
本発明の組成物は、バインダー樹脂を含有することが好ましい。
バインダー樹脂としては、線状有機ポリマーを用いることが好ましい。このような線状有機ポリマーとしては、公知のものを任意に使用することができる。好ましくは、水現像又は弱アルカリ水現像を可能とするために、水又は弱アルカリ水に可溶性又は膨潤性である線状有機ポリマーが選択される。なかでも、バインダー樹脂としては、アルカリ可溶性樹脂(アルカリ可溶性を促進する基を有する樹脂)が特に好ましい。
バインダー樹脂としては、線状有機ポリマーであって、分子(好ましくは、(メタ)アクリル系共重合体、又は、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、(メタ)アクリル系樹脂、(メタ)アクリルアミド系樹脂、(メタ)アクリル/(メタ)アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、(メタ)アクリル系樹脂、(メタ)アクリルアミド系樹脂、(メタ)アクリル/(メタ)アクリルアミド共重合体樹脂が好ましい。
アルカリ可溶性を促進する基(以下、酸基ともいう)としては、例えば、カルボキシル基、リン酸基、スルホン酸基、及び、フェノール性水酸基等が挙げられる。なかでも、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、(メタ)アクリル酸由来の構造単位を有するアルカリ可溶性樹脂がより好ましいものとして挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。 <Binder resin>
The composition of the present invention preferably contains a binder resin.
As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. Among these, as the binder resin, an alkali-soluble resin (a resin having a group that promotes alkali-solubility) is particularly preferable.
The binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferred, and developability From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acryl / (meth) acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.
また、欧州特許第993966号、欧州特許第1204000号、及び、特開2001-318463号等の各公報に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダー樹脂は、膜強度、及び、現像性のバランスに優れており、好適である。
更に、この他に水溶性線状有機ポリマーとして、ポリビニルピロリドン、及びポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるために、アルコール可溶性ナイロン、及び、2,2-ビス-(4-ヒドロキシフェニル)-プロパンとエピクロロヒドリンとの反応物であるポリエーテル等も有用である。 Examples of the binder resin include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group Resins in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated by homopolymerizing a monomer having an acid, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride Can be mentioned. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples of the monomer having an acid anhydride include And maleic anhydride. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.
Further, the acetal-modified polyvinyl alcohol-based binder resin having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has a film strength and developability. It is excellent in balance and is suitable.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
市販品としては、例えばアクリベースFF-187、FF-426(藤倉化成社製)、アクリキュア-RD-F8(日本触媒(株))、及び、ダイセルオルネクス(株)製サイクロマーP(ACA)230AA等が挙げられる。 In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
Commercially available products include, for example, Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Co., Ltd. 230AA etc. are mentioned.
グラフト鎖を有する構造単位の定義は、上述した分散剤が有するグラフト鎖を有する構造単位と同義であり、また好適範囲も同様である。
酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、又は、フェノール性水酸基等があり、好ましくは、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも1種であり、より好ましいものは、カルボン酸基である。 Moreover, it is also preferable to use a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
The definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. More preferred is a carboxylic acid group.
一般式(vii)~一般式(ix)中、R21、R22、及びR23は、好ましくは、それぞれ独立に水素原子、又は炭素数が1~3のアルキル基であり、より好ましくは、それぞれ独立に水素原子又はメチル基である。一般式(vii)中、R21及びR23は、それぞれ水素原子であることが特に好ましい。 In the general formulas (vii) to (ix), R 21 , R 22 , and R 23 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (vii) to general formula (ix), R 21 , R 22 , and R 23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (vii), R 21 and R 23 are each particularly preferably a hydrogen atom.
また、一般式(viii)中のYは、メチン基又は窒素原子を表す。 X 2 in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (viii) represents a methine group or a nitrogen atom.
また、一般式(vii)で表される単量体として、R21が水素原子又はメチル基であって、L2がアルキレン基であって、Z2がカルボン酸基であって、Yがメチン基である化合物が好ましい。
更に、一般式(ix)で表される単量体として、R24、R25、及びR26がそれぞれ独立に水素原子又はメチル基であって、Z2がカルボン酸基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (vii), R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or an oxyalkylene structure. A compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (vii), R 21 is a hydrogen atom or a methyl group, L 2 is an alkylene group, Z 2 is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (ix), a compound in which R 24 , R 25 , and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
酸基を有する構造単位の含有量は、質量換算で、上記バインダー樹脂の総質量に対して、好ましくは5~95%であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、10~90%である。 The binder resin may have one or more structural units having an acid group.
The content of the structural unit having an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder resin, and more preferably, from the viewpoint of suppressing damage to image strength due to alkali development. 10 to 90%.
バインダー樹脂は、1種単独で用いてもよいし、2種以上併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。 The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
本発明の組成物は、重合性化合物を含有することが好ましい。
重合性化合物は、エチレン性不飽和結合を有する基を1個以上有する化合物が好ましく、2個以上有する化合物がより好ましく、3個以上有することが更に好ましく、5個以上有することが特に好ましい。上限は、たとえば、15個以下である。エチレン性不飽和結合を有する基としては、例えば、ビニル基、(メタ)アリル基、及び、(メタ)アクリロイル基等が挙げられる。 <Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, still more preferably 3 or more, and particularly preferably 5 or more. The upper limit is 15 or less, for example. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
重合性化合物の分子量は、100~3000が好ましく、250~1500がより好ましい。
重合性化合物は、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。
モノマー、プレポリマーの例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸等)及びそのエステル類、アミド類、並びにこれらの多量体が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、及び不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類、並びにこれらの多量体である。また、ヒドロキシル基、アミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物、又は、上記不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との反応物、ハロゲン基又はトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との反応物も好適である。また、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。
これらの具体的な化合物としては、特開2009-288705号公報の段落〔0095〕~〔0108〕に記載されている化合物を本発明においても好適に用いることができる。 The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. Monomers are preferred.
The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group, mercapto group and the like with a monofunctional or polyfunctional isocyanate or epoxy, or the above unsaturated group A dehydration condensation reaction product of a carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups or tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.
以下に好ましい重合性化合物の態様を示す。 The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred. These oligomer types can also be used. NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used.
Preferred embodiments of the polymerizable compound are shown below.
カプロラクトン構造を有する化合物としては、分子内にカプロラクトン構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンとをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートが挙げられる。なかでも下記一般式(Z-1)で表されるカプロラクトン構造を有する化合物が好ましい。 The polymerizable compound is also preferably a compound having a caprolactone structure.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone It is done. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.
「*」は結合手であることを示す。 In general formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2,
“*” Indicates a bond.
一般式(Z-4)中、(メタ)アクリロイル基の合計は3個又は4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。
一般式(Z-5)中、(メタ)アクリロイル基の合計は5個又は6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。 In general formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —. Each represents independently an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 .
In general formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 .
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数が更に好ましい。
一般式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が更に好ましい。
また、一般式(Z-4)又は一般式(Z-5)中の-((CH2)yCH2O)-又は((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。 In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
In the general formula (Z-4) or the general formula (Z-5), — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom A form in which the terminal on the side is bonded to X is preferred.
具体的には、下記式(a)~(f)で表される化合物(以下、「例示化合物(a)~(f)」とも称する。)が挙げられ、なかでも、例示化合物(a)、(b)、(e)、(f)が好ましい。 Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a), (B), (e) and (f) are preferred.
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学社製)、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、及び、AI-600(共栄社製)等が挙げられる。 Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, or Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, or JP-B-62-39418 are also suitable. . Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, it is possible to obtain a composition excellent in the photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
なお、本明細書においてSP値は、特に断らない限り、Hoy法によって求める(H.L.Hoy Journal of Painting,1970,Vol.42,76-118)。また、SP値については単位を省略して示しているが、その単位はcal1/2cm-3/2である。 The polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and preferably 10.60 or more. Further preferred.
In this specification, the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm −3/2 .
カルド骨格を有する重合性化合物としては、9,9-ビスアリールフルオレン骨格を有する重合性化合物が好ましく、下記式(Q3)で表される化合物がより好ましい。 The composition also preferably has a polymerizable compound having a cardo skeleton from the viewpoint of improving development residue.
As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
X1~X4が表す重合性基を有する脂肪族基としては、特に制限はないが、重合性基以外における炭素数が1~12のアルキレン基であることが好ましく、炭素数2~10のアルキレン基であることがより好ましく、炭素数2~5のアルキレン基であることが更に好ましい。
また、X1~X4が表す重合性基を有する脂肪族基において、上記脂肪族基がヘテロ原子によって置換される場合は、-NR-(Rは置換基)、酸素原子、硫黄原子によって置換されていることが好ましく、上記脂肪族基中の隣り合わない-CH2-が酸素原子又は硫黄原子で置換されていることがより好ましく、上記脂肪族基中の隣り合わない-CH2-が酸素原子で置換されていることが更に好ましい。X1~X4が表す重合性基を有する脂肪族基は、ヘテロ原子によって1~2箇所置換されていることが好ましく、ヘテロ原子によって1箇所置換されていることがより好ましく、Ar11~Ar14が表す破線で囲まれたベンゼン環を含むアリール基に隣接する1箇所がヘテロ原子によって置換されていることが更に好ましい。
X1~X4が表す重合性基を有する脂肪族基に含まれる重合性基としては、ラジカル重合又はカチオン重合可能な重合性基(以下、それぞれラジカル重合性基及びカチオン重合性基とも言う)が好ましい。
ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとしてラジカル重合可能なエチレン性不飽和結合を有する重合性基を挙げることができ、具体的にはビニル基、(メタ)アクリロイルオキシ基等が挙げられる。なかでも、(メタ)アクリロイルオキシ基が好ましく、アクリロイルオキシ基がより好ましい。
カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、ビニルオキシ基等が挙げられる。なかでも、脂環式エーテル基、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、ビニルオキシ基が特に好ましい。
Ar1~Ar4が含む置換基が有する上記重合性基は、ラジカル重合性基であることが好ましい。
Ar1~Ar4のうち2つ以上は重合性基を有する置換基を含み、Ar1~Ar4のうち2~4個が重合性基を有する置換基を含むことが好ましく、Ar1~Ar4のうち2又は3個が重合性基を有する置換基を含むことがより好ましく、Ar1~Ar4のうち2個が重合性基を有する置換基を含むことが更に好ましい。
Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合は、X1~X4はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。 In the general formula (Q3), X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group having a polymerizable group.
The aliphatic group having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is still more preferable.
In the aliphatic group having a polymerizable group represented by X 1 to X 4 , when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom. The non-adjacent —CH 2 — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is More preferably, it is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar 11 to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line 14 is substituted with a heteroatom.
As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X 1 to X 4 , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively) Is preferred.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one. Specifically, A vinyl group, a (meth) acryloyloxy group, etc. are mentioned. Of these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
The polymerizable group contained in the substituent contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.
Two or more of Ar 1 ~ Ar 4 includes a substituent having a polymerizable group, preferably contains a substituent 2-4 of Ar 1 ~ Ar 4 has a polymerizable group, Ar 1 ~ Ar More preferably, 2 or 3 out of 4 contain a substituent having a polymerizable group, and more preferably 2 out of Ar 1 to Ar 4 contain a substituent having a polymerizable group.
When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X 1 to X 4 are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
上記一般式(Q3)中、c及びdはそれぞれ独立に0~5の整数を表し、0又は1であることが好ましく、c及びdがいずれも0であることがより好ましい。 In the general formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
In the general formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
上記一般式(Q3)中、Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合は、R1~R4はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。 In the general formula (Q3), R 1 to R 4 each independently represents a substituent. The substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups An aryl group, an alicyclic group, etc. are mentioned. The substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. And more preferably a methyl group, a methoxy group or a phenyl group.
In the general formula (Q3), when Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
e、f、g及びhはそれぞれ独立に0~8であることが好ましく、0~2であることがより好ましく、0であることが更に好ましい。
Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合、e、f、g及びhは0又は1であることが好ましく、0であることがより好ましい。 In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar 11 to Ar 14 can have. The value obtained by subtracting a, b, c, or d from the number of.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.
重合性化合物は、1種単独であってもよいし、2種以上を併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
本発明の組成物は、重合開始剤を含有することが好ましい。
重合開始剤としては特に制限はなく、公知の重合開始剤の中から適宜選択することができ、例えば、感光性を有するもの(いわゆる、光重合開始剤)が好ましい。
本発明の組成物は、上述の無機顔料、黒色染料の他に、光重合開始剤及び上述した重合性化合物を含有する場合には、活性光線又は放射線の照射により硬化することから、「感光性組成物」と呼ばれることがある。
光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。
また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。 <Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
When the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the above-described inorganic pigment and black dye, it is cured by irradiation with actinic rays or radiation. Sometimes called a "composition".
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本願明細書に組み込まれる。 In particular, when the composition of the present invention is used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is important that From such a viewpoint, it is preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, considering these points, it is preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、及び、IRGACURE-379EG(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤は、365nm又は405nm等の長波光源に吸収波長がマッチングされた特開2009-191179号公報に記載の化合物も用いることができる。
アシルホスフィン系開始剤としては、市販品であるIRGACURE-819又はDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。 As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.
オキシム化合物の具体例としては、特開2001-233842号公報記載の化合物、特開2000-80068号公報記載の化合物、特開2006-342166号公報記載の化合物を用いることができる。
本発明において、好適に用いることのできるオキシム化合物としては、例えば、3-ベンゾイロキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイロキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オン等が挙げられる。
また、J.C.S.Perkin II(1979年)pp.1653-1660)、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、特開2000-66385号公報記載の化合物、特開2000-80068号公報、特表2004-534797号公報、特開2006-342166号公報の各公報に記載の化合物等も挙げられる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831及びアデカアークルズNCI-930(ADEKA社製)、N-1919(カルバゾール・オキシムエステル骨格含有光開始剤(ADEKA社製)も用いることができる。 More preferred examples of the photopolymerization initiator include oxime compounds (oxime initiators). In particular, an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), N-1919 (carbazole oxime ester skeleton-containing photoinitiator) (Made by ADEKA) can also be used.
好ましくは、例えば、特開2013-29760号公報の段落0274~0275を参酌することができ、この内容は本願明細書に組み込まれる。
具体的には、オキシム化合物としては、下記式(OX-1)で表される化合物が好ましい。なお、オキシムのN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、(E)体と(Z)体との混合物であってもよい。 Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910 contained therein, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及び、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及び、アリール基等が挙げられる。
一般式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、シクロアルキレン基、又は、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
式(1)及び式(2)で表される化合物の具体例としては、例えば、特開2014-137466号公報の段落番号0076~0079に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
オキシム化合物は、365nm又は405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが更に好ましい。
化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計(Varian社製Cary-5 spctrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
本発明に用いられる光重合開始剤は、必要に応じて2種以上を組み合わせて使用してもよい。 The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is more preferable.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
本発明の組成物は、有機溶剤を含有することが好ましい。
有機溶剤の例としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、及び、乳酸エチル等が挙げられるが、これらに限定されない。 <Organic solvent>
The composition of the present invention preferably contains an organic solvent.
Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Ter, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, and ethyl lactate.
2種以上の有機溶剤を含有する場合には、上記の3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテートからなる群から選択される2種以上で構成されることが好ましい。 The composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but the inorganic pigment particles described above are prepared when the composition of the invention is prepared. It is preferable to contain two or more organic solvents from the viewpoint that the diameter variation can be suppressed.
When two or more organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
本発明の組成物は、水を含有してもよい。水は、意図的に添加されるものであってもよいし、本発明の組成物に含まれる各成分を添加することで不可避的に組成物中に含有されるものであってもよい。
水の含有量は、組成物100質量%に対して、0.01~1質量%であることが好ましく、0.05~0.8質量%であることがより好ましく、0.1~0.7質量%であることが更に好ましい。水の含有量が上記範囲内にあることで、遮光膜を作製したときのピンホールの発生を抑制できたり、遮光膜の耐湿性が向上したりする。 <Water>
The composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
The water content is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and more preferably 0.1 to 0.00% by mass with respect to 100% by mass of the composition. More preferably, it is 7 mass%. When the water content is within the above range, the generation of pinholes when the light shielding film is produced can be suppressed, or the moisture resistance of the light shielding film can be improved.
本発明の組成物中には、上述した成分以外の他の成分が含まれていてもよい。
以下、各成分について詳述する。 <Other ingredients>
In the composition of this invention, other components other than the component mentioned above may be contained.
Hereinafter, each component will be described in detail.
シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基を有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
加水分解性基とは、珪素原子に直結し、加水分解反応及び/又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及び、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を有する場合、その炭素数は6以下であることが好ましく、4以下であることがより好ましい。特に、炭素数4以下のアルコキシ基又は炭素数4以下のアルケニルオキシ基が好ましい。
また、シランカップリング剤は基板と遮光膜間の密着性を向上させるため、フッ素原子及び珪素原子(ただし、加水分解性基が結合した珪素原子は除く)を含まないことが好ましく、フッ素原子、珪素原子(ただし、加水分解性基が結合した珪素原子は除く)、珪素原子で置換されたアルキレン基、炭素数8以上の直鎖状アルキル基、及び、炭素数3以上の分鎖アルキル基は含まないことが望ましい。 (Silane coupling agent)
A silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the light shielding film, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), Silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms are It is desirable not to include.
式(Z) *-Si-(RZ1)3
式(Z)中、RZ1は加水分解性基を表し、その定義は上述の通りである。 The silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si- (R Z1 ) 3
In the formula (Z), R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
なお、上記シランカップリング剤に含まれる硬化性官能基の好適態様としては、ラジカル重合性基も挙げられる。 The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
式(W) RZ2-Lz-Si-(RZ1)3
Rz1は、加水分解性基を表し、定義は上述の通りである。
Rz2は、硬化性官能基を表し、定義は上述のとおりであり、好適範囲も上述の通りである。
Lzは、単結合又は2価の連結基を表す。Lzが2価の連結基を表す場合、2価の連結基としては、ハロゲン原子が置換していてもよいアルキレン基、ハロゲン原子が置換していてもよいアリーレン基、-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-、-SO2-、又は、これらの組み合わせが挙げられる。なかでも、炭素数2~10のハロゲン原子が置換していてもよいアルキレン基及び炭素数6~12のハロゲン原子が置換していてもよいアリーレン基からなる群から選択される少なくとも1種、又は、これらの基と-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-、及びSO2-からなる群から選択される少なくとも1種の基との組み合わせからなる基が好ましく、炭素数2~10のハロゲン原子が置換していてもよいアルキレン基、-CO2-、-O-、-CO-、-CONR12-、又は、これらの基の組み合わせからなる基がより好ましい。ここで、上記R12は、水素原子又はメチル基を表す。 One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula (W) R Z2 -Lz-Si- (R Z1 ) 3
R z1 represents a hydrolyzable group, and the definition is as described above.
R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR 12 —, —CONR 12 —, —CO—, —CO 2 —, SO 2 NR 12 —, —O—, —S—, and SO 2 —. A group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred. Here, R 12 represents a hydrogen atom or a methyl group.
このシランカップリング剤Yは、分子内に少なくとも1つの珪素原子を有すればよく、珪素原子は、以下の原子、置換基と結合できる。それらは同じ原子、置換基であっても異なっていてもよい。結合しうる原子、置換基は、水素原子、ハロゲン原子、水酸基、炭素数1から20のアルキル基、アルケニル基、アルキニル基、アリール基、アルキル基及び/又はアリール基で置換可能なアミノ基、シリル基、炭素数1から20のアルコキシ基、アリーロキシ基等が挙げられる。これらの置換基は更に、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アルキル基及び/又はアリール基で置換可能なアミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、アミド基、ウレア基、アンモニウム基、アルキルアンモニウム基、カルボキシル基、又はその塩、スルホ基、又はその塩等で置換されていてもよい。
なお、珪素原子には少なくとも一つの加水分解性基が結合している。加水分解性基の定義は、上述の通りである。
シランカップリング剤Yには、式(Z)で表される基が含まれていてもよい。 As another preferred embodiment of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided. Can be mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group and the like. These substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).
ここで、有機基としては、アルキル基、アルケニル基、アルキニル基、アリール基、又は、これらの組み合わせ等が挙げられる。これらは更に置換基を有してもよく、導入可能な置換基としては、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、カルボニルオキシ基、アミド基、ウレア基、アルキレンオキシ基アンモニウム基、アルキルアンモニウム基、カルボキシル基、又はその塩、スルホ基等が挙げられる。
また、窒素原子は、任意の有機連結基を介して硬化性官能基と結合していることが好ましい。好ましい有機連結基としては、上述の窒素原子及びそれに結合する有機基に導入可能な置換基が挙げられる。 The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The amino group structure may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxyl group, or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
シランカップリング剤Yには、硬化性官能基は一分子中に少なくとも一つ以上有していればよいが、硬化性官能基を2以上有する態様をとることも可能であり、感度、安定性の観点からは、硬化性官能基を2~20有することが好ましく、4~15有することが更に好ましく、最も好ましくは分子内に硬化性官能基を6~10有する態様である。 The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
本発明の組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、及び、シリコーン系界面活性剤等の各種界面活性剤を使用できる。 (Surfactant)
The composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。 Examples of the fluorosurfactant include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
また、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報0050~0090段落及び0289~0295段落に記載された化合物、例えばDIC社製のメガファックRS-101、RS-102、RS-718K、又は、RS-72-K等が挙げられる。 The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, or RS- 72-K and the like.
上記組成物は、重合禁止剤を含有することが好ましい。重合禁止剤を含有すると上記組成物はより優れた経時安定性を有する。
重合禁止剤の含有量は、組成物の全固形分に対して、0.00055~0.055質量%が好ましく、0.0015~0.01質量%がより好ましい。 <Polymerization inhibitor>
The composition preferably contains a polymerization inhibitor. When the polymerization inhibitor is contained, the composition has better temporal stability.
The content of the polymerization inhibitor is preferably from 0.00055 to 0.055 mass%, more preferably from 0.0015 to 0.01 mass%, based on the total solid content of the composition.
なかでも、R1及びR5はそれぞれ独立して、水素原子又はtert-ブチル基がより好ましく、R2及びR4は水素原子がより好ましく、R3は水素原子、炭素数1~5のアルキル基又は炭素数1~5のアルコキシ基がより好ましい。 R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
Among them, R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group, R 2 and R 4 are more preferably a hydrogen atom, R 3 is a hydrogen atom, and an alkyl having 1 to 5 carbon atoms. A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
また、式(IH-2)中のR7~R10は、それぞれ独立して、水素原子又はアルキル基を表す。R7~R10が表すアルキル基としては、炭素数1~5のアルキル基が好ましく、メチル基又はエチル基がより好ましい。 R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
In the formula (IH-2), R 7 to R 10 each independently represents a hydrogen atom or an alkyl group. The alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
上記重合禁止剤は、フェノール系化合物を含有することが好ましい。なかでも、経時安定性の観点から、重合禁止剤は2種以上のフェノール系化合物を含有することが好ましい。
また、上記重合禁止剤は、経時安定性の観点から、フェノール系化合物と、ヒンダードアミン系化合物とを含有することが好ましい。 As the polymerization inhibitor, each of the above compounds may be used alone, in combination of two or in combination of three or more.
The polymerization inhibitor preferably contains a phenolic compound. Especially, it is preferable that a polymerization inhibitor contains a 2 or more types of phenol type compound from a viewpoint of temporal stability.
Moreover, it is preferable that the said polymerization inhibitor contains a phenol type compound and a hindered amine type compound from a viewpoint of temporal stability.
上記組成物は、紫外線吸収剤を含有してもよい。これにより、硬化膜のパターンの形状をより優れた(精細な)ものにすることができる。
紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及びトリアジン系の紫外線吸収剤を使用することができる。これらの具体例としては、特開2012-068418号公報の段落0137~0142(対応するUS2012/0068292の段落0251~0254)の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
他にジエチルアミノ-フェニルスルホニル系紫外線吸収剤(大東化学社製、商品名:UV-503)等も好適に用いられる。
紫外線吸収剤としては、特開2012-32556号公報の段落0134~0148に例示される化合物が挙げられる。
紫外線吸収剤の含有量は、組成物の全固形分に対して、0.001~15質量%が好ましく、0.01~10質量%がより好ましく、0.1~5質量%が更に好ましい。紫外線吸収剤としては、上記の各化合物を1種単独で用いても、2種以上を併用してもよい。 <Ultraviolet absorber>
The composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the composition. As an ultraviolet absorber, each said compound may be used individually by 1 type, or may use 2 or more types together.
上記組成物は、有機顔料を含有してもよい。
有機顔料としては、例えば、カラーインデックス(C.I.)ピグメントイエロー1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等;
C.I.ピグメントオレンジ 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等;
C.I.ピグメントレッド 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279等;
C.I.ピグメントグリーン 7,10,36,37,58,59等;
C.I.ピグメントバイオレット 1,19,23,27,32,37,42等;
C.I.ピグメントブルー 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等;
が挙げられる。なお、顔料は1種を単独で用いても、2種以上を併用してもよい。 (Organic pigment)
The composition may contain an organic pigment.
Examples of the organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24. , 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 Etc. 169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned. In addition, a pigment may be used individually by 1 type, or may use 2 or more types together.
染料としては、例えば特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許4808501号明細書、米国特許5667920号明細書、米国特許505950号明細書、米国特許5667920号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、特開平6-194828号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を用いてもよい。色素多量体としては、特開2011-213925号公報、特開2013-041097号公報に記載されている化合物が挙げられる。また、分子内に重合性を有する有彩色染料重合性染料を用いてもよく、市販品としては、例えば、和光純薬株式会社製RDWシリーズが挙げられる。 <Chromatic dye>
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6- The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the chromatic dye polymeric dye which has superposition | polymerization in a molecule | numerator, As a commercial item, the RDW series by Wako Pure Chemical Industries, Ltd. is mentioned, for example.
上記着色剤は、更に赤外線吸収剤を含有してもよい。
赤外線吸収剤は、赤外領域(好ましくは、波長650~1300nm)の波長領域に吸収を有する化合物を意味する。好ましくは、赤外線吸収剤は、波長675~900nmの波長領域に極大吸収波長を有する化合物が好ましい。
このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クアテリレン化合物、ジチオール金属錯体系化合物、及びクロコニウム化合物等が挙げられる。
フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリウム化合物、及びクロコニウム化合物は、特開2010-111750号公報の段落0010~0081に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信/松岡賢/北尾悌次郎/平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本願明細書に組み込まれる。 <Infrared absorber>
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). Preferably, the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Examples include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated into. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
なお、赤外線吸収剤は1種を単独で用いても、2種以上を併用してもよい。 As the colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 It is also possible to use near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle diameter of 5 to 200 nm.
In addition, an infrared absorber may be used individually by 1 type, or may use 2 or more types together.
これらの成分は、例えば、特開2012-003225号公報の段落番号0183~0228(対応する米国特許出願公開第2013/0034812号明細書の[0237]~[0309])、特開2008-250074号公報の段落番号0101~0102、段落番号0103~0104、段落番号0107~0109、特開2013-195480号公報の段落番号0159~0184等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 In addition to the above components, the following components may be further added to the composition of the present invention. Examples include sensitizers, pigment dispersants other than those described above, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers. , Adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, perfumes, surface tension modifiers, and , Chain transfer agents and the like) may be added as necessary.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A. Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .
本発明の組成物は、上述した各種成分を公知の混合方法(例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、湿式分散機)により混合して製造することができる。
組成物の製造に際しては、組成物を構成する各種成分を一括配合してもよいし、各種成分を有機溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は、特に制約を受けない。
また、顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断及びキャビテーション等が挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化及び超音波分散等が挙げられる。また、「分散技術大全、株式会社情報機構発行、2005年7月15日」及び「サスペンション(固/液分散系)を中心とした分散技術と工業的応用の実際 総合資料集、経営開発センター出版部発行、1978年10月10日」に記載のプロセス及び分散機を好適に使用することができる。
また、顔料を分散させるプロセスにおいては、ソルトミリング工程による顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器及び処理条件等は、例えば、特開2015-194521号及び特開2012-046629号に記載のものを使用することができる。
本発明の組成物は、異物の除去又は欠陥の低減等の目的で、フィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、PTFE(ポリテトラフルオロエチレン)等のフッ素樹脂、ナイロン等のポリアミド系樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量を含む)等によるフィルタが挙げられる。これら素材のなかでもポリプロピレン(高密度ポリプロピレンを含む)、ナイロンが好ましい。
フィルタの孔径は、0.1~7.0μm程度が適しており、好ましくは0.2~2.5μm程度、より好ましくは0.2~1.5μm程度、更に好ましくは0.3~0.7μmである。この範囲とすることにより、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物又は凝集物等、微細な異物を確実に除去することが可能となる。
フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が同じ、又は、大きい方が好ましい。また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。第2のフィルタの孔径は、0.2~10.0μm程度が適しており、好ましくは0.2~7.0μm程度、より好ましくは0.3~6.0μm程度である。 <Method for producing composition>
The composition of the present invention can be produced by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
In the production of the composition, various components constituting the composition may be combined at once, or may be sequentially mixed after the various components are dissolved or dispersed in an organic solvent. In addition, the charging order and working conditions when blending are not particularly limited.
Further, in the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. In addition, “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005” and “Distribution technology and industrial application centered on suspension (solid / liquid dispersion system) and comprehensive application data collection, Management Development Center publication. The process and the dispersing machine described in “Issuance of the Department, October 10, 1978” can be preferably used.
In the process of dispersing the pigment, the pigment may be refined by a salt milling process. For example, materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, more preferably about 0.3 to 6.0 μm.
本発明の硬化膜は、上述した組成物を用いて得られる。本発明の硬化膜には、上述した無機顔料(好ましくは黒色の無機顔料であり、より好ましくは窒化物又は酸窒化物を含有する顔料)及び黒色染料が主に含まれる。
本発明の硬化膜は、遮光膜として好適に用いられ、具体的にはCCDイメージセンサー又はCMOSイメージセンサー等のイメージセンサー周辺遮光膜(額縁遮光膜)として好適に用いられる。
本発明の組成物を用いて得られるイメージセンサー周辺遮光膜は遮光性能に優れる。つまり、特定の波長領域における遮光性能の低下がなく、所定領域(例えば、可視光領域~1200nm)において最低光学濃度が充分な遮光能を与え得る範囲にある。 [Curing film (light-shielding film)]
The cured film of this invention is obtained using the composition mentioned above. The cured film of the present invention mainly contains the above-described inorganic pigment (preferably a black inorganic pigment, more preferably a pigment containing a nitride or oxynitride) and a black dye.
The cured film of the present invention is suitably used as a light-shielding film, and specifically, suitably used as a light-shielding film (frame light-shielding film) around an image sensor such as a CCD image sensor or a CMOS image sensor.
The image sensor peripheral light shielding film obtained by using the composition of the present invention is excellent in light shielding performance. That is, the light shielding performance does not deteriorate in a specific wavelength region, and the minimum optical density is within a range where sufficient light shielding ability can be provided in a predetermined region (for example, visible light region to 1200 nm).
本発明の硬化膜を、例えば、イメージセンサー周辺遮光膜とする場合、遮光膜の膜厚としては特に限定はないが、乾燥後の膜厚で、0.2μm以上50μm以下が好ましく、0.2μm以上30μm以下がより好ましく、0.2μm以上25μm以下が更に好ましく、0.2μm以上20μm以下が特に好ましく、0.2μm以上10μm以下が最も好ましい。
また、遮光膜のサイズ(一辺の長さ)としては、0.001mm以上5mm以下が好ましく、0.05mm以上4mm以下がより好ましく、0.1mm以上3.5mm以下が更に好ましい。 The film thickness of the cured film of the present invention can be appropriately selected depending on the application, and is not particularly limited.
When the cured film of the present invention is, for example, an image sensor peripheral light-shielding film, the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.2 μm. It is more preferably 30 μm or less, further preferably 0.2 μm or more and 25 μm or less, particularly preferably 0.2 μm or more and 20 μm or less, and most preferably 0.2 μm or more and 10 μm or less.
Further, the size (length of one side) of the light shielding film is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, and further preferably 0.1 mm or more and 3.5 mm or less.
次に、本発明の硬化膜(遮光膜)の製造方法は特に制限されず、公知の方法を採用できる。以下、代表例として、パターン状の硬化膜を製造する方法について詳述する。 <Method for producing cured film (light-shielding film)>
Next, the manufacturing method of the cured film (light-shielding film) of the present invention is not particularly limited, and a known method can be adopted. Hereinafter, as a representative example, a method for producing a patterned cured film will be described in detail.
以下、各工程について説明する。 Specifically, the composition of the present invention is applied on a substrate directly or via another layer to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern. By curing only the composition layer portion irradiated with light (exposure process) and developing with a developer (development process), a patterned cured film composed of pixels can be formed.
Hereinafter, each step will be described.
組成物層形成工程では、基板上に、本発明の組成物を塗布して組成物層(塗布膜)を形成する。 (Composition layer forming step)
In the composition layer forming step, the composition of the present invention is applied on a substrate to form a composition layer (coating film).
また、これらの基板上には、必要により、上部の層との密着改良、物質の拡散防止又は基板表面の平坦化のために下塗り層を設けてもよい。 Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and a transparent conductive film attached to these, photoelectric devices used in solid-state imaging devices, and the like. Examples include a conversion element substrate (for example, a silicon substrate), a CCD substrate, and a CMOS substrate.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
露光工程では、組成物層形成工程において形成された組成物層(塗布膜)を、マスクを介して露光し、光照射された塗布膜部分だけを硬化させる。
露光は、活性光線又は放射線の照射により行うことが好ましく、特に、g線、h線、又はi線等の紫外線がより好ましい。照射強度は5~1500mJ/cm2が好ましく、10~1000mJ/cm2がより好ましい。 (Exposure process)
In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation with actinic rays or radiation, and more preferably ultraviolet rays such as g-line, h-line, or i-line. The irradiation intensity is preferably 5 ~ 1500mJ / cm 2, more preferably 10 ~ 1000mJ / cm 2.
露光工程に次いで、アルカリ現像処理(現像工程)を行い、露光工程における光未照射部分をアルカリ水溶液に溶出させる。これにより、光硬化した部分(光照射された塗布膜部分)だけが残る。
現像液としては、下地の回路等にダメージを起さない、有機アルカリ現像液が望ましい。現像温度としては通常20~30℃であり、現像時間は20~90秒である。 (Development process)
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
As the developer, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
本発明の組成物を用いて形成された硬化膜は、カラーフィルタの画素ブラックマトリクス、又は、後述する画像表示装置若しくはセンサモジュール内の各種部材に適用する遮光膜として好ましく用いることができる。 [Color filter, light shielding film]
The cured film formed using the composition of the present invention can be preferably used as a pixel black matrix of a color filter or a light-shielding film applied to various members in an image display device or sensor module described later.
カラーフィルタは、CCD又はCMOS等の固体撮像素子に好適に用いることができ、特に100万画素を超えるような高解像度のCCD又はCMOS等に好適である。カラーフィルタは、例えば、CCD又はCMOSを構成する各画素の受光部と、集光するためのマイクロレンズと、の間に配置して用いることができる。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を有する撮像素子の例としては、特開2012-227478号公報、特開2014-179577号公報に記載の装置が挙げられる。
本発明のカラーフィルタは、上記硬化膜を有していれば特にその形態は限定されない。上記硬化膜は、例えば、カラーフィルタの画素ブラックマトリクスとして好適に用いることができる。 (Color filter)
The color filter can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. For example, the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light. In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
If the color filter of this invention has the said cured film, the form will not be specifically limited. The cured film can be suitably used as, for example, a pixel black matrix of a color filter.
遮光膜は、画像表示装置又はセンサモジュール内の各種部材(例えば、赤外光カットフィルタ、固体撮像素子の外周部、ウェハーレベルレンズ外周部、又は、固体撮像素子の裏面等)等に形成して用いることができる。
また、赤外光カットフィルタの表面上の少なくとも一部に、遮光膜を形成して、遮光膜付き赤外光カットフィルタとしてもよい。
遮光膜の厚さは特に制限されないが、0.2~25μmが好ましく、0.2~10μmがより好ましい。上記厚さは平均厚さであり、遮光膜の任意の5点以上の厚さを測定し、それらを算術平均した値である。
遮光膜の反射率は、10%以下が好ましく、8%以下がより好ましく、6%以下が更に好ましく、4%以下が特に好ましい。なお、遮光膜の反射率は、遮光膜に、入射角度5°で400~700nmの光を入射し、その反射率を日立ハイテクノロジーズ社製の分光器UV4100(商品名)により測定した値である。 (Light shielding film)
The light shielding film is formed on various members in the image display device or the sensor module (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of the wafer level lens, or the back surface of the solid-state imaging device). Can be used.
Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
The thickness of the light shielding film is not particularly limited, but is preferably 0.2 to 25 μm, and more preferably 0.2 to 10 μm. The thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light shielding film and arithmetically averaging them.
The reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. .
本発明の固体撮像装置は、上述のような固体撮像素子を備え、固体撮像素子の外周部又は裏面等に上記硬化膜(カラーフィルタ、遮光膜等)を備える。本発明の固体撮像装置の構成としては、上記硬化膜及び固体撮像素子を有する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 [Solid-state imaging device]
The solid-state imaging device of the present invention includes the solid-state imaging element as described above, and includes the cured film (color filter, light-shielding film, etc.) on the outer peripheral portion or the back surface of the solid-state imaging element. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the cured film and the solid-state imaging device, and examples thereof include the following configurations.
更に、デバイス保護層上であってカラーフィルタの下(基板に近い側)に集光手段(例えば、マイクロレンズ等。以下同じ)を有する構成、カラーフィルタ上に集光手段を有する構成等であってもよい。 The substrate has a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and a transfer electrode made of polysilicon, and the photodiodes receive light on the photodiodes and the transfer electrodes. A light-shielding film having an opening only in the part, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, and a color filter on the device protective film It is the composition which has.
Further, the light source has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and below the color filter (on the side close to the substrate), and a constitution having a light condensing means on the color filter. May be.
本発明の硬化膜(カラーフィルタ又は遮光膜等)は、液晶表示装置、又は、有機エレクトロルミネッセンス表示装置等の画像表示装置に用いることができる。 (Image display device)
The cured film (such as a color filter or a light-shielding film) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.
以下に、本発明のカラーフィルタを液晶表示装置に適用する場合の態様について詳述する。
本発明のカラーフィルタは、カラーTFT(Thin Film Transistor)方式の液晶表示装置に用いてもよい。カラーTFT方式の液晶表示装置については、例えば「カラーTFT液晶ディスプレイ(共立出版(株)1996年発行)」に記載されている。更に、本発明のカラーフィルタはIPS(In Plane Switching)等の横電界駆動方式、MVA(Multi-domain Vertical Alignment)等の画素分割方式等の視野角が拡大された液晶表示装置、又は、STN(Super-Twist Nematic)、TN(Twisted Nematic)、VA(Vertical Alignment)、OCS(on-chip spacer)、FFS(fringe field switching)、若しくは、R-OCB(Reflective Optically Compensated Bend)等にも適用できる。
また、本発明のカラーフィルタは、明るく高精細なCOA(Color-filter On Array)方式にも供することが可能である。COA方式の液晶表示装置にあっては、カラーフィルタに対する要求特性は、前述のような通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率及び剥離液耐性が必要とされることがある。本発明のカラーフィルタは、耐光性等に優れるので、解像度が高く長期耐久性に優れたCOA方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
これらの画像表示方式については、例えば、「EL、PDP、LCDディスプレイ-技術と市場の最新動向-(東レリサーチセンター調査研究部門 2001年発行)」の43ページ等に記載されている。 When the color filter of the present invention is applied to a liquid crystal display device, the form is not particularly limited.
Below, the aspect in the case of applying the color filter of this invention to a liquid crystal display device is explained in full detail.
The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter of the present invention is a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), or an STN ( Also applicable to Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), or R-OCB (Reflective Bench).
The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-technology and latest trends in the market-(issued in 2001 by Toray Research Center Research Division)".
バックライトに関しては、SID meeting Digest 1380(2005)(A.Konno et.al)、又は、月刊ディスプレイ 2005年12月号の18~24ページ(島 康裕)、同25~30ページ(八木隆明)等に記載されている。 In addition to the color filter of the present invention, the liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. It is described in.
マイクロLED又はマイクロOLEDの例としては、特表2015-500562号及び特表2014-533890に記載されたものが挙げられる。 Moreover, the cured film of this invention can be used also for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). Although it does not specifically limit, In addition to the optical filter or optical film used for micro LED or micro OLED, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
Examples of the micro LED or micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
量子ドットディスプレイの例としては、米国特許出願公開第2013/0335677号、米国特許出願公開第2014/0036536号、米国特許出願公開第2014/0036203号、及び、米国特許出願公開第2014/0035960号に記載されたものが挙げられる。 Moreover, the cured film obtained by hardening | curing the composition of this invention can be used also for uses, such as a quantum dot display. Although it does not specifically limit, In addition to the optical or optical film used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
なお、特に断りのない限り、「部」、「%」は、質量基準である。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.
Unless otherwise specified, “part” and “%” are based on mass.
以下、実施例及び比較例の組成物の調製にあたって、まず組成物に含まれる各成分について説明する。 〔Composition〕
Hereinafter, in preparing the compositions of Examples and Comparative Examples, each component contained in the composition will be described first.
(TiN-1)日清エンジニアリング社製(窒化チタン含有粒子、BET比表面積 55m2/g、平均一次粒径 24.2nm)
(TiN-2) Hefei社製、商品名「TiN20nm」(窒化チタン含有粒子、平均一次粒子径 41.7nm)
(TiN-3) 三菱マテリアル社製、商品名「13M-T」(酸窒化チタン含有粒子、平均一次粒子径 75nm) <Inorganic pigment (pigment containing nitride or oxynitride)>
(TiN-1) manufactured by Nissin Engineering Co., Ltd. (titanium nitride-containing particles, BET specific surface area 55 m 2 / g, average primary particle size 24.2 nm)
(TiN-2) Product name “TiN 20 nm” manufactured by Hefei (titanium nitride-containing particles, average primary particle size 41.7 nm)
(TiN-3) Product name “13M-T” manufactured by Mitsubishi Materials Corporation (titanium oxynitride-containing particles, average primary particle size 75 nm)
(染料A)
下記の手順に基づき、染料Aを合成した。 <Dye>
(Dye A)
Dye A was synthesized based on the following procedure.
特開2013-253170号公報に準じて下記構造で表される重合性基を有さないキサンテン骨格化合物を得た。 (Dye B)
A xanthene skeleton compound having no polymerizable group represented by the following structure was obtained according to JP 2013-253170 A.
特表2004-534121号公報に準じて下記構造式で表される重合性基を有さないアゾ化合物を得た。下記構造式において、Mは、pHに依存して水素原子及び/又はナトリウム原子を表す。 (Dye C)
An azo compound having no polymerizable group represented by the following structural formula was obtained according to JP-T-2004-534121. In the following structural formula, M represents a hydrogen atom and / or a sodium atom depending on pH.
バインダー樹脂として、アルカリ可溶性樹脂である以下の樹脂Aを用いた。
・樹脂A(アクリキュア RD-F8 日本触媒製、下記式参照) <Binder resin>
As binder resin, the following resin A which is alkali-soluble resin was used.
・ Resin A (ACRYCURE RD-F8 made by Nippon Shokubai, see the following formula)
分散剤として、以下の構造の分散剤A~Eを用いた。分散剤A、B、Dにおいて、各構造単位に記載の数値は、全構造単位に対する、各構造単位の質量%を意図する。また、分散剤Cにおいて、各構造単位に記載の数値(a~e)は、全構造単位に対する、各構造単位のモル比を意図し、x及びyは連結数を意図する。また、分散剤Eにおいては、Zに連結した連結基に記載の数値は、Zに連結した連結数を意図する。 <Dispersant>
Dispersants A to E having the following structures were used as the dispersants. In the dispersants A, B, and D, the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units. In the dispersant C, the numerical values (a to e) described in each structural unit are intended to be the molar ratio of each structural unit relative to all structural units, and x and y are intended to be the number of linkages. Moreover, in the dispersing agent E, the numerical value described in the coupling group linked to Z intends the number of linkages linked to Z.
重合性化合物として、以下の重合性化合物M1を用いた。
・重合性化合物M1
(日本化薬社製、商品名「KAYARAD DPHA」、下記式参照)
The following polymerizable compound M1 was used as the polymerizable compound.
Polymerizable compound M1
(Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”, see formula below)
重合開始剤として、以下のオキシム系開始剤を用いた。
・OXE-02:Irgacure OXE02(商品名、BASFジャパン社製) <Polymerization initiator>
The following oxime initiators were used as polymerization initiators.
OXE-02: Irgacure OXE02 (trade name, manufactured by BASF Japan)
有機溶剤として、以下の有機溶剤を用いた。
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
・シクロペンタノン <Organic solvent>
The following organic solvents were used as the organic solvent.
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Cyclopentanone
界面活性剤としては、以下の界面活性剤1を用いた。
(界面活性剤1)下記構造式で表される混合物F-1(重量平均分子量(Mw)=14000) <Surfactant>
The following surfactant 1 was used as the surfactant.
(Surfactant 1) Mixture F-1 represented by the following structural formula (weight average molecular weight (Mw) = 14000)
まず、窒化物又は酸窒化物を含有する顔料、分散剤及び有機溶剤を、攪拌機(IKA社製EUROSTAR)によって15分間混合し、分散物を得た。次に、得られた分散物に対して、(株)シンマルエンタープライゼス製のNPM-Pilotを使用して下記条件にて分散処理を行い、顔料分散物を得た。なお、窒化物又は酸窒化物を含有する顔料に対する分散剤の比率(質量比)(以下、「D/P」ともいう。)が第1表の各実施例及び比較例に示す割合になるように添加した。
(分散条件)
・ビーズ径:φ0.05mm、(ニッカトー製ジルコニアビーズ、YTZ)
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレータ周速:13m/s
・分散処理する混合液量:15kg
・循環流量(ポンプ供給量):90kg/hour
・処理液温度:19~21℃
・冷却水:水
・処理時間:22時間程度 <Preparation of pigment dispersion>
First, a pigment containing a nitride or oxynitride, a dispersant, and an organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a pigment dispersion. The ratio (mass ratio) of the dispersant to the pigment containing nitride or oxynitride (hereinafter also referred to as “D / P”) is the ratio shown in each example and comparative example in Table 1. Added to.
(Distribution condition)
・ Bead diameter: 0.05mm, (Nikkato zirconia beads, YTZ)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / s
・ Amount of liquid mixture to be dispersed: 15 kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: About 22 hours
次に、上記顔料分散液、黒色染料、バインダー樹脂、重合性化合物、重合開始剤、界面活性剤及び有機溶剤を混合、攪拌して、下記第1表に示す実施例及び比較例の各組成物を得た。なお、黒色染料については、表中に記載される「持ち込み剤」と黒色染料とを混合した組成物を予め調製し、これを顔料分散液等の他の成分と混合させた。
実施例及び比較例の各組成物に含まれる各成分の含有量(質量%)を、第1表に示す。 <Preparation of composition>
Next, the pigment dispersion, the black dye, the binder resin, the polymerizable compound, the polymerization initiator, the surfactant and the organic solvent are mixed and stirred, and the compositions of Examples and Comparative Examples shown in Table 1 below are mixed. Got. In addition, about black dye, the composition which mixed "carrying-in agent" and black dye which are described in a table | surface was prepared previously, and this was mixed with other components, such as a pigment dispersion liquid.
Table 1 shows the content (% by mass) of each component contained in each composition of Examples and Comparative Examples.
実施例及び比較例の各組成物の水分量について、カールフィッシャー法を測定原理とするMKV-710(商品名、京都電子工業社製)により測定した。結果を第1表に示す。
なお、組成物中の水分は、各種原料に由来するものである。 <Measurement of water content in composition>
The water content of each of the compositions of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by Kyoto Electronics Industry Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Table 1.
In addition, the water | moisture content in a composition originates in various raw materials.
実施例及び比較例の各組成物について、以下の各評価試験を行った。 [Evaluation test]
The following evaluation tests were performed on the compositions of the examples and comparative examples.
実施例及び比較例の各組成物を100mLブルームビンに入れ、45℃の環境下で7日間静置した。そして、上澄み液90mLを取り除き、残った10mLの組成物をPGMEA(プロピレングリコールモノメチルエーテルアセテート)で500倍に希釈して評価液を調製した。この評価液10ml中に含まれる10μm以上のパーティクルの数をフロー式粒子像分析装置(商品名「FPIA」、マルバーン社製)にてをカウントした。 <Number of particles>
Each composition of the examples and comparative examples was placed in a 100 mL bloom bottle and allowed to stand in an environment of 45 ° C. for 7 days. Then, 90 mL of the supernatant was removed, and the remaining 10 mL of the composition was diluted 500 times with PGMEA (propylene glycol monomethyl ether acetate) to prepare an evaluation solution. The number of particles of 10 μm or more contained in 10 ml of this evaluation liquid was counted with a flow type particle image analyzer (trade name “FPIA”, manufactured by Malvern).
厚さ0.7mm、10cm角のガラス板(EagleXG、Corning)上に、膜厚1.0μmとなる回転数にてスピンコートにより組成物を塗布して塗布膜を形成し、ホットプレート上において、塗布膜を100℃、2minの熱処理をすることにより、乾燥膜を得た。得られた乾燥膜に対し、分光光度計U-4100(日立ハイテクノロジーズ社製)によりOD(光学濃度)を測定した。波長400~1200nmにおける最低ODに基づいて、以下の基準により分光(遮光性)の評価を行った。このとき、組成物の組成を調製することにより、塗布液固形分中の50質量%が顔料とした。
「A」:最低OD>2.5
「B」:2.5≧最低OD>2.3
「C」:2.3≧最低OD>2.1
「D」:2.1≧最低OD <Spectroscopic (light shielding)>
A coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 μm, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film. The obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the minimum OD at a wavelength of 400 to 1200 nm, the spectroscopic (light shielding property) was evaluated according to the following criteria. At this time, by preparing the composition of the composition, 50% by mass in the solid content of the coating solution was used as a pigment.
“A”: Minimum OD> 2.5
“B”: 2.5 ≧ minimum OD> 2.3
“C”: 2.3 ≧ minimum OD> 2.1
“D”: 2.1 ≧ minimum OD
実施例及び比較例の組成物を23℃において10日間保存した後、7℃において90日間保存した。また、保存前後の各組成物の粘度を、E型粘度計(東機産業社製、商品名「R85形粘度計」)を用いて回転数10rpm、23℃の条件にて測定した。そして、[{(経時後の粘度-調液直後の粘度)/調液直後の粘度}×100]の値(%)を算出した。評価基準は以下の通りである。
「A」:±3%以内
「B」:±3%超、±5%以内
「C」:±5超%、±10%以内
「D」:±10%超 <Viscosity stability over time>
The compositions of Examples and Comparative Examples were stored at 23 ° C. for 10 days and then stored at 7 ° C. for 90 days. The viscosity of each composition before and after storage was measured using an E-type viscometer (trade name “R85 type viscometer” manufactured by Toki Sangyo Co., Ltd.) under the conditions of a rotation speed of 10 rpm and 23 ° C. Then, the value (%) of [{(viscosity after aging−viscosity immediately after preparation) / viscosity immediately after preparation} × 100] was calculated. The evaluation criteria are as follows.
"A": Within ± 3% "B": Over ± 3%, within ± 5% "C": Over ± 5%, within ± 10% "D": Over ± 10%
実施例及び比較例の各組成物を用いて、各組成物の塗布膜の乾燥膜厚が0.7μmになるように、表面に電極パターン(銅)が形成されたシリコンウエハの電極パターン上に、各組成物をスピンコート塗布した。その後、10分間そのままの状態で待機させ、100℃のホットプレートを用いて、各組成物が塗布されたシリコンウエハに対して120秒間加熱処理(プリベーク)を行い、塗布膜を形成した。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して365nmの波長でパターンが20μm四方のIslandパターンマスクを通して、500mJ/cm2の露光量で塗布膜を露光した。
なお、実施例及び比較例の各組成物は、露光部が硬化するネガ型の感光性樹脂組成物である。
その後、露光された塗布膜が形成されているシリコンウエハ基板をスピンシャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製、有機アルカリ液現像液)を用いて23℃で60秒間パドル現像を行った。
次いで、パドル現像後のシリコンウエハを真空チャック方式で上記水平回転テーブルに固定し、回転装置によってシリコンウエハ基板を回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥し、額縁状のパターンを有するウエハを形成した。 <Reworkability>
Using each composition of Examples and Comparative Examples, on the electrode pattern of the silicon wafer on which the electrode pattern (copper) was formed on the surface so that the dry film thickness of the coating film of each composition was 0.7 μm Each composition was spin-coated. Then, it was made to stand by for 10 minutes as it was, and it heat-processed (prebaked) for 120 second with respect to the silicon wafer with which each composition was apply | coated using the 100 degreeC hotplate, and formed the coating film.
Next, the coating film was exposed at an exposure amount of 500 mJ / cm 2 through an Island pattern mask having a pattern of 20 μm square at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).
In addition, each composition of an Example and a comparative example is a negative photosensitive resin composition which an exposure part hardens | cures.
Thereafter, the silicon wafer substrate on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. (organic alkaline solution developer).
Next, the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center from a jet nozzle. The wafer was rinsed and then spray-dried to form a wafer having a frame-like pattern.
「A」:パターンが観察されない
「B」:パターン形成領域の5%以下に粒子状の除去残渣が観察される
「C」:パターン形成面積の5%超10%以下に粒子状の除去残渣が観察される
「D」:パターン形成面積の10%超に粒子状の除去残渣が観察されるか、若しくは、パターン若しくはパターンの一部が観察される Next, the obtained wafer having a frame-like pattern is immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85 ° C. for 5 hours, and immersed in a 2 L DIW (pure water) bath at room temperature for 2 minutes. The rinse treatment was performed. The removal state of the frame-like pattern from the obtained wafer after cleaning was observed with an optical microscope (manufactured by Olympus, trade name “LEXT OLS4500”) to evaluate reworkability. The evaluation criteria are as follows.
“A”: no pattern is observed “B”: particulate removal residue is observed in 5% or less of the pattern formation region “C”: particulate removal residue is present in more than 5% and 10% or less of the pattern formation area Observed “D”: particulate removal residue is observed in more than 10% of the pattern formation area, or a pattern or a part of the pattern is observed
厚さ0.7mm、10cm角のガラス板(EagleXG、Corning)上に、膜厚1.0μmとなる回転数にてスピンコートにより組成物を塗布して塗布膜を形成し、ホットプレート上において、塗布膜を100℃、2minの熱処理をすることにより、乾燥膜を得た。得られた乾燥膜に対し、分光光度計U-4100(日立ハイテクノロジーズ社製)によりOD(光学濃度)を測定した。波長400~1200nmにおける最低ODに基づいて、分光(遮光性)の評価を行い、耐熱試験前最低ODとした。乾燥膜を265℃のホットプレート上で10分間加熱処理し、上記と同様に分光評価を行い、耐熱試験後最低ODを得た。耐熱試験での分光変動量を下記式により算出し、評価した。
「変動量={(耐熱試験後最低OD-耐熱試験前最低OD)/耐熱試験前最低OD}×100」
「A」:±3%以内
「B」:±3%超、±5%以内
「C」:±5超%、±10%以内
「D」:±10%超 <Heat resistance>
A coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 μm, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film. The obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the lowest OD at a wavelength of 400 to 1200 nm, the spectral (light-shielding property) was evaluated and set as the lowest OD before the heat resistance test. The dried film was heat-treated on a hot plate at 265 ° C. for 10 minutes, subjected to spectral evaluation in the same manner as described above, and a minimum OD was obtained after the heat resistance test. The spectral fluctuation amount in the heat resistance test was calculated by the following formula and evaluated.
“Fluctuation amount = {(minimum OD after heat test−minimum OD before heat test) / minimum OD before heat test} × 100”
"A": Within ± 3% "B": Over ± 3%, within ± 5% "C": Over ± 5%, within ± 10% "D": Over ± 10%
実施例及び比較例の組成物を用いて、スピンコーターにより、イメージセンサーデバイス基板上に塗膜を形成した。次いで、得られた塗膜に対して、ホットプレート上で100℃、2minのプリベーク処理を行った。続いて、i線露光装置(FPA、キヤノン製)を用いて上記プリベーク処理を経た塗膜を露光し、更に現像することにより、基板上の受光部外周部分にダイシングライン及び電極部以外を被覆する遮光膜を形成すると同時に、基板上に20μmの線幅を有するアライメントマークを20個形成した。
光学顕微鏡を用い、形成したアライメントマークの個数を観察することで、解像性の評価を行った。
「A」: マークが20個形成できた。
「B」: マークが19個形成できた。
「C」: マークが18個形成できた。
「D」: マークが17個以下形成できた。 <Patternability (resolution)>
Using the compositions of Examples and Comparative Examples, a coating film was formed on an image sensor device substrate by a spin coater. Next, the obtained coating film was pre-baked at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film that has been subjected to the pre-baking process is exposed using an i-line exposure apparatus (FPA, manufactured by Canon Inc.), and further developed to cover the outer periphery of the light receiving part on the substrate except for the dicing line and the electrode part. Simultaneously with the formation of the light shielding film, 20 alignment marks having a line width of 20 μm were formed on the substrate.
The resolution was evaluated by observing the number of alignment marks formed using an optical microscope.
“A”: 20 marks were formed.
“B”: 19 marks were formed.
“C”: 18 marks were formed.
“D”: 17 or less marks were formed.
実施例1にて染料Aを用いた代わりに重合性黒色染料「RDW-K01」(和光純薬工業株式会社製)を用いたこと以外は同様として組成物を調製し、評価を行ったところ、実施例1と同等の性能を有することが分かった。 (Example 22)
A composition was prepared and evaluated in the same manner except that the polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of using the dye A in Example 1. It was found to have the same performance as in Example 1.
実施例1にて染料Aを用いた代わりに、染料Aと重合性黒色染料「RDW-K01」(和光純薬工業株式会社製)を用い、質量比で1:1として使用したこと以外は同様として組成物を調製し、評価を行ったところ、実施例1と同等の性能を有することが分かった。 (Example 23)
The same as Example 1 except that Dye A and polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye A, and the mass ratio was 1: 1. When the composition was prepared and evaluated, it was found that it had the same performance as Example 1.
実施例4にて染料Bを用いた代わりに、染料Bと重合性黒色染料「RDW-K01」(和光純薬工業株式会社製)を用い、質量比で1:1として使用したこと以外は同様として組成物を調製し、評価を行ったところ、実施例4よりもより優れた評価が得られ、具体的にはリワーク性評価、耐熱性評価、パターニング性評価がいずれも「B」となることが分かった。 (Example 24)
The same as Example 4 except that Dye B and polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye B, and the weight ratio was 1: 1. As the composition was prepared and evaluated, evaluation superior to that of Example 4 was obtained. Specifically, the reworkability evaluation, the heat resistance evaluation, and the patterning evaluation were all “B”. I understood.
実施例1において、TiN-1を用いた代わりに、TiN-1とカーボンブラック(商品名「カラーブラック S170」、デグサ社製、平均一次粒子径17nm、BET比表面積200m2/g、ガスブラック方式により製造されたカーボンブラック)を用い、質量比で7:3として使用したこと以外は同様として組成物を調製し、評価を行ったところ、実施例1と同等の性能を有することが分かった。 (Example 25)
In Example 1, instead of using TiN-1, TiN-1 and carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, gas black method When the composition was prepared and evaluated in the same manner except that it was used at a mass ratio of 7: 3, it was found that it had the same performance as in Example 1.
実施例1において、TiN-1を用いた代わりに、TiN-1とピグメントイエロー150(Hangzhou Star-up Pigment Co., Ltd.製、商品名6150顔料黄5GN)を用い、質量比で9:1として使用したこと以外は同様として組成物を調製し、評価を行ったところ、実施例1と同等の性能を有することが分かった他、さらに黒味の濃い遮光膜が得られることが分かった。この結果から、他の有機顔料や、有彩色染料と併用しても本願所望の効果が得られることが推定される。 (Example 26)
In Example 1, TiN-1 and Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) were used instead of TiN-1, and the mass ratio was 9: 1. When the composition was prepared and evaluated in the same manner except that it was used as a light-shielding film, it was found that the composition had the same performance as that of Example 1, and a darker light-shielding film was obtained. From this result, it is presumed that the desired effect of the present application can be obtained even in combination with other organic pigments or chromatic dyes.
Claims (20)
- 無機顔料と、黒色染料と、を含む組成物。 A composition containing an inorganic pigment and a black dye.
- 前記無機顔料が、窒化物又は酸窒化物を含有する顔料である請求項1に記載の組成物。 The composition according to claim 1, wherein the inorganic pigment is a pigment containing a nitride or an oxynitride.
- 前記黒色染料が重合性基を有する、請求項1又は請求項2に記載の組成物。 The composition according to claim 1 or 2, wherein the black dye has a polymerizable group.
- 前記重合性基がアクリロイル基又はメタクリロイル基である、請求項3に記載の組成物。 The composition according to claim 3, wherein the polymerizable group is an acryloyl group or a methacryloyl group.
- 前記黒色染料がキサンテン系染料又はアゾ系染料である、請求項1~4のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the black dye is a xanthene dye or an azo dye.
- 前記黒色染料が染料多量体である、請求項1~5のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 5, wherein the black dye is a dye multimer.
- 更に、分散剤を含む、請求項1~6のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 6, further comprising a dispersant.
- 前記分散剤の酸価が50mgKOH/g以上である、請求項7に記載の組成物。 The composition according to claim 7, wherein the acid value of the dispersant is 50 mgKOH / g or more.
- 前記分散剤が、ポリカプロラクトン、ポリバレロラクトン、ポリアクリル酸メチル及びポリメタクリル酸メチルからなる群より選択される少なくとも1種の構造を有する、請求項7又は請求項8に記載の組成物。 The composition according to claim 7 or 8, wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate.
- 更に、重合性化合物と、重合開始剤と、を含む、請求項1~9のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 9, further comprising a polymerizable compound and a polymerization initiator.
- 更に、有機溶剤を含む、請求項1~10のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 10, further comprising an organic solvent.
- 更に、アルカリ可溶性樹脂を含む、請求項1~11のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 11, further comprising an alkali-soluble resin.
- 前記黒色染料の含有量が、前記無機顔料の含有量に対して質量比で0.3以下である、請求項1~12のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein a content of the black dye is 0.3 or less by mass ratio with respect to a content of the inorganic pigment.
- 組成物全質量に対する固形分量が10~40質量%である、請求項1~13のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 13, wherein the solid content is 10 to 40% by mass relative to the total mass of the composition.
- 前記無機顔料の含有量が、固形分量に対して30~70質量%である、請求項1~14のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 14, wherein the content of the inorganic pigment is 30 to 70 mass% with respect to the solid content.
- 請求項1~15のいずれか1項に記載の組成物を用いて得られる、硬化膜。 A cured film obtained using the composition according to any one of claims 1 to 15.
- 請求項16に記載の硬化膜を有する、カラーフィルタ。 A color filter having the cured film according to claim 16.
- 請求項16に記載の硬化膜を有する、遮光膜。 A light-shielding film having the cured film according to claim 16.
- 請求項16に記載の硬化膜を有する、固体撮像装置。 A solid-state imaging device having the cured film according to claim 16.
- 請求項16に記載の硬化膜を有する、画像表示装置。 An image display device comprising the cured film according to claim 16.
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JP7330719B2 (en) * | 2019-03-01 | 2023-08-22 | 太陽ホールディングス株式会社 | Alkali developable photocurable thermosetting resin composition |
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