JP5167602B2 - Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter - Google Patents
Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter Download PDFInfo
- Publication number
- JP5167602B2 JP5167602B2 JP2006194150A JP2006194150A JP5167602B2 JP 5167602 B2 JP5167602 B2 JP 5167602B2 JP 2006194150 A JP2006194150 A JP 2006194150A JP 2006194150 A JP2006194150 A JP 2006194150A JP 5167602 B2 JP5167602 B2 JP 5167602B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc phthalocyanine
- polyhalogenated zinc
- color filter
- polyhalogenated
- phthalocyanine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims description 132
- 150000003751 zinc Polymers 0.000 title claims description 116
- 239000000203 mixture Substances 0.000 title claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 238000002834 transmittance Methods 0.000 claims description 24
- 238000001228 spectrum Methods 0.000 claims description 22
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011164 primary particle Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000003595 spectral effect Effects 0.000 claims description 10
- 238000000411 transmission spectrum Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 19
- -1 for example Chemical group 0.000 description 17
- 239000013078 crystal Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000001052 yellow pigment Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 7
- 229910001507 metal halide Inorganic materials 0.000 description 7
- 150000005309 metal halides Chemical class 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000001056 green pigment Substances 0.000 description 5
- 238000004255 ion exchange chromatography Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZEMYZPXPNMSHCE-UHFFFAOYSA-N (3-methyl-1-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound CCC(C)CC(OC(=O)C=C)OC(=O)C=C ZEMYZPXPNMSHCE-UHFFFAOYSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- NCHBYORVPVDWBJ-UHFFFAOYSA-N 2-(3-methylbutoxy)ethanol Chemical compound CC(C)CCOCCO NCHBYORVPVDWBJ-UHFFFAOYSA-N 0.000 description 1
- INFFATMFXZFLAO-UHFFFAOYSA-N 2-(methoxymethoxy)ethanol Chemical compound COCOCCO INFFATMFXZFLAO-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical compound OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 0 Cc1c(*)c(*)c(*)c(C(*)=*2N3*45)c1C2=*C4=C1C(*)=C(*)C(N)=C(*)C1=C5*=C1*3=C(*=C2c3c(*)c(*=C)c(**)c(*)c3C(*)[*@@]2C=C)c2c1c(C)c(*)c(*)c2* Chemical compound Cc1c(*)c(*)c(*)c(C(*)=*2N3*45)c1C2=*C4=C1C(*)=C(*)C(N)=C(*)C1=C5*=C1*3=C(*=C2c3c(*)c(*=C)c(**)c(*)c3C(*)[*@@]2C=C)c2c1c(C)c(*)c(*)c2* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 206010049155 Visual brightness Diseases 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XHPWRTXYJFNZAW-UHFFFAOYSA-N [[4-[2-(4-diazonioimino-2-sulfocyclohexa-2,5-dien-1-ylidene)ethylidene]-3-sulfocyclohexa-2,5-dien-1-ylidene]hydrazinylidene]azanide Chemical compound OS(=O)(=O)C1=CC(N=[N+]=[N-])=CC=C1C=CC1=CC=C(N=[N+]=[N-])C=C1S(O)(=O)=O XHPWRTXYJFNZAW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000904 isoindolyl group Chemical class C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-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
- 238000004383 yellowing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
Landscapes
- Optical Filters (AREA)
Description
本発明は、液晶表示装置のカラーフィルターに用いるのに好適なポリハロゲン化亜鉛フタロシアニン、それを含有してなる感光性組成物およびこれを用いたカラーフィルターに関する。 The present invention relates to a polyhalogenated zinc phthalocyanine suitable for use in a color filter of a liquid crystal display device, a photosensitive composition containing the same, and a color filter using the same.
従来使用されていたカラーフィルターは高透明性であり、バックライトの輝線を良く透過させて色表示できる顔料が優れているとされていた。この技術は現在でも携帯電話やモバイルゲーム機、ＰＤＡ等、二次電池や乾電池等の限られた電気量で、バックライト光源が電気容量を小さくする必要のある機器については有利である。 Conventionally used color filters are highly transparent, and pigments that can transmit colors well through the bright lines of the backlight are considered excellent. This technology is still advantageous for devices such as mobile phones, mobile game machines, PDAs, and the like that require a limited amount of electricity, such as secondary batteries and dry batteries, and where the backlight source needs to reduce the electric capacity.
しかしながら、パーソナルコンピュータの液晶表示モニター、液晶テレビ等、電源を常につないだ状態で使用される機器に使用されるカラーフィルターは、バックライト光源が常に供給される電源を持つため、その要求特性は色純度が高く、かつ高透過性の色材が要求される。 However, color filters used in equipment that is always connected to a power source, such as a personal computer liquid crystal display monitor or a liquid crystal television, have a power source that is always supplied with a backlight light source. A highly pure and highly transparent colorant is required.
この高色純度が要求される液晶表示装置に用いられるカラーフィルターは、ガラス等の透明基板上に赤色、緑色、青色の３色のパターンが形成されたものであり、緑色の着色パターンを形成するためには、一般に塩素化銅フタロシアニン顔料（Ｃ．Ｉ．ＰＩＧＭＥＮＴ Ｇｒｅｅｎ７）や塩素化臭素化銅フタロシアニン（Ｃ．Ｉ．ＰＩＧＭＥＮＴ Ｇｒｅｅｎ３６）等の緑色顔料からなる着色剤が使用されている。 A color filter used in a liquid crystal display device that requires high color purity is obtained by forming a three-color pattern of red, green, and blue on a transparent substrate such as glass, and forms a green coloring pattern. For this purpose, a colorant composed of a green pigment such as chlorinated copper phthalocyanine pigment (CI PIGMENT Green 7) or chlorinated brominated copper phthalocyanine (CI PIGMENT Green 36) is generally used.
銅フタロシアニンは、銅原子のまわりに４個のイソインドールを持つ環状化合物であり、１分子中に４個の芳香環を有する。そして、この芳香環はそれぞれ４個の水素原子を有していて、これら合計１６個の水素原子は臭素、塩素等のハロゲン原子によって置換可能である。 Copper phthalocyanine is a cyclic compound having four isoindoles around a copper atom, and has four aromatic rings in one molecule. Each of the aromatic rings has 4 hydrogen atoms, and a total of 16 hydrogen atoms can be substituted with halogen atoms such as bromine and chlorine.
従って、高色純度が要求される液晶表示装置に用いられるカラーフィルターの緑色パターンに使用される上記着色剤は、通常、この１６個の水素原子のうちの一部またはすべてが、塩素や臭素によって置換されたポリハロゲン化銅フタロシアニン顔料を含む緑色顔料組成物が使用されていた。 Therefore, the colorant used in the green pattern of the color filter used in a liquid crystal display device that requires high color purity usually has some or all of these 16 hydrogen atoms formed by chlorine or bromine. Green pigment compositions containing substituted polyhalogenated copper phthalocyanine pigments have been used.
これとは別に、最近では特許文献１〜３にある様に、カラーフィルタの緑色画素部を、ポリハロゲン化銅フタロシアニン顔料よりも高色再現域が広く、着色力が高い、ポリハロゲン化亜鉛フタロシアニンを緑色顔料として使用して形成することが知られている。
Separately from this, as disclosed in
しかしながら、これら特許文献に従って得られる、公知のポリハロゲン化亜鉛フタロシアニンは、Ｘ線回折スペクトルにおいて、Ｃｕ−Ｋα線に対するブラッグ角（２θ±０．２゜）２５．０゜に最大回折ピークを有し、１６．８°，２３．１°，３２．４°にピークを有するポリハロゲン化亜鉛フタロシアニンであった。 However, known polyhalogenated zinc phthalocyanines obtained according to these patent documents have a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 25.0 ° with respect to the Cu—Kα ray in the X-ray diffraction spectrum. , 16.8 °, 23.1 °, and 32.4 °, polyhalogenated zinc phthalocyanine.
この様な結晶型のポリハロゲン化亜鉛フタロシアニンは、初期においては優れた性質を示すものの、機械的応力や有機溶剤との接触・浸漬、或いは熱負荷に対して比較的不安定であり、色味が安定せず発色が赤味がかったり、明度が低くなってしまい、初期の優れた性質が安定的に維持し難いという場合があった。 Although such a crystal-type polyhalogenated zinc phthalocyanine exhibits excellent properties in the initial stage, it is relatively unstable with respect to mechanical stress, contact / immersion with organic solvents, or heat load, However, it was not stable, and the color development was reddish or the brightness was low, and it was difficult to maintain the initial excellent properties stably.
本発明は前記事情に鑑みてなされたもので、初期のみならず、安定的に、黄味が強く明度の高い緑色を発色し、例えば、結果的に高輝度、高コントラストかつ高明度のカラーフィルターの緑色画素部を形成するのに適した結晶型のポリハロゲン化亜鉛フタロシアニンを提供することを課題とする。さらには調色するにしても、より少ない黄色顔料の併用で済み、調色によっても明度の低下がより小さいカラーフィルターを安定に提供することを課題とする。 The present invention has been made in view of the above circumstances, and not only in the initial stage, but also stably produces a green color with strong yellowness and high brightness, and as a result, for example, a color filter with high brightness, high contrast, and high brightness. It is an object of the present invention to provide a crystalline polyhalogenated zinc phthalocyanine suitable for forming a green pixel portion. Further, it is an object of the present invention to stably provide a color filter that can be used in combination with a smaller amount of yellow pigment and that has a smaller decrease in lightness due to the toning.
本発明は、公知のポリハロゲン化亜鉛フタロシアニンの製造方法を新たに工夫することにより、従来とは異なる新規な結晶型が出現し、それがより高輝度、より高コントラストかつより高明度を有するカラーフィルターの緑色画素部の形成に好適であることを見いだし、本発明に至ったものである。 In the present invention, by newly devising a known method for producing a polyhalogenated zinc phthalocyanine, a new crystal form different from the conventional one appears, and it has higher brightness, higher contrast and higher brightness. It has been found that the present invention is suitable for forming a green pixel portion of a filter, and the present invention has been achieved.
即ち本発明は、本発明は上記課題を解決するために、Ｘ線回折スペクトルにおいて、Ｃｕ−Ｋα線に対するブラッグ角（２θ±０．２゜）＝２６．４゜に最大回折ピークを有し、２２．６°，２４．８°,２５．７°,２７．８°にピークを有することを特徴とする、下記一般式１で表されるポリハロゲン化亜鉛フタロシアニンを提供する。
また本発明は、感光性樹脂と、前記 ポリハロゲン化亜鉛フタロシアニンを必須成分として含むカラーフィルタ 緑色画素部用感光性組成物を提供する。
更に本発明は、前記ポリハロゲン化亜鉛フタロシアニンを緑色画素部に含有するカラーフィルタを提供する。
本発明において、カラーフィルターは、カラーフィルタと読み替える。同様に、乾留は還流と読み替える。
That is, the present invention has the maximum diffraction peak at the Bragg angle (2θ ± 0.2 °) = 26.4 ° with respect to the Cu-Kα ray in the X-ray diffraction spectrum in order to solve the above-mentioned problems. A polyhalogenated zinc phthalocyanine represented by the following
The present invention also provides a photosensitive resin, a pre-Symbol color filters green pixel portions for a photosensitive composition containing as a port Riharogen zinc phthalocyanine as an essential component.
Furthermore, the present invention provides a color filter containing the polyhalogenated zinc phthalocyanine in a green pixel portion.
In the present invention, the color filter is read as a color filter. Similarly, dry distillation is read as reflux.
本発明の新規結晶型のポリハロゲン化亜鉛フタロシアニンは、Ｘ線回折スペクトルにて特定ブラッグ角にピークを有しているので、従来の結晶型のポリハロゲン化亜鉛フタロシアニンに比べて、輝度、コントラスト及び光透過率にいずれにおいても性能上優位であり、それが安定的に持続するという格別顕著な効果を奏する。したがって、本発明のポリハロゲン化亜鉛フタロシアニンは、例えばディスプレー等の大画面用のカラーフィルターの緑色画素部のパターンの形成に最適である。
また本発明の感光性組成物は、前記したＸ線回折スペクトルにて特定ブラッグ角にピークを有するポリハロゲン化亜鉛フタロシアニンを含有するので、容易に輝度、コントラスト及び光透過率にいずれにおいても性能上優位なカラーフィルターを製造出来るという格別顕著な効果を奏する。
さらに本発明のカラーフィルターは、前記したＸ線回折スペクトルにて特定ブラッグ角にピークを有するポリハロゲン化亜鉛フタロシアニンを含有するので、輝度、コントラスト及び光透過率にいずれにおいても性能上優位であるという格別顕著な効果を奏する。
Since the novel crystal-type polyhalogenated zinc phthalocyanine of the present invention has a peak at a specific Bragg angle in the X-ray diffraction spectrum, the brightness, contrast, and contrast are higher than those of the conventional crystal-type polyhalogenated zinc phthalocyanine. In any case, the light transmittance is superior in performance, and it has a particularly remarkable effect that it is stably maintained. Therefore, the polyhalogenated zinc phthalocyanine of the present invention is optimal for forming a pattern of a green pixel portion of a color filter for a large screen such as a display.
Further, since the photosensitive composition of the present invention contains polyhalogenated zinc phthalocyanine having a peak at a specific Bragg angle in the above-mentioned X-ray diffraction spectrum, it is easy in terms of performance in any of brightness, contrast and light transmittance. There is an especially remarkable effect that an excellent color filter can be manufactured.
Furthermore, since the color filter of the present invention contains polyhalogenated zinc phthalocyanine having a peak at a specific Bragg angle in the above X-ray diffraction spectrum, it is superior in performance in terms of luminance, contrast and light transmittance. There is a particularly remarkable effect.
亜鉛フタロシアニンは、フタロシアニン環中に１６個の水素原子を有しているため、これらの水素原子を、最大１６個まで臭素原子及び／又は塩素原子で置換することが出来る。これらハロゲン原子は、全て同一であっても、それぞれ異なっていてもよい。置換基数を一定とした場合には、臭素原子＞塩素原子の順に緑色が濃くなる。これら水素原子を、臭素原子と、例えば塩素原子とで置換すると、臭素原子数が０〜１６個、塩素原子数が０〜１６個、水素原子数が０〜１６個の範囲で、理論上では合計１３６種類の置換体を製造できる。 Since zinc phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms. These halogen atoms may all be the same or different. When the number of substituents is constant, green becomes darker in the order of bromine atom> chlorine atom. When these hydrogen atoms are substituted with bromine atoms, for example, chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, in theory. A total of 136 types of substitution products can be produced.
この様なポリハロゲン化亜鉛フタロシアニンは、具体的には下記一般式にて表される。 Such a polyhalogenated zinc phthalocyanine is specifically represented by the following general formula.
（上記一般式１中、Ｘ１〜Ｘ１６は、いずれも独立に塩素原子、臭素原子または水素原子である。ただし、全てのＸのうち少なくとも８つは、塩素原子または臭素である。）
(In
ここで、ポリハロゲン化亜鉛フタロシアニンは、臭素原子を８個以上含有することが、黄味を帯びた明度の高い緑色を発色し、カラーフィルターの緑色画素部パターンへの使用に最適であるので最適である。本発明では、臭素原子を８個以上含有するポリハロゲン化亜鉛フタロシアニンを、ポリ臭素化亜鉛フタロシアニンという。 Here, polyhalogenated zinc phthalocyanine is optimal because it contains 8 or more bromine atoms, which produces a yellowish, light green color and is optimal for use in the color filter green pixel pattern. It is. In the present invention, polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is referred to as polybrominated zinc phthalocyanine.
ポリハロゲン化亜鉛フタロシアニンの平均組成は、マススペクトロスコピーに基づく質量分析と、フラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から容易に求められる。 The average composition of the polyhalogenated zinc phthalocyanine can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.
また本発明のポリハロゲン化亜鉛フタロシアニンは、Ｘ線回折スペクトルにおいて、Ｃｕ−Ｋα線に対するブラッグ角（２θ±０．２゜）＝２６．４゜に最大回折ピークを有し、２２．６°，２４．８°,２５．７°,２７．８°にピークを有することを特徴とする。 Further, the polyhalogenated zinc phthalocyanine of the present invention has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) = 26.4 ° with respect to the Cu—Kα ray in the X-ray diffraction spectrum, 22.6 °, It is characterized by having peaks at 24.8 °, 25.7 °, and 27.8 °.
ポリハロゲン化亜鉛フタロシアニンは、例えば、クロルスルホン酸法、ハロゲン化フタロニトリル法、溶融法等の様な公知の製造方法で製造できる。 The polyhalogenated zinc phthalocyanine can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method.
クロルスルホン酸法としては、亜鉛フタロシアニンを、クロロスルホン酸等の硫黄酸化物系の溶媒に溶解し、これに塩素ガス、臭素を仕込みハロゲン化する方法が挙げられる。この際の反応は、温度２０〜１２０℃かつ１〜１０時間の範囲で行われる。 Examples of the chlorosulfonic acid method include a method in which zinc phthalocyanine is dissolved in a sulfur oxide-based solvent such as chlorosulfonic acid, and chlorine gas and bromine are added thereto to halogenate. The reaction at this time is carried out at a temperature of 20 to 120 ° C. and in a range of 1 to 10 hours.
ハロゲン化フタロニトリル法としては、例えば、芳香環の水素原子の一部または全部が臭素の他、塩素等のハロゲン原子で置換されたフタル酸やフタロジニトリルと、亜鉛の金属または金属塩を適宜出発原料として使用して、対応するハロゲン化金属フタロシアニンを合成する方法が挙げられる。この場合、必要に応じてモリブデン酸アンモニウム等の触媒を用いてもよい。この際の反応は、温度１００〜３００℃かつ１〜３０時間の範囲で行われる。 As the halogenated phthalonitrile method, for example, phthalic acid or phthalodinitrile in which some or all of the hydrogen atoms in the aromatic ring are substituted with halogen atoms such as chlorine in addition to bromine, and a metal or metal salt of zinc are appropriately used. A method of synthesizing a corresponding metal halide phthalocyanine using as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used as necessary. The reaction at this time is carried out at a temperature of 100 to 300 ° C. and in the range of 1 to 30 hours.
溶融法としては、塩化アルミニウム、臭化アルミニウムの様なハロゲン化アルミニウム、四塩化チタンの様なハロゲン化チタン、塩化ナトリウム、臭化ナトリウム等の様なアルカリ金属ハロゲン化物またはアルカリ土類金属ハロゲン化物〔以下、アルカリ（土類）金属ハロゲン化物という〕、塩化チオニル等、各種のハロゲン化の際に溶媒となる化合物の一種または二種以上の混合物からなる１０〜１７０℃程度の溶融物中で、亜鉛フタロシアニンをハロゲン化剤にてハロゲン化する方法が挙げられる。 Melting methods include aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides or alkaline earth metal halides such as sodium chloride and sodium bromide [ Hereinafter referred to as an alkali (earth) metal halide), thionyl chloride, etc., in a melt of about 10 to 170 ° C. composed of one kind or a mixture of two or more kinds of compounds which become solvents in the case of various halogenations. A method of halogenating phthalocyanine with a halogenating agent is mentioned.
好適なハロゲン化アルミニウムは、塩化アルミニウムである。ハロゲン化アルミニウムを用いる上記方法における、ハロゲン化アルミニウムの添加量は、金属フタロシアニンに対して、通常は、３倍モル以上であり、好ましくは１０〜２０倍モルである。 The preferred aluminum halide is aluminum chloride. In the above method using an aluminum halide, the addition amount of the aluminum halide is usually 3 times or more, preferably 10 to 20 times the mol of the metal phthalocyanine.
ハロゲン化アルミニウムは単独で用いてもよいが、アルカリ（土類）金属ハロゲン化物をハロゲン化アルミニウムに併用すると溶融温度をより下げることができ操作上有利になる。好適なアルカリ（土類）金属ハロゲン化物は、塩化ナトリウムである。加えるアルカリ（土類）金属ハロゲン化物の量は溶融塩を生成する範囲内でハロゲン化アルミニウム１０質量部に対してアルカリ（土類）金属ハロゲン化物が０〜１０質量部が好ましい。 The aluminum halide may be used alone, but when an alkali (earth) metal halide is used in combination with the aluminum halide, the melting temperature can be further lowered, which is advantageous in operation. A preferred alkali (earth) metal halide is sodium chloride. The amount of the alkali (earth) metal halide to be added is preferably 0 to 10 parts by mass of the alkali (earth) metal halide with respect to 10 parts by mass of the aluminum halide within the range in which the molten salt is formed.
また、ハロゲン化アルミニウムとして、塩化アルミニウムを用いる場合には、塩化チオニルや四塩化チタンを溶媒として用いることが好ましい。塩化チオニルや四塩化チタンの量は金属フタロシアニン１質量部に対して、１質量部以上、好ましくは２〜１０質量部である。 When aluminum chloride is used as the aluminum halide, thionyl chloride or titanium tetrachloride is preferably used as the solvent. The amount of thionyl chloride or titanium tetrachloride is 1 part by mass or more, preferably 2 to 10 parts by mass with respect to 1 part by mass of metal phthalocyanine.
ハロゲン化剤としては、塩素ガス、塩化スルフリル、臭素等がある。
ハロゲン化の温度は１０〜１７０℃が好ましいが、３０〜１４０℃がより好ましい。更に、反応速度を速くするため、加圧することも可能である。反応時間は、５〜１００時間で好ましくは、１０〜３０時間である。
Examples of the halogenating agent include chlorine gas, sulfuryl chloride, bromine and the like.
The halogenation temperature is preferably 10 to 170 ° C, more preferably 30 to 140 ° C. Furthermore, pressurization is possible to increase the reaction rate. The reaction time is 5 to 100 hours, preferably 10 to 30 hours.
前記化合物の二種以上を併用する溶融法は、溶融塩中の塩化物と臭化物とヨウ素化物の比率を調節したり、塩素ガスや臭素やヨウ素の導入量や反応時間を変化させたりすることによって、生成するポリハロゲン化亜鉛フタロシアニン中における種々のポリハロゲン化亜鉛フタロシアニンの比率を任意にコントロールすることができるので好ましい。 The melting method using two or more of the above-mentioned compounds in combination is possible by adjusting the ratio of chloride, bromide and iodide in the molten salt, or by changing the introduction amount and reaction time of chlorine gas, bromine and iodine. The ratio of various polyhalogenated zinc phthalocyanines in the resulting polyhalogenated zinc phthalocyanine can be arbitrarily controlled, which is preferable.
反応中の原料の分解が少なく原料からの収率がより優れ、強酸を用いず安価な装置にて反応を行えるので、本発明のポリハロゲン化亜鉛フタロシアニンを得る上では、溶融法が好適である。 In order to obtain the polyhalogenated zinc phthalocyanine of the present invention, the melting method is preferable because the decomposition of the raw material during the reaction is less, the yield from the raw material is better, and the reaction can be performed with an inexpensive apparatus without using a strong acid. .
上記いずれの製造方法にせよ、反応終了後、得られた混合物を水又は塩酸等の酸性水溶液中に投入すると、ポリハロゲン化亜鉛フタロシアニンが沈殿する。その後、濾過、水または硫酸水素ナトリウム水、炭酸水素ナトリウム水、水酸化ナトリウム水洗浄、必要に応じてアセトン、トルエン、メチルアルコール、エチルアルコール、ジメチルホルムアミド等の有機溶剤洗浄を行い、本発明のポリハロゲン化亜鉛フタロシアニンの原料として用いるのが好ましい。 In any of the above production methods, after completion of the reaction, when the obtained mixture is put into an acidic aqueous solution such as water or hydrochloric acid, polyhalogenated zinc phthalocyanine is precipitated. Thereafter, filtration, washing with water or sodium hydrogen sulfate aqueous solution, sodium hydrogen carbonate aqueous solution, sodium hydroxide aqueous solution, and organic solvent washing such as acetone, toluene, methyl alcohol, ethyl alcohol, dimethylformamide as necessary are performed. It is preferably used as a raw material for zinc halide phthalocyanine.
ポリハロゲン化亜鉛フタロシアニンは、前記した様な洗浄により得られたウエットケーキまたはこれを乾燥して得た乾燥物を、結晶変換させることで、新規な結晶型の本発明のポリハロゲン化亜鉛フタロシアニンとすることが出来る。 The polyhalogenated zinc phthalocyanine is obtained by subjecting the wet cake obtained by washing as described above or the dried product obtained by drying the crystal to crystal transformation to obtain a novel crystalline form of the polyhalogenated zinc phthalocyanine of the present invention. I can do it.
この結晶変換は、例えば、原料となるポリハロゲン化亜鉛フタロシアニンを有機溶剤中で加熱することにより行うことが出来る。 This crystal conversion can be performed, for example, by heating the raw material polyhalogenated zinc phthalocyanine in an organic solvent.
有機溶剤としては、例えばアルキルベンゼン、アルキルナフタレン、テトラリン等の芳香族炭化水素、メタノール、エタノール、イソブタノール等のアルコール、アルキルシクロヘキサン、デカリン、アルキルデカリン等の脂環式炭化水素、デカン、ドデカン等の脂肪族炭化水素、ニトロベンゼン、ｏ−ニトロトルエン等の芳香族ニトロ化合物、トリクロロベンゼン、ジクロロベンゼン、クロロナフタレン等の芳香族ハロゲン化炭化水素、スルホラン、ジメチルスルホラン、ジメチルスルホキシド等の硫黄化合物、キノリン等の複素環化合物等を挙げることが出来、これらの２種以上の混合物としても使用出来る。必要であれば、結晶成長や結晶変換の速度を、より制御しやすい好適な範囲とするために水が併用されても良い。 Examples of the organic solvent include aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin, alcohols such as methanol, ethanol and isobutanol, alicyclic hydrocarbons such as alkylcyclohexane, decalin and alkyldecalin, and fats such as decane and dodecane. Aromatic hydrocarbons such as aromatic hydrocarbons, nitrobenzene and o-nitrotoluene, aromatic halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene and chloronaphthalene, sulfur compounds such as sulfolane, dimethylsulfolane and dimethylsulfoxide, and heterocyclic rings such as quinoline A compound etc. can be mentioned and it can use also as a mixture of these 2 or more types. If necessary, water may be used in combination so that the rate of crystal growth and crystal conversion is within a suitable range that can be more easily controlled.
中でも、例えばトルエン、キシレン、エチルベンゼン等の常温液状の芳香族炭化水素が、少量かつより低温での加熱において、結晶成長及び結晶変換の程度を容易に制御することが出来、入手や取扱いが容易であることから好ましい。 Above all, for example, normal temperature liquid aromatic hydrocarbons such as toluene, xylene, and ethylbenzene can easily control the degree of crystal growth and crystal transformation in heating at a small amount and at a lower temperature, and are easy to obtain and handle. This is preferable.
この際の有機溶剤の使用量は、例えば、質量換算でポリハロゲン化亜鉛フタロシアニン１００部当たり、５００〜１５００部、中でも８００〜１２００部とすることが好ましい。必要であれば、結晶成長や結晶変換の速度を、より制御しやすい好適な範囲とするために水が併用することが出来る。 The amount of the organic solvent used at this time is preferably 500 to 1500 parts, more preferably 800 to 1200 parts per 100 parts of polyhalogenated zinc phthalocyanine in terms of mass. If necessary, water can be used in combination so that the rate of crystal growth and crystal conversion is within a suitable range that is more easily controlled.
またこの加熱は、常圧、加圧、減圧下のどの状態で行っても良い。有機溶剤のみまたは有機溶剤を含む液媒体での加熱は、有機溶剤が揮散しない様にして、温度、沸点±２０℃の範囲、時間、１〜１０時間の範囲で行うことが出来る。常圧においては、乾留しながら３〜８時間加熱することが好ましい。 Moreover, this heating may be performed in any state under normal pressure, pressurization, or reduced pressure. Heating with only the organic solvent or the liquid medium containing the organic solvent can be performed in the range of temperature, boiling point ± 20 ° C., time, and 1 to 10 hours so that the organic solvent is not volatilized. At normal pressure, it is preferable to heat for 3 to 8 hours while dry distillation.
こうして、Ｘ線回折スペクトルにおいて、Ｃｕ−Ｋα線に対するブラッグ角（２θ±０．２゜）２５．０゜に最大回折ピークを有し、１６．８°，２３．１°，３２．４°にピークを有するポリハロゲン化亜鉛フタロシアニンを、Ｃｕ−Ｋα線に対するブラッグ角（２θ±０．２゜）＝２６．４゜に最大回折ピークを有し、２２．６°，２４．８°,２５．７°,２７．８°にピークを有するポリハロゲン化亜鉛フタロシアニンとすることが出来る。 Thus, the X-ray diffraction spectrum has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 25.0 ° with respect to the Cu-Kα ray, and is at 16.8 °, 23.1 °, and 32.4 °. The polyhalogenated zinc phthalocyanine having a peak has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) = 26.4 ° with respect to the Cu—Kα line, and is 22.6 °, 24.8 °, 25. A polyhalogenated zinc phthalocyanine having peaks at 7 ° and 27.8 ° can be obtained.
加熱終了後は、有機溶剤を分離し、好適には、得られたポリハロゲン化亜鉛フタロシアニンを結晶変換に寄与しない液体にて洗浄し乾燥することで、本発明の新規結晶型のポリハロゲン化亜鉛フタロシアニンを得ることが出来る。 After completion of the heating, the organic solvent is separated, and preferably, the obtained polyhalogenated zinc phthalocyanine is washed with a liquid that does not contribute to crystal conversion and dried, so that the novel crystalline zinc polyhalide of the present invention is obtained. Phthalocyanine can be obtained.
こうして得られた本発明のポリハロゲン化亜鉛フタロシアニンは、必要に応じてアトライター、ボールミル、振動ミル、振動ボールミル等の粉砕機内で乾式摩砕し、次いで、ソルベントソルトミリング法やソルベント法等で顔料化することによって、一次粒子の平均粒子径が０．０１〜０．１μｍであるポリハロゲン化亜鉛フタロシアニンを得ることが出来る。この様な操作を行うことで、顔料化前よりは、分散性や着色力に優れ、かつ、黄味を帯びた明度が高く、コントラストの高い緑色を発色するポリハロゲン化亜鉛フタロシアニンとすることが出来る。 The thus obtained polyhalogenated zinc phthalocyanine of the present invention is dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill or the like, and then pigmented by a solvent salt milling method or a solvent method. As a result, polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.1 μm can be obtained. By performing such an operation, it is possible to obtain a polyhalogenated zinc phthalocyanine that is superior in dispersibility and coloring power, has a yellowish lightness, and has a high contrast green color than before pigmentation. I can do it.
なお、本発明における一次粒子の平均粒子径とは、透過型電子顕微鏡ＪＥＭ−２０１０（日本電子株式会社製）で視野内の粒子を撮影し、二次元画像上の、凝集体を構成するポリハロゲン化亜鉛フタロシアニン一次粒子の５０個につき、その長い方の径（長径）を各々求め、それを平均した値である。この際、試料であるポリハロゲン化亜鉛フタロシアニンは、これを溶媒に超音波分散させてから顕微鏡で撮影する。また、透過型電子顕微鏡の代わりに走査型電子顕微鏡を使用してもよい。 In addition, the average particle diameter of the primary particle in the present invention is a polyhalogen constituting an aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.). This is a value obtained by obtaining the longer diameter (major diameter) of 50 primary zinc phthalocyanine particles and averaging them. At this time, the sample polyhalogenated zinc phthalocyanine is ultrasonically dispersed in a solvent and then photographed with a microscope. A scanning electron microscope may be used instead of the transmission electron microscope.
前記した顔料化方法は特に制限はないが、例えば多量の有機溶剤中でハロゲン化金属フタロシアニンを加熱攪拌するソルベント処理よりも、容易に結晶成長を抑制でき、かつ平均粒子径の比較的小さい顔料粒子が得られる点で、ソルベントソルトミリング処理を採用するのが好ましい。 The above-mentioned pigmentation method is not particularly limited. For example, pigment particles that can suppress crystal growth more easily and have a relatively small average particle diameter than solvent treatment in which a metal halide phthalocyanine is heated and stirred in a large amount of an organic solvent. Therefore, it is preferable to employ a solvent salt milling treatment.
このソルベントソルトミリングとは、ポリハロゲン化亜鉛フタロシアニンと、無機塩と、有機溶剤とを混練摩砕することを意味する。勿論、前記した様に粒子径の大きいポリハロゲン化亜鉛フタロシアニンは乾式摩砕してからソルベントソルトミリングを行っても良い。具体的には、ポリハロゲン化亜鉛フタロシアニンと、無機塩と、それを溶解しない有機溶剤とを混練機に仕込み、その中で混練摩砕を行う。この際の混練機としては、例えばニーダーやミックスマーラー等が使用できる。 The solvent salt milling means kneading and grinding polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent. Of course, as described above, the polyhalogenated zinc phthalocyanine having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.
上記無機塩としては、水溶性無機塩が好適に使用でき、例えば塩化ナトリウム、塩化カリウム、硫酸ナトリウム等の無機塩を用いることが好ましい。また、平均粒子径０．５〜５０μｍの無機塩を用いることがより好ましい。この様な無機塩は、通常の無機塩を微粉砕することにより容易に得られる。 As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.
本発明では、一次粒子の平均粒子径が０．０１〜０．１μｍのポリハロゲン化亜鉛フタロシアニンをカラーフィルターの緑色画素部の形成用途に用いるのが好ましい。この様な好適な平均粒子径のポリハロゲン化亜鉛フタロシアニンを得るに当たっては、ソルベントソルトミリングにおけるポリハロゲン化亜鉛フタロシアニン使用量に対する無機塩使用量を高くするのが好ましい。即ち当該無機塩の使用量は、質量換算でポリハロゲン化亜鉛フタロシアニン１部に対して５〜２０部とするのが好ましく、７〜１５部とするのがより好ましい。 In the present invention, it is preferable to use polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.1 μm for forming a green pixel portion of a color filter. In obtaining such a polyhalogenated zinc phthalocyanine having a suitable average particle size, it is preferable to increase the amount of inorganic salt used relative to the amount of polyhalogenated zinc phthalocyanine used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts per 1 part of polyhalogenated zinc phthalocyanine in terms of mass.
有機溶剤としては、前記したのと異なり、結晶成長を抑制し得る有機溶剤を使用することが好ましく、このような有機溶剤としては水溶性有機溶剤が好適に使用でき、例えばジエチレングリコール、グリセリン、エチレングリコール、プロピレングリコール、液体ポリエチレングルコール、液体ポリプロピレングリコール、２−（メトキシメトキシ）エタノール、２−ブトキシエタノール、２ー（イソペンチルオキシ）エタノール、２−（ヘキシルオキシ）エタノール、ジエチレングリコールモノメチルエーテル、ジエチレングルコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール等を用いることができる。 As described above, it is preferable to use an organic solvent capable of suppressing crystal growth, as described above, and a water-soluble organic solvent can be suitably used as such an organic solvent, for example, diethylene glycol, glycerin, ethylene glycol. , Propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propano Le, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.
この際の水溶性有機溶剤の使用量は、特に限定されるものではないが、質量換算でポリハロゲン化亜鉛フタロシアニン１部に対して０．０１〜５部、０．８〜２部が好ましい。 Although the usage-amount of the water-soluble organic solvent in this case is not specifically limited, 0.01-5 parts and 0.8-2 parts are preferable with respect to 1 part of polyhalogenated zinc phthalocyanines in mass conversion.
ソルベントソルトミリング時の温度は、３０〜１５０℃が好ましく、８０〜１００℃がより好ましい。ソルベントソルトミリングの時間は、５〜２０時間が好ましく、８〜１８時間がより好ましい。 30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 80-100 degreeC. The solvent salt milling time is preferably 5 to 20 hours, and more preferably 8 to 18 hours.
こうして、ポリハロゲン化亜鉛フタロシアニン、無機塩、有機溶剤を主成分として含む混合物が得られるが、この混合物から有機溶剤と無機塩を除去し、必要に応じてポリハロゲン化亜鉛フタロシアニンを主体とする固形物を洗浄、濾過、乾燥、粉砕等をすることにより、微細なポリハロゲン化亜鉛フタロシアニン粉体を得ることが出来る。 In this way, a mixture containing polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and if necessary, a solid mainly composed of polyhalogenated zinc phthalocyanine is obtained. Fine polyhalogenated zinc phthalocyanine powder can be obtained by washing, filtering, drying, grinding, etc.
洗浄としては、水洗、湯洗のいずれも採用できる。洗浄回数は、１〜５回の範囲で繰り返すことも出来る。水溶性無機塩及び水溶性有機溶剤を用いた前記混合物の場合は、水洗することで容易に有機溶剤と無機塩を除去することが出来る。 As washing, either water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.
上記した濾別、洗浄後の乾燥としては、例えば、乾燥機に設置した加熱源による８０〜１２０℃の加熱等により、顔料の脱水及び／又は脱溶剤をする回分式あるいは連続式の乾燥等が挙げられ、乾燥機としては一般に箱型乾燥機、バンド乾燥機、スプレードライアー等がある。また、乾燥後の粉砕は、比表面積を大きくしたり一次粒子の平均粒子径を小さくするための操作ではなく、例えば箱型乾燥機、バンド乾燥機を用いた乾燥の場合の様に顔料がランプ状等のとなった際に顔料を解して粉体化するために行うものであり、例えば、乳鉢、ハンマーミル、ディスクミル、ピンミル、ジェットミル等による粉砕等が挙げられる。 Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles. For example, as in the case of drying using a box-type dryer or a band dryer, When it becomes a shape or the like, it is performed in order to break the pigment into powder, and examples thereof include mortar, hammer mill, disc mill, pin mill, jet mill and the like.
こうして、ポリハロゲン化亜鉛フタロシアニンの粉体が得られる。本発明のポリハロゲン化亜鉛フタロシアニンは顔料であり、従来のハロゲン化銅フタロシアニンに比べて一次粒子の凝集力が弱く、より解れやすい性質を持つ。そのため、本発明のポリハロゲン化亜鉛フタロシアニンは、公知慣用の被着色媒体の着色の用途にいずれも使用できる。中でも、前記した好適な一次粒子の平均粒子径のポリハロゲン化亜鉛フタロシアニンは、着色すべき合成樹脂等への分散性がより良好となるので、着色剤としては好適である。 In this way, a powder of polyhalogenated zinc phthalocyanine is obtained. The polyhalogenated zinc phthalocyanine of the present invention is a pigment, and has a property that the cohesion of primary particles is weaker than that of a conventional copper halide phthalocyanine, and it is easier to unravel. Therefore, any of the polyhalogenated zinc phthalocyanines of the present invention can be used for coloring known and commonly used media to be colored. Among them, the above-described preferred primary halogen particles having a mean particle diameter of polyhalogenated zinc phthalocyanine are preferable as a colorant because dispersibility in a synthetic resin to be colored becomes better.
また、前記した様な好適な一次粒子の平均粒子径を有するポリハロゲン化亜鉛フタロシアニンをカラーフィルターの画素部の形成に使用する場合においては、感光性組成物を硬化する際に多用される３６５ｎｍにおける遮光性が低下することなく、光硬化感度の低下がなく、現像時の膜へりやパターン流れも起こり難くなるので好ましい。 Further, in the case of using a polyhalogenated zinc phthalocyanine having a preferable average particle size of primary particles as described above for forming a pixel portion of a color filter, at 365 nm, which is frequently used for curing a photosensitive composition. It is preferable because the light-shielding property does not decrease, the photocuring sensitivity does not decrease, and film edge and pattern flow hardly occur during development.
本発明のポリハロゲン化亜鉛フタロシアニンの一次粒子は、更に縦横のアスペクト比が１〜３であると、各用途分野において粘度特性が向上し、流動性がより高くなる。アスペクト比を求めるには、前記した様な、一次粒子の平均粒子径を求める場合と同様に、透過型電子顕微鏡または走査型電子顕微鏡で視野内の粒子を撮影する。そして、二次元画像上の、凝集体を構成する一次粒子の５０個につき長い方の径（長径）と、短い方の径（短径）の平均値を求め、これらの値を用いて算出する。 When the primary and horizontal aspect ratios of the polyhalogenated zinc phthalocyanine of the present invention are 1 to 3, the viscosity characteristics are improved in each application field and the fluidity is further increased. In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major axis) and the shorter diameter (minor axis) is obtained for 50 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .
本発明の新規結晶型ポリハロゲン化亜鉛フタロシアニンを製造する任意の工程において、各種フタロシアニン誘導体を含有させることが出来る。新規結晶型ポリハロゲン化亜鉛フタロシアニンにフタロシアニン誘導体を併用することで、カラーフィルター緑色画素部用感光性組成物の粘度特性の向上と分散安定性の向上を達成出来る場合がある。 Various phthalocyanine derivatives can be contained in any step of producing the novel crystalline polyhalogenated zinc phthalocyanine of the present invention. By using a phthalocyanine derivative in combination with the novel crystalline polyhalogenated zinc phthalocyanine, it may be possible to improve the viscosity characteristics and the dispersion stability of the photosensitive composition for the color filter green pixel portion.
分光透過スペクトルの透過率が最大となる波長がより長波長側にあり、かつその最大透過率値も大きいことで、従来のポリハロゲン化銅フタロシアニンよりも更に黄味の緑色と優れた明度も兼備する緑色部分を有するカラーフィルターが得られる。即ち、従来のポリハロゲン化銅フタロシアニンでは達成できなかった、３８０〜７８０ｎｍにおける分光透過スペクトルの透過率が最大となる波長（Ｔmax）が５２０〜５９０ｎｍで、前記Ｔmaxにおける透過率が７０％以上、かつ、波長６５０〜７００ｎｍにおける前記分光透過スペクトルの透過率が２０％以下である緑色画素部を有するカラーフィルターが、本発明のポリハロゲン化亜鉛フタロシアニンを用いることにより、初めて、より簡便にかつより安価に得ることができる。 The wavelength at which the transmittance of the spectral transmission spectrum is maximized is on the longer wavelength side, and the maximum transmittance value is also large, so it combines yellowish green and superior lightness compared to conventional polyhalogenated copper phthalocyanine A color filter having a green portion is obtained. That is, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum, which could not be achieved with the conventional polyhalogenated copper phthalocyanine, is 520 to 590 nm, and the transmittance at Tmax is 70% or more, and For the first time, a color filter having a green pixel portion having a transmittance of 20% or less at a wavelength of 650 to 700 nm using the polyhalogenated zinc phthalocyanine of the present invention is simpler and less expensive. Can be obtained.
本発明における分光透過スペクトルとは、日本工業規格ＪＩＳ Ｚ ８７２２（色の測定方法−反射及び透過物体色）の第一種分光測光器に準じて求められるもので、ガラス基板等の上に前記所定乾燥膜厚に製膜したポリハロゲン化亜鉛フタロシアニンを含む樹脂被膜について所定波長領域の光を走査照射して、各波長における各透過率値をプロットしたものである。カラーフィルターとしての透過率は、例えば樹脂のみで同一乾燥膜厚となした被膜について同様に求めた分光透過スペクトルで補正すること（ベースライン補正等）によって、より精度良く求めることが出来る。 The spectral transmission spectrum in the present invention is obtained according to the first-class spectrophotometer of Japanese Industrial Standard JIS Z 8722 (color measurement method-reflective and transmissive object color). The resin film containing polyhalogenated zinc phthalocyanine formed into a dry film thickness is obtained by plotting each transmittance value at each wavelength by scanning and irradiating light in a predetermined wavelength region. The transmittance as a color filter can be determined with higher accuracy by correcting (baseline correction or the like), for example, with a spectral transmission spectrum similarly determined for a film having the same dry film thickness only with a resin.
本発明のカラーフィルターは、上記した特性を有するものであるが、より好適なのは、３８０〜７８０ｎｍにおける分光透過スペクトルの透過率が最大となる波長（Ｔmax）が５２０〜５９０ｎｍであり、前記Ｔmaxにおける透過率が７０〜９９％、かつ、波長６５０〜７００ｎｍにおける前記分光透過スペクトルの透過率が０〜２０％のものである。 The color filter of the present invention has the above-mentioned characteristics, but more preferably, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum is 520 to 590 nm, and the transmission at Tmax is performed. The transmittance is 70 to 99%, and the transmittance of the spectral transmission spectrum at a wavelength of 650 to 700 nm is 0 to 20%.
なお、本発明においては、カラーフィルターの緑色画素部の形成に、黄味つけのために各種黄色顔料を併用することが好ましい。即ち前記ポリハロゲン化亜鉛フタロシアニンに、黄色顔料を併用し、これに含ませることで、波長４００〜５００ｎｍにおける同分光透過スペクトルの透過率を低下させることが可能であり、例えば前記波長域における透過率を５０％以下となすことが出来る。 In the present invention, it is preferable that various yellow pigments are used in combination for yellowing in forming the green pixel portion of the color filter. That is, by using a yellow pigment in combination with the polyhalogenated zinc phthalocyanine, it is possible to reduce the transmittance of the same spectral transmission spectrum at a wavelength of 400 to 500 nm, for example, the transmittance in the wavelength range. Can be made 50% or less.
ここで併用できる黄色顔料としては、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ ＹＥＬＬＯＷ ８３、同１１０、同１３８、同１３９、同１５０、同１８０、同１８５等の黄色有機顔料が挙げられる。本発明におけるポリハロゲン化亜鉛フタロシアニンと黄色顔料との併用割合は、質量換算で、前記ポリハロゲン化亜鉛フタロシアニン１００部当たり、黄色顔料が１０〜１００部とすることが好ましい。 Examples of yellow pigments that can be used here include C.I. I. Pigment YELLOW 83, 110, 138, 139, 150, 180, 185, and the like. In the present invention, the combined proportion of the polyhalogenated zinc phthalocyanine and the yellow pigment is preferably 10 to 100 parts of the yellow pigment per 100 parts of the polyhalogenated zinc phthalocyanine in terms of mass.
本発明においては、カラーフィルターの緑色画素部の形成に、ポリハロゲン化亜鉛フタロシアニンを用いることで、黄色顔料を調色のために併用するにしてもより少量の併用で良いので、３８０〜７８０ｎｍの全域における光透過率の低下を最小限に防止できる。 In the present invention, by using polyhalogenated zinc phthalocyanine for forming the green pixel portion of the color filter, even if a yellow pigment is used for color matching, a smaller amount may be used. A decrease in light transmittance over the entire region can be prevented to a minimum.
また、本発明のポリハロゲン化亜鉛フタロシアニンを用いれば、黄色顔料を併用するにしてもより少量の併用で良いので、従来のカラーフィルター緑色画素部と同じ色の緑色画素部を有するカラーフィルターを得る場合には、併用すべき同一黄色顔料を質量換算で３０％以上、最大５０％程度削減することが出来る。 In addition, when the polyhalogenated zinc phthalocyanine of the present invention is used, even if a yellow pigment is used in combination, a smaller amount may be used, so that a color filter having a green pixel portion of the same color as the conventional color filter green pixel portion is obtained. In this case, the same yellow pigment to be used in combination can be reduced by 30% or more and by a maximum of 50% in terms of mass.
さらに、同様の理由で調色のために２種以上の異なる色の顔料を混色する従来の場合に比べて、濁りの少ない、色純度に優れた画素部とすることが出来、明るいカラーフィルターとすることが出来る。 Furthermore, for the same reason, a pixel portion with less turbidity and excellent color purity can be obtained compared to the conventional case of mixing two or more different color pigments for toning. I can do it.
例えば、従来のＣ．Ｉ．Ｐｉｇｍｅｎｔ ＧＲＥＥＮ ３６の様な緑色顔料に、上記した黄色顔料を併用した混合顔料を用いた場合に比べて、本発明のポリハロゲン化亜鉛フタロシアニンを黄色顔料と併用した場合のほうが、液晶ディスプレイとした時の明るさの低下がより小さくなるし、緑色領域の光透過量もより大きくなる。 For example, conventional C.I. I. Compared to the case where a mixed pigment using the above-mentioned yellow pigment in combination with the above-described yellow pigment is used for a green pigment such as Pigment GREEN 36, the case where the polyhalogenated zinc phthalocyanine of the present invention is used in combination with a yellow pigment is used as a liquid crystal display. The lowering of the brightness becomes smaller, and the light transmission amount in the green region also becomes larger.
本発明のポリハロゲン化亜鉛フタロシアニンは、公知の方法でカラーフィルターの緑色画素部の形成に用いることが出来る。この画素部は、典型的には、感光性樹脂と、本発明の新規結晶型ポリハロゲン化亜鉛フタロシアニンとを必須成分して含むカラーフィルター緑色画素部用感光性組成物から得ることが出来る。 The polyhalogenated zinc phthalocyanine of the present invention can be used for forming a green pixel portion of a color filter by a known method. This pixel portion can be typically obtained from a photosensitive composition for a color filter green pixel portion containing a photosensitive resin and the novel crystalline polyhalogenated zinc phthalocyanine of the present invention as essential components.
この際に使用可能な感光性樹脂としては、例えばウレタン系樹脂、アクリル系樹脂、ポリアミド酸系樹脂、ポリイミド系樹脂、スチレンマレイン酸系樹脂、スチレン無水マレイン酸系樹脂等の熱可塑性樹脂や、例えば１，６−ヘキサンジオールジアクリレート、エチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチレングリコールジアクリレート、ビス（アクリロキシエトキシ）ビスフェノールＡ、３−メチルペンタンジオールジアクリレート等のような２官能モノマー、トリメチルロールプロパトントリアクリレート、ペンタエリスリトールトリアクリレート、トリス（２−ヒドロキシエチル）イソシアネート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等のような多官能モノマー等の光重合性モノマーが挙げられる。 Examples of photosensitive resins that can be used in this case include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like, Bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, Trimethylol propaton triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate It includes photopolymerizable monomers such as polyfunctional monomers such as.
カラーフィルターの製造方法としては、例えば、このポリハロゲン化亜鉛フタロシアニンを感光性樹脂からなる分散媒に分散させた後、スピンコート法、ロールコート法、インクジェット法等でガラス等の透明基板上に塗布し、ついでこの塗布膜に対して、フォトマスクを介して紫外線によるパターン露光を行った後、未露光部分を溶剤等で洗浄して緑色パターンを得る、フォトリソグラフィーと呼ばれる方法が挙げられる。 As a method for producing a color filter, for example, this polyhalogenated zinc phthalocyanine is dispersed in a dispersion medium made of a photosensitive resin, and then applied onto a transparent substrate such as glass by a spin coat method, a roll coat method, an ink jet method or the like. Then, a method called photolithography, in which the coating film is subjected to pattern exposure with ultraviolet rays through a photomask and then an unexposed portion is washed with a solvent or the like to obtain a green pattern.
その他、電着法、転写法、ミセル電解法、ＰＶＥＤ（Ｐｈｏｔｏｖｏｌｔａｉｃ Ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ）法の方法で緑色画素部のパターンを形成して、カラーフィルターを製造してもよい。なお、赤色画素部および青色画素部の各パターンも公知の顔料を使用して、同様の方法で形成できる。 In addition, the color filter may be manufactured by forming a pattern of the green pixel portion by an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method. Each pattern of the red pixel portion and the blue pixel portion can also be formed by a similar method using a known pigment.
カラーフィルター用レジストインキを調製するには、本発明のポリハロゲン化亜鉛フタロシアニンと、感光性樹脂と、光重合開始剤と、前記樹脂を溶解する有機溶剤とを必須成分として混合する。その製造方法としては、ポリハロゲン化亜鉛フタロシアニンと有機溶剤と必要に応じて分散剤を用いて分散液を調製してから、そこに感光性樹脂等を加えてレジストインキとする方法が一般的である。 To prepare a color filter resist ink, the polyhalogenated zinc phthalocyanine of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are mixed as essential components. As a manufacturing method thereof, a method is generally used in which a dispersion liquid is prepared using polyhalogenated zinc phthalocyanine, an organic solvent, and a dispersant as required, and then a photosensitive resin is added to obtain a resist ink. is there.
光重合開始剤としては、例えばアセトフェノン、ベンゾフェノン、ベンジルジメチルケタノール、ベンゾイルパーオキサイド、２−クロロチオキサントン、１，３−ビス（４'−アジドベンザル）−２−プロパン、１，３−ビス（４'−アジドベンザル）−２−プロパン−２'−スルホン酸、４，４'−ジアジドスチルベン−２，２'−ジスルホン酸等がある。 Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′). -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.
有機溶剤としては、例えばトルエンやキシレン、メトキシベンゼン等の芳香族系溶剤、酢酸エチルや酢酸ブチル、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等の酢酸エステル系溶剤、エトキシエチルプロピオネート等のプロピオネート系溶剤、メタノール、エタノール等のアルコール系溶剤、ブチルセロソルブ、プロピ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等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、ヘキサン等の脂肪族炭化水素系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクタム、Ｎ−メチル−２−ピロリドン、アニリン、ピリジン等の窒素化合物系溶剤、γ−ブチロラクトン等のラクトン系溶剤、カルバミン酸メチルとカルバミン酸エチルの４８：５２の混合物のようなカルバミン酸エステル、水等がある。有機溶剤としては、特にプロピオネート系、アルコール系、エーテル系、ケトン系、窒素化合物系、ラクトン系、水等の極性溶媒で水可溶のものが適している。 Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvents, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, fats such as hexane Group hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, ani Emissions, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate, there is water. As the organic solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, water and the like that are water-soluble are particularly suitable.
必要に応じて用いる分散剤としては、例えば、ビックケミー社のディスパービック１３０、ディスパービック１６１、ディスパービック１６２、ディスパービック１６３、ディスパービック１７０、エフカ社のエフカ４６、エフカ４７等が挙げられる。また、レベンリグ剤、カップリング剤、カチオン系の界面活性剤なども併せて使用可能である。 Examples of the dispersing agent used as necessary include Dispavik 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 170, Fuka 46 and Fuka 47 of Fuka. In addition, a revenig rigging agent, a coupling agent, a cationic surfactant, and the like can be used together.
まず最初に、質量換算で、本発明のポリハロゲン化亜鉛フタロシアニン１００部当たり、３００〜１０００部の有機溶剤と、必要に応じて０〜１００部の分散剤及び／又は０〜２０部のフタロシアニン誘導体とを、均一となる様に攪拌分散することで分散液を得ることが出来る。次いでこの分散液に、質量換算で、ポリハロゲン化亜鉛フタロシアニン１部当たり、３〜２０部の感光性樹脂、感光性樹脂１部当たり０．０５〜３部の光重合開始剤と、必要に応じてさらに有機溶剤を添加し、均一となる様に攪拌分散することで、前記したレジストインキを得ることができる。 First, in terms of mass, per 100 parts of the polyhalogenated zinc phthalocyanine of the present invention, 300 to 1000 parts of an organic solvent, and optionally 0 to 100 parts of a dispersant and / or 0 to 20 parts of a phthalocyanine derivative. Can be dispersed by stirring and dispersing so as to be uniform. Then, to this dispersion, in terms of mass, 3 to 20 parts of photosensitive resin per part of polyhalogenated zinc phthalocyanine, 0.05 to 3 parts of photopolymerization initiator per part of photosensitive resin, and if necessary Further, an organic solvent is further added, and the resist ink described above can be obtained by stirring and dispersing so as to be uniform.
こうして調製されたカラーフィルター用レジストインキは、フォトマスクを介して紫外線によるパターン露光を行った後、未露光部分を有機溶剤やアルカリ水等で洗浄することによりカラーフィルターとなすことができる。 The resist ink for color filter thus prepared can be made into a color filter by performing pattern exposure with ultraviolet rays through a photomask and then washing the unexposed portion with an organic solvent or alkaline water.
本発明のポリハロゲン化亜鉛フタロシアニンは、黄味の緑色を有する化合物であり、顔料として上で詳述したカラーフィルター用緑色画素部への適用以外にも、塗料、プラスチック、印刷インク、ゴム、レザー、捺染、電子写真トナー、ジェットインキ、熱転写インキなどの着色に適する。 The polyhalogenated zinc phthalocyanine of the present invention is a compound having a yellowish green color, and besides being applied to the green pixel portion for a color filter described in detail above as a pigment, paint, plastic, printing ink, rubber, leather Suitable for coloring, textile printing, electrophotographic toner, jet ink, thermal transfer ink and the like.
次に本発明を実施例を示して具体的に説明する。以下、断りのない限り、％は質量％、部は質量部を意味する。 Next, the present invention will be specifically described with reference to examples. Hereinafter, unless otherwise indicated,% means mass%, and part means mass part.
［製造例１］
無水フタル酸、尿素、塩化亜鉛を原料として亜鉛フタロシアニンを製造した。これの１−クロロナフタレン溶液は、７５０〜８５０ｎｍに光の吸収を有していた。
ハロゲン化は、塩化チオニル３．２部、無水塩化アルミニウム３．８部、塩化ナトリウム０．５部を４０℃で混合し、臭素２．７部を滴下して加える。これに亜鉛フタロシアニン１部を加え、９０℃で１５時間反応し、その後反応混合物を水に投入し、ハロゲン化亜鉛フタロシアニン粗顔料を析出させる。この水性スラリーを濾過し、６０℃の湯洗浄、１％硫酸水素ナトリウム水洗浄、６０℃の湯洗浄を行い、９０℃で乾燥させ、２．７部の精製されたポリ臭素化亜鉛フタロシアニン（粗顔料）を得た。
[Production Example 1]
Zinc phthalocyanine was produced from phthalic anhydride, urea, and zinc chloride. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm.
Halogenation is performed by mixing 3.2 parts of thionyl chloride, 3.8 parts of anhydrous aluminum chloride and 0.5 parts of sodium chloride at 40 ° C., and adding 2.7 parts of bromine dropwise. 1 part of zinc phthalocyanine is added thereto and reacted at 90 ° C. for 15 hours, after which the reaction mixture is poured into water to precipitate a halogenated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% aqueous sodium hydrogen sulfate, washed with hot water at 60 ° C., dried at 90 ° C., and 2.7 parts of purified polybrominated zinc phthalocyanine (crude oil). Pigment) was obtained.
この粗顔料のＸ線回折スペクトルを図１に示した。この粗顔料は、本発明で規定するのと異なり、非晶質（アモルファス）であった。着色力も極めて劣っていた。
尚、Ｘ線回折スペクトルは、ＰＨＩＬＩＰＳ（株）製ＸＲＤ−ＸＰＥＲＴ−ＰＲＯ−ＭＰＤを用いて、管球：Ｃｕ，サンプリング角度：０．０２０゜、スキャンスピード：４．００゜／ｍｉｎ、操作角２θ／θの条件で測定した。
The X-ray diffraction spectrum of this crude pigment is shown in FIG. The crude pigment was amorphous, unlike that defined in the present invention. The coloring power was very poor.
The X-ray diffraction spectrum was measured by using PHRDIPS XRD-XPERT-PRO-MPD, tube: Cu, sampling angle: 0.020 °, scan speed: 4.00 ° / min, operating angle 2θ. Measured under the condition of / θ.
製造例１と同様の操作を行ない、６０℃の湯洗浄を行った後に、濾過することで、ウェットケーキを準備した。このウエットケーキ１００部（不揮発分３５％）とキシレン（和光純薬工業（株）製試薬１級）３５０部とを、４つ口付き１Ｌフラスコに入れ、常圧下、乾留状態で６時間加熱処理した後、濾過、メタノールで洗浄後、乾燥し、ポリ臭素化亜鉛フタロシアニンＡ ３３部を得た。
このポリハロゲン化亜鉛フタロシアニンＡは、質量分析とフラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から、平均組成ZnPcBr13.9Cl1.8H0.3であった。
このポリ臭素化亜鉛フタロシアニンＡのＸ線回折スペクトルを図２に示した。
このＸ線回折スペクトルは、ブラック角２θが２６．４゜に最大回折ピークを有し、２２．６°，２４．８°，２５．７°，２７．８°に回折ピークを有しており、本発明で規定する新規結晶型を有していた。また、一次粒子の縦横のアスペクト比は３を越えていた。
A wet cake was prepared by performing the same operation as in Production Example 1 and washing with hot water at 60 ° C., followed by filtration. 100 parts of this wet cake (non-volatile content 35%) and 350 parts of xylene (
This polyhalogenated zinc phthalocyanine A had an average composition of ZnPcBr 13.9 Cl 1.8 H 0.3 based on halogen content analysis by mass spectrometry and flask combustion ion chromatography.
The X-ray diffraction spectrum of this polybrominated zinc phthalocyanine A is shown in FIG.
This X-ray diffraction spectrum has a maximum diffraction peak at a black angle 2θ of 26.4 °, and diffraction peaks at 22.6 °, 24.8 °, 25.7 °, and 27.8 °. And had a novel crystal form as defined in the present invention. Further, the aspect ratio of the primary and horizontal particles exceeded 3.
実施例１で用いたウェットケーキの代わりに、製造例１で得られた乾燥品３５部を使用した以外は実施例１と同様の操作を行い、ポリ臭素化亜鉛フタロシアニンＢ ３２部を得た。
このポリハロゲン化亜鉛フタロシアニンＢは、質量分析とフラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から、平均組成ZnPcBr13.9Cl1.8H0.3であった。
このポリ臭素化亜鉛フタロシアニンＢは、実施例１の同Ａと同一のＸ線回折スペクトルとアスペクト比を示していた。
Instead of the wet cake used in Example 1, the same operation as in Example 1 was carried out except that 35 parts of the dried product obtained in Production Example 1 was used to obtain 32 parts of polybrominated zinc phthalocyanine B.
This polyhalogenated zinc phthalocyanine B had an average composition of ZnPcBr 13.9 Cl 1.8 H 0.3 from mass analysis and halogen content analysis by flask combustion ion chromatography.
This polybrominated zinc phthalocyanine B exhibited the same X-ray diffraction spectrum and aspect ratio as those of Example A.
実施例１のポリ臭素化亜鉛フタロシアニンＡ １部、粉砕した塩化ナトリウム１０部、ジエチレングリコール１部を双腕型ニーダーに仕込み、１００℃で８時間混練した。混練終了後、得られたマグマケーキを６０℃の温水に取り出し、１時間撹拌後、濾過、湯洗を繰り返し比電導度が０．５ｍＳ/ｃｍ以下になるまで洗浄を繰り返し、乾燥、粉砕してポリ臭素化亜鉛フタロシアニンＣ ０．９部を得た。
このポリハロゲン化亜鉛フタロシアニンＣは、質量分析とフラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から、同Ａと同一元素組成であった。
このＸ線回折スペクトルは、ブラック角２θが２６．４゜に最大回折ピークを有し、２２．６°，２４．８°，２５．７°，２７．８°に回折ピークを有しており、本発明で規定する新規結晶型を有していた。また、一次粒子の平均粒子径は５０ｎｍ、一次粒子の縦横のアスペクト比は１〜３の範囲内にあった。
1 part of polybrominated zinc phthalocyanine A of Example 1, 10 parts of crushed sodium chloride, and 1 part of diethylene glycol were charged into a double-arm kneader and kneaded at 100 ° C. for 8 hours. After kneading is completed, the obtained magma cake is taken out in warm water at 60 ° C., stirred for 1 hour, repeatedly filtered and washed with hot water until the specific conductivity becomes 0.5 mS / cm or less, and then dried and pulverized. 0.9 parts of polybrominated zinc phthalocyanine C were obtained.
This polyhalogenated zinc phthalocyanine C had the same elemental composition as A from the mass analysis and the halogen content analysis by flask combustion ion chromatography.
This X-ray diffraction spectrum has a maximum diffraction peak at a black angle 2θ of 26.4 °, and diffraction peaks at 22.6 °, 24.8 °, 25.7 °, and 27.8 °. And had a novel crystal form as defined in the present invention. The average particle diameter of the primary particles was 50 nm, and the aspect ratio of the primary particles in the vertical and horizontal directions was in the range of 1-3.
実施例１のポリ臭素化亜鉛フタロシアニンＡに代えて、実施例２のポリ臭素化亜鉛フタロシアニンＢを使用した以外は実施例３と同様に実施し、ポリ臭素化亜鉛フタロシアニンＤ ０．９部を得た。
このポリハロゲン化亜鉛フタロシアニンＤは、質量分析とフラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から、同Ｂと同一元素組成であった。 このポリ臭素化亜鉛フタロシアニンＤは、実施例３の同Ｃと同一のＸ線回折スペクトルとアスペクト比を示していた。
The same procedure as in Example 3 was carried out except that polybrominated zinc phthalocyanine B of Example 2 was used instead of polybrominated zinc phthalocyanine A of Example 1, to obtain 0.9 part of polybrominated zinc phthalocyanine D It was.
This polyhalogenated zinc phthalocyanine D had the same elemental composition as B from mass spectrometry and halogen content analysis by flask combustion ion chromatography. This polybrominated zinc phthalocyanine D exhibited the same X-ray diffraction spectrum and aspect ratio as C in Example 3.
［比較例１］
実施例１のポリ臭素化亜鉛フタロシアニンＡの代わりに、製造例１で得られたポリ臭素化亜鉛フタロシアニン（粗顔料）を使用した以外は実施例３と同様の操作を行い、ポリ臭素化亜鉛フタロシアニンＥ ０．９部を得た。
このポリ臭素化亜鉛フタロシアニンＥのＸ線回折スペクトルを図４に示した。
このＸ線回折スペクトルは、ブラック角２θが２５．０゜に最大回折ピークを有し、１６．８°，２３．１°，３２．４°に回折ピークを有しており、従来の結晶型を有していた。また、一次粒子の平均粒子径は６０ｎｍ、一次粒子の縦横のアスペクト比は１〜３の範囲内にあった。
[Comparative Example 1]
The same procedure as in Example 3 was carried out except that the polybrominated zinc phthalocyanine (crude pigment) obtained in Production Example 1 was used in place of the polybrominated zinc phthalocyanine A in Example 1. E 0.9 parts were obtained.
The X-ray diffraction spectrum of this polybrominated zinc phthalocyanine E is shown in FIG.
This X-ray diffraction spectrum has a maximum diffraction peak at a black angle 2θ of 25.0 °, and diffraction peaks at 16.8 °, 23.1 °, and 32.4 °. Had. Moreover, the average particle diameter of the primary particles was 60 nm, and the aspect ratio of the vertical and horizontal directions of the primary particles was in the range of 1-3.
上記の実施例３のポリ臭素化亜鉛フタロシアニンＣを緑色顔料として用い、フォトリソグラフィーでカラーフィルター緑色画素部を製造した。
まず、ポリ臭素化亜鉛フタロシアニンＣ １４部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １５０ ３部、Ｎ，Ｎ'−ジメチルホルムアミド２．５部、ディスパービック１６１（ビックケミー社製）１７．０部、ユーカーエステルＥＥＰ（ユニオン・カーバイド社製）６３．５部を０．５ｍｍφセプルビーズを加え、ペイントコンディショナー（東洋精機株式会社製）で１時間分散し、顔料分散液を得た。
この顔料分散液７５．００部と、ポリエステルアクリレート樹脂（アロニックスＭ７１００、東亜合成化学工業株式会社製）５．５０部、ジぺンタエリスレートヘキサアクリレート（ＫＡＹＡＲＡＤ ＤＰＨＡ、日本化薬株式会社製）５．００部、ベンゾフェノン（ＫＡＹＡＣＵＲＥ ＢＰ−１００、日本化薬株式会社製）１．００部、ユーカーエステルＥＦＰ１３．５部を分散攪拌機で攪拌し、感光性組成物であるカラーレジストを得た。カラーレジストは１ｍｍ厚ガラスに乾燥膜厚１μｍとなるように塗布した。
次いでフォトマスクを介して紫外線によるパターン露光を行った後、未露光部分を有機溶剤で洗浄することによりカラーフィルターとした。
Using the polybrominated zinc phthalocyanine C of Example 3 as a green pigment, a color filter green pixel portion was manufactured by photolithography.
First, 14 parts of polybrominated zinc phthalocyanine C, C.I. I. Pigment Yellow 150 3 parts, N, N′-dimethylformamide 2.5 parts, Dispersic 161 (manufactured by BYK Chemie) 17.0 parts, Euker ester EEP (manufactured by Union Carbide) 63.5 parts 0.5 mmφ Sepul beads And dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour to obtain a pigment dispersion.
5. 5.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerylate hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 00 parts, benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 part, and 13.5 parts of Euker ester EFP were stirred with a dispersion stirrer to obtain a color resist as a photosensitive composition. The color resist was applied to 1 mm thick glass so as to have a dry film thickness of 1 μm.
Next, pattern exposure with ultraviolet rays was performed through a photomask, and then the unexposed portion was washed with an organic solvent to obtain a color filter.
ポリ臭素化亜鉛フタロシアニンＣから製造したカラーフィルター緑色画素部のパターンの色味および明るさを目視評価した。
輝度（Ｙ値）は、大塚電子（株）製の顕微分光光度計ＭＣＰＤ−３０００を使用して、Ｆ１０光源測色で色度座標ｘ値とｙ値を算出し、両色度座標ｘ、ｙ値を合わせてＣＩＥ発色系色度におけるＹ値を測定した。ここでは、輝度（Ｙ値）が大きいほど視覚明度が高いと評価した。
コントラストは、該カラーフィルター赤色画素部を２枚の偏光板の間に設置し、一方には光源を、更にその反対側にはＣＣＤカメラを設置して輝度の測定を行った。偏光軸が平行になる時と垂直になる時との輝度（透過光強度）の比より算出した。
また、ＪＩＳ Ｚ ８７２２に規定する第一種分光測光器（分光光度計）を用いて測定したところ、３８０〜７８０ｎｍにおける分光透過スペクトルの透過率が最大となる波長（Ｔmax）＝５２５ｎｍ、波長６５０〜７００ｎｍにおける最大透過率＝６．０％であった。
これら輝度、コントラスト及びＴmaxにおける光透過率を各々表１に示した。
The color and brightness of the pattern of the color filter green pixel portion produced from polybrominated zinc phthalocyanine C were visually evaluated.
Luminance (Y value) is calculated by using a micro-spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. to calculate chromaticity coordinate x value and y value by F10 light source colorimetry. The Y value in CIE color development chromaticity was measured by combining the values. Here, it was evaluated that the visual brightness was higher as the luminance (Y value) was higher.
For contrast, the color filter red pixel portion was installed between two polarizing plates, a light source was installed on one side, and a CCD camera was installed on the opposite side, and luminance was measured. It was calculated from the ratio of luminance (transmitted light intensity) between when the polarization axis was parallel and when it was vertical.
Further, when measured using a first-type spectrophotometer (spectrophotometer) defined in JIS Z 8722, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum is 525 nm, and the wavelength is 650. The maximum transmittance at 700 nm was 6.0%.
The luminance, contrast, and light transmittance at Tmax are shown in Table 1, respectively.
実施例３のポリ臭素化亜鉛フタロシアニンＣに代えて、実施例４のポリ臭素化亜鉛フタロシアニンＤを用いる以外は、実施例５と同様の操作を行い、カラーフィルター緑色画素部を作製した。
得られたカラーフィルター緑色画素部は、実施例５と同様の測定を行った。その結果を各々表１に示した。
A color filter green pixel portion was produced in the same manner as in Example 5 except that polybrominated zinc phthalocyanine D of Example 4 was used instead of polybrominated zinc phthalocyanine C of Example 3.
The obtained color filter green pixel portion was subjected to the same measurement as in Example 5. The results are shown in Table 1.
［比較例２］
実施例３のポリ臭素化亜鉛フタロシアニンＣに代えて、比較例１のポリ臭素化亜鉛フタロシアニンＥを用いる以外は、実施例５と同様な操作を行い、カラーフィルター緑色画素部を作製した。
得られたカラーフィルター緑色画素部は、実施例５と同様の測定を行った。その結果を各々表１に示した。以下、実施例４は実施例５に、実施例５は実施例６に読み替えるものとする。
[Comparative Example 2]
A color filter green pixel portion was produced in the same manner as in Example 5 except that polybrominated zinc phthalocyanine E of Comparative Example 1 was used instead of polybrominated zinc phthalocyanine C of Example 3.
The obtained color filter green pixel portion was subjected to the same measurement as in Example 5. The results are shown in Table 1. Hereinafter, Example 4 shall be read as Example 5, and Example 5 shall be read as Example 6 .
表１から明らかなように、本発明の新規結晶型ポリハロゲン化亜鉛フタロシアニンを含有する緑色画素部を有する実施例４及び５のカラーフィルターは、比較例２の従来の結晶型のポリハロゲン化亜鉛フタロシアニンを含有する緑色画素部を有する比較例２のそれに比べて、Ｔmaxにおける光透過率が高いだけでなく、輝度及びコントラストともに非常に高いものであった。 As is apparent from Table 1, the color filters of Examples 4 and 5 having a green pixel portion containing the novel crystalline polyhalogenated zinc phthalocyanine of the present invention are the conventional crystalline zinc polyhalides of Comparative Example 2. Compared with that of Comparative Example 2 having a green pixel portion containing phthalocyanine, not only the light transmittance at Tmax was high, but also the luminance and contrast were very high.
また、実施例１及び比較例２で調製した各顔料分散液を、室温で１週間保存し同様にカラーレジストを調製し、カラーフィルター緑色画素部を製造した。その結果、実施例１の顔料分散液を経由して得られたカラーフィルターは、初期と一週間保存後の顔料分散液とで、性能に変動はなかったが、比較例２の顔料分散液の場合は、初期と一週間保存後の顔料分散液とで、性能に大きな変動があった。 In addition, each pigment dispersion prepared in Example 1 and Comparative Example 2 was stored at room temperature for 1 week to prepare a color resist in the same manner, and a color filter green pixel portion was manufactured. As a result, the color filter obtained via the pigment dispersion liquid of Example 1 had no change in performance between the initial stage and the pigment dispersion liquid after storage for one week. In the case, there was a large variation in performance between the initial stage and the pigment dispersion after storage for one week.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006194150A JP5167602B2 (en) | 2006-07-14 | 2006-07-14 | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006194150A JP5167602B2 (en) | 2006-07-14 | 2006-07-14 | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008019383A JP2008019383A (en) | 2008-01-31 |
| JP5167602B2 true JP5167602B2 (en) | 2013-03-21 |
Family
ID=39075587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006194150A Active JP5167602B2 (en) | 2006-07-14 | 2006-07-14 | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5167602B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010100789A (en) * | 2007-11-22 | 2010-05-06 | Toyo Ink Mfg Co Ltd | Green colored composition for color filter, and color filter |
| JP4826614B2 (en) * | 2008-09-30 | 2011-11-30 | 大日本印刷株式会社 | Color filter pigment dispersion, color filter negative resist composition, color filter, and liquid crystal display device |
| JP5583353B2 (en) * | 2009-03-06 | 2014-09-03 | 富士フイルム株式会社 | Colored curable composition for solid-state imaging device, color filter, and production method thereof |
| JP5535692B2 (en) | 2009-03-17 | 2014-07-02 | 富士フイルム株式会社 | Colored curable composition, color filter, and method for producing color filter |
| KR101718527B1 (en) * | 2010-04-08 | 2017-04-05 | 삼성디스플레이 주식회사 | Method of manufacturing polarizing plate, polarizing plate using the same, and liquid crystal display having the polarizing plate |
| JP6024149B2 (en) * | 2012-03-28 | 2016-11-09 | 大日本印刷株式会社 | Colored resin composition for color filter, color filter, and liquid crystal display device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172519A (en) * | 1999-12-16 | 2001-06-26 | Dainippon Ink & Chem Inc | Production method for organic pigment applying supercritical field |
| JP4407097B2 (en) * | 2001-02-23 | 2010-02-03 | Ｄｉｃ株式会社 | Color filter |
| JP4368158B2 (en) * | 2002-07-24 | 2009-11-18 | 大日本印刷株式会社 | Photosensitive coloring composition, color filter, and liquid crystal panel |
| JP4368157B2 (en) * | 2002-07-24 | 2009-11-18 | 大日本印刷株式会社 | Green pigment for color filter, green pigment dispersion, photosensitive coloring composition, color filter, and liquid crystal panel |
-
2006
- 2006-07-14 JP JP2006194150A patent/JP5167602B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008019383A (en) | 2008-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5141939B2 (en) | Polyhalogenated zinc phthalocyanine pigment composition and color filter | |
| JP6020701B2 (en) | Green pigment for color filter and color filter | |
| JP4752590B2 (en) | Polyhalogenated zinc phthalocyanine pigment composition and color filter | |
| JP6451022B2 (en) | Polyhalogenated zinc phthalocyanine, polyhalogenated zinc phthalocyanine pigment, and color filter having the same in a pixel portion | |
| JP4882515B2 (en) | Polyhalogenated zinc phthalocyanine pigment composition and color filter | |
| JP4992321B2 (en) | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter | |
| JP6041179B1 (en) | Green pigment composition for color filter and color filter | |
| JP2007284590A (en) | Polyhalogenated metal phthalocyanine crude pigment, the pigment and color filter containing the pigment in green pixel part | |
| CN109642970B (en) | Pigment composition for color filter and color filter | |
| JP5167602B2 (en) | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter | |
| JP2006184427A (en) | Method for producing green semi-crude for color filter, green pigment composition and color filter containing the semi-crude and pigment composition in green pixel part | |
| JP2019038958A (en) | Chlorinated brominated zinc phthalocyanine pigment and color filter containing the same | |
| JP2004292785A (en) | Yellow pigment composition for color filter, and color filter containing the same in colored pixel part | |
| JP2005316244A (en) | Green pigment composition for color filter, and color filter containing same in green pixel | |
| JP6711213B2 (en) | Pigment composition for color filter and color filter | |
| TWI745571B (en) | Pigment composition for color filter and color filter | |
| JP2003114324A (en) | Blue pigment composition for color filter and color filter using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090713 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110517 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110602 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110726 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20110726 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120301 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120501 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121127 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121210 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5167602 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |