JP5141939B2 - Polyhalogenated zinc phthalocyanine pigment composition and color filter - Google Patents
Polyhalogenated zinc phthalocyanine pigment composition and color filter Download PDFInfo
- Publication number
- JP5141939B2 JP5141939B2 JP2006114394A JP2006114394A JP5141939B2 JP 5141939 B2 JP5141939 B2 JP 5141939B2 JP 2006114394 A JP2006114394 A JP 2006114394A JP 2006114394 A JP2006114394 A JP 2006114394A JP 5141939 B2 JP5141939 B2 JP 5141939B2
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- JP
- Japan
- Prior art keywords
- zinc phthalocyanine
- polyhalogenated zinc
- phthalocyanine pigment
- pigment
- polyhalogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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 189
- 239000000049 pigment Substances 0.000 title claims description 183
- 150000003751 zinc Polymers 0.000 title claims description 142
- 239000000203 mixture Substances 0.000 title claims description 112
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 28
- 125000001246 bromo group Chemical group Br* 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 30
- 235000002639 sodium chloride Nutrition 0.000 description 30
- 238000000034 method Methods 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- 239000003960 organic solvent Substances 0.000 description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910017053 inorganic salt Inorganic materials 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 15
- 238000004040 coloring Methods 0.000 description 14
- 239000011164 primary particle Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- -1 aluminum halides Chemical class 0.000 description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 11
- 229910052794 bromium Inorganic materials 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 239000001052 yellow pigment Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000003801 milling Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 230000026030 halogenation Effects 0.000 description 9
- 238000005658 halogenation reaction Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000004255 ion exchange chromatography Methods 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 7
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 7
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical class C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 239000001056 green pigment Substances 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 description 5
- 238000000411 transmission spectrum Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000004820 halides 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-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
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 230000019612 pigmentation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 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
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Polymers [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 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000007788 liquid Substances 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
- 125000004433 nitrogen atom Chemical group 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-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
- 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
- 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
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
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Description
本発明は、着色力に優れ色再現域の広いポリハロゲン化亜鉛フタロシアニン顔料組成物及びそれを緑色画素部に含有する輝度が高く理想的により近いＲＧＢ色再現域を達成出来るカラーフィルタに関する。 The present invention relates to a polyhalogenated zinc phthalocyanine pigment composition having excellent coloring power and a wide color reproduction range, and a color filter containing the same in a green pixel portion and capable of achieving an RGB color reproduction range which is high in brightness and closer to ideal.
ポリハロゲン化金属フタロシアニン顔料としては、ポリハロゲン化銅フタロシアニン顔料を始めとして、それ以外のポリハロゲン化異種金属フタロシアニン顔料が知られている。
中でも、ポリハロゲン化亜鉛フタロシアニン顔料は、ポリハロゲン化アルミニウムフタロシアニンダイマー顔料の様な、それ以外のポリハロゲン化異種金属フタロシアニン顔料に無い特異的な性質を示す。
Known polyhalogenated metal phthalocyanine pigments include polyhalogenated copper phthalocyanine pigments and other polyhalogenated different metal phthalocyanine pigments.
Among them, the polyhalogenated zinc phthalocyanine pigment exhibits specific properties that are not found in other polyhalogenated heterometallic phthalocyanine pigments, such as a polyhalogenated aluminum phthalocyanine dimer pigment.
具体的には、このポリハロゲン化亜鉛フタロシアニン顔料を液晶表示装置のカラーフィルタの緑色画素部への適用が知られている。このポリハロゲン化亜鉛フタロシアニン顔料を含有する緑色画素部は、当該顔料の一次粒子の平均粒子径が大きくても、Ｔmaxが従来のポリハロゲン化銅フタロシアニン顔料を含有する緑色画素部に比べ高波長側にあり、しかも分光透過スペクトルの曲線をＴmaxにおける透過率の１／２の透過率で内挿した際の曲線上の２点間の距離（半値幅）が９０〜１１０ｎｍと非常にシャープであるので、高色純度であって、黄色顔料と混色した場合においても緑色領域の光透過量も多くなり、明るい画面が得られ、映像のコントラストが良く、高色純度カラーフィルタに好適に使用できる（特許文献１、２または３）。 Specifically, application of this polyhalogenated zinc phthalocyanine pigment to a green pixel portion of a color filter of a liquid crystal display device is known. The green pixel portion containing the polyhalogenated zinc phthalocyanine pigment has a higher Tmax than the green pixel portion containing the conventional polyhalogenated copper phthalocyanine pigment even if the average particle size of the primary particles of the pigment is large. In addition, the distance (half-value width) between two points on the curve when the spectral transmission spectrum curve is interpolated with a transmittance of 1/2 of the transmittance at Tmax is very sharp as 90 to 110 nm. High color purity, even when mixed with a yellow pigment, the amount of light transmitted in the green region is increased, a bright screen is obtained, the image contrast is good, and it can be suitably used for a high color purity color filter (patent) Literature 1, 2 or 3).
しかしながら、これら優れたポリハロゲン化亜鉛フタロシアニン顔料にあっても、着色力が不充分であり、色相が青味すぎるという欠点があり、例えば、この様な従来のポリハロゲン化亜鉛フタロシアニン顔料を緑色画素部に含有するカラーフィルタを含む液晶表示装置は、輝度も色再現性が不充分であり、更に高水準の輝度と、より理想的に近いＲＧＢ色再現性を達成することが期待されている。 However, even these excellent polyhalogenated zinc phthalocyanine pigments have the disadvantage that the coloring power is insufficient and the hue is too bluish. For example, such a conventional polyhalogenated zinc phthalocyanine pigment has a green pixel. The liquid crystal display device including the color filter contained in the part has insufficient luminance and color reproducibility, and is expected to achieve a higher level of luminance and a more ideal RGB color reproducibility.
本発明が解決しようとする第一の課題は、用途を問わず、着色力に優れ色再現域の広いポリハロゲン化亜鉛フタロシアニン顔料組成物を提供することにある。
本発明が解決しようとする第二の課題は、輝度がより高く理想的により近いＲＧＢ色再現域を達成出来る、ポリハロゲン化亜鉛フタロシアニン顔料緑色画素部を含有するカラーフィルタを提供することにある。
The first problem to be solved by the present invention is to provide a polyhalogenated zinc phthalocyanine pigment composition having an excellent coloring power and a wide color reproduction range regardless of applications.
The second problem to be solved by the present invention is to provide a color filter containing a green pixel portion of a polyhalogenated zinc phthalocyanine pigment, which can achieve a RGB color reproduction range with higher luminance and ideally closer.
本発明者等は、種々のハロゲン原子組成のポリハロゲン化亜鉛フタロシアニン顔料を製造する過程で、平均的ハロゲン原子組成が同等であっても、その塩素原子や臭素原子の置換数の統計的な生成割合如何によって、それが着色力や色相の点で相違が生じうること、そして、ある特定の統計的範囲となる様にポリハロゲン化亜鉛フタロシアニン顔料の組成を制御することにより、より高い着色力やより黄味の色相を達成することが出来ることを見い出した。
また、こうして得られたポリハロゲン化亜鉛フタロシアニン顔料を緑色画素部に含有させたカラーフィルタは、従来のポリハロゲン化亜鉛フタロシアニン顔料を緑色画素部に含有させたカラーフィルタに比べて、輝度がより高く理想的により近いＲＧＢ色再現域を達成出来ることを見い出した。本発明者等は、これらの知見により本発明を完成するに至った。
In the process of producing polyhalogenated zinc phthalocyanine pigments having various halogen atom compositions, the present inventors have statistically generated the number of substitutions of chlorine atoms and bromine atoms even if the average halogen atom composition is equivalent. Depending on the ratio, it can be different in terms of color strength and hue, and by controlling the composition of the polyhalogenated zinc phthalocyanine pigment to be in a certain statistical range, It has been found that a yellowish hue can be achieved.
In addition, the color filter containing the polyhalogenated zinc phthalocyanine pigment thus obtained in the green pixel portion has a higher luminance than the conventional color filter containing the polyhalogenated zinc phthalocyanine pigment in the green pixel portion. It has been found that an RGB color reproduction range closer to the ideal can be achieved. Based on these findings, the present inventors have completed the present invention.
即ち本発明は、ポリハロゲン化亜鉛フタロシアニン顔料を含有し、
（１）塩素原子と臭素原子の和が１６である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料７２モル％以上、
（２）塩素原子と臭素原子の和が１４〜１５である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料２６モル％以下、かつ
（３）塩素原子と臭素原子の和が１３以下である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料２モル％以下、
から構成されていることを特徴とするポリハロゲン化亜鉛フタロシアニン顔料組成物。
That is, the present invention contains a polyhalogenated zinc phthalocyanine pigment,
(1) 72 mol% or more of a polyhalogenated zinc phthalocyanine pigment of the following general formula 1 wherein the sum of chlorine atoms and bromine atoms is 16;
(2) 26 mol% or less of the polyhalogenated zinc phthalocyanine pigment of the following general formula 1 in which the sum of chlorine atoms and bromine atoms is 14 to 15; and (3) the following general in which the sum of chlorine atoms and bromine atoms is 13 or less. 2 mol% or less of the polyhalogenated zinc phthalocyanine pigment of formula 1
A polyhalogenated zinc phthalocyanine pigment composition comprising:
（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。）を提供する。 (In General Formula 1, all of X 1 to X 16 are independently a chlorine atom, a bromine atom, or a hydrogen atom).
また本発明は、前記で得られたポリハロゲン化亜鉛フタロシアニン顔料組成物を緑色画素部に含有してなるカラーフィルタを提供する。 The present invention also provides a color filter comprising the above-obtained polyhalogenated zinc phthalocyanine pigment composition in a green pixel portion.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、特定のハロゲン原子組成であるため、用途を問わず、着色力により優れ色再現域がより広いという格別顕著な効果を奏する。
またカラーフィルタは、前記したポリハロゲン化亜鉛フタロシアニン顔料組成物を緑色画素部に含有するため、輝度が高く理想的により近いＲＧＢ色再現域の液晶表示が可能であるという格別顕著な効果を奏する。
Since the polyhalogenated zinc phthalocyanine pigment composition of the present invention has a specific halogen atom composition, it has a particularly remarkable effect that it has an excellent coloring power and a wider color gamut regardless of the application.
In addition, since the color filter contains the above-described polyhalogenated zinc phthalocyanine pigment composition in the green pixel portion, the color filter has a particularly remarkable effect that the liquid crystal display in the RGB color gamut can be achieved with high brightness.
以下、本発明を詳細に説明する。
本発明におけるポリハロゲン化亜鉛フタロシアニン顔料組成物は、複数種の、特定のハロゲン原子組成のポリハロゲン化亜鉛フタロシアニン顔料を特定割合にて含有するものである。ポリハロゲン化亜鉛フタロシアニンとは、フタロシアニン分子（構造）１個当たり、塩素原子及び／又は臭素原子の合計が、最大で１６個結合した構造の物質である。分子中に結合した塩素原子及び／又は臭素原子の数が増すと、ポリハロゲン化亜鉛フタロシアニンの色相は青色から緑色となる。ポリハロゲン化亜鉛フタロシアニンが緑色となるためには、分子に結合したハロゲン原子として、臭素原子は８個以上且つ塩素は１個以上有することが好ましく、なかでも臭素原子が１２個以上且つ塩素原子は２個以上有することが、一層黄味を帯びた明度の高い緑色を発色する点でより好ましい。塩素原子に比べて臭素原子がより多く含有されていることが、より黄味の緑色を得る上では好ましい。
Hereinafter, the present invention will be described in detail.
The polyhalogenated zinc phthalocyanine pigment composition in the present invention contains a plurality of types of polyhalogenated zinc phthalocyanine pigments having a specific halogen atom composition in a specific ratio. The polyhalogenated zinc phthalocyanine is a substance having a structure in which a total of 16 chlorine atoms and / or bromine atoms are bonded per phthalocyanine molecule (structure). As the number of chlorine and / or bromine atoms bonded in the molecule increases, the hue of the polyhalogenated zinc phthalocyanine changes from blue to green. In order for the polyhalogenated zinc phthalocyanine to become green, it is preferable that the halogen atom bonded to the molecule has 8 or more bromine atoms and 1 or more chlorine atoms, among which 12 or more bromine atoms and chlorine atoms are It is more preferable to have two or more in terms of coloring a green color with a higher lightness that is more yellowish. It is preferable that more bromine atoms are contained than chlorine atoms in order to obtain a more yellowish green color.
より黄味の緑色は、より広い色再現域に繋がる。液晶表示装置のカラーフィルタにおいては、理想により近いＲＧＢ色再現域を確保出来ることに繋がる。また、より高い着色力は、液晶表示装置のカラーフィルタにおいては、より高い輝度に繋がる。 A more yellowish green leads to a wider color gamut. In the color filter of the liquid crystal display device, an RGB color reproduction range closer to the ideal can be secured. Moreover, higher coloring power leads to higher luminance in the color filter of the liquid crystal display device.
ポリハロゲン化亜鉛フタロシアニンは、上記一般式にて表される。本発明においては、一次粒子の平均粒子径が０．０１〜０．３０μｍのポリハロゲン化亜鉛フタロシアニンをポリハロゲン化亜鉛フタロシアニン顔料という。 Polyhalogenated zinc phthalocyanine is represented by the above general formula. In the present invention, a polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.30 μm is referred to as a polyhalogenated zinc phthalocyanine pigment.
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 particles in the present invention refers to halogenation that forms an aggregate on a two-dimensional image by photographing particles in the field of view with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.). For 50 zinc phthalocyanine primary particles, the longer diameter (major diameter) is determined and averaged. 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.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、複数種の、特定のハロゲン原子組成のポリハロゲン化亜鉛フタロシアニン顔料を特定割合にて含有するものである。より具体的には、
（１）塩素原子と臭素原子の和が１６であるポリハロゲン化亜鉛フタロシアニン顔料７２モル％以上、
（２）塩素原子と臭素原子の和が１４〜１５であるポリハロゲン化亜鉛フタロシアニン顔料２６モル％以下、かつ
（３）塩素原子と臭素原子の和が１３以下であるポリハロゲン化亜鉛フタロシアニン顔料２モル％以下
から構成されたポリハロゲン化亜鉛フタロシアニン顔料組成物である。
The polyhalogenated zinc phthalocyanine pigment composition of the present invention contains a plurality of polyhalogenated zinc phthalocyanine pigments having a specific halogen atom composition in a specific ratio. More specifically,
(1) 72 mol% or more of a polyhalogenated zinc phthalocyanine pigment having a sum of chlorine atoms and bromine atoms of 16,
(2) A polyhalogenated zinc phthalocyanine pigment having a sum of chlorine atoms and bromine atoms of 14 to 15 mol% or less, and (3) a polyhalogenated zinc phthalocyanine pigment 2 having a sum of chlorine atoms and bromine atoms of 13 or less. It is a polyhalogenated zinc phthalocyanine pigment composition composed of mol% or less.
ポリハロゲン化亜鉛フタロシアニン顔料組成物の平均組成は、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求められ、ポリハロゲン化亜鉛フタロシアニン顔料組成物中の個々の特定ポリハロゲン化亜鉛フタロシアニン顔料の含有モル％も、同様に質量分析の結果を解析することにより、容易に求められる。 The average composition of the polyhalogenated zinc phthalocyanine pigment composition is obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography. Similarly, the mol% of the halogenated zinc phthalocyanine pigment can be easily obtained by analyzing the results of mass spectrometry.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、少なくとも、上記した（１）〜（３）の三つの要件を満たしている必要があるが、水素原子数が少ないほど特性は好ましく、黄味を帯びた明度の高い緑色を発色し、カラーフィルタの緑色画素部のパターンへの使用に最適なものとなる。したがって上記一般式で塩素原子と臭素原子の和が１６であるポリハロゲン化亜鉛フタロシアニン顔料が７２モル％以上、かつ塩素原子と臭素原子の和が１４〜１５であるポリハロゲン化亜鉛フタロシアニン顔料が２６モル％以下、かつ塩素原子と臭素原子の和が１３以下であるポリハロゲン化亜鉛フタロシアニン顔料が２モル％以下の条件を満たす様に、ポリハロゲン化亜鉛フタロシアニン顔料組成物を調製することにより、従来品のポリハロゲン化亜鉛フタロシアニン顔料では達成できなかった黄味および明度が得られる。 The polyhalogenated zinc phthalocyanine pigment composition of the present invention needs to satisfy at least the above three requirements (1) to (3). However, the smaller the number of hydrogen atoms, the better the characteristics, It gives a green color with high brightness and is optimal for use in the pattern of the green pixel portion of the color filter. Accordingly, a polyhalogenated zinc phthalocyanine pigment having the above general formula and having a sum of chlorine and bromine atoms of 16 is 72 mol% or more, and a polyhalogenated zinc phthalocyanine pigment having a sum of chlorine and bromine atoms of 14 to 15 is 26. By preparing a polyhalogenated zinc phthalocyanine pigment composition so that a polyhalogenated zinc phthalocyanine pigment having a mol% or less and a sum of chlorine atoms and bromine atoms of 13 or less satisfies the condition of 2 mol% or less, Yellowness and lightness not achieved with the original polyhalogenated zinc phthalocyanine pigments are obtained.
なかでも、より黄味かつより高い明度となる点で、塩素原子と臭素原子の和が１６かつ塩素原子数２〜３の上記一般式のポリハロゲン化亜鉛フタロシアニン顔料を３２モル％以上含有する方が好ましく、さらには塩素原子と臭素原子の和が１６である上記一般式のポリハロゲン化亜鉛フタロシアニン顔料を７５モル％以上かつ塩素原子と臭素原子の和が１６であって塩素原子数２〜３の上記一般式のポリハロゲン化亜鉛フタロシアニン顔料を３５モル％以上含有するポリハロゲン化亜鉛フタロシアニン顔料組成物であることがより好ましい。 Among them, the one containing 32 mol% or more of the polyhalogenated zinc phthalocyanine pigment of the above general formula, wherein the sum of chlorine atoms and bromine atoms is 16 and the number of chlorine atoms is 2 to 3, in terms of yellowing and higher brightness. More preferably 75 mol% or more of the polyhalogenated zinc phthalocyanine pigment of the above general formula wherein the sum of chlorine atoms and bromine atoms is 16, and the sum of chlorine atoms and bromine atoms is 16, and the number of chlorine atoms is 2-3. More preferred is a polyhalogenated zinc phthalocyanine pigment composition containing 35 mol% or more of the polyhalogenated zinc phthalocyanine pigment of the above general formula.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、カラーフィルタ用途では、６５０〜７００ｎｍにおける分光透過率が５％以下である領域がより広く、最大透過率（Ｔmax）がより大きい点で好ましい。 The polyhalogenated zinc phthalocyanine pigment composition of the present invention is preferable for color filter applications in that the region where the spectral transmittance at 650 to 700 nm is 5% or less is wider and the maximum transmittance (Tmax) is larger.
本発明で用いるポリハロゲン化亜鉛フタロシアニン顔料組成物は、ポリハロゲン化亜鉛フタロシアニンから製造することが出来る。この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 pigment composition used in the present invention can be produced from polyhalogenated zinc phthalocyanine. This 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３〜２０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. for 3 to 20 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、対応するポリハロゲン化亜鉛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７〜３５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 polyhalogenated zinc 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 a range of 7 to 35 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、亜鉛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。
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５〜１５質量部が好ましい。
The preferred aluminum halide is aluminum chloride. In the above method using an aluminum halide, the amount of the aluminum halide added is usually 3 times or more, preferably 10 to 20 times the mol of zinc phthalocyanine.
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 5 to 15 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。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。 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. Examples of the halogenating agent include chlorine gas, sulfuryl chloride, bromine and the like.
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、３０〜４５時間である。 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 30 to 45 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、特定ハロゲン原子組成のポリハロゲン化亜鉛フタロシアニンの含有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 content ratio of the polyhalogenated zinc phthalocyanine having a specific halogen atom composition in the generated polyhalogenated zinc phthalocyanine can be arbitrarily controlled.
本発明における好適な原料たる金属フタロシアニンは、亜鉛フタロシアニンである。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、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。 The metal phthalocyanine which is a suitable raw material in the present invention is zinc phthalocyanine. In order to obtain a polyhalogenated zinc phthalocyanine, the melting method is suitable because the raw material during the reaction is less decomposed and the yield from the raw material is better, and the reaction can be carried out in an inexpensive apparatus without using a strong acid.
本発明では、原料仕込方法、触媒種や使用量、反応温度や反応時間の最適化により、既存のポリハロゲン化亜鉛フタロシアニンとは異なるハロゲン原子組成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。 In the present invention, a polyhalogenated zinc phthalocyanine having a halogen atom composition different from that of the existing polyhalogenated zinc phthalocyanine can be obtained by optimizing the raw material charging method, catalyst type and amount used, reaction temperature and reaction time.
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、生成したポリハロゲン化亜鉛フタロシアニンが沈殿する。ポリハロゲン化亜鉛フタロシアニンとしては、これをそのまま用いても良いが、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、乾燥等の後処理を行ってから用いるのが好ましい。 In any of the above production methods, when the obtained mixture is put into an acidic aqueous solution such as water or hydrochloric acid after completion of the reaction, the produced polyhalogenated zinc phthalocyanine precipitates. As the polyhalogenated zinc phthalocyanine, it may be used as it is, but then filtered, washed with water or sodium hydrogensulfate water, sodium hydrogencarbonate water, sodium hydroxide water, acetone, toluene, methyl alcohol, It is preferably used after washing with an organic solvent such as ethyl alcohol or dimethylformamide and after-treatment such as drying.
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、ついで、ソルベントソルトミリング法やソルベントボイリング法等で顔料化することによって、顔料化前よりは、分散性や着色力に優れ、かつ、黄味を帯びた明度の高い緑色を発色する顔料が得られる。 If necessary, polyhalogenated zinc phthalocyanine is dry-ground in a grinder such as an attritor, ball mill, vibration mill, vibration ball mill, etc., and then pigmented by the solvent salt milling method or solvent boiling method. A pigment which is excellent in dispersibility and coloring power and has a yellowish color with high lightness can be obtained than before.
ポリハロゲン化亜鉛フタロシアニンの顔料化方法には特に制限はなく、例えば、顔料化前のポリハロゲン化亜鉛フタロシアニンを分散媒に分散させると同時に顔料化を行ってもよいが、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、かつ比表面積の大き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。 There is no particular limitation on the method of pigmenting the polyhalogenated zinc phthalocyanine. For example, the polyhalogenated zinc phthalocyanine before pigmentation may be dispersed in a dispersion medium and pigmented at the same time, but in a large amount of organic solvent. The solvent salt milling treatment is preferably employed in that pigment particles having a large specific surface area can be obtained more easily than the solvent treatment by heating and stirring the metal halide phthalocyanine.
このソルベントソルトミリングとは、合成直後またはその後に磨砕を行った、顔料化を経ていないポリハロゲン化亜鉛フタロシアニンである粗顔料と、無機塩と、有機溶剤とを混練摩砕することを意味する。この場合、後者の粗顔料を用いるほうが好ましい。具体的には、粗顔料と、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。 This solvent salt milling means kneading and grinding a crude pigment which is a non-pigmented polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent, which are ground immediately after synthesis or thereafter. . In this case, it is preferable to use the latter crude pigment. Specifically, a crude pigment, 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０．０１〜０．１０μｍのポリハロゲン化金属フタロシアニン顔料組成物をカラーフィルタ用途に用いるのが好ましい。本発明における前記した好ましい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粗顔料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、粗顔料１質量部に対して５〜２０質量部とするのが好ましく、７〜１５質量部とするのがより好ましい。 In the present invention, a polyhalogenated metal phthalocyanine pigment composition having an average primary particle size of 0.01 to 0.10 μm is preferably used for color filters. In obtaining the above-mentioned preferable polyhalogenated zinc phthalocyanine in the present invention, it is preferable to increase the amount of inorganic salt used relative to the amount of crude pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass with respect to 1 part by mass of the crude pigment.
有機溶剤としては、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、このような有機溶媒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。当該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、粗顔料１質量部に対して０．０１〜５質量部が好ましい。 As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth, and as such an organic solvent, a water-soluble organic solvent can be suitably used. 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 mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol. Although the usage-amount of the said water-soluble organic solvent is not specifically limited, 0.01-5 mass parts is preferable with respect to 1 mass part of crude pigments.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物を製造する方法においては、粗顔料のみをソルベントソルトミリングしても良いが、ポリハロゲン化亜鉛フタロシアニンとフタロシアニン誘導体とを併用してソルベントソルトミリングすることもできる。また、フタロシアニン誘導体は、粗顔料の合成時や顔料化の後に加えてもよいが、ソルベントソルトミリングなどの顔料化工程の前に加えることがより好ましい。フタロシアニン誘導体を加えることによってカラーフィルタ用レジストインキの粘度特性の向上と分散安定性の向上が達成出来る。 In the method for producing the polyhalogenated zinc phthalocyanine pigment composition of the present invention, only the crude pigment may be subjected to solvent salt milling. it can. The phthalocyanine derivative may be added at the time of synthesizing the crude pigment or after pigmentation, but it is more preferable to add it before the pigmentation step such as solvent salt milling. By adding a phthalocyanine derivative, it is possible to improve the viscosity characteristics and the dispersion stability of the color filter resist ink.
このようなフタロシアニン誘導体としては、公知慣用のものがいずれも使用出来るが、下記一般式（２）または（３）のフタロシアニン顔料誘導体が好ましい。尚、このフタロシアニン誘導体は、ポリハロゲン化亜鉛フタロシアニンまたはその原料たる亜鉛フタロシアニンに対応するフタロシアニン誘導体であるのが好ましいが、併用する場合にも少量なので、ポリハロゲン化銅フタロシアニン誘導体や、銅フタロシアニン誘導体を用いることも出来る。 As such a phthalocyanine derivative, any known and commonly used phthalocyanine derivatives can be used, but phthalocyanine pigment derivatives of the following general formula (2) or (3) are preferred. The phthalocyanine derivative is preferably a polyhalogenated zinc phthalocyanine or a phthalocyanine derivative corresponding to zinc phthalocyanine which is a raw material thereof. It can also be used.
（式中、Ｐは中心金属を有さないまたは中心金属を有する無置換またはハロゲン化フタロシアニン環のｎ個の水素を除いた残基を表す。Ｙは第１〜３級アミノ基、カルボン酸基、スルホン酸基またはそれと塩基或いは金属との塩を表す。Ａは二価の連結基を、Ｚは第１〜２級アミノ基の窒素原子上の水素の少なくとも１つを除いた残基、又は窒素を含む複素環の窒素原子上の水素の少なくとも１つを除いた残基を表す。そしてｍは１〜４を、ｎは１〜４を表す。） (In the formula, P represents a residue obtained by removing n hydrogens of an unsubstituted or halogenated phthalocyanine ring having no central metal or having a central metal. Y represents a primary to tertiary amino group or a carboxylic acid group. Represents a sulfonic acid group or a salt thereof with a base or a metal, A is a divalent linking group, Z is a residue obtained by removing at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or (Represents a residue obtained by removing at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, and m represents 1 to 4 and n represents 1 to 4).
前記中心金属としてはＺｎで、前記第１〜２級アミノ基としては、例えばモノメチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等が挙げられる。また、前記カルボン酸基やスルホン酸基と塩を形成する塩基や金属としては、例えばアンモニアや、ジメチルアミン、ジエチルアミン、トリエチルアミンの様な有機塩基、カリウム、ナトリウム、カルシウム、ストロンチウム、アルミニウムの様な金属が挙げられ、Ａの二価の連結基としては、例えば炭素数１〜３のアルキレン基、−ＣＯ2−、−ＳＯ2−，−ＳＯ2ＮＨ（ＣＨ2）m−等の二価の連結基が挙げられる。そして、Ｚとしては、例えばフタルイミド基、モノアルキルアミノ基、ジアルキルアミノ基等が挙げられる。 The central metal is Zn, and examples of the primary and secondary amino groups include a monomethylamino group, a dimethylamino group, and a diethylamino group. Examples of the base or metal that forms a salt with the carboxylic acid group or sulfonic acid group include ammonia, organic bases such as dimethylamine, diethylamine, and triethylamine, and metals such as potassium, sodium, calcium, strontium, and aluminum. As the divalent linking group for A, for example, a divalent linking group such as an alkylene group having 1 to 3 carbon atoms, —CO 2 —, —SO 2 —, —SO 2 NH (CH 2 ) m —, etc. Groups. Examples of Z include a phthalimide group, a monoalkylamino group, and a dialkylamino group.
粗顔料調製時及び／又はソルベントソルトミリング時に粗顔料に含めることが出来るフタロシアニン誘導体は、通常、粗顔料１質量部当たり０．０１〜０．３質量部である。尚、粗顔料調製時及び／又はソルベントソルトミリング時にフタロシアニン誘導体を用いる場合には、粗顔料とフタロシアニン誘導体との合計量を粗顔料の使用量と見なして、無機塩の使用量等は、前記した範囲から選択する。 The phthalocyanine derivative that can be included in the crude pigment during the preparation of the crude pigment and / or during solvent salt milling is usually 0.01 to 0.3 parts by mass per 1 part by mass of the crude pigment. In addition, when using a phthalocyanine derivative at the time of crude pigment preparation and / or solvent salt milling, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the usage amount of the crude pigment, and the usage amount of the inorganic salt is as described above. Select from a range.
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時間から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 hours to 20 hours, more preferably 8 to 18 hours.
こうして、一次粒子の平均粒子径が０．０１〜０．１０μｍのハロゲン化亜鉛フタロシアニン顔料組成物、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顔料組成物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、ポリハロゲン化亜鉛フタロシアニン顔料組成物の粉体を得ることが出来る。 Thus, a zinc halide phthalocyanine pigment composition having an average primary particle diameter of 0.01 to 0.10 μm, a mixture containing an inorganic salt and an organic solvent as main components is obtained. From this mixture, the organic solvent and the inorganic salt are mixed. It is possible to obtain a powder of the polyhalogenated zinc phthalocyanine pigment composition by removing, washing, filtering, drying, pulverizing, etc. a solid mainly comprising the polyhalogenated zinc phthalocyanine pigment composition as necessary. I can do it.
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。必要であれば、結晶状態を変化させない様に、酸洗浄、アルカリ洗浄、溶剤洗浄を行ってもよい。 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. If necessary, acid cleaning, alkali cleaning, and solvent cleaning may be performed so as not to change the crystal state.
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。特にスプレードライ乾燥はペースト作成時に易分散であるため好ましい。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ように顔料がランプ状等のとなった際に顔料を解して粉末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。こうして、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物を主成分として含む乾燥粉末が得られる。 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 particular, spray dry drying is preferable because it is easily dispersed during paste preparation. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but for example, the pigment is a lamp as in the case of drying using a box dryer or a band dryer. When it becomes a shape, etc., 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. In this way, a dry powder containing the polyhalogenated zinc phthalocyanine pigment composition of the present invention as a main component is obtained.
尚、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、従来のハロゲン化銅フタロシアニン顔料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。電子顕微鏡写真により、従来の顔料では観察できない、凝集体を構成する個々の顔料一次粒子を観察することができる。 In addition, the polyhalogenated zinc phthalocyanine pigment composition of the present invention has a property in which the cohesion of primary particles is weaker than that of a conventional copper halide phthalocyanine pigment, and is more easily disentangled. From the electron micrograph, it is possible to observe individual pigment primary particles constituting the aggregate, which cannot be observed with a conventional pigment.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、公知慣用の用途にいずれも使用できるが、特に一次粒子の平均粒子径が０．０１〜０．１０μｍであることから、顔料凝集も比較的弱く、着色すべき合成樹脂等への分散性がより良好となる。
また、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、カラーフィルタ緑色画素部に使用する場合においては、カラーフィルタ用感光性組成物への顔料分散が容易であり、カラーフィルタ用感光性組成物を硬化する際に多用される３６５ｎｍにおける遮光性は低下し、それの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。近年要求されている鮮明度と明度とのいずれもが高いカラーフィルタ緑色画素部がより簡便に得られる。
The polyhalogenated zinc phthalocyanine pigment composition of the present invention can be used for any known and commonly used application. However, since the average particle diameter of primary particles is 0.01 to 0.10 μm, pigment aggregation is relatively weak. , Dispersibility in a synthetic resin to be colored becomes better.
Further, when the polyhalogenated zinc phthalocyanine pigment composition of the present invention is used in a color filter green pixel portion, the pigment dispersion in the color filter photosensitive composition is easy, and the color filter photosensitive composition. The light-shielding property at 365 nm, which is frequently used for curing the film, is reduced, the photocuring sensitivity is not lowered, and film edge and pattern flow during development are less likely to occur. A color filter green pixel portion having both high sharpness and high brightness demanded in recent years can be obtained more easily.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物の一次粒子は、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、まず、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。 If the primary particles of the polyhalogenated zinc phthalocyanine pigment composition of the present invention have an aspect ratio of 1 to 3 in the longitudinal and lateral directions, the viscosity characteristics are improved in each application field, and the fluidity becomes higher. In order to obtain the aspect ratio, first, as in the case of obtaining the average particle diameter of the primary particles, 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. .
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物を、少なくともカラーフィルタの緑色画素部に含有させることで、本発明のカラーフィルタを得ることが出来る。 The color filter of the present invention can be obtained by incorporating the polyhalogenated zinc phthalocyanine pigment composition of the present invention into at least the green pixel portion of the color filter.
従来のポリハロゲン化亜鉛フタロシアニン顔料と同様に、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、カラーフィルタの緑色画素部を得る場合に、特段に黄色顔料を調色のために併用することなく、或いは併用するにしてもより少量で済むため、３８０〜７８０ｎｍの全域における光透過率の低下も最小限に防止できる。特に、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、より黄味かつより高着色力を有するため、同等の色濃度であれば、黄色顔料はより少ない併用量で良いため、さらに透過率を上げることも出来、有利である。 Like the conventional polyhalogenated zinc phthalocyanine pigment, the polyhalogenated zinc phthalocyanine pigment composition of the present invention can be used without specially using a yellow pigment for color matching when obtaining a green pixel portion of a color filter. Or, even if it is used in combination, a smaller amount is required, so that a decrease in light transmittance in the entire region of 380 to 780 nm can be prevented to a minimum. In particular, since the polyhalogenated zinc phthalocyanine pigment composition of the present invention has a more yellowish color and higher coloring power, the yellow pigment may be used in a smaller amount as long as it has an equivalent color density. It can be raised and is advantageous.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、前記した様に、従来のポリハロゲン化亜鉛フタロシアニン顔料と同様に、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）は、５１０〜５２０ｎｍであり、その透過曲線の半値幅が１１０ｎｍ以下と非常にシャープである。（この波長は、後述する様な感光性樹脂による影響を受けない。）。 As described above, the polyhalogenated zinc phthalocyanine pigment composition of the present invention has a wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximized, similarly to the conventional polyhalogenated zinc phthalocyanine pigment. The transmission curve has a half-width of 110 nm or less and is very sharp. (This wavelength is not affected by the photosensitive resin as described later.)
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顔料組成物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 the pigment composition 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、ポリハロゲン化亜鉛フタロシアニン顔料組成物を緑色画素部に含有するカラーフィルタは、白色光、Ｆ１０等の光源を用いた場合、光源の緑の輝線を良く透過させることができ、かつポリハロゲン化亜鉛フタロシアニン顔料組成物の分光透過スペクトルがシャープなため、緑色の色純度、着色力を最大限に発現することができる。 The color filter containing the polyhalogenated zinc phthalocyanine pigment composition of the present invention in the green pixel portion can transmit the green emission line of the light source well when using a light source such as white light, F10, etc. Since the spectral transmission spectrum of the zinc halide phthalocyanine pigment composition is sharp, green color purity and coloring power can be expressed to the maximum.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、それだけをそのままカラーフィルタの緑色画素部の製造に用いることが出来るが、必要ならば、経済性を考慮して、公知慣用の緑色ハロゲン化銅フタロシアニンまたはその他の緑色ハロゲン化異種金属フタロシアニン顔料の様な緑色ハロゲン化金属フタロシアニン顔料を併用して用いても良い。 The polyhalogenated zinc phthalocyanine pigment composition of the present invention can be used as it is for the production of a green pixel portion of a color filter, but if necessary, in consideration of economy, a known and commonly used green copper halide phthalocyanine Alternatively, other green halogenated metal phthalocyanine pigments such as other green halogenated different metal phthalocyanine pigments may be used in combination.
本発明におけるポリハロゲン化亜鉛フタロシアニン顔料組成物：公知慣用の緑色ハロゲン化金属フタロシアニン顔料（質量比）＝１００：０〜８０：２０、好ましくは１００：０〜９０：１０として用いることが好ましい。 The polyhalogenated zinc phthalocyanine pigment composition in the present invention: a known and commonly used green halogenated metal phthalocyanine pigment (mass ratio) = 100: 0 to 80:20, preferably 100: 0 to 90:10.
また、緑色顔料の他に、特性を出現させるため調色用に黄色顔料を使用することがある。ここで併用できる黄色顔料としては、例えばＣ．Ｉ．ピグメント イエロー 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。本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物と黄色顔料との併用割合は、前記ポリハロゲン化亜鉛フタロシアニン顔料組成物１００質量部当たり、黄色顔料が１０〜１００質量部である。 In addition to the green pigment, a yellow pigment may be used for toning in order to make the characteristics appear. Examples of yellow pigments that can be used here include C.I. I. And yellow organic pigments such as CI Pigment Yellow 83, 110, 138, 139, 150, 180, and 185. The combined proportion of the polyhalogenated zinc phthalocyanine pigment composition of the present invention and the yellow pigment is 10 to 100 parts by mass of the yellow pigment per 100 parts by mass of the polyhalogenated zinc phthalocyanine pigment composition.
また、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物を用いれば、黄色顔料を調色のために併用した場合でも、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、着色力に優れ、かつ明るいカラーフィルタ緑色画素部とすることが出来る。 Moreover, when the polyhalogenated zinc phthalocyanine pigment composition of the present invention is used, even when a yellow pigment is used together for toning, in the conventional case of mixing two or more different color pigments for toning. In comparison, the color filter green pixel portion with less turbidity, excellent color purity and coloring power, and bright can be obtained.
例えば、従来のＣ．Ｉ．ピグメント グリーン ７、同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顔料組成物に黄色顔料と併用した場合のほうが、色純度、着色力が高いため、明るさの低下がより小さくなり、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 green pigment as CI Pigment Green 7 and 36 is used, the case where the yellow pigment is used in combination with the polyhalogenated zinc phthalocyanine pigment composition of the present invention is better. Since the color purity and coloring power are high, the decrease in brightness is further reduced, and the amount of light transmitted through the green region is also increased.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、公知の方法でカラーフィルタの緑色画素部のパターンの形成に用いることが出来る。典型的には、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物と、感光性樹脂とを必須成分して含むカラーフィルタ緑色画素部用感光性組成物を得ることが出来る。 The polyhalogenated zinc phthalocyanine pigment composition of the present invention can be used for forming a pattern of a green pixel portion of a color filter by a known method. Typically, a photosensitive composition for a color filter green pixel portion containing the polyhalogenated zinc phthalocyanine pigment composition of the present invention and a photosensitive resin as essential components can be obtained.
カラーフィルタ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顔料組成物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, after the polyhalogenated zinc phthalocyanine pigment composition is dispersed in a dispersion medium made of a photosensitive resin, a transparent substrate such as glass is formed by a spin coating method, a roll coating method, an ink jet method, or the like. There is a method called photolithography, which is applied onto the coating film, and then subjected to pattern exposure with ultraviolet rays through a photomask, and then the 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、カラーフィルタを製造してもよい。なお、赤色画素部のパターンおよび青色画素部の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. In addition, the pattern of a red pixel part and the pattern of a blue pixel part can also be formed by the same method using a well-known pigment.
カラーフィルタ緑色画素部用感光性組成物を調製するには、例えば、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物と、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顔料組成物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調製する方法が一般的である。 To prepare the photosensitive composition for the color filter green pixel portion, for example, the polyhalogenated zinc phthalocyanine pigment composition of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin. Is mixed as an essential component. As a production method thereof, a method of preparing a dispersion by using a polyhalogenated zinc phthalocyanine pigment composition, an organic solvent, and a dispersant as required, and then adding a photosensitive resin to the dispersion is generally used. It is.
ここでのポリハロゲン化亜鉛フタロシアニン顔料組成物としては、上記フタロシアニン誘導体を含んでいても含んでいなくても良いポリハロゲン化亜鉛フタロシアニン顔料組成物と、必要に応じて黄色顔料を用いることが出来る。 As the polyhalogenated zinc phthalocyanine pigment composition here, a polyhalogenated zinc phthalocyanine pigment composition which may or may not contain the phthalocyanine derivative, and a yellow pigment as necessary can be used. .
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（ｄｉｓｐｅｒｂｙＫ登録商標）１３０、同１６１、同１６２、同１６３、同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 Big Chemie's Disperbyk (registered K registered trademark) 130, 161, 162, 163, and 170, and 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.
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.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物１００質量部当たり、３００〜１０００質量部の有機溶剤と、必要に応じて０〜１００質量部の分散剤及び／又は０〜２０質量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して分散液を得ることができる。次いでこの分散液に、ポリハロゲン化亜鉛フタロシアニン顔料組成物１質量部当たり、３〜２０質量部の感光性樹脂、感光性樹脂１質量部当たり０．０５〜３質量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してカラーフィルタ緑色画素部用感光性組成物を得ることができる。 300 to 1000 parts by mass of an organic solvent, and optionally 0 to 100 parts by mass of a dispersant and / or 0 to 20 parts by mass of a phthalocyanine derivative, per 100 parts by mass of the polyhalogenated zinc phthalocyanine pigment composition of the present invention. Can be stirred and dispersed to obtain a dispersion. Next, to this dispersion, 3 to 20 parts by weight of the photosensitive resin per 1 part by weight of the polyhalogenated zinc phthalocyanine pigment composition, 0.05 to 3 parts by weight of the photopolymerization initiator per 1 part by weight of the photosensitive resin, If necessary, an organic solvent can be further added and stirred and dispersed so as to be uniform, whereby a photosensitive composition for a color filter green pixel portion can be obtained.
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.
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.
こうして調製されたカラーフィルタ緑色画素部用感光性組成物は、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となすことができる。 The thus-prepared photosensitive composition for green color pixel portion of the color filter becomes 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. Can do.
本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、より黄味の緑色で着色力が高く、高色純度でコントラストの高い明るい緑色を発色する。従って、詳述したカラーフィルタ用以外にも、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 pigment composition of the present invention develops a bright green color with a high yellow color and high coloring power, high color purity and high contrast. Therefore, it is suitable for coloring paints, plastics, printing inks, rubber, leather, textile printing, electronic toners, jet inks, thermal transfer inks and the like in addition to the color filters described in detail.
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］
フタロニトリル、アンモニア、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、塩化スルフリル４５．５部、無水塩化アルミニウム５４．５部、塩化ナトリウム７．５部を４０℃で混合し、亜鉛フタロシアニン１５部を加える。これに臭素７４部を滴下して加え、２５時間かけて１３０℃まで昇温し1時間保持する。その後反応混合物を水に取り出し、ポリ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ハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 1]
Zinc phthalocyanine was produced from phthalonitrile, ammonia and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm.
For halogenation, 45.5 parts of sulfuryl chloride, 54.5 parts of anhydrous aluminum chloride and 7.5 parts of sodium chloride are mixed at 40 ° C., and 15 parts of zinc phthalocyanine is added. 74 parts of bromine is added dropwise thereto, and the temperature is raised to 130 ° C. over 25 hours and held for 1 hour. The reaction mixture is then taken up in water and the polyhalogenated zinc phthalocyanine crude pigment is precipitated. 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 a purified polyhalogenated zinc phthalocyanine crude pigment Got.
このポリハロゲン化亜鉛フタロシアニン粗顔料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。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕し、ポリハロゲン化亜鉛フタロシアニン顔料組成物Ａを得た（以下、顔料組成物Ａ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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ZnPcBr12.8Cl2.9H0.3であった。
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 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, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition A (hereinafter referred to as pigment composition A).
This polyhalogenated zinc phthalocyanine pigment composition had an average composition of ZnPcBr 12.8 Cl 2.9 H 0.3 from mass spectrometry and halogen content analysis by flask combustion ion chromatography.
［製造例２］
フタロニトリル、アンモニア、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、塩化スルフリル４５．５部、無水塩化アルミニウム５４．５部、塩化ナトリウム７．５部を４０℃混合し、亜鉛フタロシアニン１５部を加える。これに臭素７２部を滴下して加え、２５．５時間かけて１３０℃まで昇温し1時間保持する。その後反応混合物を水に投入し、ポリ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、７％のトルエンを含んだアセトン洗浄、６０℃の湯洗浄を行い、９０℃で乾燥させ、２．６部の精製されたポリハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 2]
Zinc phthalocyanine was produced from phthalonitrile, ammonia and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm. For halogenation, 45.5 parts of sulfuryl chloride, 54.5 parts of anhydrous aluminum chloride and 7.5 parts of sodium chloride are mixed at 40 ° C., and 15 parts of zinc phthalocyanine is added. 72 parts of bromine is added dropwise thereto, and the temperature is raised to 130 ° C. over 25.5 hours and held for 1 hour. Thereafter, the reaction mixture is poured into water to precipitate a polyhalogenated 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 acetone containing 7% toluene, washed with hot water at 60 ° C., dried at 90 ° C., and 2.6 parts. A purified polyhalogenated zinc phthalocyanine crude pigment was obtained.
このポリハロゲン化亜鉛フタロシアニン粗顔料１部、粉砕した塩化ナトリウム７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、８０℃で８時間混練した。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕し、ポリハロゲン化亜鉛フタロシアニン顔料組成物Ｂを得た（以下、顔料組成物Ｂ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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。
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride and 1 part of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition B (hereinafter referred to as pigment composition B).
This polyhalogenated zinc phthalocyanine pigment composition 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.
［製造例３］
フタロニトリル、アンモニア、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、塩化スルフリル５５部、無水塩化アルミニウム５４．５部、塩化ナトリウム７部を４０℃で混合し、亜鉛フタロシアニン１５部を加える。これに臭素７５部を滴下して加え、２５．２５時間かけて１３０℃まで昇温し1時間保持する。その後反応混合物を水に取り出し、ポリ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ハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 3]
Zinc phthalocyanine was produced from phthalonitrile, ammonia and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm.
For halogenation, 55 parts of sulfuryl chloride, 54.5 parts of anhydrous aluminum chloride and 7 parts of sodium chloride are mixed at 40 ° C., and 15 parts of zinc phthalocyanine is added. 75 parts of bromine is added dropwise thereto, and the temperature is raised to 130 ° C. over 25.25 hours and held for 1 hour. The reaction mixture is then taken up in water and the polyhalogenated zinc phthalocyanine crude pigment is precipitated. 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 a purified polyhalogenated zinc phthalocyanine crude pigment Got.
[比較例１]
このポリハロゲン化亜鉛フタロシアニン粗顔料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。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕し、ポリハロゲン化亜鉛フタロシアニン顔料組成物Ｃを得た（以下、顔料組成物Ｃ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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ZnPcBr14.2Cl1.5H0.3であった。
[Comparative Example 1]
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 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, it was taken out in 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition C (hereinafter referred to as pigment composition C).
This polyhalogenated zinc phthalocyanine pigment composition had an average composition of ZnPcBr 14.2 Cl 1.5 H 0.3 based on halogen content analysis by mass spectrometry and flask combustion ion chromatography.
［製造例４］
フタロニトリル、アンモニア、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、塩化スルフリル５３．５部、無水塩化アルミニウム５４．５部、塩化ナトリウム７部を４０℃混合し、亜鉛フタロシアニン１５部を加える。これに臭素７５部を滴下して加え、２５．３時間かけて１３０℃まで昇温し1時間保持する。その後反応混合物を水に投入し、ポリ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、７％のトルエンを含んだアセトン洗浄、６０℃の湯洗浄を行い、９０℃で乾燥させ、２．６部の精製されたポリハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 4]
Zinc phthalocyanine was produced from phthalonitrile, ammonia and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm. For halogenation, 53.5 parts of sulfuryl chloride, 54.5 parts of anhydrous aluminum chloride and 7 parts of sodium chloride are mixed at 40 ° C., and 15 parts of zinc phthalocyanine is added. 75 parts of bromine is added dropwise thereto, and the temperature is raised to 130 ° C. over 25.3 hours and held for 1 hour. Thereafter, the reaction mixture is poured into water to precipitate a polyhalogenated 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 acetone containing 7% toluene, washed with hot water at 60 ° C., dried at 90 ° C., and 2.6 parts. A purified polyhalogenated zinc phthalocyanine crude pigment was obtained.
[比較例２]
このポリハロゲン化亜鉛フタロシアニン粗顔料１部、粉砕した塩化ナトリウム７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、８０℃で８時間混練した。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕し、ポリハロゲン化亜鉛フタロシアニン顔料組成物Ｄを得た（以下、顔料組成物Ｄ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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ZnPcBr13.3Cl2.2H0.5であった。
[Comparative Example 2]
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride and 1 part of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition D (hereinafter referred to as pigment composition D).
This polyhalogenated zinc phthalocyanine pigment composition had an average composition of ZnPcBr 13.3 Cl 2.2 H 0.5 from mass analysis and halogen content analysis by flask combustion ion chromatography.
［製造例５］
フタロニトリル、アンモニア、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、塩化スルフリル１５０部、無水塩化アルミニウム１７５部、塩化ナトリウム２２．６部を４０℃混合し、亜鉛フタロシアニン４８部を加える。これに臭素２７０部を滴下して加え、３８．７５時間かけて１３０℃まで昇温し３時間保持する。その後反応混合物を水に投入し、ポリ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、７％のトルエンを含んだアセトン洗浄、６０℃の湯洗浄を行い、９０℃で乾燥させ、２．６部の精製されたポリハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 5]
Zinc phthalocyanine was produced from phthalonitrile, ammonia and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm. For halogenation, 150 parts of sulfuryl chloride, 175 parts of anhydrous aluminum chloride and 22.6 parts of sodium chloride are mixed at 40 ° C., and 48 parts of zinc phthalocyanine are added. 270 parts of bromine is added dropwise thereto, and the temperature is raised to 130 ° C. over 38.75 hours and held for 3 hours. Thereafter, the reaction mixture is poured into water to precipitate a polyhalogenated 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 acetone containing 7% toluene, washed with hot water at 60 ° C., dried at 90 ° C., and 2.6 parts. A purified polyhalogenated zinc phthalocyanine crude pigment was obtained.
このポリハロゲン化亜鉛フタロシアニン粗顔料１部、粉砕した塩化ナトリウム７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、８０℃で８時間混練した。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕し、ポリハロゲン化亜鉛フタロシアニン顔料組成物Ｅを得た（以下、顔料組成物Ｅ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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ZnPcBr13.6Cl2.1H0.3であった。
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride and 1 part of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition E (hereinafter referred to as pigment composition E).
This polyhalogenated zinc phthalocyanine pigment composition had an average composition of ZnPcBr 13.6 Cl 2.1 H 0.3 from mass analysis and halogen content analysis by flask combustion ion chromatography.
［製造例６］
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取り出し、ポリ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ハロゲン化亜鉛フタロシアニン粗顔料を得た。
[Production Example 6]
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, and then the reaction mixture is taken out into water to precipitate a polyhalogenated 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 a purified polyhalogenated zinc phthalocyanine crude pigment Got.
[比較例３]
このポリハロゲン化亜鉛フタロシアニン粗顔料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。混練後８０℃の水１００部に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕しポリハロゲン化亜鉛フタロシアニン顔料組成物Ｆを得た（以下、顔料組成物Ｆ）。
このポリハロゲン化亜鉛フタロシアニン顔料組成物は、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ZnPcBr14Cl1Hであった。
[Comparative Example 3]
1 part of this polyhalogenated zinc phthalocyanine crude pigment, 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, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a polyhalogenated zinc phthalocyanine pigment composition F (hereinafter referred to as pigment composition F).
This polyhalogenated zinc phthalocyanine pigment composition had an average composition of ZnPcBr 14 Cl 1 H based on halogen content analysis by mass spectrometry and flask combustion ion chromatography.
これら実施例１〜３及び比較例１〜３の各ポリハロゲン化亜鉛フタロシアニン顔料組成物について、それを構成する、塩素原子と臭素原子の置換数が異なる各ポリハロゲン化亜鉛フタロシアニン顔料のモル％を、質量分析に基づいて置換基数に対応させて集計した結果を表１に示した。Ｂｒ＋Ｃｌ＝１６とは、臭素原子と塩素原子の和が１６のポリハロゲン化亜鉛フタロシアニン顔料を示す。 For each of the polyhalogenated zinc phthalocyanine pigment compositions of Examples 1 to 3 and Comparative Examples 1 to 3, the mol% of each of the polyhalogenated zinc phthalocyanine pigments having different numbers of substitution of chlorine atoms and bromine atoms is used. Table 1 shows the results of aggregation based on the number of substituents based on mass spectrometry. Br + Cl = 16 indicates a polyhalogenated zinc phthalocyanine pigment having a sum of bromine and chlorine atoms of 16.
尚、実施例１〜３のポリハロゲン化亜鉛フタロシアニン顔料組成物は、いずれも、一次粒子の平均粒子径が０．０１〜０．１０μｍの範囲内かつ縦横のアスペクト比が１〜３の範囲内であった。 In addition, as for the polyhalogenated zinc phthalocyanine pigment composition of Examples 1-3, all are within the range whose average particle diameter of a primary particle is 0.01-0.10 micrometer, and the aspect ratio of length and width is 1-3. Met.
表１ Table 1
上記の実施例１で得られた顔料組成物Ａ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Ａを製造した。
カラーフィルタの製造方法としては、顔料組成物１０部、Ｎ，Ｎ'−ジメチルホルムアミド２．５部、ＤｉｓｐｅｒｂｙＫ（登録商標）１６１（ビックケミー社製）６．７８部、ユーカーエステルＥＥＰ（ユニオン・カーバイド社製）８０．８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（アロニックス登録商標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登録商標 ＤＰＨＡ、日本化薬株式会社製）５．００部、ベンゾフェノン（ＫＡＹＡＣＵＲＥ登録商標 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、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とした。
これらの顔料組成物Ａから製造したカラーフィルタＡのＣ光源２°視野におけるＸＹＺ表色系での色度を、微分光高度計（大塚電子製ＭＣＰＤ−３０００）を使用し測定した（このときｙ＝０．４２０での色度を測定）。この結果を表２に示した。
A color filter A was produced by photolithography using the pigment composition A obtained in Example 1 as a green pigment.
As a method for producing a color filter, 10 parts of a pigment composition, 2.5 parts of N, N′-dimethylformamide, 6.78 parts of DisperbyK (registered trademark) 161 (manufactured by BYK Chemie), Euker ester EEP (Union Carbide) 80.8 parts of 0.5 mmφ sepul beads were added and dispersed for 1 hour with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix registered trademark M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerylate hexaacrylate (KAYARAD registered trademark DPHA, manufactured by Nippon Kayaku Co., Ltd.) ) 5.00 parts, benzophenone (KAYACURE registered trademark BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts and Euker ester EFP 13.5 parts were stirred with a dispersion stirrer to obtain a color resist. The color resist was applied to 1 mm thick glass so as to have a dry film thickness of 1 μm.
Subsequently, after pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed with an organic solvent to obtain a color filter.
The chromaticity in the XYZ color system of the color filter A produced from these pigment compositions A in the C light source 2 ° field of view was measured using a differential light altimeter (MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.). Measure chromaticity at 0.420). The results are shown in Table 2.
実施例１で得られた顔料組成物Ａを実施例２で得られた顔料組成物Ｂに代えた以外は、実施例５と同様にしてカラーフィルタＢを製造し、色度を測定した。この結果を表２に示した。 A color filter B was produced in the same manner as in Example 5 except that the pigment composition A obtained in Example 1 was replaced with the pigment composition B obtained in Example 2, and the chromaticity was measured. The results are shown in Table 2.
実施例１で得られた顔料組成物Ａを実施例３で得られた顔料組成物Ｅに代えた以外は、実施例４と同様にしてカラーフィルタＥを製造し、色度を測定した。この結果を表２に示した。 A color filter E was produced in the same manner as in Example 4 except that the pigment composition A obtained in Example 1 was replaced with the pigment composition E obtained in Example 3, and the chromaticity was measured. The results are shown in Table 2.
［比較例４〜６］
実施例４〜６と同様にして、比較例１〜３の顔料組成物Ｃ、Ｄ、Ｆ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を作製し、同様に色度を測定した。この結果を表２に示した。
[Comparative Examples 4 to 6]
In the same manner as in Examples 4 to 6, pigment compositions C, D, and F of Comparative Examples 1 to 3 were used as green pigments, color filters were produced by photolithography, and chromaticity was measured in the same manner. The results are shown in Table 2.
表２ Table 2
表２中のＹ値は、着色力の程度を示す指標の一つであり、カラーフィルタ分野においては、輝度の指標である。一方、ｘ値は、緑色における黄味の程度を示しており、色再現域の広さを推定するための指標の一つであると共に、カラーフィルタ分野においては、ＲＧＢ色再現域の広さを推定するための指標である。ｘ値が大きいほど、色相はより黄味が強い緑色であることになる。Ｙ値もｘ値も、数値が大きいほど好ましい。 The Y value in Table 2 is one of indices indicating the degree of coloring power, and is a brightness index in the color filter field. On the other hand, the x value indicates the degree of yellowishness in green, and is one of the indexes for estimating the width of the color reproduction range. In the color filter field, the width of the RGB color reproduction range is indicated. It is an index for estimation. The greater the x value, the greener the hue is more yellowish. Both the Y value and the x value are preferably as large as possible.
表２から明らかなように、本発明の顔料組成物から作られた実施例のカラーフィルタは、比較例に対し、Ｙ値が高くより高輝度であり、かつｘ値が高く色相がより黄味が強くより広い色再現域を表現出来ること示しており、カラーフィルタ用緑色顔料としてより望ましい特性を有していることは明白である。また本特許の最も好ましい範囲の顔料組成物から作られた実施例５及び６のカラーフィルタは、更にY値が高い値を示し、最も優れた特性を示していることがわかる。 As is clear from Table 2, the color filter of the example made from the pigment composition of the present invention has a higher Y value and higher luminance, and a higher x value and higher hue than the comparative example. Is strong and can express a wider color gamut, and clearly has more desirable characteristics as a green pigment for color filters. In addition, it can be seen that the color filters of Examples 5 and 6 made from the pigment composition in the most preferable range of this patent have a higher Y value and the most excellent characteristics.
以上説明したように、本発明のポリハロゲン化亜鉛フタロシアニン顔料組成物は、より黄味の強い色相を有し、さらに非常に高い輝度を示す。したがって、ディスプレー等の大画面用カラーフィルタの緑色画素部のパターン形成に最適である。 As described above, the polyhalogenated zinc phthalocyanine pigment composition of the present invention has a more yellowish hue and exhibits extremely high luminance. Therefore, it is most suitable for pattern formation of the green pixel portion of a large screen color filter such as a display.
Claims (4)
（１）塩素原子と臭素原子の和が１６である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料７２モル％以上１００モル％未満、
（２）塩素原子と臭素原子の和が１４〜１５である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料０モルを越えて２６モル％以下、かつ
（３）塩素原子と臭素原子の和が１３以下である下記一般式１のポリハロゲン化亜鉛フタロシアニン顔料０モルを越えて２モル％以下、
から構成されていることを特徴とするポリハロゲン化亜鉛フタロシアニン顔料組成物。
(1) A polyhalogenated zinc phthalocyanine pigment of the following general formula 1 having a sum of 16 chlorine atoms and bromine atoms of 72 mol% or more and less than 100 mol% ,
(2) The sum of chlorine atoms and bromine atoms is 14 to 15 and exceeds 26 mol% of the polyhalogenated zinc phthalocyanine pigment of the following general formula 1, and (3) the sum of chlorine atoms and bromine atoms is 13 2 mol% or less beyond the as polyhalogenated zinc phthalocyanine pigment 0 mol of the following general formulas 1 or less,
A polyhalogenated zinc phthalocyanine pigment composition comprising:
Priority Applications (1)
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