JP6851878B2 - Azo compounds or salts thereof, and pigment compositions containing them. - Google Patents
Azo compounds or salts thereof, and pigment compositions containing them. Download PDFInfo
- Publication number
- JP6851878B2 JP6851878B2 JP2017065381A JP2017065381A JP6851878B2 JP 6851878 B2 JP6851878 B2 JP 6851878B2 JP 2017065381 A JP2017065381 A JP 2017065381A JP 2017065381 A JP2017065381 A JP 2017065381A JP 6851878 B2 JP6851878 B2 JP 6851878B2
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- pigment
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- 239000000049 pigment Substances 0.000 title claims description 91
- 239000000203 mixture Substances 0.000 title claims description 57
- 150000003839 salts Chemical class 0.000 title claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- -1 azo compound Chemical class 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- 239000012860 organic pigment Substances 0.000 claims description 23
- 239000002270 dispersing agent Substances 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 4
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 239000000976 ink Substances 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 15
- 125000000753 cycloalkyl group Chemical group 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical group C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Chemical group O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical group OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- HDHQZCHIXUUSMK-UHFFFAOYSA-N 4-hydroxy-2-quinolone Chemical compound C1=CC=C2C(O)=CC(=O)NC2=C1 HDHQZCHIXUUSMK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 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 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ANZCWTMNWQPOQI-UHFFFAOYSA-N 2-(4-amino-3-sulfophenyl)-6-methyl-1,3-benzothiazole-7-sulfonic acid Chemical compound S1C2=C(S(O)(=O)=O)C(C)=CC=C2N=C1C1=CC=C(N)C(S(O)(=O)=O)=C1 ANZCWTMNWQPOQI-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101001057956 Homo sapiens 55 kDa erythrocyte membrane protein Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-XVBQNVSMSA-N [(1S,6R)-7-oxabicyclo[4.1.0]heptan-3-yl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CC[C@H]2O[C@H]2C1 FYYIUODUDSPAJQ-XVBQNVSMSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical group [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、液晶ディスプレイや撮像素子などの製造に使用されるカラーフィルター用レジストやインクジェット用インクに用いられるアゾ化合物又はそれらの塩、並びに該化合物を含有する流動性や透明性に優れる顔料組成物に関する。 The present invention relates to an azo compound or a salt thereof used in a color filter resist or an inkjet ink used in the manufacture of a liquid crystal display, an image sensor, or the like, and a pigment composition containing the compound and having excellent fluidity and transparency. Regarding.
塗料や印刷インキ、近年ではカラーフィルター用レジストやインクジェット用インクの着色剤として、顔料が利用されている。顔料は、耐熱性、耐候性、耐マイグレーション等の諸特性で、染料と比較して堅牢性の面で優れるが、一方で組成物にした際の凝集、沈降、経時的な粘度の増加、異種顔料と混合した際の色分かれ等の潜在的な問題を有している。 Pigments have been used as colorants for paints and printing inks, and in recent years, resists for color filters and ink jet inks. Pigments have various properties such as heat resistance, weather resistance, and migration resistance, and are superior to dyes in terms of toughness. On the other hand, pigments agglomerate, precipitate, increase viscosity over time, and are different from each other when made into a composition. It has potential problems such as color coding when mixed with pigments.
また最近では、液晶ディスプレイの高コントラスト化や撮像素子の微細化、インクジェットインクの高着色や高鮮明化等を達成するために、顔料の微粒子化および顔料組成物中における顔料の高濃度化の要求が高まっているが、粒子径の微細化に伴い、また顔料の高濃度化に伴い凝集が起こりやすくなり、安定な分散体を得ることが困難となっている。 Recently, in order to achieve high contrast of liquid crystal displays, miniaturization of image pickup elements, high coloring and high sharpening of inkjet inks, etc., there is a demand for finer pigments and higher pigment concentrations in pigment compositions. However, as the particle size becomes finer and the concentration of the pigment increases, aggregation tends to occur, making it difficult to obtain a stable dispersion.
こうした問題を解決するために、顔料自体の改良検討（顔料表面処理）や顔料に対して良好な吸着性を有する分散剤、界面活性剤の開発、および顔料誘導体等の提案がこれまでに行われてきた。顔料誘導体とは微粒子化する顔料と同構造あるいは類似構造の顔料に、酸性や塩基性等の置換基を導入した化合物で、顔料との親和性や吸着性を有し、且つ酸・塩基相互作用により分散剤とも強い結合力を有する為、顔料の微粒子化・分散安定化を向上する性質があり、顔料の粉砕・分散微粒子化工程等において使用されている。カラーフィルターやインクジェットで用いられる顔料としては、フタロシアニン系顔料、ジケトピロロピロール系顔料、アンスラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリン系顔料、イソインドリノン系顔料、アゾ系顔料、染料レーキ顔料等が挙げられ、特にフタロシアニン系顔料、アンスラキノン系顔料、キナクリドン系顔料を中心に数々の顔料誘導体が報告されてきた。例えば、顔料のスルホン化物あるいはその金属塩を顔料と混和する方法（特許文献１乃至３）、置換アミノメチル誘導体を混和する方法（特許文献４）フタルイミドメチル誘導体を混和する方法（特許文献５）等が知られている。 In order to solve these problems, improvement studies of the pigment itself (pigment surface treatment), development of dispersants and surfactants having good adsorptivity to pigments, and proposals of pigment derivatives and the like have been made so far. I came. A pigment derivative is a compound in which a substituent such as acidity or basicity is introduced into a pigment having the same structure or a structure similar to that of a pigment to be atomized, and has affinity and adsorptivity with the pigment and acid-base interaction. Because it has a strong binding force with the dispersant, it has the property of improving the fine particle formation and dispersion stabilization of the pigment, and is used in the pigment pulverization / dispersion fine particle formation step and the like. Pigments used in color filters and inkjets include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthracinone pigments, quinacridone pigments, dioxazine pigments, isoindolin pigments, isoindolinone pigments, and azo pigments. Dye lake pigments and the like have been mentioned, and a number of pigment derivatives have been reported, especially phthalocyanine pigments, anthracinone pigments and quinacridone pigments. For example, a method of mixing a sulfonated pigment or a metal salt thereof with a pigment (Patent Documents 1 to 3), a method of mixing a substituted aminomethyl derivative (Patent Document 4), a method of mixing a phthalimidomethyl derivative (Patent Document 5), and the like. It has been known.
これらの方法は、特定の骨格を有する顔料に対する効果は認められるものの、スルホン基、アミノメチル基、フタルイミドメチル基などを導入することが構造上難しい顔料に対しては、導入する置換基の数や位置の制御が難しく、結果として分散剤としての効果が不充分であり、しかも色調にも悪影響を及ぼす副生成物が多量に生成し、顔料分散液の品質が安定しない等の課題を有する。
また、これまでカラーフィルターのレッド用の顔料として広く使用されているピグメントレッド２５４を用いた顔料組成物は、透過率の向上が課題であった。
Although these methods are effective for pigments having a specific skeleton, the number of substituents to be introduced and the number of substituents to be introduced for pigments for which it is structurally difficult to introduce sulfone groups, aminomethyl groups, phthalimidemethyl groups, etc. It is difficult to control the position, and as a result, the effect as a dispersant is insufficient, and a large amount of by-products that adversely affect the color tone are generated, and the quality of the pigment dispersion is not stable.
Further, in the pigment composition using Pigment Red 254, which has been widely used as a pigment for red of a color filter, improvement in transmittance has been an issue.
本発明が解決しようとする課題は、Ｃ．Ｉ．ピグメントレッド２５４をはじめとするレッド系等の有機顔料を含む顔料組成物（顔料分散液）を、凝集、沈降、経時的な粘度の増加を引き起こすことなく顔料の微粒子化及び高濃度化することであり、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な組成物（分散体）を提供することにある。 The problem to be solved by the present invention is C.I. I. By making a pigment composition (pigment dispersion) containing organic pigments such as red pigments such as Pigment Red 254 into fine particles and increasing the concentration of the pigment without causing aggregation, sedimentation, and an increase in viscosity over time. An object of the present invention is to provide a stable composition (dispersion) as a colorant for a color filter resist or an inkjet ink.
本発明者は、上記の課題を解決するために鋭意検討した結果、アゾ誘導体からなる化合物を用いることにより、上記課題を解決し得ることを見出し、本発明を完成させたものである。
すなわち、本発明は、
（１）下記式（１）
As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by using a compound composed of an azo derivative, and has completed the present invention.
That is, the present invention
(1) The following formula (1)
（式（１）中、Ｒ1は水素原子、メチル基、又はエチル基を表す。Ｒ2乃至Ｒ5は水素原子、又は−ＳＯ3Ｍ基を表す。但し、Ｒ2乃至Ｒ5の少なくとも一つは−ＳＯ3Ｍ基を表す。Ｍは水素原子、アルカリ金属原子、アルカリ土類金属原子又は−ＮＺ1Ｚ2Ｚ3Ｚ4基を表す。Ｚ1乃至Ｚ4は水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のヒドロキシアルキル基、アラルキル基、炭素数５若しくは炭素数６のシクロアルキル基、アリール基、又は炭素数５若しくは炭素数６のシクロアルキル基が置換した炭素数１乃至４のアルキル基を表す。）で表される構造を有するアゾ化合物又はそれらの塩、
（２）Ｒ1、Ｒ3、及びＲ4、Ｒ5が水素原子であり、Ｒ2が−ＳＯ3Ｍ基であり、Ｍが水素原子、セシウム原子、カルシウム原子、バリウム原子又はロジンアンモニウム（アビエタ−８，１１，１３−トリエン−１８−アンモニウム）である前項（１）に記載のアゾ化合物又はそれらの塩、
（３）Ｍが水素原子、又はカルシウム原子である前項（２）に記載のアゾ化合物又はそれらの塩、
（４）前項（１）乃至（３）のいずれか一項に記載のアゾ化合物又はそれらの塩、有機顔料及び樹脂分散剤を含有する顔料組成物、
（５）樹脂分散剤がカチオン系の樹脂分散剤である前項（４）に記載の顔料組成物、
（６）有機顔料１００質量部に対するアゾ化合物又はそれらの塩の添加量が１乃至５０質量部である前項（４）又は（５）に記載の顔料組成物、
（７）有機顔料がジケトピロロピロール骨格を有する顔料である前項（４）乃至（６）のいずれか一項に記載の顔料組成物、
（８）前項（４）乃至（７）のいずれか一項に記載の顔料組成物、バインダー樹脂及び重合性化合物を含有するカラーレジスト、
（９）前項（１）乃至（３）のいずれか一項に記載のアゾ化合物又はそれらの塩を含有するインクジェット用インク組成物、及び
（１０）更に、少なくとも一種以上の有機溶媒を含有する前項（９）に記載のインクジェット用インク組成物、
に関する。
(In the formula (1), R 1 represents a hydrogen atom, a methyl group, or an ethyl group. R 2 to R 5 represent a hydrogen atom or a -SO 3 M group, provided that at least one of R 2 to R 5 is used. One represents -SO 3 M group. M represents hydrogen atom, alkali metal atom, alkaline earth metal atom or -NZ 1 Z 2 Z 3 Z 4 group. Z 1 to Z 4 are hydrogen atom and carbon number 1 A carbon substituted with an alkyl group of 4 to 4, a hydroxyalkyl group having 1 to 4 carbon atoms, an aralkyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group, or a cycloalkyl group having 5 or 6 carbon atoms. An azo compound having a structure represented by (representing an alkyl group of the number 1 to 4) or a salt thereof,
(2) R 1 , R 3 , and R 4 , R 5 are hydrogen atoms, R 2 is -SO 3 M group, M is hydrogen atom, cesium atom, calcium atom, barium atom or rosin ammonium (avieta). -8,11,13-triene-18-ammonium) The azo compound according to the previous item (1) or a salt thereof,
(3) The azo compound according to the previous item (2) or a salt thereof, wherein M is a hydrogen atom or a calcium atom.
(4) A pigment composition containing the azo compound according to any one of (1) to (3) above or a salt thereof, an organic pigment and a resin dispersant.
(5) The pigment composition according to (4) above, wherein the resin dispersant is a cationic resin dispersant.
(6) The pigment composition according to (4) or (5) above, wherein the amount of the azo compound or a salt thereof added to 100 parts by mass of the organic pigment is 1 to 50 parts by mass.
(7) The pigment composition according to any one of (4) to (6) above, wherein the organic pigment is a pigment having a diketopyrrolopyrrole skeleton.
(8) A color resist containing the pigment composition, binder resin and polymerizable compound according to any one of (4) to (7) above.
(9) An inkjet ink composition containing the azo compound according to any one of (1) to (3) above or a salt thereof, and (10) further containing at least one or more organic solvents. The inkjet ink composition according to (9),
Regarding.
本発明の式（１）で示されるアゾ化合物又はそれらの塩は製造が極めて容易であり、該化合物を使用することにより、Ｃ．Ｉ．ピグメントレッド２５４等の顔料を含む顔料組成物を、凝集、沈降、経時的な粘度の増加を引き起こすことなく微粒子化・高濃度化することが可能となり、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な分散体を得ることができる。 The azo compound represented by the formula (1) of the present invention or a salt thereof is extremely easy to produce, and by using the compound, C.I. I. A pigment composition containing a pigment such as Pigment Red 254 can be made into fine particles and have a high concentration without causing aggregation, precipitation, and an increase in viscosity over time, and is a colorant for color filter resists and inkjet inks. As a result, a stable dispersion can be obtained.
以下に本発明を詳細に説明する。
本発明のアゾ化合物又はそれらの塩は下記式（１）で表される構造を有する。
The present invention will be described in detail below.
The azo compound of the present invention or a salt thereof has a structure represented by the following formula (1).
本発明のアゾ化合物又はそれらの塩は、カラーフィルター用レジストやインクジェット用インクの着色剤として好適に用いることができる。以下、便宜上、「本発明のアゾ化合物又はそれらの塩」を含めて、単に「本発明の化合物」と簡略して記載することもある。 The azo compound of the present invention or a salt thereof can be suitably used as a colorant for a resist for a color filter or an ink for inkjet. Hereinafter, for convenience, the term "compound of the present invention" may be simply referred to as "the azo compound of the present invention or a salt thereof".
式（１）中、Ｒ1は水素原子、メチル基、又はエチル基を表す。
式（１）におけるＲ1としては、水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。
In formula (1), R 1 represents a hydrogen atom, a methyl group, or an ethyl group.
R 1 in the formula (1) is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
式（１）中、Ｒ2乃至Ｒ5は水素原子、又は−ＳＯ3Ｍ基を表す。但し、Ｒ2乃至Ｒ5の少なくとも一つは−ＳＯ3Ｍ基を表す。 In formula (1), R 2 to R 5 represent a hydrogen atom or a -SO 3 M group. However, at least one of R 2 to R 5 represents a -SO 3 M group.
式（１）中、Ｍは水素原子、アルカリ金属原子、アルカリ土類金属原子又は−ＮＺ1Ｚ2Ｚ3Ｚ4基を表す。Ｚ1乃至Ｚ4は素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のヒドロキシアルキル基、アラルキル基、炭素数５若しくは炭素数６のシクロアルキル基、アリール基、又は炭素数５若しくは炭素数６のシクロアルキル基が置換した炭素数１乃至４のアルキル基を表す。
式（１）中のＭが表すアルカリ金属原子及びアルカリ土類金属原子の具体例としては、リチウム原子、ナトリウム原子、カリウム原子、ルビジウム原子、セシウム原子、フランシウム原子、カルシウム原子、ストロンチウム原子、バリウム原子及びラジウム原子が挙げられ、リチウム原子、ナトリウム原子、カリウム原子、セシウム原子、カルシウム原子、ストロンチウム原子又はバリウム原子であることが好ましく、セシウム原子、カルシウム原子又はバリウム原子であることがよりこの好ましく、セシウム原子又はカルシウム原子であることが更に好ましく、カルシウム原子であることが特に好ましい。
尚、Ｍがアルカリ土類金属の場合、該−ＳＯ3Ｍ基との結合に関与しない一方の正の電荷は、負の電荷を有するいかなる物質や化合物等と結合していても構わず、これらは全て本発明の式（１）で表される構造を有するアゾ化合物またはそれらの塩の範疇に含まれる。
In formula (1), M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or -NZ 1 Z 2 Z 3 Z 4 groups. Z 1 to Z 4 are elementary atoms, alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups having 1 to 4 carbon atoms, aralkyl groups, cycloalkyl groups having 5 or 6 carbon atoms, aryl groups, or 5 carbon atoms. Alternatively, it represents an alkyl group having 1 to 4 carbon atoms substituted with a cycloalkyl group having 6 carbon atoms.
Specific examples of the alkali metal atom and alkaline earth metal atom represented by M in the formula (1) include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, franchium atom, calcium atom, strontium atom, and barium atom. And a radium atom, preferably a lithium atom, a sodium atom, a potassium atom, a cesium atom, a calcium atom, a strontium atom or a barium atom, and more preferably a cesium atom, a calcium atom or a barium atom. It is more preferably an atom or a calcium atom, and particularly preferably a calcium atom.
When M is an alkaline earth metal, one of the positive charges that does not participate in the bond with the -SO 3 M group may be bonded to any substance or compound having a negative charge. Are all included in the category of azo compounds having a structure represented by the formula (1) of the present invention or salts thereof.
式（１）中のＺ1乃至Ｚ4が表す炭素数１乃至４のアルキル基は直鎖、分岐鎖のいずれでもよいが、直鎖であることが好ましく、その具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基及びｔｅｒｔ−ブチル基等が挙げられ、好ましくはメチル基又はエチル基である。
式（１）中のＺ1乃至Ｚ4が表すヒドロキシアルキル基の具体例としては、ヒドロキシメチル基、ヒドロキシエチル基、３−ヒドロキシプロピル基、２−ヒドロキシプロピル基、４−ヒドロキシブチル基、３−ヒドロキシブチル基及び２−ヒドロキシブチル基等が挙げられ、好ましくはヒドロキシエチル基である。
式（１）中のＺ1乃至Ｚ4が表すアラルキル基の具体例としては、ベンジル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基が挙げられ、好ましくはベンジル基である。
式（１）中のＺ1乃至Ｚ4が表す炭素数５若しくは炭素数６のシクロアルキル基の具体例としては、シクロペンチル基、シクロヘキシル基が挙げられ、好ましくはシクロヘキシル基である。尚、ここで言うシクロアルキル基は飽和炭化水素環および／又は不飽和炭化水素環で増環されていてもよく、シクロアルキル基の環上の水素原子および／又は増環上の水素原子はアルキル基等の置換基で置換されていてもよい。増環されており、かつアルキル基を有する炭素数５若しくは炭素数６のシクロアルキル基を有する−ＮＺ1Ｚ2Ｚ3Ｚ4基の具体例としては、ロジンアンモニウム（アビエタ−８，１１，１３−トリエン−１８−アンモニウム）が好ましい。
式（１）中のＺ1乃至Ｚ4が表すアリール基の具体例としては、フェニル基及びナフチル基が挙げられ、好ましくはフェニル基である。
The alkyl group having 1 to 4 carbon atoms represented by Z 1 to Z 4 in the formula (1) may be either a straight chain or a branched chain, but is preferably a straight chain, and specific examples thereof include a methyl group. Examples thereof include an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group, and a methyl group or an ethyl group is preferable.
Specific examples of the hydroxyalkyl groups represented by Z 1 to Z 4 in the formula (1) include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and 3-. Examples thereof include a hydroxybutyl group and a 2-hydroxybutyl group, and a hydroxyethyl group is preferable.
Specific examples of the aralkyl group represented by Z 1 to Z 4 in the formula (1) include a benzyl group, a phenylethyl group, a phenylpropyl group and a phenylbutyl group, and a benzyl group is preferable.
Specific examples of the cycloalkyl group having 5 or 6 carbon atoms represented by Z 1 to Z 4 in the formula (1) include a cyclopentyl group and a cyclohexyl group, and a cyclohexyl group is preferable. The cycloalkyl group referred to here may be expanded with a saturated hydrocarbon ring and / or an unsaturated hydrocarbon ring, and the hydrogen atom on the ring of the cycloalkyl group and / or the hydrogen atom on the expanded ring is alkyl. It may be substituted with a substituent such as a group. Specific examples of -NZ 1 Z 2 Z 3 Z 4 groups having a cycloalkyl group having 5 carbon atoms or 6 carbon atoms which are ring-reinforced and have an alkyl group include rosin ammonium (avieta-8,11,13). −Triene-18-ammonium) is preferred.
Specific examples of the aryl group represented by Z 1 to Z 4 in the formula (1) include a phenyl group and a naphthyl group, and a phenyl group is preferable.
式（１）中のＺ1乃至Ｚ4が表す炭素数５若しくは炭素数６のシクロアルキル基が置換した炭素数１乃至４のアルキル基とは、炭素数５若しくは炭素数６のシクロアルキル基を置換基として有する炭素数１乃至４のアルキル基、即ちシクロアルキル置換アルキル基であり、該シクロアルキルアルキル基中の炭素数５若しくは炭素数６のシクロアルキル基の具体例としては、式（１）中のＺ1乃至Ｚ4が表す炭素数５若しくは炭素数６のシクロアルキル基の具体例と同じものが挙げられ、また該シクロアルキル基中の炭素数１乃至４のアルキル基の具体例としては、式（１）中のＺ1乃至Ｚ4が表す炭素数１乃至４のアルキル基の具体例と同じものが挙げられる。 The alkyl group having 1 to 4 carbon atoms substituted by the cycloalkyl group having 5 or 6 carbon atoms represented by Z 1 to Z 4 in the formula (1) is a cycloalkyl group having 5 or 6 carbon atoms. An alkyl group having 1 to 4 carbon atoms as a substituent, that is, a cycloalkyl-substituted alkyl group, and a specific example of the cycloalkyl group having 5 or 6 carbon atoms in the cycloalkylalkyl group is the formula (1). Specific examples of cycloalkyl groups having 5 or 6 carbon atoms represented by Z 1 to Z 4 in the group can be mentioned, and specific examples of alkyl groups having 1 to 4 carbon atoms in the cycloalkyl group include those. , The same specific examples of alkyl groups having 1 to 4 carbon atoms represented by Z 1 to Z 4 in the formula (1) can be mentioned.
式（１）におけるＭとしては水素原子、バリウム原子、カルシウム原子、セシウム原子又はロジンアンモニウム（アビエタ−８，１１，１３−トリエン−１８−アンモニウム）が好ましく、水素原子又はカルシウム原子がより好ましい。
式（１）におけるＲ2乃至Ｒ5としては、Ｒ2がＳＯ3Ｍ基であって、Ｒ3乃至Ｒ5の全てが水素原子であるか若しくはＲ3乃至Ｒ5のいずれか一つがＳＯ3Ｍ基で残りの二つが水素原子であること、又はＲ２、Ｒ4及びＲ5が水素原子であって、Ｒ3がＳＯ3Ｍ基であることが好ましく、Ｒ2がＳＯ3Ｍ基であって、Ｒ3乃至Ｒ5の全てが水素原子であるか若しくはＲ3が水素原子でＲ4とＲ5の一方が水素原子で他方がＳＯ3Ｍ基であること、又はＲ２、Ｒ4及びＲ5が水素原子であって、Ｒ3がＳＯ3Ｍ基であることがより好ましく、Ｒ2がＳＯ3Ｍ基であって、Ｒ3乃至Ｒ5の全てが水素原子であることが更に好ましい。
As M in the formula (1), a hydrogen atom, a barium atom, a calcium atom, a cesium atom or a rosin ammonium (avieta-8,11,13-triene-18-ammonium) is preferable, and a hydrogen atom or a calcium atom is more preferable.
As R 2 to R 5 in the formula (1), R 2 is an SO 3 M group and all of R 3 to R 5 are hydrogen atoms, or any one of R 3 to R 5 is SO 3 It is preferable that there are M groups and the remaining two are hydrogen atoms, or R 2 , R 4 and R 5 are hydrogen atoms and R 3 is SO 3 M groups, and R 2 is SO 3 M groups. There, all of R 3 to R 5 are hydrogen atoms, or R 3 is a hydrogen atom and one of R 4 and R 5 is a hydrogen atom and the other is a SO 3 M group, or R 2 , R 4 and a R 5 is a hydrogen atom, more preferably R 3 is SO 3 M group, a R 2 is SO 3 M group, further that all R 3 to R 5 is a hydrogen atom preferable.
本発明の式（１）で表されるアゾ化合物又はそれらの塩としては、上記したＲ1乃至Ｒ5Ｍ（並びに−ＮＺ1Ｚ2Ｚ3Ｚ4基中のＭ、Ｚ1乃至Ｚ4）それぞれの好ましいものを組み合わせた化合物又はそれらの塩がより好ましく、より好ましいものを組み合わせた化合物又はそれらの塩が更に好ましい。 Examples of the azo compound represented by the formula (1) of the present invention or a salt thereof include the above-mentioned R 1 to R 5 M (and M, Z 1 to Z 4 in -NZ 1 Z 2 Z 3 Z 4 groups). Compounds in which each of the preferred compounds is combined or salts thereof are more preferable, and compounds in which more preferred compounds are combined or salts thereof are further preferred.
式（１）の化合物を造塩する際に用いられるアミンとしては、例えば、アンモニア、ジエチルアミン、トリエタノールアミン、ベンジルアミン、ロジンアミン（１８−アミノアビエタ−８，１１，１３−トリエン）等が挙げられる。 Examples of the amine used when salt-forming the compound of the formula (1) include ammonia, diethylamine, triethanolamine, benzylamine, rosinamine (18-aminoavieta-8,11,13-triene) and the like.
前記式（１）で表されるアゾ化合物の塩は、遊離酸やその互変異性体、およびそれら各種の塩の混合物であってもよい。例えば遊離酸とアンモニウム塩の混合物、遊離酸とカルシウム塩の混合物、リチウム塩、セシウム塩および遊離酸の混合物など、いずれの組み合わせを用いても良い。塩の種類によって溶解性などの物性値が異なる場合も有り、必要に応じて適宜塩の種類を選択したり、複数の塩などを含む場合にはその比率を変化させることにより、目的に適う物性を有する混合物を得ることもできる。 The salt of the azo compound represented by the formula (1) may be a free acid, a tautomer thereof, or a mixture of various salts thereof. Any combination may be used, for example, a mixture of free acid and ammonium salt, a mixture of free acid and calcium salt, a mixture of lithium salt, cesium salt and free acid. Physical properties such as solubility may differ depending on the type of salt, and the physical properties suitable for the purpose can be selected by appropriately selecting the type of salt as necessary, or by changing the ratio when multiple salts are contained. It is also possible to obtain a mixture having.
式（１）で示される本発明のアゾ化合物は、例えば、下記式（２）で表される化合物をジアゾ化した後、下記式（３）で表される化合物とカップリング反応を行うことにより、合成することが出来る。下記式（２）及び（３）においてＲ1乃至Ｒ5、及びＭは上記式（１）におけるＲ1乃至Ｒ5、及びＭと同じ意味を表す。 The azo compound of the present invention represented by the formula (1) is obtained by, for example, diazotizing the compound represented by the following formula (2) and then performing a coupling reaction with the compound represented by the following formula (3). , Can be synthesized. Following formula (2) and R 1 to R 5 in (3), and M have the same meanings as R 1 to R 5, and M in the formula (1).
前記式（１）で表される本発明の化合物の具体例を下記表１に示すが、本発明はこれらの具体例に限定されるものではない。 Specific examples of the compound of the present invention represented by the above formula (1) are shown in Table 1 below, but the present invention is not limited to these specific examples.
なお、下記表１内にある略語は、以下の意味を有する。
Ｈ：水素原子、Ｍｅ：メチル基、Ｃａ：カルシウム原子、Ｃｓ：セシウム原子、Ｂａ：バリウム原子
The abbreviations in Table 1 below have the following meanings.
H: Hydrogen atom, Me: Methyl group, Ca: Calcium atom, Cs: Cesium atom, Ba: Barium atom
本発明の顔料組成物は、本発明の化合物、有機顔料及び樹脂分散剤を含有する。
本発明の顔料組成物が含有する有機顔料は、カラーインデックスに記載されたものなど従来公知のものであれば特に限定されないが、本発明の式（１）で表される化合物自体がレッド系の色相を有するため、有機顔料本来の色相を損なわない意味ではレッド系の有機顔料を用いるのが好ましく、カラーインデックスでピグメントレッドに分類される有機顔料を用いるのがより好ましく、Ｃ．Ｉ．ピグメントレッド２５４が更に好ましい。また、本発明の化合物と混合した際の分散安定性に優れるという意味で、顔料組成物が含有する有機顔料は、ジケトピロロピロール骨格を有する有機顔料であることが好ましい。
The pigment composition of the present invention contains the compound of the present invention, an organic pigment and a resin dispersant.
The organic pigment contained in the pigment composition of the present invention is not particularly limited as long as it is conventionally known, such as those described in the color index, but the compound itself represented by the formula (1) of the present invention is red. Since it has a hue, it is preferable to use a red-based organic pigment in the sense that the original hue of the organic pigment is not impaired, and it is more preferable to use an organic pigment classified as pigment red by the color index. I. Pigment Red 254 is even more preferred. Further, the organic pigment contained in the pigment composition is preferably an organic pigment having a diketopyrrolopyrrole skeleton in the sense that it is excellent in dispersion stability when mixed with the compound of the present invention.
本発明の顔料組成物が含有する樹脂分散剤は、公知の樹脂分散剤であれば特に限定されないが、本発明の化合物との親和性を考慮した場合、カチオン系の樹脂分散剤が好ましい。カチオン系の樹脂分散剤としては、例えば、ビッグケミージャパン株式会社のＢＹＫ１１２、１１６、１４０、１４２、１６１、１６２、１６４、１６６、１８２、２０００、２００１、２０５０、２０７０、２１５０、エフカ社のＥＦＫＡ４０１０、４０１５、４０２０、４０５０、４０５５、４０６０、４３００、４３３０、４４００、４４０６、日本ルーブリゾール株式会社のソルスパース、２４０００、３２５００、味の素ファインテクノ社のアジスパーＰＢ７１１、８２１、８２２、８８１などが挙げられる。樹脂分散剤の添加量は、有機顔料１００質量部に対して通常５乃至１００質量部、好ましくは１０乃至５０質量部である。樹脂分散剤の添加量が５質量部よりも少ない場合は、良好な分散安定性を得ることができない。 The resin dispersant contained in the pigment composition of the present invention is not particularly limited as long as it is a known resin dispersant, but a cationic resin dispersant is preferable in consideration of affinity with the compound of the present invention. Examples of the cationic resin dispersant include BYK112, 116, 140, 142, 161, 162, 164, 166, 182, 2000, 2001, 2050, 2070, 2150 of Big Chemie Japan Co., Ltd., and EFKA4010 of Fuka Co., Ltd. Examples thereof include 4015, 4020, 4050, 4055, 4060, 4300, 4330, 4400, 4406, Solspers of Japan Lubrizol Co., Ltd., 24000, 32500, and Ajinomoto Fine-Techno's Ajisper PB711, 821, 822, 881. The amount of the resin dispersant added is usually 5 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the organic pigment. When the amount of the resin dispersant added is less than 5 parts by mass, good dispersion stability cannot be obtained.
本発明の顔料組成物には、必要により有機溶剤を加えることができる。用い得る有機溶剤は特に限定されないが、例えば、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メチルエーテル、プロピレングリコールモノエチルエーテル、エチルセロソルブアセテート、ブチルセロソルブアセテート、エチルセロソルブ、シクロヘキサノン、シクロペンタノン、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、酢酸エチル、酢酸ブチル、メタノール、エタノール、イソプロピルアルコールなどが挙げられる。これらは単独で用いても２種以上を混合して用いてもよい。有機溶剤は顔料組成物中に９０質量％以下を占める量が用いられる。 If necessary, an organic solvent can be added to the pigment composition of the present invention. The organic solvent that can be used is not particularly limited, and for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve, cyclohexanone, cyclopentanone, ethylene glycol diethyl ether, Examples thereof include diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, methanol, ethanol and isopropyl alcohol. These may be used alone or in combination of two or more. The amount of the organic solvent used is 90% by mass or less in the pigment composition.
本発明のカラーレジストは、本発明の顔料組成物、バインダー樹脂及び重合性化合物を含有する。
本発明のカラーレジストに用い得るバインダー樹脂は特に限定されないが、例えば、スチレン系（共）重合体、（メタ）アクリル酸エステル系（共）重合体、スチレン−マレイン酸エステル系共重合体、セルロースアセテート系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂などが挙げられる。これらは単独で用いても２種類以上を組み合わせて用いてもよい。バインダー樹脂は顔料組成物中に５０質量％以下を占める量が用いられる。
The color resist of the present invention contains the pigment composition, binder resin and polymerizable compound of the present invention.
The binder resin that can be used for the color resist of the present invention is not particularly limited, and for example, a styrene-based (co) polymer, a (meth) acrylic acid ester-based (co) polymer, a styrene-maleic acid ester-based copolymer, and cellulose. Examples thereof include acetate-based resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, and polyimide-based resins. These may be used alone or in combination of two or more. The amount of the binder resin used is 50% by mass or less in the pigment composition.
本発明のカラーフィルターレジストに用い得る重合性化合物としては、光重合モノマー、エポキシ化合物及びメラミン系化合物等が挙げられる。これらの重合性化合物の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコー（メタ）アクリレート、テトラエチレングリコール（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセロール（メタ）アクリレート、ビスフェノール−Ａ型エポキシジ（メタ）アクリレート、ビスフェノール−Ｆ型エポキシジ（メタ）アクリレート、ビスフェノール−フルオレン型エポキシジ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化グリセリントリ（メタ）アクリレート、エトキシ化イソシアヌル酸トリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、９,９−ビス〔４−（２−アクリロイルオキシエトキシ）フェニル〕フルオレン、カヤラッドＲＰ−１０４０（日本化薬製）、カヤラッドＤＰＣＡ−３０（日本化薬製）、ＵＡ−３３Ｈ（新中村化学製)、ＵＡ−５３Ｈ（新中村化学製)及びＭ−８０６０（東亞合成製)等の（メタ）アクリレートモノマー；ＴＥＭＰＩＣ（堺化学製)、ＴＭＭＰ（堺化学製)、ＰＥＭＰ（堺化学製）及びＤＰＭＰ（堺化学製）等のチオール系重合モノマー；日本化薬製品のＮＣ−６０００、ＮＣ−６３００、ＮＣ−６３００Ｈ、ＮＣ−３０００、ＥＯＣＮ−１０２０、ＸＤ−１０００、ＥＰＰＮ−５０１Ｈ、ＢＲＥＮ−Ｓ、ＮＣ−７３００Ｌ、ダイセル化学製品のセロキサイト２０２１Ｐ、ＥＨＰＥ３１５０、サイクロマーＭ１００、エポリードＰＢ３６００、ジャパンエポキシレジン製品のエピコート８２８、エピコートＹＸ８０００、エピコートＹＸ４０００、プリンテック製品のＶＧ−３１０１Ｌ、サイラエースＳ５１０（チッソ）、ＴＥＰＩＣ（日産化学工業）等のエポキシ化合物；並びにメチロール化メラミン及びＭｗ−３０（三和ケミカル）等のメラミン系化合物が挙げられるが、これらに限定されるものではない。
これらの重合性化合物には、必要により重合開始剤や硬化促進剤等を併用することが好ましい。
Examples of the polymerizable compound that can be used in the color filter resist of the present invention include photopolymerizable monomers, epoxy compounds, and melamine compounds. Specific examples of these polymerizable compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, Triethylene Glyco (Meta) Acrylate, Tetraethylene Glycol (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate , Dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, trimethyl ethoxylated Propanetri (meth) acrylate, propoxylated trimetyl propanetri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, ethoxylated pentaerythritol Tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayarad RP-1040 (manufactured by Nippon Kayaku), Kayarad DPCA-30 (manufactured by Nihon Kayaku), UA-33H (Meta) acrylate monomers such as (Shin-Nakamura Chemical), UA-53H (Shin-Nakamura Chemical) and M-8060 (Toa Synthetic); TEMPIC (Sakai Chemical), TMMP (Sakai Chemical), PEMP (Sakai) Thiol-based polymerized monomers such as (manufactured by Chemical) and DPMP (manufactured by Sakai Chemical); NC-6000, NC-6300, NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, Nippon Kayaku products. BREN-S, NC-7300L, Celokisite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin Products Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec Products VG-3101L, Cyra Ace S510 (Chisso) ), TEPIC (Nissan Chemical Industry), etc.; and methylolated melamine And melamine compounds such as Mw-30 (Sanwa Chemical), but are not limited thereto.
It is preferable to use a polymerization initiator, a curing accelerator, or the like in combination with these polymerizable compounds, if necessary.
本発明の顔料組成物に必要により加えることのできるその他の添加剤としては、例えばチクソ付与剤、重合開始剤や硬化剤、硬化促進剤、重合禁止剤、有機又は無機フィラー、カップリング剤等が挙げられるが、これらは顔料組成物の具体的な目的用途によって選択すればよく上記に限定されない。また、その添加量も、具体的な目的用途に合わせて選択すれば良い。 Other additives that can be added to the pigment composition of the present invention as necessary include, for example, thixo-imparting agents, polymerization initiators and curing agents, curing accelerators, polymerization inhibitors, organic or inorganic fillers, coupling agents and the like. These may be selected depending on the specific purpose and application of the pigment composition, and are not limited to the above. In addition, the amount of the addition may be selected according to the specific purpose and application.
本発明の顔料組成物は、例えば次のような方法で調整することができる。すなわち、有機顔料および本発明の化合物の配合の方法としては、従来公知の種々の方法、例えば、それぞれの乾燥粉末やプレスケーキを単に混合する方法やニーダー、ビーズミル、ディゾルバー、アトライター等の各種分散機により機械的に混合する方法、水又は有機溶剤中に有機顔料を懸濁させ、その中に本発明の化合物を添加混合して有機顔料の表面に均一に沈着する方法などが挙げられる。次に、得られた有機顔料および本発明の化合物の混合物に、樹脂分散剤と必要に応じて各種有機溶剤、樹脂ワニス、各種添加剤等を配合して、サンドミル、アニュラー型ビーズミル、アトライター等で分散することにより、所望の顔料組成物を製造することができる。或いは簡便的には、有機顔料、本発明の化合物及び樹脂分散剤と必要に応じてその他の成分を、一括で混合及び分散しても構わない。なお、本発明の顔料組成物における本発明の化合物の添加量は、有機顔料１００質量部に対して通常０．１乃至７０質量部であり、好ましくは０．５乃至６０質量部、より好ましくは１乃至５０質量部である。本発明の化合物の配合割合が少なすぎると、目的とする分散安定性および有機顔料の微粒子化が達成されず、また配合割合を増やしすぎても分散安定性の低下が認められるため、配合量の最適化が必要である。 The pigment composition of the present invention can be prepared, for example, by the following method. That is, as a method for blending the organic pigment and the compound of the present invention, various conventionally known methods, for example, a method of simply mixing the respective dry powders and press cakes, and various dispersions of a kneader, a bead mill, a dissolver, an attritor, etc. Examples thereof include a method of mechanically mixing by a machine, a method of suspending an organic pigment in water or an organic solvent, adding and mixing the compound of the present invention into the suspension, and uniformly depositing on the surface of the organic pigment. Next, a resin dispersant and, if necessary, various organic solvents, resin varnishes, various additives, etc. are mixed with the obtained mixture of the organic pigment and the compound of the present invention, and a sand mill, an annual bead mill, an attritor, etc. By dispersing in, a desired pigment composition can be produced. Alternatively, for convenience, the organic pigment, the compound of the present invention, the resin dispersant and, if necessary, other components may be mixed and dispersed all at once. The amount of the compound of the present invention added to the pigment composition of the present invention is usually 0.1 to 70 parts by mass, preferably 0.5 to 60 parts by mass, and more preferably 0.5 to 60 parts by mass with respect to 100 parts by mass of the organic pigment. It is 1 to 50 parts by mass. If the compounding ratio of the compound of the present invention is too small, the desired dispersion stability and fine particle formation of the organic pigment cannot be achieved, and if the compounding ratio is increased too much, the dispersion stability is lowered. Optimization is needed.
本発明の顔料組成物の用途は特に限定されず、例えばグラビア印刷インキなどの各種印刷インキ、塗料、電子写真用乾式トナー又は湿式トナー、インクジェット記録用インキ、カラーフィルター用レジスト着色剤などの種々の用途が挙げられる。特に、本発明の顔料組成物は、顔料の微粒子化および高い安定性が要求されるカラーフィルター用レジスト着色剤、インクジェット記録用インキとして有用である。 The use of the pigment composition of the present invention is not particularly limited, and various printing inks such as gravure printing inks, paints, dry or wet toners for electrophotographic photography, ink jet recording inks, resist colorants for color filters, and the like. Uses can be mentioned. In particular, the pigment composition of the present invention is useful as a resist colorant for a color filter and an ink for inkjet recording, which require fine particle formation and high stability of the pigment.
以下に本発明を実施例により具体的に説明する。尚、本文中「部」及び「％」とあるのは、特別の記載のない限り質量基準である。実施例における極大吸収波長は分光光度計「（株）島津製作所製ＵＶ−３１５０」で測定した値であり、酸価はＪＩＳ Ｋ−００７０：１９９２に準拠した測定方法で測定した値である。また、重量平均分子量はゲルパーミエイションクロマトグラフィーの測定結果に基づいて、ポリスチレン換算で算出した値である。 Hereinafter, the present invention will be specifically described with reference to Examples. In addition, "part" and "%" in the text are based on mass unless otherwise specified. The maximum absorption wavelength in the examples is a value measured by a spectrophotometer "UV-3150 manufactured by Shimadzu Corporation", and the acid value is a value measured by a measuring method based on JIS K-0070: 1992. The weight average molecular weight is a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography.
実施例１（上記具体例化合物のＮｏ．１で示される化合物の合成）
（工程１）
２−（３−スルホ−４−アミノフェニル）−６−メチルベンゾチアゾール−７−スルホン酸１４．４部を、水１５０部及び水酸化ナトリウムでｐＨ７に調整しながら溶解し、０乃至１０℃に冷却した後、３５％塩酸１１．３部及び亜硝酸ナトリウム２．６部を加え、１０℃以下で３０分間撹拌してジアゾ化反応を行い、ジアゾ反応液を調製した。一方、２，４−ジヒドロキシキノリン４．８部を、水酸化ナトリウムでｐＨ１０に調整しながら水２００部に溶解し、先に調製したジアゾ反応液を加え、０乃至１５℃、ｐＨ７．５乃至９．０で１時間撹拌した。反応液中に析出した固体を濾過分取することにより、具体例化合物Ｎｏ．１で示される化合物を含むウェットケーキ５０部を得た。
Example 1 (Synthesis of the compound represented by No. 1 of the above-mentioned specific example compound)
(Step 1)
14.4 parts of 2- (3-sulfo-4-aminophenyl) -6-methylbenzothiazole-7-sulfonic acid was dissolved in 150 parts of water and sodium hydroxide while adjusting the pH to 7 to 0 to 10 ° C. After cooling, 11.3 parts of 35% hydrochloric acid and 2.6 parts of sodium nitrite were added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out a diazotization reaction to prepare a diazo reaction solution. On the other hand, 4.8 parts of 2,4-dihydroxyquinoline was dissolved in 200 parts of water while adjusting the pH to 10 with sodium hydroxide, the previously prepared diazo reaction solution was added, and the pH was 7.5 to 9 at 0 to 15 ° C. The mixture was stirred at 0.0 for 1 hour. By filtering and separating the solid precipitated in the reaction solution, Specific Example Compound No. 50 parts of a wet cake containing the compound represented by 1 was obtained.
（工程２）
工程１で得られた具体例化合物Ｎｏ．１で示される化合物を含むウェットケーキ５０部を水５００部に懸濁させ、３５％塩酸を加えｐＨ１以下とし、１時間撹拌した後に、ろ過を行い、得られたウェットケーキを８０℃の熱風乾燥機で乾燥させることにより、具体例化合物Ｎｏ．１で示される化合物１０．８部を得た。該化合物の極大吸収波長λｍａｘは４５３ｎｍ（ＮＭＰ）であった。
(Step 2)
Specific Example Compound No. obtained in Step 1. 50 parts of the wet cake containing the compound shown in 1 was suspended in 500 parts of water, 35% hydrochloric acid was added to adjust the pH to 1 or less, the mixture was stirred for 1 hour, filtered, and the obtained wet cake was dried with hot air at 80 ° C. By drying with a machine, Specific Example Compound No. 10.8 parts of the compound represented by 1 was obtained. The maximum absorption wavelength λmax of the compound was 453 nm (NMP).
実施例２（上記具体例化合物のＮｏ．２で示される化合物の合成）
（工程３）
工程１で得られた具体例化合物Ｎｏ．１で表される化合物を含むウェットケーキ５０部を水５００部に懸濁させ、２５％水酸化ナトリウムを加え、ｐＨ９乃至１０とし、この懸濁液に塩化カルシウム１．７部を加え、１時間撹拌した後にろ過を行い、得られたウェットケーキを８０℃の熱風乾燥機で乾燥させることにより、具体例化合物Ｎｏ．２で示される化合物１１．４部を得た。該化合物の極大吸収波長λｍａｘは４５３ｎｍ（ＮＭＰ）であった。
Example 2 (Synthesis of the compound represented by No. 2 of the above-mentioned specific example compound)
(Step 3)
Specific Example Compound No. obtained in Step 1. 50 parts of a wet cake containing the compound represented by 1 is suspended in 500 parts of water, 25% sodium hydroxide is added to adjust the pH to 9 to 10, and 1.7 parts of calcium chloride is added to this suspension for 1 hour. After stirring, filtration was performed, and the obtained wet cake was dried in a hot air dryer at 80 ° C. to obtain Compound No. 11.4 parts of the compound represented by 2 was obtained. The maximum absorption wavelength λmax of the compound was 453 nm (NMP).
合成例１（バインダー樹脂Ａの調整）
５００ｍｌの四つ口フラスコにメチルエチルケトン１６０部、メタクリル酸１０部、ベンジルメタクリレート３３部、α，α’−アゾビス（イソブチロニトリル）１部を仕込み、攪拌しながら３０分間窒素ガスをフラスコ内に流入した。その後、８０℃まで昇温し、８０乃至８５℃でそのまま４時間攪拌した。反応終了後、室温まで冷却し、無色透明で均一なバインダー樹脂溶液を得た。これをイソプロピルアルコールと水の１：１混合溶液中で沈殿させ、濾過し、固形分を取り出し、乾燥させ、バインダー樹脂Ａを得た。得られたバインダー樹脂Ａのポリスチレン換算重量平均分子量は１８０００であり、酸価は１５２であった。
Synthesis Example 1 (Adjustment of binder resin A)
160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate, and 1 part of α, α'-azobis (isobutyronitrile) are charged in a 500 ml four-necked flask, and nitrogen gas flows into the flask for 30 minutes with stirring. did. Then, the temperature was raised to 80 ° C., and the mixture was stirred as it was at 80 to 85 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature to obtain a colorless, transparent and uniform binder resin solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a binder resin A. The polystyrene-equivalent weight average molecular weight of the obtained binder resin A was 18,000, and the acid value was 152.
実施例３（本発明の顔料組成物の調製）
有機顔料としてＣ．Ｉ．ピグメントレッド２５４ １０．０部、本発明の化合物として実施例１で得られたＮｏ．１で示される化合物１．０部、バインダー樹脂として合成例１で得られたアクリル樹脂Ａ１．８部、樹脂分散剤としてアジスパーＰＢ８８１（味の素ファインテクノ社製）、溶剤としてプロピレングリコールモノメチルエーテルアセテート８２部を配合し、プレミキシングの後、０．３ｍｍのジルコニアビーズを用いて、ペイントシェーカーで６０分間分散した。得られた分散液を５μｍのフィルタでろ過することにより顔料組成物を調製した。
Example 3 (Preparation of Pigment Composition of the Present Invention)
As an organic pigment, C.I. I. Pigment Red 254 10.0 parts, No. 1 obtained in Example 1 as the compound of the present invention. 1.0 part of the compound shown in 1, 1.8 parts of the acrylic resin A obtained in Synthesis Example 1 as the binder resin, Azisper PB881 (manufactured by Ajinomoto Fine-Techno) as the resin dispersant, 82 parts of propylene glycol monomethyl ether acetate as the solvent. Was compounded, and after premixing, it was dispersed in a paint shaker for 60 minutes using 0.3 mm zirconia beads. The pigment composition was prepared by filtering the obtained dispersion with a filter of 5 μm.
実施例４（本発明の顔料組成物の調製）
実施例１で得られたＮｏ．１で示される化合物の代わりに実施例２で得られたＮｏ．２で示される化合物を用いた以外は実施例３と同じ方法で、顔料組成物を調製した。
Example 4 (Preparation of Pigment Composition of the Present Invention)
No. obtained in Example 1. No. 1 obtained in Example 2 instead of the compound shown in 1. A pigment composition was prepared in the same manner as in Example 3 except that the compound shown in 2 was used.
比較例１（比較用の顔料組成物の調製）
実施例１で得られたＮｏ．１で示される化合物を用いなかったこと以外は実施例４と同じ方法で顔料組成物を調製した。
Comparative Example 1 (Preparation of Pigment Composition for Comparison)
No. obtained in Example 1. A pigment composition was prepared in the same manner as in Example 4 except that the compound shown in 1 was not used.
（顔料組成物の分散安定性評価）
実施例３、４及び比較例１で得られた顔料組成物について、Ｂ型粘度計を用い、室温（２５℃）１０ｒｐｍの条件で粘度を測定し、下記の基準で評価した。尚、保存安定性を確認するために、初期（調整直後）の他に４０℃で３日放置後の粘度も測定及び評価した。結果を表２に示した。
・評価基準
初期粘度：２０ｍＰａ・ｓ未満○、２０ｍＰａ・ｓ以上×
４０℃×３日後粘度増加率：２０％未満○、２０％以上×
尚、調製直後にゲル化したものについては、４０℃で３日放置後の粘度は「評価不能」とした。
(Evaluation of dispersion stability of pigment composition)
The pigment compositions obtained in Examples 3 and 4 and Comparative Example 1 were measured in viscosity at room temperature (25 ° C.) and 10 rpm using a B-type viscometer, and evaluated according to the following criteria. In addition to the initial stage (immediately after adjustment), the viscosity after standing at 40 ° C. for 3 days was also measured and evaluated in order to confirm the storage stability. The results are shown in Table 2.
・ Evaluation criteria Initial viscosity: less than 20 mPa ・ s ○, 20 mPa ・ s or more ×
40 ° C x 3 days Viscosity increase rate: Less than 20% ○, 20% or more ×
For the gelled product immediately after preparation, the viscosity after being left at 40 ° C. for 3 days was regarded as "unevaluable".
表２から明らかなように、実施例３及び４の顔料組成物は、本顔料誘導体を添加しない比較例１と比べて初期粘度が低く抑えられており、実際に使用する際の作業性並びにレジストやインクの品質を損なわないものである。更に保存安定性についても、比較例と比べて良好な結果を示した。
具体的には、実施例３及び４は比較例１がゲル化により分散不可であるのに対し、４０℃×３日後の粘度増加率は２０％以下であった。
As is clear from Table 2, the pigment compositions of Examples 3 and 4 have lower initial viscosities than Comparative Example 1 to which the present pigment derivative is not added, and the workability and resist in actual use are suppressed. And does not impair the quality of the ink. Furthermore, the storage stability was also better than that of the comparative example.
Specifically, in Examples 3 and 4, while Comparative Example 1 could not be dispersed due to gelation, the viscosity increase rate after 40 ° C. × 3 days was 20% or less.
本発明のアゾ化合物を用いることにより、凝集、沈降、経時的な粘度の増加をすることなく、微粒子化・高濃度化することが可能であり、顔料誘導体は、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な分散体を得るために非常に有用である。
By using the azo compound of the present invention, it is possible to make fine particles and increase the concentration without aggregation, sedimentation, and increase in viscosity with time, and the pigment derivative can be a color filter resist or an inkjet ink. As a colorant for Azo, it is very useful for obtaining a stable dispersion.
Claims (8)
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