JP2007070568A - Aqueous pigment dispersion and aqueous ink for inkjet recording - Google Patents
Aqueous pigment dispersion and aqueous ink for inkjet recording Download PDFInfo
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- JP2007070568A JP2007070568A JP2005262108A JP2005262108A JP2007070568A JP 2007070568 A JP2007070568 A JP 2007070568A JP 2005262108 A JP2005262108 A JP 2005262108A JP 2005262108 A JP2005262108 A JP 2005262108A JP 2007070568 A JP2007070568 A JP 2007070568A
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- Prior art keywords
- copolymer
- water
- pigment dispersion
- unsaturated monomer
- ink
- Prior art date
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- Granted
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- 239000006185 dispersion Substances 0.000 title claims abstract description 90
- 239000000049 pigment Substances 0.000 title claims abstract description 90
- 229920001577 copolymer Polymers 0.000 claims abstract description 110
- 239000000178 monomer Substances 0.000 claims abstract description 77
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012860 organic pigment Substances 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 33
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 18
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 6
- 239000000976 ink Substances 0.000 description 52
- 239000002253 acid Substances 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- -1 2-phenoxyethyl Chemical group 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 230000002378 acidificating effect Effects 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000011324 bead Substances 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
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [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
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 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 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 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 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 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 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-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
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 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 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
Abstract
Description
本発明は、専用紙における光沢性が改良されたインクジェット記録用水性インク及びそれを容易に調製することが出来る水性顔料分散体に関する。 The present invention relates to a water-based ink for ink-jet recording having improved gloss on a special paper and an aqueous pigment dispersion that can be easily prepared.
カーボンブラック又は有機顔料と、アシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレートの様な燐酸基含有モノエチレン性不飽和単量体とその他の共重合可能なモノエチレン性不飽和単量体との共重合体と、塩基性物質と、水とを必須成分として含有してなるインクジェット記録用水性インクは、特許文献１にある様に知られている。 Carbon black or organic pigment, and phosphoric acid group-containing monoethylenically unsaturated monomer such as acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate and other copolymerizable monoethylenically unsaturated monomer A water-based ink for ink-jet recording comprising a copolymer, a basic substance, and water as essential components is known as in Patent Document 1.
この特許文献１では、ホスホリル化重合体分散剤として、２−フェノキシエチル（メタ）アクリレートの様なベンゼン環を含有するアルキル（メタ）アクリレートとアシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレートの様な燐酸基含有モノエチレン性不飽和単量体とを必須成分として重合させた共重合体が各種記載されており、それらを用いてインクジェット記録用水性インクが記載されている。 In Patent Document 1, as a phosphorylated polymer dispersant, an alkyl (meth) acrylate containing a benzene ring such as 2-phenoxyethyl (meth) acrylate and an acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate are used. Various copolymers obtained by polymerizing a monoethylenically unsaturated monomer containing a phosphoric acid group as an essential component are described, and water-based inks for ink jet recording are described using these copolymers.
しかしながら、特許文献１に記載されている様なインクジェット記録用水性インクは、普通紙における発色性だけをとってみれば優れたものではあるが、専用紙における光沢性は依然として不満足なものであった。 However, the water-based ink for ink-jet recording as described in Patent Document 1 is excellent if only the color developability of plain paper is taken, but the glossiness of the special paper is still unsatisfactory. .
インクジェット記録方法においては、印字すべき紙のタイプ毎に、インクを交換することは困難であり、一つのインクで、普通紙における発色性と専用紙における光沢性のいずれにも優れていることが要求される。 In the ink jet recording method, it is difficult to exchange ink for each type of paper to be printed, and one ink is excellent in both color development on plain paper and gloss on special paper. Required.
本発明が解決しようとする課題は、普通紙における発色性と専用紙における光沢性のいずれにも優れるインクジェット記録用水性インク及びそれを容易に調製することが出来る水性顔料分散体を提供することにある。 The problem to be solved by the present invention is to provide a water-based ink for ink-jet recording which is excellent in both color developability on plain paper and gloss on special paper, and an aqueous pigment dispersion capable of easily preparing the same. is there.
本発明者等は、普通紙における発色性と専用紙における光沢性のいずれにも優れるインクジェット記録用水性インク及びそれを容易に調製することが出来る水性顔料分散体について鋭意検討したところ、燐酸基含有モノエチレン性不飽和単量体とその他の共重合可能なエチレン性不飽和単量体との共重合体として、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体を用いることで前記課題が解決されることを見い出し、本発明を完成するに至った。 The inventors of the present invention have studied diligently about water-based ink for ink-jet recording excellent in both color developability on plain paper and gloss on special paper and an aqueous pigment dispersion that can be easily prepared. As copolymers of monoethylenically unsaturated monomers and other copolymerizable ethylenically unsaturated monomers, phosphate group-containing monoethylenically unsaturated monomers, glycidyl (meth) acrylate and other copolymers It has been found that the above problems can be solved by using a copolymer obtained by polymerizing a polymerizable monoethylenically unsaturated monomer as an essential component, and the present invention has been completed.
即ち本発明は、カーボンブラック又は有機顔料（Ａ）と、燐酸基含有モノエチレン性不飽和単量体とその他の共重合可能なエチレン性不飽和単量体との共重合体（Ｂ）と、塩基性物質（Ｃ）と、水（Ｄ）とを必須成分として含有してなるインクジェット記録用水性インク調製のための水性顔料分散体において、前記共重合体（Ｂ）が、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体であることを特徴とするインクジェット記録用水性インク調製のための水性顔料分散体を提供する。 That is, the present invention relates to a carbon black or organic pigment (A), a copolymer (B) of a phosphoric acid group-containing monoethylenically unsaturated monomer and another copolymerizable ethylenically unsaturated monomer, In an aqueous pigment dispersion for preparing an aqueous ink for ink jet recording, comprising a basic substance (C) and water (D) as essential components, the copolymer (B) is a phosphoric acid group-containing monoethylene. Preparation of water-based ink for ink-jet recording, comprising a copolymer obtained by polymerizing a polymerizable unsaturated monomer, glycidyl (meth) acrylate and other copolymerizable monoethylenically unsaturated monomer as essential components An aqueous pigment dispersion for is provided.
または本発明は、前記した水性顔料分散体を含有してなるインクジェット記録用水性インクを提供する。 Alternatively, the present invention provides a water-based ink for ink jet recording comprising the above-described water-based pigment dispersion.
本発明の水性顔料分散体は、共重合体として、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した分子内架橋した部位を含有する共重合体を用いるので、燐酸基含有モノエチレン性不飽和単量体とジアクリレートの様な多官能アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合し架橋した部位を含有する共重合体を分散剤として用いた時には奏し得ない、普通紙における発色性と専用紙における光沢性のいずれにも優れるという格別顕著な効果を奏する。 The aqueous pigment dispersion of the present invention contains, as a copolymer, a phosphoric acid group-containing monoethylenically unsaturated monomer, glycidyl (meth) acrylate, and other copolymerizable monoethylenically unsaturated monomers as essential components. As a copolymer containing an intramolecular cross-linked site polymerized as a polyfunctional acrylate such as a phosphate group-containing monoethylenically unsaturated monomer and diacrylate and other copolymerizable monoethylenically unsaturated When using a copolymer containing a monomer as an essential component and containing a cross-linked site as a dispersant, it is extremely remarkable that it is excellent in both color development on plain paper and gloss on special paper. There is an effect.
次に本発明を詳細に説明する。
本発明は、カーボンブラック又は有機顔料（Ａ）と、燐酸基含有モノエチレン性不飽和単量体とその他の共重合可能なエチレン性不飽和単量体との共重合体（Ｂ）と、塩基性物質（Ｃ）と、水（Ｄ）とを必須成分として含有してなるインクジェット記録用水性インク調製のための水性顔料分散体において、前記共重合体（Ｂ）が、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体であることを特徴とするインクジェット記録用水性インク調製のための水性顔料分散体である。
Next, the present invention will be described in detail.
The present invention relates to a carbon black or organic pigment (A), a copolymer (B) of a phosphoric acid group-containing monoethylenically unsaturated monomer and another copolymerizable ethylenically unsaturated monomer, a base In the aqueous pigment dispersion for preparing an aqueous ink for ink-jet recording, which comprises a water-soluble substance (C) and water (D) as essential components, the copolymer (B) is a monoethylenic acid containing phosphoric acid group. A water-based ink for ink-jet recording characterized by being a copolymer obtained by polymerizing an unsaturated monomer, glycidyl (meth) acrylate and other copolymerizable monoethylenically unsaturated monomer as essential components For aqueous pigment dispersions.
本発明においては、この様な水性顔料分散体に含有させる共重合体として、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体を用いることで、印字画像に高発色性と高光沢性とを兼備させる。 In the present invention, as a copolymer to be contained in such an aqueous pigment dispersion, a monoethylenically unsaturated monomer capable of being copolymerized with a phosphate group-containing monoethylenically unsaturated monomer, glycidyl (meth) acrylate, and the like. By using a copolymer obtained by polymerizing a monomer as an essential component, the printed image has both high color developability and high glossiness.
本発明においては、水不溶性の着色剤、具体的には、カーボンブラック又は有機顔料（Ａ）が用いられる。本発明における有機顔料としては、公知慣用の有機顔料がいずれも使用出来る。具体的には例えば、不溶性アゾ顔料、溶性アゾ顔料、インダンスレン系顔料、フタロシアニン系顔料、キナクリドン系顔料、ペリレン系顔料、イソインドリノン系顔料、キノフタロン系顔料、アントラキノン系顔料、ジケトピロロピロール系顔料等が挙げられる。 In the present invention, a water-insoluble colorant, specifically, carbon black or organic pigment (A) is used. Any known and commonly used organic pigments can be used as the organic pigment in the present invention. Specifically, for example, insoluble azo pigment, soluble azo pigment, indanthrene pigment, phthalocyanine pigment, quinacridone pigment, perylene pigment, isoindolinone pigment, quinophthalone pigment, anthraquinone pigment, diketopyrrolopyrrole And pigments.
本発明における共重合体（Ｂ）は、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体である。この共重合体（Ｂ）は、燐酸基含有モノエチレン性不飽和単量体の重合部位に含まれる燐酸基とグリシジル（メタ）アクリレートの重合部位に含まれるエポキシ基とが分子内で架橋反応を起こした部位を含有する。この様な共重合体構造とすることで、ジアクリレートの様な多官能アクリレートで架橋した部位を含有する共重合体では発現し得ない特徴が発現するようにした。共重合体（Ｂ）中の燐酸基が、後記する塩基性物質（Ｃ）で中和されることで、水に対しての溶解性や分散性が確保される。 The copolymer (B) in the present invention was polymerized using a phosphoric acid group-containing monoethylenically unsaturated monomer, glycidyl (meth) acrylate, and other copolymerizable monoethylenically unsaturated monomers as essential components. It is a copolymer. In this copolymer (B), the phosphoric acid group contained in the polymerization site of the phosphate group-containing monoethylenically unsaturated monomer and the epoxy group contained in the polymerization site of glycidyl (meth) acrylate undergo a crosslinking reaction in the molecule. Contains the raised site. By adopting such a copolymer structure, characteristics that cannot be expressed in a copolymer containing a site crosslinked with a polyfunctional acrylate such as diacrylate are developed. By neutralizing the phosphate group in the copolymer (B) with a basic substance (C) described later, solubility and dispersibility in water are ensured.
燐酸基含有モノエチレン性不飽和単量体とは、燐酸基ＰＯ3Ｈ2と、重合性エチレン性不飽和二重結合の一つとを含有する単量体である。この様な燐酸基含有モノエチレン性不飽和単量体としては、例えば、ビニルホスホン酸や、下記一般式で表されるものである（以下、あわせて燐酸モノマーと略記する。）。本発明において、（メタ）アクリレート、（メタ）アクリル酸とは、それぞれ順にアクリレートとメタクリレート、アクリル酸とメタクリル酸を意味するものとする。 The phosphate group-containing monoethylenically unsaturated monomer is a monomer containing a phosphate group PO 3 H 2 and one of polymerizable ethylenically unsaturated double bonds. Examples of such a phosphoric acid group-containing monoethylenically unsaturated monomer include vinylphosphonic acid and those represented by the following general formula (hereinafter collectively referred to as phosphoric acid monomer). In the present invention, (meth) acrylate and (meth) acrylic acid mean acrylate and methacrylate, and acrylic acid and methacrylic acid, respectively.
（上記式中、ａは０または１であり、ａが１のときＸは炭素原子数１〜９のアルキレン基であり、ｂ及びｃは独立して０〜１０であり、同時に０ではなくなる様に選択され、Ｒ3は水素原子またはメチル基である。） (In the above formula, a is 0 or 1; when a is 1, X is an alkylene group having 1 to 9 carbon atoms; b and c are independently 0 to 10; And R 3 is a hydrogen atom or a methyl group.)
この様な燐酸モノマーとしては、例えば、アシッドホスホシキエチルモノ（メタ）アクリレート、アシッドホスホシキプロピルモノ（メタ）アクリレート、アシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレート等が挙げられる。重合制御の容易さの観点から、本発明における好適な燐酸モノマーは、アシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレートであり、これに該当するモノマーとしては、例えば、アシッドホスホキシポリエチレングリコールモノ（メタ）アクリレート、アシッドホスホキシポリ（オキシエチレンオキシプロピレン）グリコールモノ（メタ）アクリレート等が挙げられる。親水性を高める観点からは、アシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレートに含有されるポリオキシアルキレン骨格は、ポリオキシエチレン骨格のみ又はポリオキシエチレンを主体としたポリオキシアルキレン骨格であることが好ましい。燐酸モノマーとしては、ユニケミカル株式会社のＰｈｏｓｍｅｒ（ホスマー）Ｍ、同ＰＥ、同ＰＰ等や、米国デュポン社製のモノマーがある。 Examples of such phosphoric acid monomers include acid phosphooxyethyl mono (meth) acrylate, acid phosphooxypropyl mono (meth) acrylate, and acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate. From the viewpoint of ease of polymerization control, a preferred phosphoric acid monomer in the present invention is acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate, and examples of such a monomer include acid phosphoxypolyethylene glycol mono ( And (meth) acrylate, acid phosphoxy poly (oxyethyleneoxypropylene) glycol mono (meth) acrylate, and the like. From the viewpoint of enhancing hydrophilicity, the polyoxyalkylene skeleton contained in the acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate is only a polyoxyethylene skeleton or a polyoxyalkylene skeleton mainly composed of polyoxyethylene. Is preferred. Examples of phosphoric acid monomers include Phosmer M, PE, PP, etc. from Unichemical Co., Ltd., and monomers manufactured by DuPont, USA.
本発明の共重合体（Ｂ）は、燐酸基とポリオキシアルキレン基の機能を分離させて、燐酸モノマーとしてのアシッドホスホシキアルキルモノ（メタ）アクリレートと、後記するその他の共重合可能なモノエチレン性不飽和単量体としてのアルコキシポリアルキレングリコールモノ（メタ）アクリレートとを組合せて用いたこれらの重合単位を含有する共重合体であっても良いが、各官能基の機能が統合された、燐酸基とポリオキシアルキレン基とを一分子中に含有する燐酸モノマーであるアシッドホスホキシポリオキシアルキレングリコールモノ（メタ）アクリレートを用いたこれの重合単位を含有する共重合体であることが、専用紙における光沢性をより高められる点で好ましい。 The copolymer (B) of the present invention is obtained by separating the functions of a phosphoric acid group and a polyoxyalkylene group, and an acid phosphosiloxane mono (meth) acrylate as a phosphoric acid monomer and other copolymerizable monoethylene described later. It may be a copolymer containing these polymerized units used in combination with an alkoxypolyalkylene glycol mono (meth) acrylate as a polymerizable unsaturated monomer, but the function of each functional group is integrated, It is a copolymer containing polymer units of acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate, which is a phosphoric acid monomer containing a phosphoric acid group and a polyoxyalkylene group in one molecule. This is preferable in that the glossiness of paper can be further improved.
共重合体（Ｂ）は、燐酸モノマーの重合単位を含有していれば良いが、共重合体（Ｂ）は、酸価４０〜２２０ｍｇＫＯＨ／ｇ、中でもより水に分散させた際の分散性や分散安定性及び印字の光沢性により優れる点で、酸価１４０〜２００ｍｇＫＯＨ／ｇあることが好ましい。ここで酸価とは、共重合体の不揮発分１ｇを中和するのに必要な水酸化カリウムのｍｇ数を言う。理論酸価は、用いた燐酸モノマーとその使用量に基づいて算術的に求めることも出来る。酸価が低すぎる場合には顔料分散や保存安定性が低下し、またインクジェット記録用水性顔料インクを調製した場合に、印字安定性が悪くなるので好ましくない。酸価が高すぎる場合には、着色画像の耐水性が低下するのでやはり好ましくない。共重合体（Ｂ）を該酸価の範囲内とするには、燐酸モノマーを、前記酸価の範囲内となる様に含めて共重合すれば良い。 The copolymer (B) only needs to contain a polymerization unit of a phosphoric acid monomer. However, the copolymer (B) has an acid value of 40 to 220 mgKOH / g, and more particularly dispersibility when dispersed in water. An acid value of 140 to 200 mgKOH / g is preferable because it is superior in dispersion stability and gloss of printing. Here, the acid value refers to the number of mg of potassium hydroxide necessary to neutralize 1 g of the nonvolatile content of the copolymer. The theoretical acid value can also be obtained arithmetically based on the phosphoric acid monomer used and the amount used. When the acid value is too low, the pigment dispersion and storage stability are lowered, and when an aqueous pigment ink for inkjet recording is prepared, the printing stability is deteriorated. If the acid value is too high, the water resistance of the colored image is lowered, which is also not preferable. In order to bring the copolymer (B) within the range of the acid value, the phosphoric acid monomer may be included and copolymerized so as to be within the range of the acid value.
その他の共重合可能なモノエチレン性不飽和単量体は、燐酸基含有モノエチレン性不飽和単量体、グリシジル（メタ）アクリレート以外のモノエチレン性不飽和単量体である。この様なモノエチレン性不飽和単量体単量体としては、例えば、スチレン、α−メチルスチレン、ジメチルスチレン、ｔｅｒｔ−ブチルスチレン、クロロスチレン、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉｓｏ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェニルエチル（メタ）アクリレート、フェニルプロピル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、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、メトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシポリ（オキシエチレンオキシプロピレン）グリコールモノ（メタ）アクリレート等が挙げられる。 Other copolymerizable monoethylenically unsaturated monomers are monoethylenically unsaturated monomers other than phosphoric acid group-containing monoethylenically unsaturated monomers and glycidyl (meth) acrylates. Examples of such monoethylenically unsaturated monomer include styrene, α-methylstyrene, dimethylstyrene, tert-butylstyrene, chlorostyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n -Propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (Meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, phenoxyethyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypoly (oxyethyleneoxypropylene) ) Glycol mono (meth) acrylate and the like.
共重合体（Ｂ）には、例えば、スチレン、α−メチルスチレン、ジメチルスチレン、ｔｅｒｔ−ブチルスチレン、クロロスチレン、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェニルエチル（メタ）アクリレート、フェニルプロピル（メタ）アクリレート等のベンゼン環を含有するモノエチレン性不飽和単量体の重合単位を含有させることが、印字画像に、より高い発色性及び／又はより高いと光沢性をもたせるために好ましい。 Examples of the copolymer (B) include styrene, α-methylstyrene, dimethylstyrene, tert-butylstyrene, chlorostyrene, benzyl (meth) acrylate, phenyl (meth) acrylate, phenylethyl (meth) acrylate, and phenylpropyl. It is preferable to contain a polymerized unit of a monoethylenically unsaturated monomer containing a benzene ring such as (meth) acrylate so that the printed image has higher color developability and / or higher gloss.
なかでも共重合体（Ｂ）は、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとスチレン系単量体とを必須成分として重合した共重合体であることが好ましい。ベンゼン環を含有するモノエチレン性不飽和単量体として、そこにエステル結合等の親水性原子団を含まない、例えば、スチレン、α−メチルスチレン、ジメチルスチレン、ｔｅｒｔ−ブチルスチレン、クロロスチレン等のスチレン系単量体は、その重合単位を含有する共重合体の同一酸価対比において、より共重合体の疎水性を高め、共重合体の顔料表面への吸着がより強固となることから好ましい。 Among these, the copolymer (B) is preferably a copolymer obtained by polymerizing a phosphoric acid group-containing monoethylenically unsaturated monomer, glycidyl (meth) acrylate, and a styrene monomer as essential components. The monoethylenically unsaturated monomer containing a benzene ring does not contain a hydrophilic atomic group such as an ester bond, for example, styrene, α-methylstyrene, dimethylstyrene, tert-butylstyrene, chlorostyrene, etc. Styrenic monomers are preferred because the hydrophobicity of the copolymer is further increased and the adsorption of the copolymer to the pigment surface is more robust in the same acid value comparison of the copolymer containing the polymer unit. .
共重合体（Ｂ）におけるスチレン系単量体は、質量換算で共重合体を構成する全単量体の合計を１００部とした時、３０〜７０部となる様にすることが、同一共重合量において、ベンゼン環とエステル結合等とを含有する単量体を用いた場合より共重合体の疎水性を高め、共重合体の顔料表面への吸着がより強固となることから好ましい。 The styrene monomer in the copolymer (B) may be 30 to 70 parts when the total of all monomers constituting the copolymer is 100 parts in terms of mass. The amount of polymerization is preferable because the hydrophobicity of the copolymer is increased and the adsorption of the copolymer to the pigment surface becomes stronger than when a monomer containing a benzene ring and an ester bond is used.
共重合体（Ｂ）は、グリシジル（メタ）アクリレートの重合単位が含有された共重合体である。このグリシジル（メタ）アクリレートは、燐酸基含有モノエチレン性不飽和単量体及びその他の共重合可能なモノエチレン性不飽和単量体と共重合するためのエチレン不飽和二重結合と、燐酸基含有モノエチレン性不飽和単量体の燐酸基と反応し架橋し得るエポキシ基を含有する。これらは、エチレン不飽和二重結合により重合し、燐酸基とエポキシ基により架橋することで共重合体を形成する。 The copolymer (B) is a copolymer containing polymerized units of glycidyl (meth) acrylate. This glycidyl (meth) acrylate comprises an ethylenically unsaturated double bond for copolymerization with a phosphate group-containing monoethylenically unsaturated monomer and other copolymerizable monoethylenically unsaturated monomers, and a phosphate group. It contains an epoxy group that can react with the phosphoric acid group of the monoethylenically unsaturated monomer and crosslink. These are polymerized by an ethylenically unsaturated double bond, and form a copolymer by crosslinking with a phosphoric acid group and an epoxy group.
本発明においては、この様な共重合体（Ｂ）を用いることで、燐酸基とエポキシ基との架橋に基づく分子内架橋による固有の作用を有効に活用する。実質的に架橋部分を含有する共重合体（Ｂ）は、より耐熱性に優れるために、熱履歴のかかるサーマル方式ノズルのインクジェット記録装置用の水性インクの調製に好適である。 In the present invention, by using such a copolymer (B), an inherent action by intramolecular crosslinking based on crosslinking between a phosphoric acid group and an epoxy group is effectively utilized. The copolymer (B) substantially containing a crosslinking moiety is more excellent in heat resistance, and is therefore suitable for preparing a water-based ink for an ink jet recording apparatus using a thermal nozzle with a thermal history.
共重合体（Ｂ）に含有させる、グリシジル（メタ）アクリレートの重合単位の含有量は、特に制限されるものではないが、質量換算で、共重合体（Ｂ）を構成する全単量体を１００部とした時、グリシジル（メタ）アクリレートが、０．１〜５部となる様にすることが好ましい。 The content of the polymerization unit of glycidyl (meth) acrylate to be contained in the copolymer (B) is not particularly limited, but all monomers constituting the copolymer (B) are calculated in terms of mass. When it is 100 parts, it is preferable that glycidyl (meth) acrylate is 0.1 to 5 parts.
本発明における共重合体（Ｂ）は、燐酸モノマーとグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体の少なくとも一種の共重合体であれば良く、それらの三元共重合体であっても更に二種以上のその他の共重合可能なモノエチレン性不飽和単量体との四元以上の多元共重合体であっても良い。 The copolymer (B) in the present invention may be at least one copolymer of a phosphoric acid monomer, glycidyl (meth) acrylate, and other copolymerizable monoethylenically unsaturated monomers, and their ternary Even a copolymer may be a quaternary or multi-component copolymer with two or more other copolymerizable monoethylenically unsaturated monomers.
本発明で用いる共重合体（Ｂ）は、必要であれば、本発明の効果を損ねない範囲において、各種のエチレン性不飽和二重結合を２〜６つ含有するエチレン性不飽和単量体を更に極少量共重合させた共重合体とすることも出来る。 If necessary, the copolymer (B) used in the present invention is an ethylenically unsaturated monomer containing 2 to 6 various ethylenically unsaturated double bonds within a range not impairing the effects of the present invention. Further, a copolymer obtained by copolymerizing a very small amount of can also be used.
本発明における共重合体（Ｂ）の分子量としては特に制限されないが、例えば、皮膜形成性の観点から、重量平均分子量５，０００〜１０００，０００、中でも、低粘度で取り扱いが容易な点で、５，０００〜２０，０００であることが好ましい。 The molecular weight of the copolymer (B) in the present invention is not particularly limited. For example, from the viewpoint of film formation, the weight average molecular weight is 5,000 to 1,000,000. Among them, the viscosity is low and the handling is easy. It is preferable that it is 5,000-20,000.
本発明においては、用いる各単量体の反応率等は略同一と考えて、各単量体の仕込割合を、各単量体の重合単位の質量換算の含有割合と見なすものとする。本発明における共重合体（Ｂ）は、塊状重合、溶液重合、懸濁重合、乳化重合等の従来より公知の種々の反応方法によって合成することが出来る。この際には、公知慣用の重合開始剤、連鎖移動剤（重合度調整剤）、界面活性剤及び消泡剤を併用することも出来る。 In the present invention, the reaction rate and the like of each monomer used is considered to be substantially the same, and the charging ratio of each monomer is regarded as the content ratio in terms of mass of the polymerization unit of each monomer. The copolymer (B) in the present invention can be synthesized by various conventionally known reaction methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. In this case, a known and usual polymerization initiator, chain transfer agent (polymerization degree adjusting agent), surfactant and antifoaming agent can be used in combination.
本発明において共重合体（Ｂ）を製造するに当たり、エチレン性不飽和二重結合に基づく重合と、燐酸基とエポキシ基の架橋反応のどちらが先となる様に反応を行っても構わないが、分子内架橋の作用を有効に利用するためには、エチレン性不飽和二重結合に基づく重合により線状（リニアー）の共重合体構造がある程度形成されてから燐酸基とエポキシ基との架橋が行われることが好ましいため、この反応条件としては、エチレン性不飽和二重結合に基づく重合がより優先して行われる様な条件を選択することが好ましい。 In the production of the copolymer (B) in the present invention, the reaction may be performed so that either the polymerization based on the ethylenically unsaturated double bond or the crosslinking reaction of the phosphoric acid group and the epoxy group precedes. In order to effectively utilize the action of intramolecular crosslinking, the crosslinking between the phosphate group and the epoxy group is performed after a linear copolymer structure is formed to some extent by polymerization based on ethylenically unsaturated double bonds. Since the reaction is preferably performed, it is preferable to select the reaction condition such that the polymerization based on the ethylenically unsaturated double bond is more preferentially performed.
共重合体（Ｂ）を中和する塩基性物質（Ｃ）としては、公知慣用のものがいずれも使用出来、例えば、水酸化ナトリウム、水酸化カリウム、アンモニアの様な無機塩基性物質や、トリエチルアミン、アルカノールアミンの様な有機塩基性物質を用いることが出来る。共重合体（Ｂ）中に含まれる燐酸基は二塩基酸であるため、中和のための塩基性物質（Ｃ）は、従来の様な、カルボキシル基を中和する場合に比べてより多くを必要とする。 As the basic substance (C) for neutralizing the copolymer (B), any known and commonly used substances can be used. For example, inorganic basic substances such as sodium hydroxide, potassium hydroxide and ammonia, triethylamine, and the like. An organic basic substance such as alkanolamine can be used. Since the phosphoric acid group contained in the copolymer (B) is a dibasic acid, the basic substance (C) for neutralization is more in comparison with the conventional case of neutralizing the carboxyl group. Need.
本発明の水性顔料分散体は、これら有機顔料（Ａ）、共重合体（Ｂ）、塩基性物質（Ｃ）とを水（Ｄ）中に含有してなる。本発明における水（Ｄ）としては、例えば、蒸留水、イオン交換水、純水、超純水等、ｐＨ６．５〜７．５かつ遊離イオンを含有しない水が好ましい。 The aqueous pigment dispersion of the present invention comprises these organic pigment (A), copolymer (B), and basic substance (C) in water (D). As the water (D) in the present invention, for example, distilled water, ion-exchanged water, pure water, ultrapure water, etc., water having a pH of 6.5 to 7.5 and containing no free ions is preferable.
本発明の水性顔料分散体では、質量基準で、共重合体（Ｂ）合計不揮発分／有機顔料（Ａ）は、０．２を越えて〜２．０以下であることが好ましく、中でも０．２を越えて〜１．０以下であることがより好ましく、特に０．２０を越えて〜０．６５以下であることが最も好ましい。この比率が低すぎる場合には、着色画像の耐擦過性と水性インク自体の分散安定性が低下し、逆に高すぎる場合には水性インクの粘度が高くなり、その吐出安定性が損なわれる傾向があり好ましくない。共重合体（Ｂ）合計不揮発分／有機顔料（Ａ）は、０．２以下では分散安定性が不充分となりやすいので好ましくない。 In the aqueous pigment dispersion of the present invention, the copolymer (B) total non-volatile content / organic pigment (A) is preferably more than 0.2 and not more than 2.0, in terms of mass basis. More preferably, it is more than 2 and ˜1.0 or less, particularly preferably more than 0.20 and ˜0.65 or less. When this ratio is too low, the scratch resistance of the colored image and the dispersion stability of the water-based ink itself are lowered. On the other hand, when it is too high, the viscosity of the water-based ink is increased, and the ejection stability tends to be impaired. Is not preferable. When the copolymer (B) total non-volatile content / organic pigment (A) is 0.2 or less, the dispersion stability tends to be insufficient, which is not preferable.
本発明の水性顔料分散体は、例えば、有機顔料（Ａ）と、共重合体（Ｂ）と、塩基性物質（Ｃ）と、水（Ｄ）とを必須成分として混合することで調製することが出来る。 The aqueous pigment dispersion of the present invention is prepared, for example, by mixing organic pigment (A), copolymer (B), basic substance (C), and water (D) as essential components. I can do it.
前記した水性顔料分散体は、例えば、後記する様な１）〜４）の方法で製造することが出来る。
１）共重合体（Ｂ）とそれを中和するための塩基性物質（Ｃ）とを含有する水性エマルジョンに有機顔料（Ａ）を機械的に強制分散する水性顔料分散体の製造方法。
２）有機顔料（Ａ）の存在下の水中で分散剤と中和のための塩基性物質（Ｃ）とを用いて、前記した共重合体（Ｂ）を得るための各単量体を重合させ共重合体とし必要に応じて会合させる水性顔料分散体の製造方法。
３）有機顔料（Ａ）と共重合体（Ｂ）と有機溶剤の混合物を、水と中和のための塩基性物質（Ｃ）を用いて徐徐に油相から水相に転相させてから脱溶剤する水性顔料分散体の製造方法。
４）有機顔料（Ａ）と共重合体（Ｂ）と中和のための塩基性物質（Ｃ）と有機溶剤と水との均一混合物から脱溶剤を行い、酸性物質を加えて酸析し析出物を洗浄後、この析出物を中和のための塩基性物質と共に水に分散させる水性顔料分散体の製造方法。
The above-mentioned aqueous pigment dispersion can be produced, for example, by the methods 1) to 4) as described later.
1) A method for producing an aqueous pigment dispersion in which an organic pigment (A) is mechanically and forcibly dispersed in an aqueous emulsion containing a copolymer (B) and a basic substance (C) for neutralizing the copolymer (B).
2) Polymerizing each monomer for obtaining the above-mentioned copolymer (B) using a dispersant and a basic substance (C) for neutralization in water in the presence of the organic pigment (A). A method for producing a water-based pigment dispersion that is made into a copolymer as necessary.
3) The mixture of the organic pigment (A), copolymer (B) and organic solvent is gradually phase-inverted from the oil phase to the aqueous phase using water and a basic substance (C) for neutralization. A method for producing an aqueous pigment dispersion for solvent removal.
4) Organic solvent (A), copolymer (B), basic substance for neutralization (C), organic solvent and water are removed from the homogeneous mixture, acid substance is added and acid precipitation is carried out. A method for producing an aqueous pigment dispersion in which a precipitate is washed in water together with a basic substance for neutralization after washing.
本発明の水性顔料分散体としては、共重合体（Ｂ）で被覆された有機顔料（Ａ）粒子を含有する水性顔料分散体が好ましい。 The aqueous pigment dispersion of the present invention is preferably an aqueous pigment dispersion containing organic pigment (A) particles coated with the copolymer (B).
水性顔料分散体や水性顔料インクにおいて、分散粒子は、有機顔料（Ａ）粒子と共重合体（Ｂ）との相互作用が強く働いているものの方が分散安定性等の点で好ましく、前記方法３）及び４）により製造される水性顔料分散体は、共重合体（Ｂ）で被覆された有機顔料（Ａ）粒子を主成分として含有するものとなるので、前記方法１）及び２）により製造される水性顔料分散体に比べ、分散粒子の分散安定性が高いだけでなく、水性顔料分散体の粘度もより低くなるので好ましい。インクジェット記録方式では、ノズルからインク液滴を飛ばすためにはそれが低粘度であることが望まれることから、それを調製するための水性顔料分散体自体の粘度も低いことが好まれる。 In the aqueous pigment dispersion or the aqueous pigment ink, the dispersed particles are preferably those in which the interaction between the organic pigment (A) particles and the copolymer (B) works strongly in terms of dispersion stability, etc. Since the aqueous pigment dispersion produced by 3) and 4) contains the organic pigment (A) particles coated with the copolymer (B) as a main component, the above-mentioned methods 1) and 2) Compared to the aqueous pigment dispersion to be produced, not only the dispersion stability of the dispersed particles is high, but also the viscosity of the aqueous pigment dispersion is preferred. In the ink jet recording system, in order to eject ink droplets from a nozzle, it is desired that the ink droplet has a low viscosity. Therefore, it is preferable that the viscosity of the aqueous pigment dispersion itself for preparing it is also low.
本発明では、前記いずれの製造方法をとるにせよ、有機顔料（Ａ）、共重合体（Ｂ）、塩基性物質（Ｃ）及び水（Ｄ）からなる混合物を分散する工程を必須として含ませることが好ましい。分散に用いる液媒体は、水１００％であるのが最適ではあるが、水と有機溶剤との混合物であって、質量換算で水を６０％以上含有する水性媒体であっても良い。水（Ｃ）には水溶性有機溶剤を含有させるのが好ましい。より具体的には、少なくとも有機顔料（Ａ）、共重合体（Ｂ）、塩基性物質（Ｃ）、水溶性有機溶剤及び水（Ｄ）からなる混合物を分散する工程（分散工程）を含ませることが好ましい。水（Ｄ）に水溶性有機溶剤を併用することにより分散工程における液粘度を低下させることが出来る場合がある。 In the present invention, regardless of which production method is used, the step of dispersing the mixture comprising the organic pigment (A), the copolymer (B), the basic substance (C), and water (D) is included as an essential step. It is preferable. The liquid medium used for dispersion is optimally 100% water, but it may be a mixture of water and an organic solvent and an aqueous medium containing 60% or more of water in terms of mass. Water (C) preferably contains a water-soluble organic solvent. More specifically, a step (dispersing step) of dispersing a mixture of at least the organic pigment (A), the copolymer (B), the basic substance (C), the water-soluble organic solvent and water (D) is included. It is preferable. By using a water-soluble organic solvent in combination with water (D), the liquid viscosity in the dispersion step may be reduced.
水溶性有機溶剤としては、例えば、アセトン、メチルエチルケトン（ＭＥＫ）、メチルブチルケトン、メチルイソブチルケトン、等のケトン類；メタノール、エタノール、２−プロパノール（ＩＰＡ）、２−メチル−１−プロパノール、１−ブタノール、２−メトキシエタノール、等のアルコール類；テトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、等のエーテル類；ジメチルホルムアミド、Ｎ−メチルピロリドン、等のアミド類が挙げられ、とりわけ炭素原子数が３〜６のケトン及び炭素原子数が１〜５のアルコールからなる群から選ばれる化合物を用いるのが好ましい。これらの水溶性有機溶剤は、前記共重合体溶液として用いられても良く、別途独立に分散工程中において前記混合物中に含有させても良い。 Examples of the water-soluble organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol (IPA), 2-methyl-1-propanol, 1- Examples include alcohols such as butanol and 2-methoxyethanol; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; amides such as dimethylformamide and N-methylpyrrolidone, and particularly carbon. It is preferable to use a compound selected from the group consisting of a ketone having 3 to 6 atoms and an alcohol having 1 to 5 carbon atoms. These water-soluble organic solvents may be used as the copolymer solution or separately contained in the mixture during the dispersion step.
本発明における水性顔料分散体の調製に当たっては、最適には、質量換算で有機顔料（Ａ）１００部当たり、共重合体（Ｂ）の不揮発分２０部を越えて〜６５部以下かつ水溶性有機溶媒を含む水性媒体２３５〜２８０部となる様に、前記した原料を用いて製造することが出来る。 In the preparation of the aqueous pigment dispersion in the present invention, optimally, the water-soluble organic material is contained in an amount of more than 20 parts of the non-volatile content of the copolymer (B) in excess of 20 parts per 100 parts of the organic pigment (A) in terms of mass. It can manufacture using an above-described raw material so that it may become 235-280 parts of aqueous medium containing a solvent.
分散工程において用いることの出来る分散装置としては、既に公知の種々の方式による装置がいずれも使用出来、特に限定されるものではない。この様な分散装置としては、例えば、スチール、ステンレス、ジルコニア、アルミナ、窒化ケイ素、ガラス等でできた直径０．１〜１０ｍｍ程度の球状分散媒体の運動エネルギーを利用する方式、機械的攪拌による剪断力を利用する方式、高速で供給された被分散物流束の圧力変化、流路変化あるいは衝突に伴って発生する力を利用する方式、等の分散方式の分散装置を挙げることが出来る。 As a dispersion apparatus that can be used in the dispersion step, any of various known apparatuses can be used and is not particularly limited. Examples of such a dispersing device include a method using kinetic energy of a spherical dispersion medium having a diameter of about 0.1 to 10 mm made of steel, stainless steel, zirconia, alumina, silicon nitride, glass, etc., shearing by mechanical stirring. Examples of the dispersion device include a dispersion method such as a force utilization method, a pressure change of a dispersed flow bundle supplied at high speed, a flow passage change, or a force utilization force generated by a collision.
こうした分散工程を実施することで、共重合体（Ｂ）を含有する液媒体中に有機顔料（Ａ）が分散した状態が形成される。 By carrying out such a dispersion step, a state in which the organic pigment (A) is dispersed in the liquid medium containing the copolymer (B) is formed.
分散工程に引き続き、分散工程において水溶性有機溶剤を使用した場合に、これを除去する工程、所望の固形分濃度にするため余剰の水を除去する工程（蒸留工程）を実施することが出来る。水性顔料分散体としては水溶性有機溶剤を含まないものが臭気がなく、作業環境を良好と出来る点で好ましい。 Subsequent to the dispersion step, when a water-soluble organic solvent is used in the dispersion step, a step of removing this, and a step of removing excess water (distillation step) to obtain a desired solid content concentration can be performed. As the aqueous pigment dispersion, those containing no water-soluble organic solvent are preferred because they have no odor and can improve the working environment.
水性顔料分散体は、分散到達レベル、分散所要時間及び分散安定性の全ての面で、より優れた特性を発揮させるに当たって、前記した通り、有機顔料（Ａ）と共重合体（Ｂ）とは、より相互作用が強く働き分散していることが好ましい。 As described above, the water-based pigment dispersion exhibits excellent properties in all aspects of dispersion achievement level, dispersion time, and dispersion stability. As described above, the organic pigment (A) and the copolymer (B) are: It is preferable that the interaction is stronger and dispersed.
分散粒子の相互作用を高めるため、溶解状態にある共重合体（Ｂ）に有機顔料（Ａ）表面を密着させる工程を、前記分散工程の後工程として組み込むことが好ましい。 In order to enhance the interaction of the dispersed particles, it is preferable to incorporate a step of bringing the surface of the organic pigment (A) into close contact with the copolymer (B) in a dissolved state as a subsequent step of the dispersing step.
溶解状態にある共重合体（Ｂ）を有機顔料（Ａ）表面に密着させる工程としては、有機顔料（Ａ）と中和のための塩基性物質（Ｃ）により溶解している共重合体（Ｂ）とを含有する液媒体を酸性化することにより、共重合体中のイオン化した燐酸基を、中和される前の燐酸基に戻して、共重合体（Ｂ）を析出させる工程（酸析工程）が好ましい。 As a step of bringing the copolymer (B) in a dissolved state into close contact with the surface of the organic pigment (A), a copolymer (A) dissolved with the organic pigment (A) and a basic substance (C) for neutralization ( B) is a step of acidifying the liquid medium containing B) to return the ionized phosphoric acid group in the copolymer to the phosphoric acid group before being neutralized, thereby precipitating the copolymer (B). Analysis step).
酸析工程は、前記分散工程と必要に応じて実施される蒸留工程を経て得られた水性顔料分散体に塩酸、硫酸、酢酸等の酸性物質を加えて酸性化し、中和のための塩基性物質（Ｃ）と塩を形成することによって溶解状態にある共重合体（Ｂ）を有機顔料（Ａ）表面に析出させる工程である。この工程により、有機顔料（Ａ）と共重合体（Ｂ）との相互作用を高めることが出来る。こうして相互作用を高めて得られた析出物を洗浄してから、再度塩基性物質（Ｃ）と共に水に分散させることで、より分散安定性に優れた水性顔料分散体とすることが出来る。前記した様な析出を容易とするために、必要であれば、塩基性物質でも酸性物質でもない無機塩類を併用することも出来る。 The acid precipitation step is acidified by adding an acidic substance such as hydrochloric acid, sulfuric acid, acetic acid, etc. to the aqueous pigment dispersion obtained through the dispersion step and the distillation step performed as necessary, and is basic for neutralization. In this step, the copolymer (B) in a dissolved state is precipitated on the surface of the organic pigment (A) by forming a salt with the substance (C). By this step, the interaction between the organic pigment (A) and the copolymer (B) can be enhanced. The precipitate obtained by increasing the interaction in this manner is washed, and then dispersed again in water together with the basic substance (C), whereby an aqueous pigment dispersion having more excellent dispersion stability can be obtained. In order to facilitate the precipitation as described above, if necessary, inorganic salts that are neither basic substances nor acidic substances can be used in combination.
有機顔料（Ａ）表面と共重合体（Ｂ）との相互作用を高めて得られた析出物を洗浄するに当たっては、その前工程として、析出物のみを濾別する工程を設けることが好ましい。この析出物は有機顔料（Ａ）と共重合体（Ｂ）とからなる固形分である。この工程は前記した酸析工程後の固形分をフィルタープレス、ヌッチェ式濾過装置、加圧濾過装置等により濾過する工程である。 In washing the precipitate obtained by enhancing the interaction between the surface of the organic pigment (A) and the copolymer (B), it is preferable to provide a step of filtering only the precipitate as a previous step. This deposit is a solid content composed of the organic pigment (A) and the copolymer (B). This step is a step of filtering the solid content after the acid precipitation step with a filter press, a Nutsche filtration device, a pressure filtration device or the like.
洗浄工程は、前記濾過工程で濾別された析出物を洗浄濾過する工程であり、この工程を実施することにより、最終的に得られる水性顔料分散体に含有する無機塩類の低減又は除去が可能になる。 The washing step is a step of washing and filtering the precipitate separated in the filtration step. By performing this step, inorganic salts contained in the finally obtained aqueous pigment dispersion can be reduced or removed. become.
前記方法４）に従って水性顔料分散体を製造する場合には、有機顔料（Ａ）に含有する無機塩類とその他の要因で混入してきた無機塩類とをこの洗浄工程で一括して低減又は除去出来ることから、その他の製造方法において前記同様の問題が発生した際に必要となる、有機顔料（Ａ）自体の事前洗浄を独立して行う必要がなく、単位操作がより簡便で済むという長所がある。特に有機顔料は、その原料、反応や微細化等の工程において、無機塩類が混入する余地がカーボンブラックに比べて多いため、この洗浄濾過の工程を経て水性顔料分散体を調製する意義は大きい。 When the aqueous pigment dispersion is produced according to the above method 4), the inorganic salts contained in the organic pigment (A) and the inorganic salts mixed in due to other factors can be reduced or removed in a lump in this washing step. Therefore, there is an advantage that the unit operation is simpler because it is not necessary to independently perform the pre-cleaning of the organic pigment (A) itself, which is necessary when other problems occur in the other production methods. In particular, organic pigments have a lot of room for mixing inorganic salts in the raw material, reaction, refinement, and other steps as compared with carbon black. Therefore, it is significant to prepare an aqueous pigment dispersion through this washing filtration step.
再分散工程は、前記酸析工程、濾過工程によって得られた固形分に中和のための塩基性物質（Ｃ）及び必要により水（Ｄ）や添加物を加えて、再び水性顔料分散体とする工程である。この工程では、共重合体（Ｂ）中のイオン化した燐酸基の対イオンを分散工程で用いたのとは異なる塩基性物質に変更することが出来る。 In the redispersion step, a basic substance (C) for neutralization and, if necessary, water (D) and an additive are added to the solid content obtained by the acid precipitation step and the filtration step, and the aqueous pigment dispersion is again formed. It is a process to do. In this step, the counter ion of the ionized phosphate group in the copolymer (B) can be changed to a basic substance different from that used in the dispersion step.
酸析工程と再分散工程を必須の工程として、好ましくは濾過工程と洗浄工程をも含む製造方法で水性顔料分散体を製造すると、分散粒子として前記した様に有機顔料（Ａ）と共重合体（Ｂ）との相互作用がより高まった状態を容易に形成させることができ、水性顔料分散体として、分散到達レベルや分散安定性等の物性面や耐溶剤性等の使用適性の面で、より優れた特性を発揮させることが出来る。水性顔料分散体は、分散粒子径がメジアン径で２００ｎｍ以下となる様に調製されることが好ましい。 When the aqueous pigment dispersion is produced by a production method including an acid precipitation step and a redispersion step as essential steps, preferably including a filtration step and a washing step, the organic pigment (A) and copolymer are dispersed as described above. The state in which the interaction with (B) is further increased can be easily formed, and as an aqueous pigment dispersion, in terms of physical properties such as dispersion reaching level and dispersion stability and suitability for use such as solvent resistance, More excellent characteristics can be exhibited. The aqueous pigment dispersion is preferably prepared such that the dispersed particle diameter is 200 nm or less in terms of median diameter.
本発明の水性顔料分散体には、更に、公知慣用のスチレン−（メタ）アクリル酸エステル共重合体、ポリエステル樹脂、ポリウレタン樹脂またはその水溶液や水分散液を含めることも出来る。 The aqueous pigment dispersion of the present invention may further contain a known and commonly used styrene- (meth) acrylic acid ester copolymer, polyester resin, polyurethane resin, or an aqueous solution or aqueous dispersion thereof.
この混合は、両者を混合して撹拌することにより容易に調製することが出来る。前記水性顔料分散体に各種樹脂またはその水溶液や水分散液を添加混合して調製しても良いし、その逆の方法で調製しても良い。こうして、後混合された各種樹脂は、水性顔料分散体中の有機顔料（Ａ）に直接的に作用することなく、共重合体（Ｂ）よりも外側に配置される。 This mixing can be easily prepared by mixing and stirring both. The aqueous pigment dispersion may be prepared by adding and mixing various resins or an aqueous solution or aqueous dispersion thereof, or by the reverse method. Thus, the various resins after-mixing are arranged outside the copolymer (B) without directly acting on the organic pigment (A) in the aqueous pigment dispersion.
本発明において水性顔料分散体を製造するに当たっては、有機顔料（Ａ）と、共重合体（Ｂ）と、塩基性物質（Ｃ）と、有機溶剤と、水（Ｄ）とを混合し脱溶剤した後に、酸性物質を加えて濾過水洗し、再度塩基性物質で水へ再分散させて得たインクジェット記録用水性顔料インク調製のための水性顔料分散体とすることが好ましい。 In producing the aqueous pigment dispersion in the present invention, the organic pigment (A), the copolymer (B), the basic substance (C), the organic solvent, and water (D) are mixed to remove the solvent. After that, an aqueous pigment dispersion for preparing an aqueous pigment ink for ink-jet recording obtained by adding an acidic substance, washing with filtered water, and redispersing in water with a basic substance is preferable.
本発明の水性インクは、前記した様な水性顔料分散体を含有する。水性顔料分散体は、そこに、インクジェット記録用水性インクの技術分野で公知慣用となっている各種添加剤、液媒体を含有させることにより、インクジェット記録用水性インクとすることが出来る。具体的には、水性顔料分散体は、質量基準で、有機顔料（Ａ）固形分１〜１０％となる様に水やその他の液媒体で希釈することで、インクジェット記録用水性インクとすることが出来る。粗大粒子や過小粒子の除去や、分散粒子の粒子径分布を調整するために、超遠心分離やミクロフィルターによる濾過を更に行っても良い。 The aqueous ink of the present invention contains the aqueous pigment dispersion as described above. The water-based pigment dispersion can be made into a water-based ink for ink-jet recording by containing various additives and liquid media that are known and commonly used in the technical field of water-based ink for ink-jet recording. Specifically, the water-based pigment dispersion is diluted with water or other liquid medium so that the solid content of the organic pigment (A) is 1 to 10% on a mass basis to form a water-based ink for inkjet recording. I can do it. Ultracentrifugation or filtration with a microfilter may be further performed in order to remove coarse particles and undersized particles and to adjust the particle size distribution of dispersed particles.
こうして得られたインクジェット記録用水性インクは、ピエゾ方式ノズル又はサーマル方式ノズルの各インクジェット記録装置に適用することが出来、公知慣用の被記録媒体に印字記録することが出来る。この際の被記録媒体としては、例えば、ＰＰＣ紙の様な普通紙、写真用紙（光沢）、写真用紙（絹目調）等の様なインクジェット用専用紙、ＯＨＰフィルムの様な合成樹脂フィルム、アルミニウム箔の様な金属箔等の各種フィルム・シートが挙げられる。 The water-based ink for ink jet recording thus obtained can be applied to each ink jet recording apparatus of a piezo type nozzle or a thermal type nozzle, and can be recorded on a known recording medium. As the recording medium at this time, for example, plain paper such as PPC paper, exclusive paper for inkjet such as photographic paper (glossy), photographic paper (silk), synthetic resin film such as OHP film, Various films and sheets, such as metal foils, such as aluminum foil, are mentioned.
以下、実施例および比較例を用いて本発明をさらに詳細に説明する。以下の実施例および比較例において、「部」および「％」は、いずれも質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples and comparative examples, “part” and “%” are both based on mass.
＜合成例１＞
攪拌装置、滴下装置、温度センサー、および上部に窒素導入装置を有する還流装置を取り付けた反応容器を有する自動重合反応装置（重合試験機ＤＳＬ−２ＡＳ型、轟産業（株）製）の反応容器にＩＰＡ ４８０．０部を仕込み、攪拌しながら反応容器内を窒素置換した。反応容器内を窒素雰囲気に保ちながら８０℃に昇温させた後、滴下装置よりメタクリル酸２−ヒドロキシエチル ３０．０部、スチレン １６６．７部、ホスマーＰＥ（一般式において、Ｒ３＝メチル基、ａ＝ｃ＝０、ｂ＝４〜５である、アシッドホスホキシポリエチレングリコールモノメタクリレート。ユニケミカル(株)製） ２０４．０部、メタクリル酸グリシジル １２．０部、ブレンマーＴＧＬ（重合度調整剤） １６．０部およびパーブチル（登録商標）Ｏ（重合開始剤。いずれも日本油脂（株）製） ３２．０部の混合液を４時間かけて滴下した。滴下終了後、さらに同温度で７時間反応を継続させて、酸価１５０、重量平均分子量１１，４００、不揮発分４３．４８％の共重合体Ｂ−１のＩＰＡ溶液を得た。
<Synthesis Example 1>
The reaction vessel of the automatic polymerization reaction device (polymerization tester DSL-2AS type, manufactured by Sakai Sangyo Co., Ltd.) having a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introduction device at the top is IPA. 480.0 parts was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature in the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 30.0 parts of 2-hydroxyethyl methacrylate, 166.7 parts of styrene, phosmer PE (in the general formula, R 3 = methyl group) A = c = 0, b = 4-5, acid phosphoxypolyethylene glycol monomethacrylate (manufactured by Unichemical Co., Ltd.) 204.0 parts, glycidyl methacrylate 12.0 parts, Blemmer TGL (polymerization degree modifier) ) 16.0 parts and perbutyl (registered trademark) O (polymerization initiator, both manufactured by NOF Corporation) 32.0 parts was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was further continued at the same temperature for 7 hours to obtain an IPA solution of copolymer B-1 having an acid value of 150, a weight average molecular weight of 11,400, and a nonvolatile content of 43.48%.
＜合成例２＞
ＩＰＡ １２０．０部、メタクリル酸２−ヒドロキシエチル ７．５部、スチレン ３５．９部、ホスマーＭ（一般式において、Ｒ３＝メチル基、ａ＝ｃ＝０、ｂ＝１である、アシッドホスホキシエチルモノメタクリレート。ユニケミカル(株)製） ３０．４部、メトキシポリエチレングリコールモノメタクリレート（Ｃ２Ｈ４Ｏの繰り返し単位数≒９） ２６．２部、メタクリル酸グリシジル ３．０部、ブレンマーＴＧＬ（重合度調整剤）４．０部およびパーブチル（登録商標）Ｏ ８．０部を用いる以外は合成例１と同様にして、酸価１５０、重量平均分子量７，２００、不揮発分４３．２７％の共重合体Ｂ−２のＩＰＡ溶液を得た。
<Synthesis Example 2>
120.0 parts of IPA, 7.5 parts of 2-hydroxyethyl methacrylate, 35.9 parts of styrene, Phosmer M (in the general formula, R 3 = methyl group, a = c = 0, b = 1, acid phospho Xiethyl monomethacrylate (manufactured by Unichemical Co., Ltd.) 30.4 parts, methoxypolyethylene glycol monomethacrylate (number of C 2 H 4 O repeating units ≈ 9) 26.2 parts, glycidyl methacrylate 3.0 parts, Blemmer TGL (Polymerization degree adjusting agent) Acid value 150, weight average molecular weight 7,200, non-volatile content 43.27% in the same manner as in Synthesis Example 1 except that 4.0 parts and 8.0 parts of perbutyl (registered trademark) O were used. An IPA solution of the copolymer B-2 was obtained.
比較合成例
ＩＰＡ ５６０．０部、メタクリル酸２−ヒドロキシエチル ３０．０部、スチレン １６６．７部、ホスマーＰＥ ２０４．０部およびエチレングリコールジメタクリレート １２部を用いる以外は合成例１と同様にして、酸価１５０、不揮発分４０．３３％の共重合体Ｂ−３のＩＰＡ溶液を得た。
Comparative Synthesis Example Same as Synthesis Example 1 except that 560.0 parts IPA, 30.0 parts 2-hydroxyethyl methacrylate, 166.7 parts styrene, 204.0 parts phosmer PE and 12 parts ethylene glycol dimethacrylate are used. An IPA solution of copolymer B-3 having an acid value of 150 and a nonvolatile content of 40.33% was obtained.
合成例１で得た共重合体Ｂ−１、５％水酸化カリウム水溶液、Ｆａｓｔｇｅｎ（登録商標）Ｂｌｕｅ ５３１０ＳＤ（大日本インキ化学工業（株）社製銅フタロシアニン系顔料）を仕込み、混合した。ここでそれぞれの仕込量は、銅フタロシアニン系顔料が１０００部、共重合体Ｂ−１は顔料に対して不揮発分で３０質量％の比率となる量、５％水酸化カリウム水溶液は共重合体Ｂ−１の酸価が９５％中和される量、水は混合液の不揮発分を２６．６０％とするのに必要な量である。
上記の混合液をペイントコンディショナー（直径０．５mmのジルコニアビーズ使用）で２時間分散した。分散終了後、水を５０００部追加し、ジルコニアビーズを除いて得られた液を遠心分離処理（６０００ G、３０分間）して粗大粒子を除くことにより、不揮発分１２．４７％の水性顔料分散体Ｂ−１を得た。
Copolymer B-1 obtained in Synthesis Example 1 and a 5% aqueous potassium hydroxide solution and Fastgen (registered trademark) Blue 5310SD (copper phthalocyanine pigment manufactured by Dainippon Ink & Chemicals, Inc.) were charged and mixed. Here, the amount charged is 1000 parts of copper phthalocyanine pigment, the amount of copolymer B-1 is 30% by mass in terms of non-volatile content with respect to the pigment, and the 5% aqueous potassium hydroxide solution is copolymer B. The amount by which the acid value of -1 is neutralized by 95%, and water is the amount necessary to make the nonvolatile content of the mixed solution 26.60%.
The above mixture was dispersed with a paint conditioner (using zirconia beads having a diameter of 0.5 mm) for 2 hours. After completion of dispersion, 5000 parts of water was added, and the liquid obtained by removing zirconia beads was centrifuged (6000 G, 30 minutes) to remove coarse particles, thereby dispersing an aqueous pigment having a nonvolatile content of 12.47%. Body B-1 was obtained.
合成例１で得た共重合体Ｂ−１溶液に代えて、合成例２で得た共重合体Ｂ−２溶液を不揮発分で同量となるように用いた以外は、実施例１と同様の操作を行って、不揮発分１２．３９％の水性顔料分散体Ｂ−２を得た。 Instead of the copolymer B-1 solution obtained in Synthesis Example 1, the copolymer B-2 solution obtained in Synthesis Example 2 was used in the same manner as in Example 1 except that the same amount was used for the nonvolatile content. As a result, an aqueous pigment dispersion B-2 having a nonvolatile content of 12.39% was obtained.
比較例１
合成例１で得た共重合体Ｂ−１溶液に代えて、比較合成例で得た共重合体Ｂ−３溶液を不揮発分で同量となるように用いた以外は、実施例１と同様の操作を行って、不揮発分１１．９１％の水性顔料分散体Ｂ−３を得た。
Comparative Example 1
In place of the copolymer B-1 solution obtained in Synthesis Example 1, the copolymer B-3 solution obtained in Comparative Synthesis Example was used in the same manner as in Example 1 except that the same amount of non-volatile content was used. As a result, an aqueous pigment dispersion B-3 having a nonvolatile content of 11.91% was obtained.
（ピエゾ方式インクジェット記録用水性顔料インクの適性評価）
特開平７−２２８８０８号公報記載の実施例１を参考にして、本発明の実施例１の水性顔料分散体を用いてピエゾ方式インクジェット記録用水性顔料インクを調製した。インク組成を以下に示す。
(Appropriate evaluation of water-based pigment ink for piezo inkjet recording)
With reference to Example 1 described in JP-A-7-228808, an aqueous pigment ink for piezo ink jet recording was prepared using the aqueous pigment dispersion of Example 1 of the present invention. The ink composition is shown below.
水性顔料分散体（実施例１） ４２．７部
（顔料分換算で４％となる量）
トリエチレングリコールモノブチルエーテル １０．０部
（インク全体の１０％相当量）
ジエチレングリコール １５．０部
（インク全体の１５％相当量）
サーフィノール４６５（エアプロダクツ社製） ０．８部
（インク全体の０．８％相当量）
水 ３１．５部
（全体で１００％となる様に加える）
Aqueous pigment dispersion (Example 1) 42.7 parts (amount to be 4% in terms of pigment content)
Triethylene glycol monobutyl ether 10.0 parts (equivalent to 10% of the total ink)
Diethylene glycol 15.0 parts (equivalent to 15% of the total ink)
Surfinol 465 (Air Products) 0.8 part (equivalent to 0.8% of the total ink)
31.5 parts of water (added to 100% in total)
（インクジェット記録用水性顔料インクの性能評価）
上記実施例３にて調製したインクジェット記録用水性顔料インクを、市販のピエゾ方式インクジェットプリンタ（ＥＭ−９３０Ｃ型、セイコーエプソン（株）製）のカートリッジに充填し、各種の被記録媒体に印字した。
(Performance evaluation of water-based pigment ink for inkjet recording)
The aqueous pigment ink for inkjet recording prepared in Example 3 was filled in a cartridge of a commercially available piezo inkjet printer (EM-930C type, manufactured by Seiko Epson Corporation), and printed on various recording media.
（普通紙発色評価）
普通紙である、記録紙Ｘｅｒｏｘ ４０２４〔富士ゼロックス（株）製〕への印刷物のベタ部濃度をマクベス反射濃度計スペクトルアイで光学濃度を測定して、普通紙特性として、発色性を評価した。表中にＯＤとして表示した。
○：（ＯＤ）≧１．００
×：（ＯＤ）＜１．００
(Normal paper color evaluation)
The solid density of the printed material on recording paper Xerox 4024 (manufactured by Fuji Xerox Co., Ltd.), which is plain paper, was measured for optical density with a Macbeth reflection densitometer spectrum eye, and the color development was evaluated as the plain paper characteristics. Displayed as OD in the table.
○: (OD) ≧ 1.00
×: (OD) <1.00
（専用紙光沢評価）
専用紙である、インク受理層を有する写真用紙（光沢）〔セイコーエプソン（株）製〕にDuty６０％、８０％及び１００％（ベタ）にて印字した。ＢＹＫガードナー社製ヘイズグロスメータを用いて、得られた印字物表面の２０°グロス値を測定した。得られたグロス値を合計し、専用紙特性として、光沢性を判定した。表中にグロスとして表示した。
(Exclusive paper gloss evaluation)
Printing was performed on 60%, 80%, and 100% (solid) Duty 60%, 80%, and 100% on photographic paper (glossy) (manufactured by Seiko Epson Corporation) having an ink receiving layer, which is a dedicated paper. Using a BYK Gardner haze gloss meter, the 20 ° gloss value of the surface of the obtained printed matter was measured. The gloss values obtained were summed up, and glossiness was determined as a dedicated paper characteristic. Displayed as gross in the table.
（擦過性）
専用紙である、写真用紙（絹目調）〔セイコーエプソン（株）製〕を用いて評価を行った。同写真用紙にベタ印字を行い、印字直後、１０分乾燥後にそれぞれ印字部を指で擦過し、こすれ具合を目視で評価した。表中に擦過性評価として表示した。評価基準を以下に記す。
Ａ：印字は全くとれない
Ｂ：印字は殆どとれず、下地は汚れない
Ｃ：印字が擦りとられるが、下地は汚れない
Ｄ：印字が擦りとられ、下地が汚れる
Ｅ：印字が顕著に擦りとられ、下地もひどく汚れる
表中、左側のアルファベットが印字直後、右側のそれが１０分乾燥後の評価結果である。
(Abrasion)
Evaluation was performed using photographic paper (silk-tone) [manufactured by Seiko Epson Corporation], which is a dedicated paper. Solid printing was carried out on the same photographic paper. Immediately after printing, the printed part was rubbed with a finger after drying for 10 minutes, and the rubbing condition was visually evaluated. It was displayed in the table as a scratch resistance evaluation. The evaluation criteria are described below.
A: Printing is not taken at all B: Printing is hardly taken and the ground is not soiled C: Printing is scraped, but the ground is not soiled D: Printing is scraped, ground is soiled E: Printing is scraped remarkably In the table, the left alphabet is immediately after printing, and the right one is the evaluation result after drying for 10 minutes.
実施例１の水性顔料分散体に代えて、実施例２の水性顔料分散体を用いて同様にピエゾ方式インクジェット記録用水性顔料インクを調製し、同様に評価した。 In place of the aqueous pigment dispersion of Example 1, an aqueous pigment ink for piezo ink jet recording was similarly prepared using the aqueous pigment dispersion of Example 2, and evaluated in the same manner.
〔比較例２〕
実施例１の水性顔料分散体に代えて、比較例１の水性顔料分散体を用いて同様にピエゾ方式インクジェット記録用水性顔料インクを調製し、同様に評価した。
[Comparative Example 2]
In place of the aqueous pigment dispersion of Example 1, an aqueous pigment ink for piezo ink jet recording was similarly prepared using the aqueous pigment dispersion of Comparative Example 1 and evaluated in the same manner.
これらの各評価項目の測定結果は、まとめて表１に示した。 The measurement results for each of these evaluation items are collectively shown in Table 1.
表１ Table 1
上記表１からわかる通り、本発明の水性顔料分散体から得られるインクジェット記録用水性インクは、同じ架橋系の同様インクでの光沢性が改良されており、普通紙上における発色性と専用紙上における光沢性のいずれにも優れていることがわかる。
これに対して、比較例のインクジェット記録用水性インクは、普通紙上における発色性には優れるものの専用紙上における光沢性が劣ったものであった。
As can be seen from Table 1 above, the aqueous ink for inkjet recording obtained from the aqueous pigment dispersion of the present invention has improved glossiness with the same ink of the same cross-linking system, color development on plain paper, and gloss on special paper. It turns out that it is excellent in both of sex.
In contrast, the water-based ink for inkjet recording of the comparative example was excellent in color development on plain paper, but inferior in gloss on special paper.
Claims (6)
前記共重合体（Ｂ）が、燐酸基含有モノエチレン性不飽和単量体とグリシジル（メタ）アクリレートとその他の共重合可能なモノエチレン性不飽和単量体とを必須成分として重合した共重合体であることを特徴とするインクジェット記録用水性インク調製のための水性顔料分散体。 A copolymer (B) of carbon black or organic pigment (A), a phosphoric acid group-containing monoethylenically unsaturated monomer and another copolymerizable ethylenically unsaturated monomer, and a basic substance (C ) And water (D) as essential components, an aqueous pigment dispersion for preparing an aqueous ink for inkjet recording,
Copolymer in which the copolymer (B) is polymerized using a phosphoric acid group-containing monoethylenically unsaturated monomer, glycidyl (meth) acrylate and other copolymerizable monoethylenically unsaturated monomer as essential components A water-based pigment dispersion for preparing a water-based ink for ink-jet recording, which is a coalescence.
A water-based ink for ink-jet recording comprising the water-based pigment dispersion according to any one of claims 1 to 5.
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| JP2008255170A (en) * | 2007-04-02 | 2008-10-23 | Kao Corp | Water-based ink for inkjet recording |
| KR101166183B1 (en) | 2010-10-29 | 2012-07-17 | 주식회사 유엔아이 | Pigment dispersion composite with excellent solvent resistance for color filter and its manufacturing method |
| JP2014101436A (en) * | 2012-11-19 | 2014-06-05 | Ricoh Co Ltd | Ink for inkjet recording, ink cartridge, inkjet recording method, inkjet recording device, and ink recorded material |
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