JP5919021B2 - Pigment water dispersion for inkjet recording - Google Patents
Pigment water dispersion for inkjet recording Download PDFInfo
- Publication number
- JP5919021B2 JP5919021B2 JP2012030406A JP2012030406A JP5919021B2 JP 5919021 B2 JP5919021 B2 JP 5919021B2 JP 2012030406 A JP2012030406 A JP 2012030406A JP 2012030406 A JP2012030406 A JP 2012030406A JP 5919021 B2 JP5919021 B2 JP 5919021B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- pigment
- dispersion
- preferable
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000006185 dispersion Substances 0.000 title claims description 189
- 239000000049 pigment Substances 0.000 title claims description 153
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 64
- 229920000642 polymer Polymers 0.000 claims description 135
- 239000000178 monomer Substances 0.000 claims description 104
- 239000003960 organic solvent Substances 0.000 claims description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- -1 Direct Black 22 Chemical compound 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- DHQJMKJYFOHOSY-UHFFFAOYSA-L disodium 4-amino-3-[[4-[4-[(2,4-diaminophenyl)diazenyl]-3-methylphenyl]-2-methylphenyl]diazenyl]-5-oxido-6-phenyldiazenyl-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Cc1cc(ccc1N=Nc1ccc(N)cc1N)-c1ccc(N=Nc2c(N)c3c(O)c(N=Nc4ccccc4)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(C)c1 DHQJMKJYFOHOSY-UHFFFAOYSA-L 0.000 claims description 9
- XRPLBRIHZGVJIC-UHFFFAOYSA-L chembl3182776 Chemical compound [Na+].[Na+].NC1=CC(N)=CC=C1N=NC1=CC=C(C=2C=CC(=CC=2)N=NC=2C(=CC3=CC(=C(N=NC=4C=CC=CC=4)C(O)=C3C=2N)S([O-])(=O)=O)S([O-])(=O)=O)C=C1 XRPLBRIHZGVJIC-UHFFFAOYSA-L 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- UZZFFIUHUDOYPS-UHFFFAOYSA-L disodium 4-amino-3,6-bis[[4-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]-5-oxido-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccc(cc4)N=Nc4ccc(N)cc4N)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 UZZFFIUHUDOYPS-UHFFFAOYSA-L 0.000 claims description 6
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 221
- 239000000976 ink Substances 0.000 description 94
- 239000000243 solution Substances 0.000 description 60
- 239000002904 solvent Substances 0.000 description 40
- 238000003860 storage Methods 0.000 description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 239000002245 particle Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 238000005299 abrasion Methods 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 125000000524 functional group Chemical group 0.000 description 20
- 239000012528 membrane Substances 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000001965 increasing effect Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 230000003472 neutralizing effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 238000000108 ultra-filtration Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000035515 penetration Effects 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IQFVPQOLBLOTPF-UHFFFAOYSA-L Congo Red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- BPHHNXJPFPEJOF-UHFFFAOYSA-J chembl296966 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=C(N)C2=C(O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=C4C(N)=C(C=C(C4=CC=3)S([O-])(=O)=O)S([O-])(=O)=O)O)OC)=CC=C21 BPHHNXJPFPEJOF-UHFFFAOYSA-J 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
- YRIOTLGRXFJRTJ-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)(COP(O)(=O)O)C1=CC=CC=C1 YRIOTLGRXFJRTJ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- DAVVKEZTUOGEAK-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOC(=O)C(C)=C DAVVKEZTUOGEAK-UHFFFAOYSA-N 0.000 description 1
- JSMWMVVVPBPVPX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxymethyl)butanedioic acid Chemical compound CC(=C)C(=O)OCC(C(O)=O)CC(O)=O JSMWMVVVPBPVPX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 239000011362 coarse particle Substances 0.000 description 1
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- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000006233 lamp black Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([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
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000001577 simple distillation Methods 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、インクジェット記録用顔料水分散液及びその製造方法、並びにインクジェット記録用顔料水分散液を含有するインクジェット記録用顔料水系インクに関する。 The present invention relates to a pigment aqueous dispersion for inkjet recording, a method for producing the same, and a pigment aqueous ink for inkjet recording containing the pigment aqueous dispersion for inkjet recording.
インクジェット記録方式は、非常に微細なノズルからインク液滴を記録部材に直接吐出し、付着させて、文字や画像を得る記録方式である。この方式は、フルカラー化が容易で、かつ安価であり、記録部材として普通紙が使用可能、被印字物に対して非接触、という数多くの利点があるため普及が著しい。
最近では、印刷物に耐候性や耐水性を付与するために、インクジェット記録方式において、着色剤として顔料を用いるインクジェット記録用インクが広く用いられている。
The ink jet recording system is a recording system in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle and attaching them to a recording member. This method is widely spread because it is easy to make full color and is inexpensive, and has many advantages such as the ability to use plain paper as a recording member and non-contact with the object to be printed.
Recently, in order to impart weather resistance and water resistance to printed matter, ink for ink jet recording using a pigment as a colorant is widely used in the ink jet recording method.
顔料インクを用いたインクジェット記録方式においては、印刷後の印刷物の表面に顔料粒子が残留するため、得られた印刷物同士が擦れあうことにより、顔料が剥がれて印字が薄くなる等の問題があった。
この問題に対して、染料構造を有する基を含むポリマーを、インクに含有させることが行われている。
例えば、特許文献１には、染料とオレフィン含有反応性物質との縮合反応により調製されるオレフィン系モノマーから生成する着色樹脂エマルション粒子と、顔料とを含む水性インクジェット用インク組成物が、用紙のカール、画像のスミア等を抑制することが開示されている。
特許文献２には、アゾメチン染料、インドアニリン染料、又はアゾ染料がポリマー骨格に連結したコポリマーを含有するインキジェット用インクが、優れた耐水堅牢性及び耐摩耗性等を示し、長い保存時間の後でもノズルを目詰まりさせないことが開示されている。
一方、染料構造を有する基を含むポリマーを含有するインクとして、特許文献３には、平均分子量が５０００〜１５万の高分子染料、顔料、特定の高分子化合物及び／又は界面活性剤、水、並びに水溶性有機溶媒を主成分とする記録用インクが、画像にじみの抑制、耐水性及び吐出信頼性に優れることが開示されている。
In the ink jet recording system using pigment ink, since pigment particles remain on the surface of the printed matter after printing, there is a problem that the printed matter is rubbed with each other, so that the pigment is peeled off and the printing becomes thin. .
In order to solve this problem, a polymer containing a group having a dye structure is included in the ink.
For example, Patent Document 1 discloses an aqueous ink-jet ink composition containing colored resin emulsion particles produced from an olefin-based monomer prepared by a condensation reaction of a dye and an olefin-containing reactive substance, and a pigment. In addition, it is disclosed to suppress smear and the like of an image.
In Patent Document 2, an ink for an ink jet containing an azomethine dye, an indoaniline dye, or a copolymer in which an azo dye is linked to a polymer skeleton exhibits excellent water fastness and abrasion resistance, and after a long storage time. However, it is disclosed that the nozzle is not clogged.
On the other hand, as an ink containing a polymer containing a group having a dye structure, Patent Document 3 discloses that a polymer dye, pigment, specific polymer compound and / or surfactant having an average molecular weight of 5000 to 150,000, water, In addition, it is disclosed that a recording ink containing a water-soluble organic solvent as a main component is excellent in suppression of image bleeding, water resistance and ejection reliability.
顔料インクを用いたインクジェット記録方式は、少量多品種でバリアブルなフルカラー印刷を安価で得られることから、商業印刷に使用され始めている。しかしながら、商業印刷に用いるためには、さらなる耐擦性の向上や裏抜けの抑制が求められ、従来の技術では不十分である。
本発明の課題は、耐擦性に優れ、裏抜けが抑制された印刷物を与えるインクジェット記録用顔料水分散液及びその製造方法、並びに該顔料水分散液を用いたインクジェット記録用インクを提供することにある。
Inkjet recording systems using pigment inks are beginning to be used in commercial printing because they can produce a variety of small-variety and variable full-color printing at low cost. However, for use in commercial printing, further improvement in abrasion resistance and suppression of back-through are required, and conventional techniques are insufficient.
An object of the present invention is to provide a pigment aqueous dispersion for inkjet recording which gives a printed matter having excellent abrasion resistance and suppressed penetration, a method for producing the same, and an inkjet recording ink using the aqueous pigment dispersion. It is in.
本発明者は、上記の問題を解決するための方針として、インクを記録媒体に定着する際に、記録媒体を構成するセルロース繊維とインク構成成分である色材樹脂との間に形成される分子間力が重要であると考えて検討を行った。その結果、特定の染料構造を有する基を含むポリマーを含有する顔料水分散液を用いたインクジェット記録用インクが、耐擦性に優れ、裏抜けが抑制されることを見出した。
すなわち、本発明は、次の［１］〜［３］に関する。
［１］染料構造を有する基を含むポリマーと顔料とを含有するインクジェット記録用顔料水分散液であって、前記染料構造がDirect Black19、Direct Black22、Direct Black38、Direct Black154、及びDirect blue 2に由来する構造からなる群から選ばれる１種以上である、インクジェット記録用顔料水分散液。
［２］上記のインクジェット記録用顔料水分散液を含有するインクジェット記録用水系インク。
［３］下記の工程（１）〜（２）を含む、上記のインクジェット記録用顔料水分散液の製造方法。
工程（１）：前記染料構造を有する基を含むポリマー、有機溶媒、顔料、及び水を含有する混合物を分散処理して、分散処理物を得る工程
工程（２）：工程（１）で得られた分散処理物から前記有機溶媒を除去して、顔料水分散液を得る工程
As a policy for solving the above problems, the present inventor, when fixing the ink to the recording medium, molecules formed between the cellulose fibers constituting the recording medium and the color material resin which is an ink constituent component. Considering that interactivity is important. As a result, it has been found that an ink for inkjet recording using an aqueous pigment dispersion containing a polymer containing a group having a specific dye structure is excellent in abrasion resistance and can be prevented from see-through.
That is, the present invention relates to the following [1] to [3].
[1] An aqueous pigment dispersion for inkjet recording containing a polymer containing a group having a dye structure and a pigment, wherein the dye structure is derived from Direct Black 19, Direct Black 22, Direct Black 38, Direct Black 154, and Direct blue 2 A pigment aqueous dispersion for inkjet recording, which is at least one selected from the group consisting of:
[2] A water-based ink for ink-jet recording containing the aqueous pigment dispersion for ink-jet recording described above.
[3] A method for producing the above-described aqueous pigment dispersion for inkjet recording, comprising the following steps (1) to (2).
Step (1): A step of dispersing a mixture containing a polymer having a group having a dye structure, an organic solvent, a pigment, and water to obtain a dispersion-treated product Step (2): obtained in Step (1) Removing the organic solvent from the dispersion treatment product to obtain a pigment aqueous dispersion
本発明のインクジェット記録用顔料水分散液及びこれを含有するインクは、耐擦性に優れ、裏抜けが抑制された印刷物を与える効果を奏するものである。 The aqueous pigment dispersion for ink jet recording of the present invention and the ink containing the same exhibit an effect of giving a printed matter that is excellent in abrasion resistance and suppressed from see-through.
本発明のインクジェット記録用顔料水分散液（以下、「顔料水分散液」ともいう）は、染料構造を有する基を含むポリマー（以下、「染料含有ポリマー」ともいう）と顔料とを含有するインクジェット記録用顔料水分散液であって、前記染料構造がDirect Black19、Direct Black22、Direct Black38、Direct Black154、及びDirect blue 2に由来する構造からなる群から選ばれる１種以上であるものである。 The aqueous pigment dispersion for inkjet recording of the present invention (hereinafter also referred to as “pigment aqueous dispersion”) is an inkjet containing a polymer containing a group having a dye structure (hereinafter also referred to as “dye-containing polymer”) and a pigment. An aqueous recording pigment dispersion, wherein the dye structure is at least one selected from the group consisting of structures derived from Direct Black 19, Direct Black 22, Direct Black 38, Direct Black 154, and Direct blue 2.
本発明のインクジェット記録用顔料水分散液が、耐擦性に優れ、裏抜けが抑制された印刷物を与える効果を奏する理由は定かではないが、以下のように考えられる。
紙を構成するセルロースは、Ｄ−グルコースがβ−１，４結合で長く繋がったポリマーであり、平板状の疎水性面を備えている。この平板状の疎水性面は、インクジェット記録用インクに一般に用いられているアクリルポリマー等とは分子間力が発揮されず、当該インクジェット記録用インクは定着性に劣る。
これに対し、広いπ電子平面を持つ染料構造をポリマーに含有させることで、染料構造とセルロース疎水性面との間で相互作用が多点で発生し、ポリマーの紙への定着性及び耐擦過性が向上するものと考えられる。特にこの相互作用は、インクの溶媒の誘電率による影響を受けないため、水等の溶媒中でも減衰しない。
また、その染料構造を、π電子平面を持つ骨格もしくは置換基の種類、位置等によって非対称性にし、π電子平面上の電子密度に偏りを生じさせることで、インク浸透時のセルロースへの親和性が高まり、顔料粒子の紙表面近傍への定着性が向上し、裏抜けが抑制されると考えられる。なお、後述するとおり、本発明の染料構造は、式（１）〜（５）に示す染料に由来するために非対称性となっているのに対して、比較例で用いるポリマーの染料構造は、式（６）及び式（７）に示す染料に由来するために対称性となっている。
上記作用により、顔料粒子の紙表面近傍への定着性が向上し、その結果、耐擦性及び耐裏抜け性が改善されると考えられる。
The reason why the aqueous pigment dispersion for inkjet recording of the present invention has an effect of giving a printed matter excellent in abrasion resistance and suppressed from see-through is not clear, but is considered as follows.
Cellulose constituting the paper is a polymer in which D-glucose is long connected by β-1,4 bonds, and has a flat hydrophobic surface. This flat hydrophobic surface does not exhibit intermolecular force with an acrylic polymer or the like generally used for ink jet recording ink, and the ink jet recording ink is poor in fixability.
In contrast, by incorporating a dye structure having a wide π-electron plane into the polymer, multiple interactions occur between the dye structure and the hydrophobic surface of the cellulose, thereby fixing the polymer to paper and scratch resistance. This is considered to improve the performance. In particular, since this interaction is not affected by the dielectric constant of the ink solvent, it is not attenuated even in a solvent such as water.
In addition, the dye structure is made asymmetric depending on the skeleton or substituent type, position, etc. of the π-electron plane, and the electron density on the π-electron plane is biased. It is considered that the fixability of the pigment particles to the vicinity of the paper surface is improved, and the back-through is suppressed. As will be described later, the dye structure of the present invention is asymmetric because it is derived from the dyes represented by the formulas (1) to (5), whereas the dye structure of the polymer used in the comparative example is: Since it is derived from the dyes represented by the formulas (6) and (7), it is symmetrical.
By the above action, it is considered that the fixability of the pigment particles to the vicinity of the paper surface is improved, and as a result, the abrasion resistance and the penetration resistance are improved.
［顔料］
本発明に用いられる顔料としては、無機顔料及び有機顔料のいずれであってもよい。
無機顔料としては、例えば、カーボンブラック、金属酸化物等が挙げられ、特に黒色インクにおいては、カーボンブラックが好ましい。カーボンブラックとしては、ファーネスブラック、サーマルランプブラック、アセチレンブラック、チャンネルブラック等が挙げられる。
有機顔料としては、例えば、アゾ顔料、ジアゾ顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリノン顔料、ジオキサジン顔料、ペリレン顔料、ペリノン顔料、チオインジゴ顔料、アントラキノン顔料、キノフタロン顔料等が挙げられる。
色相は特に限定されず、イエロー、マゼンタ、シアン、赤色、青色、オレンジ、グリーン等の有彩色顔料をいずれも用いることができる。
染料含有ポリマーの色相への影響を低減する観点から、色相は黒色が好ましく、用いる顔料としては、カーボンブラックが好ましい。
[Pigment]
The pigment used in the present invention may be either an inorganic pigment or an organic pigment.
Examples of the inorganic pigment include carbon black and metal oxide, and carbon black is particularly preferable for black ink. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.
Examples of the organic pigment include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments.
The hue is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, red, blue, orange, and green can be used.
From the viewpoint of reducing the influence of the dye-containing polymer on the hue, the hue is preferably black, and the pigment used is preferably carbon black.
［染料含有ポリマー］
＜染料構造を有する基＞
本発明に用いられる染料含有ポリマーは、Direct Black19、Direct Black22、Direct Black38、Direct Black154、及びDirect blue 2といった染料からなる群から選ばれる１種以上に由来する染料構造を有する基を含むものである。
これらの染料の中で、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、Direct Black22、Direct Black38、Direct Black154が好ましい。
染料含有ポリマー中における染料に由来する部分を染料構造という。染料中のアミノ基の部位が、染料含有ポリマー中の他の構成部分と結合される。
また、染料含有ポリマーは２種以上の染料構造を有する基を含んでもよい。
なお、Direct Black19、Direct Black22、Direct Black38、Direct Black154、及びDirect blue 2の化学式は、それぞれ、下記式（１）〜（５）に示すとおりである。下記式（１）〜（５）に示す染料を、以下総称して「染料」という。
[Dye-containing polymer]
<Group having dye structure>
The dye-containing polymer used in the present invention includes a group having a dye structure derived from one or more selected from the group consisting of dyes such as Direct Black 19, Direct Black 22, Direct Black 38, Direct Black 154, and Direct blue 2.
Among these dyes, Direct Black 22, Direct Black 38, and Direct Black 154 are preferable from the viewpoint of obtaining a printed material having excellent abrasion resistance and suppressed penetration.
A portion derived from a dye in the dye-containing polymer is referred to as a dye structure. The site of the amino group in the dye is bonded to other components in the dye-containing polymer.
The dye-containing polymer may contain a group having two or more dye structures.
The chemical formulas of Direct Black 19, Direct Black 22, Direct Black 38, Direct Black 154, and Direct blue 2 are as shown in the following formulas (1) to (5), respectively. The dyes represented by the following formulas (1) to (5) are hereinafter collectively referred to as “dyes”.
＜染料含有ポリマーの種類＞
本発明に用いられる染料含有ポリマーとしては、例えば、
（Ｉ）該染料構造を有する基を含むモノマー（以下、「染料含有モノマー」ともいう）を重合させて得られるポリマー（以下、「染料含有ポリマー（Ｉ）」ともいう）、及び、
（ＩＩ）染料と反応する官能基を有するポリマーと該染料とを反応させて得られるポリマー（以下、「染料含有ポリマー（ＩＩ）」ともいう）、
の２種類が挙げられるが、未反応の染料を低減し、ポリマー中の染料の含有量を高める観点から、染料含有ポリマー（Ｉ）が好ましい。
以下、染料含有ポリマー（Ｉ）について説明する。
<Types of dye-containing polymer>
As the dye-containing polymer used in the present invention, for example,
(I) a polymer obtained by polymerizing a monomer having a group having the dye structure (hereinafter also referred to as “dye-containing monomer”) (hereinafter also referred to as “dye-containing polymer (I)”), and
(II) a polymer obtained by reacting the dye with a polymer having a functional group that reacts with the dye (hereinafter also referred to as “dye-containing polymer (II)”),
The dye-containing polymer (I) is preferable from the viewpoint of reducing the unreacted dye and increasing the content of the dye in the polymer.
Hereinafter, the dye-containing polymer (I) will be described.
＜染料含有ポリマー（Ｉ）＞
染料含有モノマーを重合させて得られるポリマーとしては、ポリエステル、ポリウレタン、ビニル系ポリマー等が挙げられるが、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、ビニル単量体の付加重合により得られるビニル系ポリマーが好ましい。
<Dye-containing polymer (I)>
Examples of the polymer obtained by polymerizing the dye-containing monomer include polyesters, polyurethanes, and vinyl polymers. From the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the vinyl monomer is used. A vinyl polymer obtained by addition polymerization of is preferred.
染料含有ポリマーとしては、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、染料含有モノマー（ａ）（以下、「（ａ）成分」ともいう）と、イオン性モノマー（ｂ）（以下、「（ｂ）成分」ともいう）とを含むモノマー混合物（以下、「モノマー混合物」ともいう）を共重合させてなる染料含有ポリマーが好ましい。この染料含有ポリマーは、（ａ）成分由来の構成単位と（ｂ）成分由来の構成単位を有する。
また、本発明に用いられる染料含有ポリマーには、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、更に（ｃ）疎水性モノマー（以下、「（ｃ）成分」ともいう）をモノマー成分として用いるのが好ましい。更に、（ｄ）ノニオン性モノマー（以下、「（ｄ）成分」ともいう）をモノマー成分として用いてもよい。
ビニル系ポリマーとしては、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、（ａ）成分と、（ｂ）成分と、更に必要に応じて（ｃ）成分及び／又は（ｄ）成分とを含むモノマー混合物を共重合させてなるビニル系ポリマーが好ましい。このビニル系ポリマーは、（ａ）成分由来の構成単位及び（ｂ）成分由来の構成単位を有し、必要に応じて更に（ｃ）成分由来の構成単位及び／又は（ｄ）成分由来の構成単位を有する。
As the dye-containing polymer, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the dye-containing monomer (a) (hereinafter also referred to as “component (a)”), an ionic monomer ( b) (hereinafter also referred to as “component (b)”) is preferably a dye-containing polymer obtained by copolymerizing a monomer mixture (hereinafter also referred to as “monomer mixture”). This dye-containing polymer has a structural unit derived from the component (a) and a structural unit derived from the component (b).
In addition, the dye-containing polymer used in the present invention further includes (c) a hydrophobic monomer (hereinafter referred to as “component (c)”) from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink. Are preferably used as monomer components. Furthermore, (d) a nonionic monomer (hereinafter also referred to as “component (d)”) may be used as a monomer component.
As the vinyl polymer, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the component (a), the component (b), and, if necessary, the component (c) and / or A vinyl polymer obtained by copolymerizing a monomer mixture containing the component (d) is preferable. This vinyl-based polymer has a structural unit derived from the component (a) and a structural unit derived from the component (b), and if necessary, a structural unit derived from the component (c) and / or a structure derived from the component (d). Has units.
（染料含有モノマー（ａ））
染料含有モノマー（ａ）は、該染料構造を有する基とビニル基とを含むものが好適である。染料含有モノマー（ａ）は、未反応の染料を低減し、ポリマー中の染料の含有量を高める観点から、該染料とグリシジル（メタ）アクリレートを反応させて得られるモノマーが好ましい。ここで、「（メタ）アクリレート」は、アクリレート及び／又はメタクリレートを示す。
また、上記染料含有モノマー（ａ）は、染料から持ち込まれる食塩、芒硝等を除去する観点及び染料含有モノマー（ａ）の生産性を向上させる観点から、染料を精製したものを用いることが好ましい。
これらの観点から、染料含有モノマー（ａ）は、染料を精製して精製染料を得る工程（４）、工程（４）で得られた精製染料とグリシジル(メタ)アクリレートを反応させて染料含有モノマー（ａ）を得る工程（５）によって得られるモノマーが好ましい。
(Dye-containing monomer (a))
The dye-containing monomer (a) preferably contains a group having the dye structure and a vinyl group. The dye-containing monomer (a) is preferably a monomer obtained by reacting the dye with glycidyl (meth) acrylate from the viewpoint of reducing unreacted dye and increasing the content of the dye in the polymer. Here, “(meth) acrylate” refers to acrylate and / or methacrylate.
The dye-containing monomer (a) is preferably a purified dye from the viewpoint of removing salt, mirabilite, etc. brought from the dye and improving the productivity of the dye-containing monomer (a).
From these viewpoints, the dye-containing monomer (a) is a dye-containing monomer obtained by reacting the purified dye obtained in step (4) and glycidyl (meth) acrylate with a purified dye obtained by purifying the dye. Monomers obtained by step (5) to obtain (a) are preferred.
《精製染料を得る工程（４）》
工程（４）は、染料を染料の良溶媒中に溶解させ、次いで貧溶媒中に添加することで精製染料を得る工程である。
良溶媒としては、染料を溶解させる観点から、ジメチルホルムアミド、２―ピロリドン、ジメチルスルホキシドが好ましく、ジメチルホルムアミドがより好ましい。
染料に対する良溶媒の重量比（良溶媒／染料）は、染料の溶解を促進させ、精製染料の生産性を向上させる観点及び染料の析出を容易にする観点から、１〜１０が好ましく、２〜８がより好ましく、２〜５が更に好ましい。
染料を良溶媒に溶解させる温度は、染料の溶解を促進させる観点及び精製染料の生産性を向上させる観点から、０〜７０℃が好ましく、１０〜４０℃がより好ましく、１５〜３５℃が更に好ましい。
<< Step of obtaining purified dye (4) >>
Step (4) is a step of obtaining a purified dye by dissolving the dye in a good solvent of the dye and then adding the dye in a poor solvent.
The good solvent is preferably dimethylformamide, 2-pyrrolidone or dimethylsulfoxide, more preferably dimethylformamide from the viewpoint of dissolving the dye.
The weight ratio of the good solvent to the dye (good solvent / dye) is preferably 1 to 10 from the viewpoint of promoting dissolution of the dye, improving the productivity of the purified dye, and facilitating precipitation of the dye. 8 is more preferable, and 2 to 5 is still more preferable.
The temperature at which the dye is dissolved in the good solvent is preferably 0 to 70 ° C, more preferably 10 to 40 ° C, and further preferably 15 to 35 ° C from the viewpoint of promoting the dissolution of the dye and improving the productivity of the purified dye. preferable.
染料を良溶媒に溶解した後、染料含有モノマーの生産性を向上させる観点から、溶解液をろ過することで、良溶媒中に溶けにくい食塩、芒硝等を除去することが好ましい。
ろ過は、ろ紙や金属メッシュフィルターを用いて行うことができる。
From the viewpoint of improving the productivity of the dye-containing monomer after dissolving the dye in a good solvent, it is preferable to filter the solution to remove salt, sodium sulfate, etc., which are hardly soluble in the good solvent.
Filtration can be performed using a filter paper or a metal mesh filter.
前記良溶媒の染料溶液に貧溶媒を添加し、染料を析出させて精製染料を得る。
貧溶媒としては、染料を析出させる観点から、トルエン、メチルエチルケトン、酢酸エチル、ヘキサン、２−プロパノール、エタノール、メタノール等が挙げられ、ヘキサンと２−プロパノールが好ましい。
染料と良溶媒の親和性が、貧溶媒と良溶媒の親和性よりも高い場合、あらかじめ良溶媒との親和性の低いヘキサン等の貧溶媒中に染料溶液を滴下し、この混合溶液を撹拌しながら良溶媒との親和性が高い２−プロパノール等の貧溶媒を滴下することで、染料溶液から有効に良溶媒を除去することが好ましい。
良溶媒に対する貧溶媒の重量比（貧溶媒／良溶媒）は、染料の析出を容易にする観点及び精製染料の生産性を向上させる観点から、０．５〜２０が好ましく、１．５〜１０がより好ましく、３〜５が更に好ましい。
析出した染料は、遠心分離等の分離方法で分離することができる。
さらに、析出した染料に残った良溶媒及び塩を除去する観点から、誘電率の高いアルコール類等の貧溶媒で染料を洗浄、ろ過することが好ましい。
さらに、残留した溶媒を除去する観点から、染料を加熱乾燥することが好ましい。乾燥温度は、乾燥効率を向上させる観点から、貧溶媒の沸点以上が好ましく、染料の耐熱性の観点から、１２０℃以下がより好ましく、８０〜１２０℃が更に好ましい。
A poor solvent is added to the dye solution of the good solvent to precipitate the dye to obtain a purified dye.
Examples of the poor solvent include toluene, methyl ethyl ketone, ethyl acetate, hexane, 2-propanol, ethanol, methanol and the like from the viewpoint of precipitating the dye, and hexane and 2-propanol are preferable.
If the affinity between the dye and the good solvent is higher than the affinity between the poor solvent and the good solvent, drop the dye solution in advance in a poor solvent such as hexane, which has a low affinity with the good solvent, and stir the mixed solution. However, it is preferable to effectively remove the good solvent from the dye solution by dropping a poor solvent such as 2-propanol having high affinity with the good solvent.
The weight ratio of the poor solvent to the good solvent (poor solvent / good solvent) is preferably 0.5 to 20, preferably 1.5 to 10 from the viewpoint of facilitating the precipitation of the dye and improving the productivity of the purified dye. Is more preferable, and 3 to 5 is still more preferable.
The precipitated dye can be separated by a separation method such as centrifugation.
Further, from the viewpoint of removing the good solvent and salt remaining in the deposited dye, it is preferable to wash and filter the dye with a poor solvent such as an alcohol having a high dielectric constant.
Furthermore, it is preferable to heat-dry the dye from the viewpoint of removing the remaining solvent. From the viewpoint of improving the drying efficiency, the drying temperature is preferably equal to or higher than the boiling point of the poor solvent, more preferably 120 ° C. or less, and further preferably 80 to 120 ° C. from the viewpoint of heat resistance of the dye.
《染料含有モノマーを得る工程（５）》
工程（５）は、工程（４）で得られた精製染料とグリシジル（メタ）アクリレートを溶媒中にて反応させ、染料含有モノマーを得る工程である。
溶媒としては、染料を溶解させる観点及びグリシジル（メタ）アクリレートと反応し難いという観点から、２−ピロリドン、ジメチルスルホキシドが好ましい。
また、重合禁止剤を用いることが好ましく、重合禁止剤としては、p-メトキシフェノール等が好ましい。
グリシジル（メタ）アクリレートと染料の反応性を高める観点から、反応促進剤を用いることが好ましく、反応促進剤としてはテトラブチルアンモニウムブロミド等が好ましい。
<< Step of obtaining dye-containing monomer (5) >>
Step (5) is a step of obtaining the dye-containing monomer by reacting the purified dye obtained in step (4) with glycidyl (meth) acrylate in a solvent.
As the solvent, 2-pyrrolidone and dimethyl sulfoxide are preferable from the viewpoint of dissolving the dye and being difficult to react with glycidyl (meth) acrylate.
A polymerization inhibitor is preferably used, and as the polymerization inhibitor, p-methoxyphenol or the like is preferable.
From the viewpoint of increasing the reactivity between glycidyl (meth) acrylate and the dye, a reaction accelerator is preferably used, and the reaction accelerator is preferably tetrabutylammonium bromide.
反応温度は、反応速度および収率を高める観点から、５０〜１２０℃が好ましく、８５〜１１０℃がより好ましく、９０〜９８℃が更に好ましい。
反応時間は、収率を高める観点及び染料含有モノマーの生産性を高める観点から、１〜２０時間であることが好ましく、５〜１５時間がより好ましく、６〜１０時間が更に好ましい。
また、熱等で発生するラジカルによるビニル基の反応を抑制する観点から、ラジカル捕捉剤として酸素を含む空気を反応溶液中にバブリングさせることが好ましい。
また、必要に応じて、反応溶液から再沈澱、溶媒留去等の公知の方法により、生成したモノマーを単離することができる。
The reaction temperature is preferably 50 to 120 ° C, more preferably 85 to 110 ° C, and still more preferably 90 to 98 ° C from the viewpoint of increasing the reaction rate and yield.
The reaction time is preferably 1 to 20 hours, more preferably 5 to 15 hours, and further preferably 6 to 10 hours from the viewpoint of increasing the yield and increasing the productivity of the dye-containing monomer.
From the viewpoint of suppressing the reaction of the vinyl group by radicals generated by heat or the like, it is preferable to bubble air containing oxygen as a radical scavenger into the reaction solution.
Moreover, the produced | generated monomer can be isolated from a reaction solution by well-known methods, such as reprecipitation and solvent distillation, as needed.
（（ｂ）イオン性モノマー）
（ｂ）イオン性モノマーは、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、染料含有ポリマーのモノマー成分として用いられる。イオン性モノマーとしては、アニオン性モノマー及びカチオン性モノマーが挙げられ、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点、吐出性を向上させる観点から、アニオン性モノマーが好ましい。
アニオン性モノマーとしては、カルボン酸モノマー、スルホン酸モノマー、リン酸モノマー等が挙げられる。
カルボン酸モノマーとしては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、シトラコン酸、２−メタクリロイルオキシメチルコハク酸等が挙げられる。
スルホン酸モノマーとしては、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、３−スルホプロピル（メタ）アクリレート等が挙げられる。
リン酸モノマーとしては、ビニルホスホン酸、ビニルホスフェート、ビス（メタクリロキシエチル）ホスフェート、ジフェニル−２−アクリロイルオキシエチルホスフェート、ジフェニル−２−メタクリロイルオキシエチルホスフェート等が挙げられる。
上記アニオン性モノマーの中では、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、カルボン酸モノマーが好ましく、アクリル酸及びメタクリル酸がより好ましく、メタクリル酸が更に好ましい。
((B) ionic monomer)
(B) The ionic monomer is used as a monomer component of the dye-containing polymer from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink. Examples of the ionic monomer include an anionic monomer and a cationic monomer, and the anionic monomer is preferable from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability.
Examples of the anionic monomer include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.
Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
Examples of the sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 3-sulfopropyl (meth) acrylate.
Examples of the phosphoric acid monomer include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like.
Among the anionic monomers, carboxylic acid monomers are preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is still more preferable from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink.
（（ｃ）疎水性モノマー）
（ｃ）疎水性モノマーとしては、芳香族基含有モノマー、アルキル（メタ）アクリレート等が挙げられる。
芳香族基含有モノマーとしては、炭素数６〜２２の芳香族基を有するビニルモノマーが好ましく、スチレン系モノマーや芳香族基含有（メタ）アクリレート等がより好ましい。
スチレン系モノマーとしてはスチレン、２−メチルスチレンが好ましく、スチレンがより好ましい。
また、芳香族基含有（メタ）アクリレートとしては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートが好ましく、ベンジル（メタ）アクリレートがより好ましい。
顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、芳香族基含有（メタ）アクリレートが好ましく、芳香族基含有（メタ）アクリレートとスチレン系モノマーを併用することも好ましい。
((C) hydrophobic monomer)
(C) As a hydrophobic monomer, an aromatic group containing monomer, an alkyl (meth) acrylate, etc. are mentioned.
As the aromatic group-containing monomer, a vinyl monomer having an aromatic group having 6 to 22 carbon atoms is preferable, and a styrene monomer, an aromatic group-containing (meth) acrylate, and the like are more preferable.
As the styrene monomer, styrene and 2-methylstyrene are preferable, and styrene is more preferable.
Moreover, as an aromatic group containing (meth) acrylate, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable, and benzyl (meth) acrylate is more preferable.
From the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, an aromatic group-containing (meth) acrylate is preferable, and it is also preferable to use the aromatic group-containing (meth) acrylate and a styrene monomer in combination.
アルキル（メタ）アクリレートとしては、炭素数１〜２２、好ましくは炭素数６〜１８のアルキル基を有するものが好ましく、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、（イソ）プロピル（メタ）アクリレート、（イソ又はターシャリー）ブチル（メタ）アクリレート、（イソ）アミル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、（イソ）オクチル（メタ）アクリレート、（イソ）デシル（メタ）アクリレート、（イソ）ドデシル（メタ）アクリレート、（イソ）ステアリル（メタ）アクリレート等が挙げられる。
なお、「（イソ又はターシャリー）」及び「（イソ）」は、これらの基が存在する場合としない場合の双方を意味し、これらの基が存在しない場合には、ノルマルを示す。
As the alkyl (meth) acrylate, those having an alkyl group having 1 to 22 carbon atoms, preferably 6 to 18 carbon atoms are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meta) ) Acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) Examples include decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, and (iso) stearyl (meth) acrylate.
In addition, “(iso or tertiary)” and “(iso)” mean both cases in which these groups are present and cases in which these groups are not present.
（ｃ）疎水性モノマーとして、マクロマーを用いてもよい。
マクロマーは、片末端に重合性官能基を有する数平均分子量５００〜１００，０００の化合物であり、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、１，０００〜１０，０００が好ましい。なお、数平均分子量は、溶媒として１ｍｍｏｌ／Ｌのドデシルジメチルアミンを含有するクロロホルムを用いたゲル浸透クロマトグラフィー法により、標準物質としてポリスチレンを用いて測定される値である。
片末端に存在する重合性官能基としては、（メタ）アクリロイルオキシ基が好ましく、メタクリロイルオキシ基がより好ましい。
マクロマーとしては、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、芳香族基含有モノマー系マクロマー及びシリコーン系マクロマーが好ましく、芳香族基含有モノマー系マクロマーがより好ましい。
芳香族基含有モノマー系マクロマーを構成する芳香族基含有モノマーとしては、前記（ｃ）疎水性モノマーで記載した芳香族基含有モノマーが挙げられ、スチレン及びベンジル（メタ）アクリレートが好ましく、スチレンがより好ましい。
スチレン系マクロマーの具体例としては、ＡＳ−６（Ｓ）、ＡＮ−６（Ｓ）、ＨＳ−６（Ｓ）（東亞合成株式会社製の商品名）等が挙げられる。
シリコーン系マクロマーとしては、片末端に重合性官能基を有するオルガノポリシロキサン等が挙げられる。
(C) A macromer may be used as the hydrophobic monomer.
The macromer is a compound having a polymerizable functional group at one end and a number average molecular weight of 500 to 100,000. From the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, 1,000 to 10 are used. 1,000 is preferred. The number average molecular weight is a value measured using polystyrene as a standard substance by gel permeation chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent.
The polymerizable functional group present at one end is preferably a (meth) acryloyloxy group, and more preferably a methacryloyloxy group.
As the macromer, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, an aromatic group-containing monomer macromer and a silicone macromer are preferable, and an aromatic group-containing monomer macromer is more preferable.
Examples of the aromatic group-containing monomer constituting the aromatic group-containing monomer-based macromer include the aromatic group-containing monomers described in the above (c) hydrophobic monomer, styrene and benzyl (meth) acrylate are preferable, and styrene is more preferable. preferable.
Specific examples of the styrenic macromer include AS-6 (S), AN-6 (S), HS-6 (S) (trade name, manufactured by Toagosei Co., Ltd.), and the like.
Examples of the silicone macromer include organopolysiloxane having a polymerizable functional group at one end.
（（ｄ）ノニオン性モノマー）
（ｄ）ノニオン性モノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、ポリプロピレングリコール（ｎ＝２〜３０、ｎはオキシアルキレン基の平均付加モル数を示す。以下同じ）（メタ）アクリレート等のポリアルキレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（ｎ＝１〜３０）（メタ）アクリレート等のアルコキシポリアルキレングリコール（メタ）アクリレート、フェノキシ（エチレングリコール・プロピレングリコール共重合）（ｎ＝１〜３０、その中のエチレングリコール：１〜２９）（メタ）アクリレート等のアラルコキシポリアルキレングリコール（メタ）アクリレートが挙げられ、なかでもポリプロピレングリコール（ｎ＝２〜３０）（メタ）アクリレート、フェノキシ（エチレングリコール・プロピレングリコール共重合）（メタ）アクリレートが好ましく、これらを併用することがより好ましい。
商業的に入手しうる（ｃ）成分の具体例としては、新中村化学工業株式会社製のＮＫエステルＭ−２０Ｇ、同４０Ｇ、同９０Ｇ等、日油株式会社製のブレンマーＰＥ−９０、同２００、同３５０、ＰＭＥ−１００、同２００、同４００等、ＰＰ−５００、同８００等、ＡＰ−１５０、同４００、同５５０等、５０ＰＥＰ−３００、５０ＰＯＥＰ−８００Ｂ、４３ＰＡＰＥ−６００Ｂ等が挙げられる。
((D) Nonionic monomer)
(D) As a nonionic monomer, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polypropylene glycol (n = 2 to 30, n represents the average number of added moles of an oxyalkylene group. Same) Polyalkylene glycol (meth) acrylate such as (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate such as methoxypolyethylene glycol (n = 1-30) (meth) acrylate, phenoxy (ethylene glycol / propylene glycol copolymer) ) (N = 1 to 30, ethylene glycol: 1 to 29 therein) Aralkoxy polyalkylene glycol (meth) acrylate such as (meth) acrylate, polypropylene glycol (n = 2 to 30) among others Meth) acrylate, phenoxy (ethylene glycol-propylene glycol copolymer) (meth) acrylate are preferable, it is more preferable to use them.
Specific examples of the commercially available component (c) include NK ester M-20G, 40G, and 90G manufactured by Shin-Nakamura Chemical Co., Ltd., Bremer PE-90 and 200 manufactured by NOF Corporation. 350, PME-100, 200, 400, etc., PP-500, 800, etc., AP-150, 400, 550, 50PEP-300, 50POEP-800B, 43PAPE-600B, and the like.
上記（ａ）〜（ｄ）成分は、それぞれ単独で又は２種以上を組み合わせて用いることができる。
染料含有ポリマー製造時における、上記（ａ）成分〜（ｄ）成分のモノマー混合物中における含有量（未中和量としての含有量。以下同じ）、すなわち染料含有ポリマー中における（ａ）成分〜（ｄ）成分に由来の構成単位の含有量は、次のとおりである。
（ａ）成分の含有量は、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、７０〜９９．０重量％が好ましく、９０〜９８．９重量％がより好ましく９５．０〜９８．８重量％が更に好ましい。
（ｂ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、０．５〜５重量％が好ましく、０．７〜２重量％がより好ましく、０．８〜１．２重量％が更に好ましい。
（ｃ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から０．３〜２５重量％が好ましく、０．４〜１０重量％がより好ましく、０．５〜３．０重量％が更に好ましい。
（ｄ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、０〜５重量％が好ましく、０〜２重量％がより好ましく、実質的に含有しないことが更に好ましい。
The components (a) to (d) can be used alone or in combination of two or more.
The content of the component (a) to the component (d) in the monomer mixture during the production of the dye-containing polymer (content as an unneutralized amount; the same applies hereinafter), that is, the component (a) in the dye-containing polymer ( Content of the structural unit derived from d) component is as follows.
The content of the component (a) is preferably 70 to 99.0% by weight, more preferably 90 to 98.9% by weight, from the viewpoint of obtaining a printed material having excellent abrasion resistance and suppressed penetration. More preferred is ˜98.8% by weight.
The content of the component (b) is preferably 0.5 to 5% by weight, and 0.7 to 2% by weight from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. More preferred is 0.8 to 1.2% by weight.
The content of the component (c) is preferably from 0.3 to 25% by weight, more preferably from 0.4 to 10% by weight from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. Preferably, 0.5 to 3.0% by weight is more preferable.
The content of the component (d) is preferably 0 to 5% by weight, more preferably 0 to 2% by weight from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. More preferably, it is not contained.
＜染料含有ポリマー（Ｉ）の製造＞
染料含有ポリマーは、上記の染料含有モノマー（ａ）、イオン性モノマー（ｂ）、更に必要に応じて上記疎水性モノマー（ｃ）、ノニオン性モノマー（ｄ）、及びその他のモノマーの混合物を公知の重合法により共重合させることによって製造される。重合法としては溶液重合法が好ましい。
溶液重合法で用いる有機溶媒に制限はないが、染料含有モノマーの溶解性を向上させる観点から、２−ピロリドン、ジメチルスルホキシド等が好ましい。
重合の際には、重合開始剤や重合連鎖移動剤を用いることができる。重合開始剤としては、アゾ化合物が好ましく、２，２'−アゾビス（２，４−ジメチルバレロニトリル）がより好ましい。
重合連鎖移動剤としては、メルカプタン類が好ましく、２−メルカプトエタノールがより好ましい。
<Production of dye-containing polymer (I)>
The dye-containing polymer is a known mixture of the above-mentioned dye-containing monomer (a), ionic monomer (b), and if necessary, the hydrophobic monomer (c), nonionic monomer (d), and other monomers. It is produced by copolymerization by a polymerization method. As the polymerization method, a solution polymerization method is preferable.
The organic solvent used in the solution polymerization method is not limited, but 2-pyrrolidone, dimethyl sulfoxide, and the like are preferable from the viewpoint of improving the solubility of the dye-containing monomer.
In the polymerization, a polymerization initiator or a polymerization chain transfer agent can be used. As the polymerization initiator, an azo compound is preferable, and 2,2′-azobis (2,4-dimethylvaleronitrile) is more preferable.
As the polymerization chain transfer agent, mercaptans are preferable, and 2-mercaptoethanol is more preferable.
好ましい重合条件は、重合開始剤の種類等によって異なるが、重合温度は５０〜９０℃が好ましく、６０〜９０℃がより好ましく、７０〜８５℃が更に好ましい。重合時間は１〜２０時間が好ましく、４〜１５時間がより好ましく、６〜１０時間が更に好ましい。また、重合雰囲気は、窒素ガス雰囲気、アルゴン等の不活性ガス雰囲気であることが好ましい。
重合反応の終了後、反応溶液から再沈澱、膜分離、クロマトグラフ法、抽出法等により、未反応のモノマー等を除去することができる。
Although preferable polymerization conditions vary depending on the type of polymerization initiator and the like, the polymerization temperature is preferably 50 to 90 ° C, more preferably 60 to 90 ° C, and still more preferably 70 to 85 ° C. The polymerization time is preferably 1 to 20 hours, more preferably 4 to 15 hours, and still more preferably 6 to 10 hours. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
After completion of the polymerization reaction, unreacted monomers and the like can be removed from the reaction solution by reprecipitation, membrane separation, chromatographic methods, extraction methods and the like.
＜染料含有ポリマー（ＩＩ）＞
次に、染料と反応する官能基を有するポリマーと該染料とを反応させて得られるポリマー（染料含有ポリマー（ＩＩ））について説明する。
染料と反応する官能基を有するポリマーは、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、染料と反応する官能基を有するモノマー（ｅ）（以下、「（ｅ）成分」ともいう）と、イオン性モノマー（ｂ）（以下、「（ｂ）成分」ともいう）とを含むモノマー混合物（以下、「モノマー混合物」ともいう）を共重合させてなる染料含有ポリマーが好ましい。この染料と反応する官能基を有するポリマーは、（ｅ）成分由来の構成単位と（ｂ）成分由来の構成単位を有する。
また、本発明に用いられる染料と反応する官能基を有するポリマーは、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、更に（ｃ）疎水性モノマー（以下、「（ｃ）成分」ともいう）由来の構成単位を有するのが好ましい。更に、（ｄ）ノニオン性モノマー（以下、「（ｄ）成分」ともいう）由来の構成単位を有してもよい。
ビニル系ポリマーとしては、顔料水分散液の分散安定性及びインクの保存安定性を向上させる観点から、（ｅ）成分と、（ｂ）成分と、更に必要に応じて（ｃ）成分及び／又は（ｄ）成分とを含むモノマー混合物を共重合させてなるビニル系ポリマーが好ましい。このビニル系ポリマーは、（ｅ）成分由来の構成単位及び（ｂ）成分由来の構成単位を有し、必要に応じて更に（ｃ）成分由来の構成単位及び／又は（ｄ）成分由来の構成単位を有する。
<Dye-containing polymer (II)>
Next, the polymer (dye-containing polymer (II)) obtained by reacting a polymer having a functional group that reacts with the dye and the dye will be described.
The polymer having a functional group that reacts with a dye is a monomer (e) having a functional group that reacts with a dye (hereinafter referred to as “(e)” from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink. A dye-containing polymer obtained by copolymerizing a monomer mixture (hereinafter also referred to as “monomer mixture”) containing an ionic monomer (b) (hereinafter also referred to as “component (b)”). preferable. The polymer having a functional group that reacts with the dye has a structural unit derived from the component (e) and a structural unit derived from the component (b).
In addition, the polymer having a functional group that reacts with the dye used in the present invention may further include (c) a hydrophobic monomer (hereinafter referred to as “(”) from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink. It is preferable to have a structural unit derived from c) component). Further, it may have a structural unit derived from (d) a nonionic monomer (hereinafter also referred to as “component (d)”).
As the vinyl polymer, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the component (e), the component (b), and the component (c) and / or A vinyl polymer obtained by copolymerizing a monomer mixture containing the component (d) is preferable. This vinyl polymer has a structural unit derived from the component (e) and a structural unit derived from the component (b), and a structural unit derived from the component (c) and / or a component derived from the component (d) as necessary. Has units.
（ｂ）〜（ｄ）成分としては、上記の態様と同様である。
染料と反応する官能基を有するモノマー（ｅ）は、染料と反応する官能基とビニル基とを含むものが好適である。染料と反応する官能基としては、染料との反応性を高める観点から、エポキシ基が好ましい。また、染料と反応する官能基を有するモノマー（ｅ）としては、同様の観点から、エポキシ基とビニル基を含有するものが好ましく、グリシジル（メタ）アクリレートがより好ましい。
The components (b) to (d) are the same as in the above embodiment.
The monomer (e) having a functional group that reacts with the dye preferably contains a functional group that reacts with the dye and a vinyl group. The functional group that reacts with the dye is preferably an epoxy group from the viewpoint of increasing the reactivity with the dye. Moreover, as a monomer (e) which has a functional group which reacts with dye, what contains an epoxy group and a vinyl group is preferable from the same viewpoint, and glycidyl (meth) acrylate is more preferable.
上記（ｂ）〜（ｅ）成分は、それぞれ単独で又は２種以上を組み合わせて用いることができる。
染料と反応する官能基を有するポリマー製造時における、上記（ｂ）成分〜（ｅ）成分のモノマー混合物中における含有量（未中和量としての含有量。以下同じ）、すなわち染料と反応する官能基を有するポリマー中における（ｂ）成分〜（ｅ）成分に由来の構成単位の含有量は、次のとおりである。
（ｂ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、３〜７重量％が好ましく、４〜６重量％がより好ましく、４．５〜５．５重量％が更に好ましい。
（ｃ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から１〜７５重量％が好ましく、２〜４０重量％がより好ましく、３〜２０重量％が更に好ましい。
（ｄ）成分の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、０〜８重量％が好ましく、０〜４重量％がより好ましく、実質的に含有しないことが更に好ましい。
（ｅ）成分の含有量は、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、２０〜９６重量％が好ましく、３０〜９４重量％がより好ましく７５〜９２重量％が更に好ましい。
The components (b) to (e) can be used alone or in combination of two or more.
The content of the component (b) to (e) in the monomer mixture (content as an unneutralized amount; the same applies hereinafter), that is, the functionality that reacts with the dye, during the production of the polymer having a functional group that reacts with the dye. Content of the structural unit derived from the component (b) to the component (e) in the polymer having a group is as follows.
The content of the component (b) is preferably 3 to 7% by weight, more preferably 4 to 6% by weight, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. More preferably, it is 0.5 to 5.5% by weight.
The content of the component (c) is preferably 1 to 75% by weight, more preferably 2 to 40% by weight from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. More preferred is 20% by weight.
The content of the component (d) is preferably 0 to 8% by weight, more preferably 0 to 4% by weight, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. More preferably, it is not contained.
The content of the component (e) is preferably 20 to 96% by weight, more preferably 30 to 94% by weight, and even more preferably 75 to 92% by weight, from the viewpoint of obtaining a printed material excellent in abrasion resistance and suppressed through-through. preferable.
（染料と反応する官能基を有するポリマーの製造）
染料と反応する官能基を有するポリマーは、モノマー混合物を公知の重合法により共重合させることによって製造される。重合法としては溶液重合法が好ましい。
溶液重合法で用いる溶媒に制限はないが、炭素数４〜８のケトン、アルコール、エーテル及びエステルから選ばれる１種以上の化合物が好ましく、なかでも炭素数４〜８のケトンが好ましく、その中でもメチルエチルケトンが好ましい。
重合の際には、重合開始剤や重合連鎖移動剤を用いることができる。好ましい重合開始剤、重合連鎖移動剤は、上記染料含有ポリマー（Ｉ）の製造の態様と同様である。
また、好ましい重合条件は、上記染料含有ポリマー（Ｉ）の製造の態様と同様である。
(Production of a polymer having a functional group that reacts with a dye)
A polymer having a functional group that reacts with a dye is produced by copolymerizing a monomer mixture by a known polymerization method. As the polymerization method, a solution polymerization method is preferable.
Although there is no restriction | limiting in the solvent used by the solution polymerization method, 1 or more types of compounds chosen from a C4-C8 ketone, alcohol, ether, and ester are preferable, Especially a C4-C8 ketone is preferable, Among these. Methyl ethyl ketone is preferred.
In the polymerization, a polymerization initiator or a polymerization chain transfer agent can be used. Preferred polymerization initiators and polymerization chain transfer agents are the same as those in the production of the dye-containing polymer (I).
Further, preferable polymerization conditions are the same as those in the production of the dye-containing polymer (I).
＜染料含有ポリマー（ＩＩ）の製造＞
上記染料と反応する官能基を有するポリマーと染料とを反応させて得られる。染料は、染料含有ポリマーの生産性を向上させる観点から、上記精製染料を用いることが好ましい。
溶媒としては、染料を溶解させる観点及び染料と反応する官能基と反応し難いという観点から、２−ピロリドン、ジメチルスルホキシドが好ましい。
染料と反応する官能基と染料の反応性を高める観点から、反応促進剤を用いることが好ましく、反応促進剤としてはテトラブチルアンモニウムブロミド等が好ましい。
<Production of dye-containing polymer (II)>
It is obtained by reacting a polymer having a functional group that reacts with the dye and the dye. From the viewpoint of improving the productivity of the dye-containing polymer, the purified dye is preferably used as the dye.
As the solvent, 2-pyrrolidone and dimethyl sulfoxide are preferable from the viewpoint of dissolving the dye and being difficult to react with a functional group that reacts with the dye.
From the viewpoint of increasing the reactivity between the functional group that reacts with the dye and the dye, a reaction accelerator is preferably used, and the reaction accelerator is preferably tetrabutylammonium bromide.
反応温度は、反応速度および収率を高める観点から、５０〜１２０℃が好ましく、８５〜１１０℃がより好ましい。
反応時間は、収率を高める観点及び染料含有ポリマーの生産性を高める観点から、１〜２０時間であることが好ましく、５〜１５時間がより好ましい。
また、必要に応じて、反応溶液から再沈澱、溶媒留去等の公知の方法により、生成したポリマーを単離することができる。
From the viewpoint of increasing the reaction rate and yield, the reaction temperature is preferably 50 to 120 ° C, more preferably 85 to 110 ° C.
The reaction time is preferably 1 to 20 hours and more preferably 5 to 15 hours from the viewpoint of increasing the yield and increasing the productivity of the dye-containing polymer.
If necessary, the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation.
＜染料含有ポリマーの重量平均分子量＞
染料含有ポリマーの重量平均分子量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点及び印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、５，０００〜５０万が好ましく、１万〜３０万がより好ましく、３万〜２０万が更に好ましく、４万〜１５万がより更に好ましく、５万〜１０万がより更に好ましい。なお、重量平均分子量は、実施例に記載の方法により求めることができる。
<Weight average molecular weight of dye-containing polymer>
The weight-average molecular weight of the dye-containing polymer is that the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, the viewpoint of improving the ejection property, the printing density is high, the rub resistance is excellent, and the print-through is suppressed. From the viewpoint of obtaining, 5,000 to 500,000 are preferable, 10,000 to 300,000 are more preferable, 30,000 to 200,000 are more preferable, 40,000 to 150,000 are still more preferable, and 50,000 to 100,000 are still more preferable. . In addition, a weight average molecular weight can be calculated | required by the method as described in an Example.
［顔料水分散液の製造］
顔料と染料含有ポリマーを含有する顔料水分散液は、下記の工程（１）〜（３）を有する方法により、効率的に製造することができる。
工程（１）：染料含有ポリマー、有機溶媒、顔料、及び水を含有する混合物を分散処理して、分散処理物を得る工程
工程（２）：工程（１）で得られた分散処理物から前記有機溶媒を除去して、顔料水分散液を得る工程
また、任意の工程であるが、更に工程（３）を行ってもよく、工程（３）と工程（２）はどちらを先に行ってもよい。
工程（３）：工程（１）で得られた分散処理物又は工程（２）で得られた水分散液と架橋剤とを混合し、架橋処理して分散処理物又は水分散液を得る工程
工程（３）を行うことにより、染料構造中のアミノ基と架橋剤が反応し、アミノ基の水素がアルキル基等に置換され、π電子平面上の電子密度の偏りがさらに強まり、耐擦性に優れ、裏抜けが抑制された印刷物を得ることができる。
[Production of pigment aqueous dispersion]
The pigment aqueous dispersion containing the pigment and the dye-containing polymer can be efficiently produced by a method having the following steps (1) to (3).
Step (1): A step of dispersing a mixture containing a dye-containing polymer, an organic solvent, a pigment, and water to obtain a dispersion-treated product Step (2): From the dispersion-treated product obtained in Step (1) Step of removing the organic solvent to obtain the pigment aqueous dispersion In addition, although it is an optional step, step (3) may be further performed, and either step (3) or step (2) is performed first. Also good.
Step (3): A step of mixing the dispersion-treated product obtained in Step (1) or the aqueous dispersion obtained in Step (2) and a crosslinking agent, followed by crosslinking treatment to obtain a dispersion-treated product or an aqueous dispersion. By performing step (3), the amino group in the dye structure reacts with the cross-linking agent, the hydrogen of the amino group is substituted with an alkyl group, etc., and the deviation of the electron density on the π-electron plane is further increased, resulting in abrasion resistance. It is possible to obtain a printed material that is excellent in color and has suppressed see-through.
＜工程（１）＞
工程（１）は、染料含有ポリマー、有機溶媒、顔料、及び水を含有する混合物を分散処理して、分散処理物を得る工程である。
<Step (1)>
Step (1) is a step of obtaining a dispersion-treated product by subjecting a mixture containing a dye-containing polymer, an organic solvent, a pigment, and water to a dispersion treatment.
（染料含有ポリマー）
染料含有ポリマーとしては、前記の染料含有ポリマーの製造によって得られた染料含有ポリマーの有機溶媒溶液を用いてもよいが、当該有機溶媒溶液中の有機溶媒（前述した２−ピロリドン、ジメチルスルホキシド等）の沸点が高く、工程（２）での除去が困難であるという観点から、当該高沸点の有機溶媒を除去した染料含有ポリマーの水分散体を用いることが好ましい。次に、染料含有ポリマーの水分散体の好適な製造例を説明する。
（染料含有ポリマーの水分散体の製造）
染料含有ポリマーの水分散体は、染料含有ポリマー溶液にイオン交換水を添加して染料含有ポリマー希釈液を調製し、限外濾過膜を用いて有機溶媒を除去することにより好適に得られる。
加えるイオン交換水の量は、染料含有ポリマーの水分散体の生産性を向上させる観点から、希釈液の染料含有ポリマー濃度が１〜３重量％になる量が好ましく、染料含有ポリマー溶液に対するイオン交換水の重量比（イオン交換水／染料含有ポリマー溶液）は１〜５が好ましく、２〜４がより好ましく、２．５〜３．５が更に好ましい。
限外濾過膜としては、再生セルロース（セロファン）、アセチルセルロース、ポリアクリロニトリル、テフロン（登録商標）、ポリエステル系ポリマーアロイ、ポリスルホンあるいは親水性ポリエーテルスルホンの多孔質膜等が使用できる。染料含有ポリマーの水分散体の生産性を向上させる観点から、親水性ポリエーテルスルホンの多孔質膜が好ましく、具体的には、ミリポア社製Ｐｅｌｌｉｃｏｎ−２ Ｂｉｏｍａｘ−１０００等が挙げられる。限外濾過膜の性能指標は分画分子量で表され、好ましくは１０ｋ〜５０００ｋDa、より好ましくは１００ｋ〜３０００ｋDa、更に好ましくは５００ｋ〜２０００ｋDaである。１ｋDaとは分子量１０００以下の物を分画し除去する性能を示し、生産性の観点から分離したい溶質の分子量に比べ、１０倍程度の大きさの膜を選択することが好ましい。
限外濾過膜により、染料含有ポリマー希釈液から水と有機溶媒を抽出する際に、染料含有ポリマー希釈液中の染料濃度上昇による抽出効率の低下を抑制する観点から、抽出した水及び有機溶媒と同重量のイオン交換水を適宜染料含有ポリマー希釈液に添加し、染料含有ポリマー希釈液中の染料濃度を一定に保ちつつ、限外濾過膜処理をすることが好ましい。
限外濾過膜処理の終了は、抽出液の吸光度で判断することができ、抽出液の吸光度が染料の吸光度の０．１%以下、好ましくは０．０５％以下になった時点で、限外濾過膜処理を終了することが好ましい。
(Dye-containing polymer)
As the dye-containing polymer, an organic solvent solution of the dye-containing polymer obtained by the production of the dye-containing polymer may be used, but the organic solvent in the organic solvent solution (2-pyrrolidone, dimethyl sulfoxide, etc. described above) From the viewpoint that the boiling point is high and removal in the step (2) is difficult, it is preferable to use an aqueous dispersion of a dye-containing polymer from which the high-boiling organic solvent has been removed. Next, a preferred production example of an aqueous dispersion of a dye-containing polymer will be described.
(Production of aqueous dispersion of dye-containing polymer)
The aqueous dispersion of the dye-containing polymer can be suitably obtained by adding ion-exchanged water to the dye-containing polymer solution to prepare a dye-containing polymer diluent, and removing the organic solvent using an ultrafiltration membrane.
The amount of ion-exchanged water to be added is preferably such that the concentration of the dye-containing polymer in the diluted solution is 1 to 3% by weight from the viewpoint of improving the productivity of the aqueous dispersion of the dye-containing polymer. 1-5 are preferable, as for the weight ratio (ion-exchange water / dye containing polymer solution) of water, 2-4 are more preferable, and 2.5-3.5 are still more preferable.
As the ultrafiltration membrane, regenerated cellulose (cellophane), acetylcellulose, polyacrylonitrile, Teflon (registered trademark), polyester polymer alloy, polysulfone or hydrophilic polyethersulfone porous membrane can be used. From the viewpoint of improving the productivity of the aqueous dispersion of the dye-containing polymer, a porous membrane of hydrophilic polyethersulfone is preferable, and specific examples include Pellicon-2 Biomax-1000 manufactured by Millipore. The performance index of the ultrafiltration membrane is represented by a molecular weight cut-off, preferably 10 k to 5000 kDa, more preferably 100 k to 3000 kDa, and still more preferably 500 k to 2000 kDa. 1 kDa indicates the ability to fractionate and remove substances having a molecular weight of 1000 or less. From the viewpoint of productivity, it is preferable to select a membrane about 10 times larger than the molecular weight of the solute to be separated.
When extracting water and an organic solvent from the dye-containing polymer diluent with an ultrafiltration membrane, the extracted water and organic solvent It is preferable to add the same amount of ion-exchanged water to the dye-containing polymer diluent as appropriate, and perform ultrafiltration membrane treatment while keeping the dye concentration in the dye-containing polymer diluent constant.
The end of the ultrafiltration membrane treatment can be judged by the absorbance of the extract. When the absorbance of the extract becomes 0.1% or less, preferably 0.05% or less of the absorbance of the dye, the ultrafiltration membrane treatment is terminated. It is preferable to end the filtration membrane treatment.
有機溶媒の残留量は、染料１００重量部に対して、５重量部以下が好ましく、１重量部以下がより好ましく、０．１重量部以下が更に好ましい。
有機溶媒の残留量は、ＮＭＲ、液相クロマトグラフィー等で求めることができる。
染料含有ポリマーの水分散体の固形分濃度は、顔料水分散液の生産性を向上させる観点から、５〜２０重量％が好ましく、８〜１５重量％がより好ましい。限外濾過膜処理した染料含有ポリマー希釈液を、限外濾過膜もしくは減圧蒸留装置等を用いて水を除去し濃縮することで、固形分濃度を調製することができる。
The residual amount of the organic solvent is preferably 5 parts by weight or less, more preferably 1 part by weight or less, and still more preferably 0.1 parts by weight or less with respect to 100 parts by weight of the dye.
The residual amount of the organic solvent can be determined by NMR, liquid phase chromatography or the like.
The solid content concentration of the aqueous dispersion of the dye-containing polymer is preferably 5 to 20% by weight and more preferably 8 to 15% by weight from the viewpoint of improving the productivity of the pigment aqueous dispersion. The concentration of solid content can be adjusted by removing the water from the dye-containing polymer diluted solution treated with the ultrafiltration membrane using an ultrafiltration membrane or a vacuum distillation apparatus and concentrating.
工程（１）では、まず、染料含有ポリマーの水分散体、水、有機溶媒、顔料及び必要に応じて、中和剤、界面活性剤等を混合し、混合物を得ることが好ましい。加える順序に制限はないが、染料含有ポリマーの水分散体、有機溶媒、中和剤、及び顔料はこの順に加えることが好ましい。 In the step (1), it is preferable to first obtain a mixture by mixing an aqueous dispersion of a dye-containing polymer, water, an organic solvent, a pigment, and, if necessary, a neutralizing agent and a surfactant. The order of addition is not limited, but the aqueous dispersion of the dye-containing polymer, the organic solvent, the neutralizing agent, and the pigment are preferably added in this order.
（有機溶媒）
有機溶媒に制限はないが、前記の染料含有ポリマーの有機溶媒溶液中における有機溶媒よりも低沸点のものが好ましい。この有機溶媒としては、炭素数１〜３の脂肪族アルコール、ケトン類、エーテル類、エステル類等が好ましく、顔料への濡れ性及び顔料へのポリマーの吸着性を向上させる観点から、メチルエチルケトンがより好ましい。
有機溶媒に対する染料含有ポリマーの重量比［染料含有ポリマー／有機溶媒］は、顔料の濡れ性及び顔料へのポリマーの吸着性を向上させる観点から、０．１０〜０．６０が好ましく、０．２０〜０．５０がより好ましく、０．２５〜０．４５がさらに好ましい。
(Organic solvent)
Although there is no restriction | limiting in an organic solvent, The thing of a low boiling point is preferable rather than the organic solvent in the organic solvent solution of the said dye containing polymer. As the organic solvent, aliphatic alcohols having 1 to 3 carbon atoms, ketones, ethers, esters and the like are preferable. From the viewpoint of improving the wettability to the pigment and the adsorptivity of the polymer to the pigment, methyl ethyl ketone is more preferable. preferable.
The weight ratio of the dye-containing polymer to the organic solvent [dye-containing polymer / organic solvent] is preferably 0.10 to 0.60 from the viewpoint of improving the wettability of the pigment and the adsorptivity of the polymer to the pigment, and is 0.20. -0.50 is more preferable, and 0.25-0.45 is further more preferable.
（中和剤）
顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、中和剤を用いることが好ましい。中和剤を用いる場合、顔料水分散液のｐＨが７〜１１になるように中和することが好ましい。
用いられる中和剤としては、アルカリ金属の水酸化物、アンモニア、有機アミンが挙げられ、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、アルカリ金属の水酸化物、アンモニアが好ましく、アルカリ金属の水酸化物がより好ましい。
アルカリ金属の水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウムが挙げられ、水酸化ナトリウムが好ましい。
中和剤は、十分に中和を促進させる観点から、中和剤水溶液として用いることが好ましい。中和剤水溶液の濃度は、十分に中和を促進させる観点から、３〜３０重量％が好ましく、１０〜２５重量％がより好ましく、１５〜２５重量％が更に好ましい。
有機溶媒に対する中和剤水溶液の重量比［中和剤水溶液／有機溶媒］は、顔料へのポリマーの付着とポリマーの中和を促進して顔料粒子の分散性を高める観点、その結果、粗大粒子を低減し、インクの吐出性を向上させる観点から、０．０１０〜０．１０が好ましく、０．０２０〜０．０６０がより好ましく、０．０２５〜０．０５０がさらに好ましい。
中和剤及び中和剤水溶液は、単独で又は２種以上を混合して用いてもよい。
染料含有ポリマーの中和度は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、１０〜１００モル％であることが好ましく、１０〜５０モル％がより好ましく、１５〜３０モル％が更に好ましい。
ここで中和度とは、中和剤のモル当量を染料含有ポリマーのアニオン性基のモル量で除したものである。前記アニオン性基は、染料構造に含まれるスルホン酸基、及びカルボン酸基、又はイオン性モノマーのカルボン酸基等が含まれる。
(Neutralizer)
From the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability, it is preferable to use a neutralizing agent. When using a neutralizing agent, it is preferable to neutralize so that the pH of the pigment aqueous dispersion becomes 7-11.
Examples of the neutralizing agent used include alkali metal hydroxides, ammonia, and organic amines. From the viewpoint of improving the dispersion stability of the pigment water dispersion, the storage stability of the ink, and the discharge performance, the alkali metal water is used. Oxides and ammonia are preferred, and alkali metal hydroxides are more preferred.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide, and sodium hydroxide is preferable.
The neutralizing agent is preferably used as an aqueous neutralizing agent solution from the viewpoint of sufficiently promoting neutralization. The concentration of the neutralizing agent aqueous solution is preferably 3 to 30% by weight, more preferably 10 to 25% by weight, and still more preferably 15 to 25% by weight, from the viewpoint of sufficiently promoting neutralization.
The weight ratio of the neutralizing agent aqueous solution to the organic solvent [neutralizing agent aqueous solution / organic solvent] is a viewpoint of enhancing the dispersibility of the pigment particles by promoting the adhesion of the polymer to the pigment and the neutralization of the polymer, resulting in coarse particles. From the standpoint of reducing ink and improving ink ejection properties, 0.010 to 0.10 is preferred, 0.020 to 0.060 is more preferred, and 0.025 to 0.050 is even more preferred.
You may use a neutralizing agent and neutralizing agent aqueous solution individually or in mixture of 2 or more types.
The degree of neutralization of the dye-containing polymer is preferably from 10 to 100 mol%, more preferably from 10 to 50 mol%, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the ejection properties. Preferably, 15 to 30 mol% is more preferable.
Here, the neutralization degree is obtained by dividing the molar equivalent of the neutralizing agent by the molar amount of the anionic group of the dye-containing polymer. The anionic group includes a sulfonic acid group and a carboxylic acid group included in the dye structure, or a carboxylic acid group of an ionic monomer.
顔料の含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、顔料水分散液の生産性を向上させる観点から、混合物中、２．０〜２０重量％が好ましく、３．０〜１２重量％がより好ましく、４．５〜８．０重量％が更に好ましい。
染料含有ポリマーの含有量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、混合物中、２．０〜２０重量％が好ましく、４．０〜８．０重量％がより好ましく、７．０〜７．５重量％が更に好ましい。
有機溶媒の含有量は、顔料の濡れ性及び顔料へのポリマーの吸着性を向上させる観点から、混合物中、１０〜２５重量％が好ましく、１３〜２０重量％がより好ましく、１５〜１８重量％が更に好ましい。
水の含有量は、顔料水分散液の分散安定性を向上させる観点及び顔料水分散液の生産性を向上させる観点から、混合物中、５０〜８０重量％が好ましく、６０〜７５重量％がより好ましく、６５〜７５重量％が更に好ましい。
The content of the pigment is 2.0 to 20% by weight in the mixture from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the dischargeability, and the productivity of the pigment aqueous dispersion. % Is preferable, 3.0 to 12% by weight is more preferable, and 4.5 to 8.0% by weight is still more preferable.
The content of the dye-containing polymer is preferably 2.0 to 20% by weight in the mixture, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability. 0 weight% is more preferable and 7.0-7.5 weight% is still more preferable.
The content of the organic solvent is preferably 10 to 25% by weight, more preferably 13 to 20% by weight, and more preferably 15 to 18% by weight in the mixture from the viewpoint of improving the wettability of the pigment and the adsorptivity of the polymer to the pigment. Is more preferable.
The content of water is preferably 50 to 80% by weight, more preferably 60 to 75% by weight in the mixture from the viewpoint of improving the dispersion stability of the pigment water dispersion and improving the productivity of the pigment water dispersion. Preferably, 65 to 75% by weight is more preferable.
染料含有ポリマーの量に対する顔料の量の重量比〔顔料／染料含有ポリマー〕は、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させるから、３０／７０〜７０／３０であることが好ましく、４０／６０〜６０／４０であることがより好ましく、４０／６０〜５０／５０が更に好ましい。 The weight ratio of the amount of the pigment to the amount of the dye-containing polymer [pigment / dye-containing polymer] is excellent in abrasion resistance and from the viewpoint of obtaining a printed matter in which the back-through is suppressed, dispersion stability of the pigment aqueous dispersion, and storage of the ink In order to improve stability and dischargeability, it is preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and still more preferably 40/60 to 50/50.
工程（１）において、さらに混合物を分散して分散処理物を得る。分散処理物を得る分散方法に特に制限はない。本分散だけで顔料粒子の平均粒径を所望の粒径となるまで微粒化することもできるが、好ましくは予備分散させた後、さらに剪断応力を加えて本分散を行い、顔料粒子の平均粒径を所望の粒径とするよう制御することが好ましい。
工程（１）の予備分散における温度は、０〜４０℃が好ましく、０〜２０℃がより好ましく、０〜１０℃が更に好ましく、分散時間は１〜３０時間が好ましく、２〜１０時間がより好ましく、２〜５時間が更に好ましい。
混合物を予備分散させる際には、アンカー翼、ディスパー翼等の一般に用いられている混合撹拌装置、なかでも高速撹拌混合装置が好ましい。
In step (1), the mixture is further dispersed to obtain a dispersion-treated product. There is no particular limitation on the dispersion method for obtaining the dispersion treatment product. Although the average particle size of the pigment particles can be atomized only by the main dispersion until the desired particle size is obtained, preferably the pre-dispersion is performed, and then the main dispersion is further performed by applying a shear stress to obtain the average particle size of the pigment particles. It is preferable to control the diameter to a desired particle diameter.
The temperature in the preliminary dispersion in step (1) is preferably 0 to 40 ° C, more preferably 0 to 20 ° C, still more preferably 0 to 10 ° C, and the dispersion time is preferably 1 to 30 hours, more preferably 2 to 10 hours. Preferably, 2 to 5 hours are more preferable.
When the mixture is predispersed, a generally used mixing and stirring device such as an anchor blade or a disper blade, particularly a high-speed stirring and mixing device is preferable.
本分散の剪断応力を与える手段としては、例えば、ロールミル、ニーダー等の混練機、マイクロフルイダイザー（Microfluidics 社、商品名）等の高圧ホモジナイザー、ペイントシェーカー、ビーズミル等のメディア式分散機が挙げられる。市販のメディア式分散機としては、ウルトラ・アペックス・ミル（寿工業株式会社製、商品名）、ピコミル（浅田鉄工株式会社製、商品名）等が挙げられる。これらの装置は複数を組み合わせることもできる。これらの中では、顔料を小粒子径化する観点から、高圧ホモジナイザーを用いることが好ましい。
高圧ホモジナイザーを用いて本分散を行う場合、処理圧力やパス回数の制御により、顔料を所望の粒径になるように制御することができる。
処理圧力は、６０〜２００ＭＰａが好ましく、１００〜１８０ＭＰａがより好ましく、１３０〜１６０ＭＰａが更に好ましい。また、パス回数は、３〜３０が好ましく、１０〜２５がより好ましく、１５〜２５が更に好ましい。
Examples of means for applying the shear stress of the present dispersion include a kneader such as a roll mill and a kneader, a high-pressure homogenizer such as a microfluidizer (trade name), a media type disperser such as a paint shaker and a bead mill. Examples of commercially available media dispersers include Ultra Apex Mill (trade name, manufactured by Kotobuki Industries Co., Ltd.), Pico Mill (trade name, manufactured by Asada Tekko Co., Ltd.), and the like. A plurality of these devices can be combined. Among these, it is preferable to use a high-pressure homogenizer from the viewpoint of reducing the particle size of the pigment.
When this dispersion is performed using a high-pressure homogenizer, the pigment can be controlled to have a desired particle size by controlling the processing pressure and the number of passes.
The processing pressure is preferably 60 to 200 MPa, more preferably 100 to 180 MPa, and still more preferably 130 to 160 MPa. The number of passes is preferably 3 to 30, more preferably 10 to 25, and still more preferably 15 to 25.
＜工程（２）＞
工程（２）は、工程（１）で得られた分散処理物から前記有機溶媒を除去して、顔料水分散液を得る工程である。
公知の方法で有機溶媒を除去することで、顔料水分散液を得ることができる。
有機溶媒を除去する過程で凝集物が発生することを抑制し、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、有機溶媒を除去する前に、分散処理物に水を添加して、水に対する有機溶媒の重量比（有機溶媒／水）を０．１５〜０．４０に調整することが好ましく、０．２０〜０．３０に調整することがより好ましい。
また、水に対する有機溶媒の重量比を調整した後の顔料水分散液の不揮発成分濃度（固形分濃度）は、有機溶媒を除去する過程で凝集物の発生を抑制する観点及び顔料水分散液の生産性を向上させる観点から、５〜３０重量％が好ましく、８〜２０重量％がより好ましく、１０〜１６重量％が更に好ましい。なお、上記分散液に含有される水の一部が有機溶媒と同時に除去されてもよい。
<Step (2)>
Step (2) is a step of removing the organic solvent from the dispersion-treated product obtained in step (1) to obtain a pigment water dispersion.
A pigment aqueous dispersion can be obtained by removing the organic solvent by a known method.
From the viewpoint of suppressing the generation of aggregates during the process of removing the organic solvent and improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the discharge performance, the dispersion treatment is performed before removing the organic solvent. It is preferable to adjust the weight ratio of organic solvent to water (organic solvent / water) to 0.15 to 0.40, more preferably 0.20 to 0.30 by adding water to the product. .
In addition, the non-volatile component concentration (solid content concentration) of the pigment aqueous dispersion after adjusting the weight ratio of the organic solvent to water is determined based on the viewpoint of suppressing the generation of aggregates in the process of removing the organic solvent and the pigment aqueous dispersion. From the viewpoint of improving productivity, 5 to 30% by weight is preferable, 8 to 20% by weight is more preferable, and 10 to 16% by weight is still more preferable. A part of the water contained in the dispersion may be removed simultaneously with the organic solvent.
本工程において用いられる有機溶媒を除去するための装置としては、回分単蒸留装置、減圧蒸留装置、フラッシュエバポレーター等の薄膜式蒸留装置、回転式蒸留装置、攪拌式蒸発装置等が挙げられる。効率よく有機溶媒を除去する観点から、回転式蒸留装置及び攪拌式蒸発装置が好ましく、回転式蒸留装置がより好ましく、ロータリーエバポレーターが更に好ましい。
有機溶媒を除去する際の分散処理物の温度は、用いる有機溶媒の種類によって適宜選択できるが、減圧下、２５〜８０℃が好ましく、２５〜７０℃がより好ましく、３０〜６５℃が更に好ましい。このときの圧力は、０．０１〜０．５ＭＰａが好ましく、０．０２〜０．２ＭＰａがより好ましく、０．０５〜０．１ＭＰａが更に好ましい。除去時間は、１〜２４時間が好ましく、２〜１２時間がより好ましく、５〜１０時間が更に好ましい。
得られた顔料水分散液中の有機溶媒は実質的に除去されていることが好ましいが、本発明の目的を損なわない限り、残存していてもよい。残留有機溶媒の量は０．１重量％以下が好ましく、０．０１重量％以下であることがより好ましい。
得られた顔料水分散液の不揮発成分濃度（固形分濃度）は、顔料水分散液の分散安定性を向上させる観点及びインクの調製を容易にする観点から、１０〜３０重量％が好ましく、１５〜２５重量％がより好ましく、１８〜２２重量％が更に好ましい。
Examples of the apparatus for removing the organic solvent used in this step include a batch simple distillation apparatus, a vacuum distillation apparatus, a thin film distillation apparatus such as a flash evaporator, a rotary distillation apparatus, and a stirring evaporation apparatus. From the viewpoint of efficiently removing the organic solvent, a rotary distillation apparatus and a stirring evaporation apparatus are preferable, a rotary distillation apparatus is more preferable, and a rotary evaporator is further preferable.
The temperature of the dispersion-treated product when removing the organic solvent can be appropriately selected depending on the type of the organic solvent to be used, but is preferably 25 to 80 ° C, more preferably 25 to 70 ° C, and still more preferably 30 to 65 ° C under reduced pressure. . The pressure at this time is preferably 0.01 to 0.5 MPa, more preferably 0.02 to 0.2 MPa, and even more preferably 0.05 to 0.1 MPa. The removal time is preferably 1 to 24 hours, more preferably 2 to 12 hours, and still more preferably 5 to 10 hours.
The organic solvent in the obtained pigment aqueous dispersion is preferably substantially removed, but may remain as long as the object of the present invention is not impaired. The amount of the residual organic solvent is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less.
The non-volatile component concentration (solid content concentration) of the obtained pigment aqueous dispersion is preferably 10 to 30% by weight from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and facilitating ink preparation. -25% by weight is more preferable, and 18-22% by weight is still more preferable.
得られた顔料水分散液は、顔料と染料含有ポリマーの固体分が水を主媒体とする中に分散しているものである。
顔料水分散液中の顔料粒子の平均粒径は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点及び印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、４０〜２００ｎｍが好ましく、５０〜１５０ｎｍがより好ましく、６０〜１２０ｎｍが更に好ましい。該平均粒径は、後述する実施例に記載した方法にて測定することができる。
The obtained pigment aqueous dispersion is obtained by dispersing the solid content of the pigment and the dye-containing polymer in water as a main medium.
The average particle size of the pigment particles in the pigment aqueous dispersion is high in dispersion stability of the pigment water dispersion and storage stability of the ink, and the viewpoint of improving the ejection property, and the printing density is high, and is excellent in abrasion resistance and show-through. From the viewpoint of obtaining a suppressed printed material, 40 to 200 nm is preferable, 50 to 150 nm is more preferable, and 60 to 120 nm is still more preferable. The average particle diameter can be measured by the method described in Examples described later.
＜工程（３）＞
工程（３）は、任意の工程であるが、工程（１）で得られた分散処理物又は工程（２）で得られた水分散体と架橋剤を混合し、架橋処理して分散処理物あるいは水分散液を得る工程である。
耐擦性に優れ、裏抜けが抑制された印刷物を得る観点、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点から、工程（３）を行うことが好ましい。
また、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、及び印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、工程（１）で得られた分散処理物と架橋剤を混合し、架橋処理された分散処理物を得ることが好ましい。この場合、工程（３）は、工程（１）と工程（２）の間に行う。
このように架橋処理を経て得られた顔料水分散液及びインクは、架橋処理を経ずに得られたものと比べて、耐擦性、耐裏抜け性、及び吐出性の１つ以上に優れる。
<Step (3)>
Step (3) is an optional step, but the dispersion-treated product obtained in step (1) or the aqueous dispersion obtained in step (2) and a crosslinking agent are mixed and subjected to crosslinking treatment to obtain a dispersion-treated product. Or it is the process of obtaining an aqueous dispersion.
The step (3) is preferably performed from the viewpoint of obtaining a printed matter having excellent abrasion resistance and suppressed penetration, and improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the ink, and the dischargeability.
In addition, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink and the dischargeability, and from the viewpoint of obtaining a printed matter having a high print density, excellent scratch resistance, and suppressed back-through. It is preferable that the dispersion-treated product obtained in 1) and the crosslinking agent are mixed to obtain a crosslinked-treated dispersion-treated product. In this case, step (3) is performed between step (1) and step (2).
Thus, the pigment aqueous dispersion and ink obtained through the cross-linking treatment are superior in at least one of abrasion resistance, anti-penetration resistance, and ejection property compared to those obtained without the cross-linking treatment. .
ここで、架橋剤としては、染料含有ポリマーのアミノ基、あるいはアニオン性基と反応する官能基を有する化合物が好ましく、該官能基を分子中に２以上、好ましくは２〜６有する化合物がより好ましい。
架橋剤の好適例としては、分子中に２以上のエポキシ基を有する化合物、分子中に２以上のオキサゾリン基を有する化合物、分子中に２以上のイソシアネート基を有する化合物が挙げられ、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、これらの中では、分子中に２以上のエポキシ基を有する化合物が好ましく、トリメチロールプロパンポリグリシジルエーテルがより好ましい。
架橋剤の使用量は、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、該染料含有ポリマー中の染料構造のモル数に対して、エポキシ当量として５０〜３００モル％添加することが好ましく、１００〜２００モル％添加することがより好ましい。
Here, as the crosslinking agent, a compound having a functional group that reacts with an amino group or an anionic group of the dye-containing polymer is preferable, and a compound having 2 or more, preferably 2 to 6 in the molecule is more preferable. .
Preferred examples of the crosslinking agent include compounds having two or more epoxy groups in the molecule, compounds having two or more oxazoline groups in the molecule, and compounds having two or more isocyanate groups in the molecule. From the viewpoint of improving the dispersion stability of the liquid and the storage stability of the ink and the ejection property, and from the viewpoint of obtaining a printed matter with high printing density, excellent abrasion resistance, and suppressed see-through, among these, A compound having two or more epoxy groups is preferable, and trimethylolpropane polyglycidyl ether is more preferable.
The amount of the crosslinking agent used is the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the ejection property, the viewpoint of obtaining a printed matter having a high printing density, excellent rub resistance, and suppressed see-through. From the viewpoint of the number of moles of the dye structure in the dye-containing polymer, the epoxy equivalent is preferably 50 to 300 mol%, more preferably 100 to 200 mol%.
また、反応性を向上させ顔料分散体の生産性を高める観点、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、架橋剤を複数回にわけて添加して反応させることが好ましい。
工程（１）ないし（２）で得られた分散処理物あるいは水分散体と架橋剤との反応において、反応温度は、反応性を向上させ顔料分散体の生産性を高める観点、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、６０〜９５℃が好ましく、７０〜９０℃がより好ましい。
また、反応時間は、反応性を向上させ顔料分散体の生産性を高める観点、顔料水分散液の分散安定性及びインクの保存安定性、吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、０．１５〜１２時間が好ましく、０．２５〜８時間がより好ましく、０．５〜４時間がさらに好ましい。
Also, from the viewpoint of improving the reactivity and increasing the productivity of the pigment dispersion, the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, the viewpoint of improving the ejection property, the printing density is high, and the abrasion resistance is excellent. From the viewpoint of obtaining a printed matter in which show-through is suppressed, it is preferable to add a crosslinking agent in a plurality of times and react.
In the reaction between the dispersion-treated product or the aqueous dispersion obtained in the steps (1) and (2) and the crosslinking agent, the reaction temperature improves the reactivity and increases the productivity of the pigment dispersion. 60 to 95 ° C. is preferable from the viewpoint of improving the dispersion stability of the ink and the storage stability and ejection properties of the ink, and from the viewpoint of obtaining a printed matter having high print density, excellent abrasion resistance, and suppressed see-through. 90 ° C. is more preferable.
In addition, the reaction time is improved from the viewpoint of improving the reactivity and improving the productivity of the pigment dispersion, the dispersion stability of the pigment aqueous dispersion and the storage stability of the ink, and the viewpoint of improving the discharge performance, the printing density is high, and the abrasion resistance is increased. From the viewpoint of obtaining a printed material having excellent properties and suppressed see-through, 0.15 to 12 hours is preferable, 0.25 to 8 hours is more preferable, and 0.5 to 4 hours is further preferable.
［インクジェット記録用水系インク］
本発明のインクジェット記録方法に用いられる水系インクは水分散液を含有するものであり、水分散液をそのまま水系インクとして用いることもできる。水系インクには、水系インクに通常用いられる溶媒、浸透剤、分散剤、界面活性剤、粘度調整剤、消泡剤、防錆剤、防腐剤、防黴剤、防錆剤等を添加することができる。
顔料の含有量は、インクの保存安定性及び吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、水系インク中、１〜２０重量％が好ましく、２〜１５重量％がより好ましく、４〜１０重量％が更に好ましく、４〜８重量％がより更に好ましい。
染料含有ポリマーの含有量は、インクの保存安定性及び吐出性を向上させる観点、印字濃度が高く、耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、水系インク中、好ましくは２〜１５重量％、より好ましくは３〜１４重量％、更に好ましくは４〜１２重量％、より更に好ましくは５〜１０重量である。
水の含有量は、インクの保存安定性及び吐出性を向上させる観点から、水系インク中、好ましくは４０〜８５重量％、より好ましくは５０〜８５重量％、更に好ましくは６０〜８０重量％、より更に好ましくは６５〜７５重量％である。
[Water-based ink for inkjet recording]
The aqueous ink used in the ink jet recording method of the present invention contains an aqueous dispersion, and the aqueous dispersion can be used as it is as an aqueous ink. Solvents, penetrants, dispersants, surfactants, viscosity modifiers, antifoaming agents, rust preventives, antiseptics, antifungal agents, rust preventives, etc., commonly used in water-based inks should be added to water-based inks Can do.
The content of the pigment is from 1 to 20 weights in the water-based ink from the viewpoint of improving the storage stability and dischargeability of the ink, and from the viewpoint of obtaining a printed matter having high printing density, excellent abrasion resistance, and suppressed see-through. % Is preferable, 2 to 15% by weight is more preferable, 4 to 10% by weight is further preferable, and 4 to 8% by weight is still more preferable.
The content of the dye-containing polymer is preferably in the water-based ink from the viewpoint of improving the storage stability and dischargeability of the ink, and from the viewpoint of obtaining a printed matter with high print density, excellent abrasion resistance, and suppressed penetration. It is 2 to 15% by weight, more preferably 3 to 14% by weight, still more preferably 4 to 12% by weight, and still more preferably 5 to 10% by weight.
The water content is preferably 40 to 85% by weight, more preferably 50 to 85% by weight, and still more preferably 60 to 80% by weight in the water-based ink from the viewpoint of improving the storage stability and dischargeability of the ink. More preferably, it is 65 to 75% by weight.
水系インクの２０℃における静的表面張力は、インクの吐出性を向上させる観点及び耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、好ましくは２２〜４０ｍＮ／ｍ、より好ましくは２５〜３５ｍＮ／ｍ、更に好ましくは２８〜３３ｍＮ／ｍである。
また、水系インクの３２℃における粘度は、インクの吐出性を向上させる観点及び耐擦性に優れ、裏抜けが抑制された印刷物を得る観点から、好ましくは４〜１０ｍＰａ・ｓであり、より好ましくは５〜７ｍＰａ・ｓである。
The static surface tension of the water-based ink at 20 ° C. is preferably 22 to 40 mN / m, more preferably from the viewpoint of improving the ink dischargeability and the printed matter with excellent scratch resistance and suppressed penetration. It is 25 to 35 mN / m, more preferably 28 to 33 mN / m.
The viscosity of the water-based ink at 32 ° C. is preferably 4 to 10 mPa · s, more preferably 4 to 10 mPa · s, from the viewpoint of improving the ink dischargeability and the excellent scratch resistance and obtaining a printed matter in which show-through is suppressed. Is 5 to 7 mPa · s.
以下の製造例、調製例、実施例及び比較例において、「部」及び「％」は特記しない限り「重量部」及び「重量％」である。
なお、ポリマーの重量平均分子量、ポリマー水分散液及び顔料水分散液の固形分濃度、染料モノマー溶液の固形分濃度、水系インクの表面張力、並びに顔料水分散液中の顔料粒子の平均粒径の測定は、以下の方法により行った。
In the following production examples, preparation examples, examples and comparative examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified.
The weight average molecular weight of the polymer, the solid content concentration of the polymer water dispersion and the pigment water dispersion, the solid content concentration of the dye monomer solution, the surface tension of the water-based ink, and the average particle diameter of the pigment particles in the pigment water dispersion The measurement was performed by the following method.
（１）ポリマーの重量平均分子量の測定
Ｎ，Ｎ−ジメチルホルムアミドに、リン酸及びリチウムブロマイドをそれぞれ６０ｍｍｏｌ／Ｌと５０ｍｍｏｌ／Ｌの濃度となるように溶解した液を溶離液として、ゲルクロマトグラフィー法〔東ソー株式会社製ＧＰＣ装置（ＨＬＣ−８１２０ＧＰＣ）、東ソー株式会社製カラム（ＴＳＫ−ＧＥＬ、α−Ｍ×２本）、流速：１ｍＬ／ｍｉｎ〕により、標準物質としてポリスチレンを用いて測定した。
(1) Measurement of polymer weight average molecular weight Gel chromatography method using a solution prepared by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide so as to have concentrations of 60 mmol / L and 50 mmol / L, respectively. [Tosoh Corporation GPC apparatus (HLC-8120GPC), Tosoh Corporation column (TSK-GEL, α-M × 2), flow rate: 1 mL / min] was measured using polystyrene as a standard substance.
（２）ポリマー水分散液、顔料水分散液の固形分濃度の測定
３０ｍｌのポリプレピレン製容器（φ＝４０ｍｍ、高さ＝３０ｍｍ）にデシケーター中で恒量化した硫酸ナトリウム１０．０ｇを量り取り、そこへサンプル約１．０ｇを添加して、混合させた後、正確に秤量し、１０５℃で２時間維持して、揮発分を除去し、更にデシケーター内で更に１５分間放置し、重量を測定した。揮発分除去後のサンプルの重量を固形分として、添加したサンプルの重量で除して固形分濃度とした。
(2) Measurement of solid concentration of polymer aqueous dispersion and pigment aqueous dispersion Weigh 10.0 g of sodium sulfate constant in a desiccator into a 30 ml polypropylene container (φ = 40 mm, height = 30 mm) About 1.0 g of sample was added to the sample and mixed, then accurately weighed and maintained at 105 ° C. for 2 hours to remove volatiles, and then left in a desiccator for an additional 15 minutes to measure the weight. . The weight of the sample after removing the volatile matter was taken as the solid content and divided by the weight of the added sample to obtain the solid content concentration.
（３）染料モノマー溶液の固形分濃度
染料モノマー溶液１ｇを２−ピロリドン９９gに溶解させ、撹拌し染料モノマー希釈溶液を作製した。次いで該希釈溶液から４ｇ採取し、イオン交換水４６ｇに希釈した後、λ＝５５０ｎｍの吸光度を測定した。吸光度測定には日立株式会社製 自記分光光度計 Ｕ−３０１０を用い、１０ｍｍのセルを用いた。得られた吸光度を精製染料の吸光度と比較し、精製染料の固形分濃度を１００％として、吸光度の強度比から含まれる染料の固形分濃度を計算した。得られた染料の固形分濃度に対して、（染料の分子量＋グリシジルメタクリレートの分子量）／染料の分子量を積算し、染料モノマー溶液の固形分濃度とした。
(3) Solid content concentration of dye monomer solution 1 g of dye monomer solution was dissolved in 99 g of 2-pyrrolidone and stirred to prepare a dye monomer diluted solution. Next, 4 g of the diluted solution was sampled and diluted with 46 g of ion-exchanged water, and then the absorbance at λ = 550 nm was measured. For the absorbance measurement, a self-recording spectrophotometer U-3010 manufactured by Hitachi, Ltd. was used, and a 10 mm cell was used. The obtained absorbance was compared with the absorbance of the purified dye, and the solid content concentration of the dye was calculated from the intensity ratio of absorbance with the solid content concentration of the purified dye as 100%. The molecular weight of (dye molecular weight + glycidyl methacrylate molecular weight) / dye molecular weight was integrated with respect to the solid content concentration of the obtained dye to obtain the solid content concentration of the dye monomer solution.
（４）水系インクの表面張力
表面張力計（協和界面科学株式会社製、商品名：ＣＢＶＰ−Ｚ）を用いて、白金プレートを５ｇの水性インクの入った円柱ポリエチレン製容器（直径3.6cm×深さ1.2cm）に浸漬させ、２０℃にて水性インクの静的表面張力を測定した。
（５）顔料水分散液中の顔料粒子の平均粒径
顔料水分散液を、あらかじめ０．２μｍのフィルターでろ過したイオン交換水を用いて希釈し、大塚電子製 レーザー粒径解析システム ＥＬＳ−６１００を用いて２５℃にて粒径測定を行った。
(4) Surface tension of water-based ink Using a surface tension meter (trade name: CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.), a platinum plate was placed in a cylindrical polyethylene container (diameter 3.6 cm × depth) containing 5 g of water-based ink. And the static surface tension of the water-based ink was measured at 20 ° C.
(5) Average particle diameter of pigment particles in pigment aqueous dispersion The pigment water dispersion is diluted with ion-exchanged water that has been filtered through a 0.2 μm filter in advance, and laser particle size analysis system ELS-6100 manufactured by Otsuka Electronics Co., Ltd. Was used to measure the particle size at 25 ° C.
製造例１＜染料の精製１＞
ジメチルホルムアミド（以下、ＤＭＦ）２０００ｇ中に、Direct Black 154（日本化薬社製 Kayarus Direct Deep Black XA）５００ｇを２５℃にて撹拌しながら添加し、さらに２５℃にて1時間撹拌し、Direct Black 154を溶解させた。得られた染料のＤＭＦ溶液を５Ａのろ紙にてろ過し、ＤＭＦ中に溶解しなかった染料と塩を除去した。
ろ過した染料のＤＭＦ溶液全量をヘキサン５０００ｇ中に添加した。これにより、染料のＤＭＦ溶液は下部に沈んだ。この溶液を撹拌しながら、２−プロパノール２５００ｇを１分かけて滴下した。析出した染料を遠心分離操作により分離し、分離した染料を２−プロパノールにて２回洗浄した後、常圧下１００℃にて乾燥させ、精製染料（ａ）を得た。
Production Example 1 <Dye Purification 1>
Direct Black 154 (Kayarus Direct Deep Black XA, manufactured by Nippon Kayaku Co., Ltd.) 500 g was added to 2000 g of dimethylformamide (hereinafter DMF) while stirring at 25 ° C., and further stirred at 25 ° C. for 1 hour. 154 was dissolved. The DMF solution of the obtained dye was filtered with 5A filter paper to remove the dye and salt that did not dissolve in DMF.
The entire DMF solution of the filtered dye was added to 5000 g of hexane. This caused the DMF solution of the dye to sink to the bottom. While stirring this solution, 2500 g of 2-propanol was added dropwise over 1 minute. The precipitated dye was separated by centrifugation, and the separated dye was washed twice with 2-propanol and then dried at 100 ° C. under normal pressure to obtain a purified dye (a).
製造例２＜染料の精製２＞
Direct Black 154を、Direct Black 38（東京化成工業株式会社製、試薬）、Direct Black 22（日本化薬株式会社製 Kayarus Black B 300）、Direct Black 19（日本化薬株式会社製 Kayafect Black LW）、Direct Blue 2（東京化成工業株式会社製、試薬）、Direct Blue 1（東京化成工業株式会社製、試薬）、Direct Red 28（東京化成工業株式会社製、試薬）にそれぞれ代えた以外は製造例１と同様にして、精製染料（ｂ）〜（ｇ）を得た。
なお、Direct Blue 1及びDirect Red 28の化学式は、下記式（６）及び（７）に示すとおりである。
Production Example 2 <Dye Purification 2>
Direct Black 154, Direct Black 38 (Tokyo Kasei Kogyo Co., Ltd., reagent), Direct Black 22 (Nippon Kayaku Kayarus Black B 300), Direct Black 19 (Nippon Kayaku Kayafect Black LW), Production Example 1 except that Direct Blue 2 (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), Direct Blue 1 (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), and Direct Red 28 (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) were used. In the same manner as above, purified dyes (b) to (g) were obtained.
The chemical formulas of Direct Blue 1 and Direct Red 28 are as shown in the following formulas (6) and (7).
製造例３＜染料モノマー溶液１の合成＞
２−ピロリドン４５０ｇにジメチルスルホキシド４５０ｇを添加し、２５℃にて撹拌混合した後、さらに撹拌しながら、精製染料（ａ）１００ｇを添加した。この溶液を撹拌しながら９０℃に加熱し、精製染料（ａ）を溶解させた後、２５℃に冷却し、４００メッシュの金網でろ過を行った。精製染料（ａ）とグリシジルメタクリレートとのモル比が１：１になるように、上記の染料溶液にグリシジルメタクリレート１８．４ｇを添加すると共に、パラメトキシフェノール（重合禁止剤）０．６１ｇ、テトラブチルアンモニウムブロミド（反応促進剤） ５．９７ｇを添加し、２５℃にて３０分間撹拌した。さらに、溶液中に空気のバブリングを行いながら、９５℃で８時間加熱撹拌を行った後、２５℃まで冷却し、染料モノマー溶液１を得た。染料モノマー溶液１の固形分濃度を表１に示す。
Production Example 3 <Synthesis of Dye Monomer Solution 1>
After 450 g of dimethyl sulfoxide was added to 450 g of 2-pyrrolidone and stirred and mixed at 25 ° C., 100 g of the purified dye (a) was added with further stirring. This solution was heated to 90 ° C. with stirring to dissolve the purified dye (a), cooled to 25 ° C., and filtered through a 400 mesh wire net. While adding 18.4 g of glycidyl methacrylate to the above dye solution so that the molar ratio of the purified dye (a) to glycidyl methacrylate is 1: 1, 0.61 g of paramethoxyphenol (polymerization inhibitor), tetrabutyl Ammonium bromide (reaction accelerator) 5.97 g was added and stirred at 25 ° C. for 30 minutes. Further, the solution was stirred with heating at 95 ° C. for 8 hours while bubbling air in the solution, and then cooled to 25 ° C. to obtain a dye monomer solution 1. The solid content concentration of the dye monomer solution 1 is shown in Table 1.
製造例４＜染料モノマー溶液２〜７の合成＞
表１に記載の原料、溶媒、重合禁止剤、反応促進剤を用いて、製造例３と同様の操作を行い、染料モノマー溶液２〜７を得た。染料モノマー溶液２〜７の固形分濃度を表１に示す。
Production Example 4 <Synthesis of Dye Monomer Solutions 2-7>
Using the raw materials, solvents, polymerization inhibitors and reaction accelerators shown in Table 1, the same operations as in Production Example 3 were performed to obtain dye monomer solutions 2 to 7. The solid content concentrations of the dye monomer solutions 2 to 7 are shown in Table 1.
製造例５＜ポリマー溶液１〜１０の製造＞
２つの滴下ロート１及び２を備えた反応容器内に、表２及び表３の「初期仕込みモノマー溶液」欄に示すモノマー、溶媒、重合連鎖移動剤を入れて混合し、窒素ガス置換を行い、初期仕込みモノマー溶液を得た。
一方、表２及び表３の「滴下モノマー溶液１」欄及び「滴下モノマー溶液２」欄に示すモノマー、溶媒、重合開始剤、重合連鎖移動剤を混合して、滴下モノマー溶液１と滴下モノマー溶液２を得、それぞれ滴下ロート１及び滴下ロート２中に入れて、窒素ガス置換を行った。
窒素雰囲気下、反応容器内の初期仕込みモノマー溶液を攪拌しながら７５℃に維持し、滴下ロート１中の滴下モノマー溶液１を３時間かけて反応容器内に滴下し、次いで滴下ロート２中の滴下モノマー溶液２を２時間かけて反応容器内に滴下した。滴下終了後、反応容器内の混合溶液を７５℃で２時間攪拌した。重合開始剤（Ｖ−６５）１．５部をポリマー溶液１〜９ではジメチルスルホキシド１０部に、ポリマー溶液１０ではメチルエチルケトン１０部に溶解した重合開始剤溶液を調製し、該混合溶液に加え、７５℃で1時間攪拌することで熟成を行った。前記重合開始剤溶液の調製、添加及び熟成を更に２回行った。次いで反応容器内の反応溶液を８５℃に２時間維持し、ポリマー溶液１〜１０を得た。
Production Example 5 <Production of Polymer Solutions 1 to 10>
In a reaction vessel equipped with two dropping funnels 1 and 2, the monomers, solvent, and polymerization chain transfer agent shown in the “initially charged monomer solution” column of Tables 2 and 3 are mixed and mixed, and nitrogen gas replacement is performed. An initial charge monomer solution was obtained.
On the other hand, a monomer, a solvent, a polymerization initiator, and a polymerization chain transfer agent shown in the “Drip monomer solution 1” column and the “Drip monomer solution 2” column in Tables 2 and 3 are mixed to prepare a drop monomer solution 1 and a drop monomer solution. 2 were put in the dropping funnel 1 and the dropping funnel 2, respectively, and nitrogen gas substitution was performed.
Under a nitrogen atmosphere, the initially charged monomer solution in the reaction vessel is maintained at 75 ° C. with stirring, the dropped monomer solution 1 in the dropping funnel 1 is dropped into the reaction vessel over 3 hours, and then dropped in the dropping funnel 2. Monomer solution 2 was dropped into the reaction vessel over 2 hours. After completion of dropping, the mixed solution in the reaction vessel was stirred at 75 ° C. for 2 hours. A polymerization initiator solution in which 1.5 parts of the polymerization initiator (V-65) was dissolved in 10 parts of dimethyl sulfoxide in the polymer solutions 1 to 9 and 10 parts of methyl ethyl ketone in the polymer solution 10 was prepared and added to the mixed solution. Aging was carried out by stirring at 1 ° C. for 1 hour. The polymerization initiator solution was further prepared, added and aged twice. Next, the reaction solution in the reaction vessel was maintained at 85 ° C. for 2 hours to obtain polymer solutions 1 to 10.
製造例６＜ポリマー水分散液１〜９の製造＞
得られたポリマー溶液１〜８ ５０００ｇにイオン交換水１５０００ｇを添加、及びポリマー溶液９ ４３８５ｇにイオン交換水１５６１５ｇを添加した後、限外濾過膜（ミリポア社製 商品名：Ｐｅｌｌｉｃｏｎ−２ Ｂｉｏｍａｘ−１０００、分画分子量：１０００ｋＤａ）を用いて、液量を２００００ｇに保つように水を適宜追加しながら、２−ピロリドン及びジメチルスルホキシドをポリマー溶液から除去した。抽出液の吸光度が精製染料の吸光度に対して０．０５％以下になった時点で水の追加を止め、ポリマーの固形分濃度が５％になるまで、限外濾過膜を用いて濃縮した。得られた濃縮液を更に２Ｌのナスフラスコに投入し、減圧蒸留装置〔ロータリーエバポレーター、東京理化器械株式会社製、商品名：Ｎ−１０００Ｓ〕を用いて、６２℃に調整した温浴中、０．０７ＭＰａの圧力で減圧蒸留により水分を除去し、固形分濃度１０％のポリマー水分散液１〜９を得た。
得られたポリマー水分散液１〜９の一部を乾燥させることによりポリマー１〜９を得、重量平均分子量を測定した。結果を表４に示す。
なお、ポリマー溶液１０中に存在するポリマー１０の重量平均分子量は、ポリマー溶液１０ ０．５ｇを、Ｎ，Ｎ-ジメチルホルムアミド １６ｇに溶解させて測定した。
Production Example 6 <Production of Polymer Aqueous Dispersions 1-9>
After adding 15000 g of ion-exchanged water to the obtained polymer solutions 1 to 85000 g and adding 15615 g of ion-exchanged water to 4385 g of the polymer solution 9, ultrafiltration membrane (trade name: Pellicon-2 Biomax-1000 manufactured by Millipore) 2-pyrrolidone and dimethyl sulfoxide were removed from the polymer solution while adding water appropriately so as to keep the liquid volume at 20000 g using a molecular weight cut-off: 1000 kDa). When the absorbance of the extract was 0.05% or less with respect to the absorbance of the purified dye, the addition of water was stopped and the solution was concentrated using an ultrafiltration membrane until the solid content concentration of the polymer reached 5%. The obtained concentrated liquid was further poured into a 2 L eggplant flask, and 0. 0 in a warm bath adjusted to 62 ° C. using a vacuum distillation apparatus [rotary evaporator, manufactured by Tokyo Rika Kikai Co., Ltd., trade name: N-1000S]. Water was removed by distillation under reduced pressure at a pressure of 07 MPa to obtain polymer aqueous dispersions 1 to 9 having a solid content concentration of 10%.
A part of the obtained polymer aqueous dispersions 1 to 9 was dried to obtain polymers 1 to 9, and the weight average molecular weight was measured. The results are shown in Table 4.
The weight average molecular weight of the polymer 10 present in the polymer solution 10 was measured by dissolving 0.5 g of the polymer solution 10 in 16 g of N, N-dimethylformamide.
製造例７＜顔料水分散液１〜１４の製造＞
（１）工程（１）
容器２Ｌのディスパー（プライミクス株式会社製、Ｔ．Ｋ．ロボミックス、撹拌部ホモディスパー２．５型、羽直径４０ｍｍ）に、表５及び表６に示す所定量のポリマー水分散液１〜９又はポリマー溶液１０を投入し、１４００ｒｐｍの条件で撹拌しながら、表５及び表６に示す所定量のメチルエチルケトン（ＭＥＫ）を加え、さらにイオン交換水及び５Ｎ（１６．９重量％）水酸化ナトリウム水溶液を添加し、０℃の水浴で冷却しながら、１４００ｒｐｍで１５分間撹拌した。撹拌後、表５及び表６に示す所定量のカーボンブラック「モナーク８８０」（キャボット社製）を加え、６０００ｒｐｍの条件にて３時間撹拌した。得られた混合物をマイクロフルイダイザー（Microfluidics社製、商品名：型式Ｍ−１４０Ｋ）を用いて、１５０ＭＰａの圧力にて、２０パス分散処理した。
Production Example 7 <Production of pigment aqueous dispersions 1 to 14>
(1) Step (1)
In a container 2L disper (Primix Co., Ltd., TK Robotics, stirrer homodisper 2.5 type, feather diameter 40 mm), a predetermined amount of polymer aqueous dispersion 1 to 9 shown in Tables 5 and 6 or While stirring the polymer solution 10 and stirring at 1400 rpm, a predetermined amount of methyl ethyl ketone (MEK) shown in Table 5 and Table 6 was added, and ion-exchanged water and 5N (16.9 wt%) sodium hydroxide aqueous solution were further added. The mixture was added and stirred at 1400 rpm for 15 minutes while cooling with a 0 ° C. water bath. After stirring, a predetermined amount of carbon black “Monarch 880” (manufactured by Cabot Corporation) shown in Table 5 and Table 6 was added, and the mixture was stirred for 3 hours at 6000 rpm. The obtained mixture was subjected to 20-pass dispersion treatment at a pressure of 150 MPa using a microfluidizer (manufactured by Microfluidics, trade name: Model M-140K).
（２）工程（２）
分散処理物を２Ｌナスフラスコに入れ、表５及び表６に示す所定量のイオン交換水を加え、減圧蒸留装置〔ロータリーエバポレーター、東京理化器械株式会社製、商品名：Ｎ−１０００Ｓ〕を用いて、３２℃に調整した温浴中、０．０９ＭＰａの圧力で３時間保持して、有機溶媒を除去した。更に、温浴を６２℃に調整し、圧力を０．０７ＭＰａに下げて４時間保持し、有機溶媒及び一部の水を除去した。５μｍと１．２μｍのメンブランフィルター〔Sartorius社製、商品名：Minisart〕を用いて順に濾過し、顔料水分散液１〜１４を得た。顔料水分散液１〜１４の固形分濃度及び顔料粒子の平均粒径を表５及び表６に示す。
(2) Step (2)
The dispersion-processed product is put into a 2 L eggplant flask, a predetermined amount of ion-exchanged water shown in Table 5 and Table 6 is added, and a vacuum distillation apparatus [Rotary evaporator, manufactured by Tokyo Rika Kikai Co., Ltd., trade name: N-1000S] is used. In a warm bath adjusted to 32 ° C., the pressure was held at 0.09 MPa for 3 hours to remove the organic solvent. Furthermore, the warm bath was adjusted to 62 ° C., the pressure was lowered to 0.07 MPa and held for 4 hours, and the organic solvent and some water were removed. Filtration was sequentially performed using 5 μm and 1.2 μm membrane filters (manufactured by Sartorius, trade name: Minisart) to obtain pigment aqueous dispersions 1 to 14. Tables 5 and 6 show the solid content concentrations of the pigment aqueous dispersions 1 to 14 and the average particle size of the pigment particles.
製造例８＜顔料水分散液１５、１６の製造＞
（１）工程（１）
表７に示す所定量のポリマー水分散液、メチルエチルケトン、イオン交換水、５Ｎ水酸化ナトリウム水溶液及びカーボンブラックを用いて、製造例７の工程１と同様の操作を行い、分散処理物を得た。
（２）工程（３）
工程（１）で得た分散処理物に、表７に示す所定量のイオン交換水、エポキシ架橋剤（トリメチロールプロパンポリグリシジルエーテル、ナガセケムテックス株式会社製、商品名：デナコールＥＸ３２１Ｌ、エポキシ当量１２９）を添加し、７０℃で１時間撹拌し、更に、前記エポキシ架橋剤を添加し７０℃で１時間攪拌した。
（３）工程（２）
次に、製造例７の工程（２）と同様の操作を行い、顔料水分散液１５、１６を得た。顔料水分散液１５、１６の固形分濃度及び顔料粒子の平均粒径を表７に示す。
Production Example 8 <Production of pigment aqueous dispersions 15 and 16>
(1) Step (1)
Using a predetermined amount of the polymer aqueous dispersion shown in Table 7, methyl ethyl ketone, ion-exchanged water, 5N aqueous sodium hydroxide and carbon black, the same operation as in Step 1 of Production Example 7 was performed to obtain a dispersion-treated product.
(2) Step (3)
To the dispersion treated product obtained in the step (1), a predetermined amount of ion exchange water shown in Table 7 and an epoxy crosslinking agent (trimethylolpropane polyglycidyl ether, manufactured by Nagase ChemteX Corporation, trade name: Denacol EX321L, epoxy equivalent 129) ) Was added and stirred at 70 ° C. for 1 hour, and the epoxy crosslinking agent was further added and stirred at 70 ° C. for 1 hour.
(3) Step (2)
Next, the same operation as in step (2) of Production Example 7 was performed to obtain pigment aqueous dispersions 15 and 16. Table 7 shows the solid content concentrations of the pigment aqueous dispersions 15 and 16 and the average particle diameter of the pigment particles.
製造例９＜インク１〜１７の製造＞
表８、９に示す所定量の顔料水分散液、ジエチレングリコール（和光純薬工業株式会社製、試薬）、２−ピロリドン（和光純薬工業株式会社製、試薬）、プロキセルＬＶＳ（アーチケミカルズジャパン株式会社製、１，２−ベンゾイソチアゾール−３（２Ｈ）−オン、有効分２０％、防黴剤）、エチレンジアミン四酢酸二ナトリウム二水和物（シグマアルドリッチ社製、凝集防止剤）、ベンゾトリアゾール（和光純薬工業株式会社製、防錆剤）、オルフィンＥ１０１０（日信化学工業株式会社製、アセチレンジオールのエチレンオキシド（１０モル）付加物、界面活性剤）、精製染料（インク１６のみ）、及びイオン交換水を添加、混合し、得られた混合液を０．４５μｍのメンブランフィルター〔Sartorius社製、商品名：Minisart〕で濾過し、インク１〜１７を得た。得られたインク１〜１７の２０℃における表面張力は３０ｍＮ／ｍであった。
Production Example 9 <Production of Inks 1 to 17>
Predetermined amounts of pigment aqueous dispersions shown in Tables 8 and 9, diethylene glycol (Wako Pure Chemical Industries, Reagent), 2-pyrrolidone (Wako Pure Chemical Industries, Reagent), Proxel LVS (Arch Chemicals Japan Co., Ltd.) 1,2-benzoisothiazol-3 (2H) -one, effective 20%, antifungal agent), disodium ethylenediaminetetraacetate dihydrate (manufactured by Sigma-Aldrich, anti-aggregation agent), benzotriazole ( Wako Pure Chemical Industries, Ltd., rust preventive), Olphine E1010 (Nisshin Chemical Industry Co., Ltd., acetylene diol ethylene oxide (10 mol) adduct, surfactant), purified dye (ink 16 only), and ions Exchange water was added and mixed, and the resulting mixture was filtered through a 0.45 μm membrane filter (Sartorius, trade name: Minisart). 1 to 17 were obtained. The obtained inks 1 to 17 had a surface tension at 20 ° C. of 30 mN / m.
実施例１〜１３、比較例１〜４
温度２５±１℃、相対湿度３０±５％の環境で、インクジェットヘッド（京セラ株式会社製、商品名：ＫＪ４Ｂ-ＨＤ０６ＭＨＧ-ＳＴＤＶ）を装備した印字評価装置（株式会社トライテック製、商品名：ＯｎｅＰａｓｓＪｅｔ）に製造例９で得られたインクを充填した。
印刷条件として、ヘッド電圧２６Ｖ、周波数３０ｋＨｚ、吐出液適量７ｐｌ、ヘッド温度３２℃、吐出前フラッシング回数２００発、負圧−４．０ｋＰａを設定した。耐擦性評価用としてＡ４サイズの微塗工紙(Ｚｉｅｇｌｅｒ社製、商品名：Ziegler Evolution、坪量９０ｇ／ｍ2)を紙の長手方向と紙の搬送方向が同じになる向きに搬送台に減圧で固定した。印字命令を前記印字評価装置に転送し、２００回フラッシング後、インクをインクジェット記録方式で微塗工紙上に付与し、Ａ４ベタ画像を有する印刷物を作成した。同様に、裏抜け評価用としてＡ４サイズの非塗工紙（ＵＰＭ社製、商品名：Digibrite、坪量５５ｇ／ｍ2）に印字を行い、Ａ４ベタ画像を有する印刷物を作成した。
得られたベタ画像について、次のようにして微塗工紙の耐擦性及び非塗工紙の耐裏抜け性を評価した。
Examples 1-13, Comparative Examples 1-4
Print evaluation device (trade name: OnePassJet, manufactured by Tritech Co., Ltd.) equipped with an inkjet head (trade name: KJ4B-HD06MHG-STDV, manufactured by Kyocera Corporation) in an environment of temperature 25 ± 1 ° C. and relative humidity 30 ± 5%. ) Was filled with the ink obtained in Production Example 9.
As printing conditions, a head voltage of 26 V, a frequency of 30 kHz, an appropriate amount of discharge liquid of 7 pl, a head temperature of 32 ° C., a pre-discharge flushing count of 200, and a negative pressure of −4.0 kPa were set. A4 size fine coated paper (made by Ziegler, trade name: Ziegler Evolution, basis weight 90 g / m 2 ) for rubbing resistance evaluation is placed on the transport stand in the same direction as the paper longitudinal direction and paper transport direction. Fixed under reduced pressure. A print command was transferred to the print evaluation apparatus, and after flushing 200 times, ink was applied onto fine coated paper by an inkjet recording method to produce a printed matter having an A4 solid image. Similarly, A4 size non-coated paper (manufactured by UPM, trade name: Digibrite, basis weight 55 g / m 2 ) was printed for back-through evaluation, and a printed matter having an A4 solid image was produced.
About the obtained solid image, the abrasion resistance of the fine coated paper and the through-through resistance of the non-coated paper were evaluated as follows.
試験例１（印刷物の耐擦性）
重さ４６０ｇの錘の底面（１インチ×１インチ）に、微塗工紙（Ziegler Evolution、坪量９０ｇ／ｍ2、Ziegler社製）を両面テープで貼り付けた。
実施例１〜１３及び比較例１〜４で得られた印刷物の印刷面上に、上記錘底面の微塗工紙と印字物の印字面が接触する様に置いて、ベタ印字部分に対し、４インチの幅で１０回往復擦過した。
その後、前記錘に貼り付けた微塗工紙を剥がし、微塗工紙の擦過面の光学濃度（黒の光学濃度として出力される値）をマクベス濃度計（グレタグマクベス社製、品番：スペクトロアイ、測定条件 観測視野角：２度、観測光源：Ｄ６５、白色基準：紙基準、偏光フィルター：なし、濃度基準：ＤＩＮ）で計５点測定し、その平均値を求めた。光学濃度の値が小さいほど、耐擦性は良好である。結果を表１０に示す。
Test Example 1 (Abrasion resistance of printed matter)
A finely coated paper (Ziegler Evolution, basis weight 90 g / m 2 , manufactured by Ziegler) was attached to the bottom surface (1 inch × 1 inch) of a weight of 460 g with a double-sided tape.
On the printed surface of the printed matter obtained in Examples 1 to 13 and Comparative Examples 1 to 4, the fine coated paper on the bottom surface of the weight and the printed surface of the printed matter are placed in contact with each other. Rubbing was repeated 10 times with a width of 4 inches.
Thereafter, the finely coated paper attached to the weight is peeled off, and the optical density (value output as the black optical density) of the scratched surface of the finely coated paper is measured with a Macbeth densitometer (product number: Spectroeye). Measurement conditions Observation angle: 2 degrees, observation light source: D65, white standard: paper standard, polarizing filter: none, density standard: DIN), a total of five points were measured, and the average value was obtained. The smaller the value of the optical density, the better the scratch resistance. The results are shown in Table 10.
試験例２（印刷物の耐裏抜け性）
印字面ベタ部の紙の裏面の光学濃度（黒の光学濃度として出力される値）をマクベス濃度計（グレタグマクベス社製、品番：スペクトロアイ、測定条件 観測視野角：２度、観測光源：Ｄ６５、白色基準：紙基準、偏光フィルター：なし、濃度基準：ＤＩＮ）で計５点測定し、その平均値を求めた。光学濃度の値が小さいほど、裏抜けが抑制され優れている。結果を表１０に示す。
Test Example 2 (Print-through resistance of printed matter)
Macbeth densitometer (manufactured by Gretag Macbeth, product number: spectroeye, measurement conditions) Observation viewing angle: 2 degrees, observation light source: D65 , White standard: paper standard, polarizing filter: none, density standard: DIN), a total of five points were measured, and the average value was obtained. The smaller the value of the optical density, the better the see-through is suppressed. The results are shown in Table 10.
試験例３（吐出性）
インク１，１２，１３について、上記印刷の終了後、２５℃湿度４０％で３０分間ノズルを放置した。次いで、ノズルチェックパターンを印字した際に、目詰まりが発生し、吐出しなくなるノズルの数を数えた。数値は小さい方が吐出性に優れる。結果を表１０に示す。
Test Example 3 (Dischargeability)
For the inks 1, 12, and 13, after completion of the printing, the nozzles were left for 30 minutes at 25 ° C. and 40% humidity. Next, when the nozzle check pattern was printed, the number of nozzles that were clogged and no longer discharged was counted. The smaller the value, the better the discharge performance. The results are shown in Table 10.
Claims (9)
工程（１）：前記染料構造を有する基を含むポリマー、有機溶媒、顔料、及び水を含有する混合物を分散処理して、分散処理物を得る工程
工程（２）：工程（１）で得られた分散処理物から前記有機溶媒を除去して、顔料水分散液を得る工程 The manufacturing method of the pigment aqueous dispersion for inkjet recording in any one of Claims 1-6 including following process (1)-(2).
Step (1): A step of dispersing a mixture containing a polymer having a group having a dye structure, an organic solvent, a pigment, and water to obtain a dispersion-treated product Step (2): obtained in Step (1) Removing the organic solvent from the dispersion treatment product to obtain a pigment aqueous dispersion
工程（３）：工程（１）で得られた分散処理物又は工程（２）で得られた顔料水分散液と、架橋剤とを混合し、架橋処理して分散処理物又は顔料水分散液を得る工程 The manufacturing method of the pigment aqueous dispersion for inkjet recording of Claim 8 including the following process (3) after the following process (1) or (2).
Step (3): The dispersion-treated product obtained in Step (1) or the pigment aqueous dispersion obtained in Step (2) and the crosslinking agent are mixed and subjected to crosslinking treatment to obtain a dispersion-treated product or pigment aqueous dispersion. The process of obtaining
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