JP2013095766A - Encapsulated pigment, aqueous ink, and ink set - Google Patents
Encapsulated pigment, aqueous ink, and ink set Download PDFInfo
- Publication number
- JP2013095766A JP2013095766A JP2011236771A JP2011236771A JP2013095766A JP 2013095766 A JP2013095766 A JP 2013095766A JP 2011236771 A JP2011236771 A JP 2011236771A JP 2011236771 A JP2011236771 A JP 2011236771A JP 2013095766 A JP2013095766 A JP 2013095766A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- ink
- encapsulated pigment
- water
- encapsulated
- 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.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 117
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 17
- 125000002091 cationic group Chemical group 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 25
- -1 sulfate ester Chemical class 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 17
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000007639 printing Methods 0.000 abstract description 19
- 239000004753 textile Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 52
- 239000006185 dispersion Substances 0.000 description 33
- 239000000178 monomer Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000004744 fabric Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000740 bleeding effect Effects 0.000 description 10
- 239000002609 medium Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003254 radicals Chemical class 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000005968 oxazolinyl group Chemical group 0.000 description 2
- 238000000614 phase inversion technique Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-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
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- MHJFWPOZAIOCQL-UHFFFAOYSA-N 2-phenylpropan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)C(=O)OOC(C)(C)C1=CC=CC=C1 MHJFWPOZAIOCQL-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 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
- 239000000693 micelle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 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
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、捺染印刷に適したカプセル化顔料および水性インク並びにインクセットに関するものである。 The present invention relates to encapsulated pigments and aqueous inks and ink sets suitable for textile printing.
インクジェットプリンターは手軽にフルカラー印刷を行うことができ、紙以外のメディアへのプリントが可能である。応用用途としてシール、ラベル、ポスター、掲示板、屋外用のサインディスプレイおよびバスラップのようなものの他、繊布、不繊布などの布帛への印刷が挙げられる。布帛への印刷を行う捺染印刷には、印刷された画像に対し、高い洗濯堅牢性が求められる。また、耐光性が高い、複数の繊維種に対応できる、色材除去工程が不要である等の利点から、色材として顔料が好まれている。この顔料定着のために、インクにはバインダー成分を添加する必要がある。しかし、インクジェット用インクでは吐出安定性およびヘッド放置後の吐出性、目詰まりの観点から、バインダー成分を多量に使用することができず、洗濯および摩擦に対する堅牢性は不十分なものとなってしまう。 An inkjet printer can easily perform full-color printing and can print on media other than paper. Applications include printing on fabrics such as seals, labels, posters, bulletin boards, outdoor sign displays and bath wraps, and fabrics such as fabrics and non-woven fabrics. In textile printing for printing on a fabric, high wash fastness is required for the printed image. In addition, pigments are preferred as color materials because of their advantages such as high light resistance, compatibility with a plurality of fiber types, and the absence of a color material removal step. In order to fix the pigment, it is necessary to add a binder component to the ink. However, in ink jet ink, a binder component cannot be used in a large amount from the viewpoint of ejection stability, ejection performance after leaving the head, and clogging, and the fastness to washing and friction becomes insufficient. .
例えば、特許文献１には、布帛のような記録媒体に、多価金属塩を含む反応液と、顔料と樹脂エマルションとを含むインク組成物とを付着させて印字を行う、二液を用いたインクジェット記録方法が開示されている。この方法によれば、印字の滲みや印字ムラをおさえ、カラーブリードを有効に防止できるが、布帛への定着性には課題が残る。 For example, Patent Document 1 uses two liquids that perform printing by attaching a reaction liquid containing a polyvalent metal salt and an ink composition containing a pigment and a resin emulsion to a recording medium such as a fabric. An ink jet recording method is disclosed. According to this method, it is possible to suppress color bleeding and print unevenness effectively, but to effectively prevent color bleeding, but there remains a problem in the fixability to the fabric.
特許文献２には、布帛を多価金属塩とノニオン性樹脂エマルションで前処理し、アニオン性高分子分散剤で分散された顔料とノニオン性樹脂エマルションからなるインクで画像形成する方法が開示されている。また特許文献３には、布帛を多価金属塩で前処理し、顔料とアニオン性樹脂エマルションからなるインクで画像形成する方法が開示されている。これらの方法では、多価金属塩と、顔料またはアニオン性樹脂エマルションの凝集が布帛表面で起こり、印字の滲みや印字ムラを抑えることはできるが、定着樹脂が布内部まで浸透しないので、アイロン等で加熱・加圧を施しても、定着樹脂は布帛表面に物理的についているだけであるため定着性が弱く、洗濯時に画像部分をもむと剥離する場合があり改善の余地がある。 Patent Document 2 discloses a method in which a fabric is pretreated with a polyvalent metal salt and a nonionic resin emulsion, and an image is formed with an ink comprising a pigment dispersed with an anionic polymer dispersant and a nonionic resin emulsion. Yes. Patent Document 3 discloses a method in which a fabric is pretreated with a polyvalent metal salt and an image is formed with an ink comprising a pigment and an anionic resin emulsion. In these methods, aggregation of the polyvalent metal salt and the pigment or anionic resin emulsion occurs on the surface of the fabric, and it is possible to suppress printing bleeding and printing unevenness. However, since the fixing resin does not penetrate into the fabric, iron or the like Even if heat and pressure are applied, the fixing resin is only physically attached to the surface of the fabric, so that the fixing property is weak.
特許文献４には、カチオン処理された記録媒体をオキサゾリン基を有する重合体で処理し、その上に塩基で中和されたカルボキシル基を有する樹脂に包含された顔料着色樹脂粒子（カプセル化顔料）からなる水性インク組成物で画像形成し、画像形成後に加熱反応させる印刷方法が開示されている。カプセル化顔料はカプセル樹脂に定着性能を付与させることができ、必要以上の樹脂成分をインク中に含ませる必要がないので良好な定着性の実現が期待できる。 Patent Document 4 discloses pigment-colored resin particles (encapsulated pigments) which are obtained by treating a cation-treated recording medium with a polymer having an oxazoline group and then having a carboxyl group neutralized with a base thereon. A printing method is disclosed in which an image is formed with a water-based ink composition comprising: The encapsulated pigment can impart fixing performance to the capsule resin, and since it is not necessary to include an unnecessary resin component in the ink, it can be expected to realize good fixability.
しかし、特許文献４に記載された印刷方法は、カルボキシル基を有する樹脂を塩基で中和しているためオキサゾリン基との反応性が悪く、反応させるためには塩基を飛ばす必要がある。このため、特許文献４に記載された印刷方法の場合、耐洗濯性のある良好な定着性を実現するためには、加熱条件をかなり厳しくする必要があるため実用的とは言えない。オキサゾリン基との反応性を良くするためには、カルボキシル基を酸の状態にしておくことが必要であるが、カルボキシル基が酸の状態のままでは通常、カプセル化顔料の安定性が悪くなる。 However, since the printing method described in Patent Document 4 neutralizes a resin having a carboxyl group with a base, the reactivity with the oxazoline group is poor, and it is necessary to skip the base in order to cause the reaction. For this reason, in the case of the printing method described in Patent Document 4, it is not practical because it is necessary to make heating conditions considerably strict in order to achieve good fixability with washing resistance. In order to improve the reactivity with the oxazoline group, it is necessary to keep the carboxyl group in an acid state. However, if the carboxyl group is in an acid state, the stability of the encapsulated pigment usually deteriorates.
本発明は上記事情に鑑みなされたものであり、捺染印刷に適した安定性の良好なカプセル化顔料、および滲みを抑制することができ、良好な洗濯堅牢性を実現することができる水性インク、並びに水性インクと前処理液とをセットしたインクセットを提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and has a stable encapsulated pigment suitable for textile printing, and a water-based ink capable of suppressing bleeding and realizing good washing fastness, An object of the present invention is to provide an ink set in which an aqueous ink and a pretreatment liquid are set.
本発明のカプセル化顔料は、少なくともカルボキシル基と硫酸エステル塩基とを含む樹脂で被覆されたことを特徴とするものである。
前記硫酸エステル塩基は、アニオン性反応性乳化剤由来であることが好ましい。
前記樹脂中にポリオキシエチレン鎖を含むことが好ましい。
The encapsulated pigment of the present invention is characterized in that it is coated with a resin containing at least a carboxyl group and a sulfate ester base.
The sulfate ester base is preferably derived from an anionic reactive emulsifier.
The resin preferably contains a polyoxyethylene chain.
本発明の水性インクは、上記カプセル化顔料と、水と、水溶性有機溶剤を含むことを特徴とするものである。
本発明の水性インクは、インクジェット用インクであってもよい。
本発明のインクセットは前記水性インクと、オキサゾリン基を含む重合体とカチオン性物質とを含む前処理液とからなることを特徴とするものである。
前記カチオン性物質は、カチオン性樹脂エマルションであることが好ましい。
The water-based ink of the invention includes the encapsulated pigment, water, and a water-soluble organic solvent.
The water-based ink of the present invention may be an inkjet ink.
The ink set of the present invention comprises the aqueous ink, and a pretreatment liquid containing a polymer containing an oxazoline group and a cationic substance.
The cationic substance is preferably a cationic resin emulsion.
本発明のカプセル化顔料およびこのカプセル化顔料を含むインクは、顔料がカルボキシル基と硫酸エステル塩基とを含む樹脂で被覆されているので、前処理液に含まれるオキサゾリン基との反応性が良く、加熱時間が短くても洗濯堅牢性のある良好な定着性を実現することができる。また、本発明のカプセル化顔料はカルボキシル基以外に硫酸エステル塩基を含むため、カルボキシル基が酸の状態のままであっても安定性が高いものとすることができる。 The encapsulated pigment of the present invention and the ink containing the encapsulated pigment have good reactivity with the oxazoline group contained in the pretreatment liquid because the pigment is coated with a resin containing a carboxyl group and a sulfate ester base. Even when the heating time is short, good fixability with fastness to washing can be realized. Further, since the encapsulated pigment of the present invention contains a sulfate ester base in addition to the carboxyl group, it can be highly stable even if the carboxyl group remains in an acid state.
本発明のカプセル化顔料は、少なくともカルボキシル基と硫酸エステル塩基とを含む樹脂で被覆されたことを特徴とする。
カプセル化顔料の作製方法としては、酸析再溶解法、転相法あるいはミニエマルション重合法が知られている。酸析再溶解法は、アニオン性基含有樹脂を中和し、水性媒体中で顔料を分散し、ｐＨを酸性にすることで樹脂と顔料を析出させ、顔料に樹脂を固着させた後、塩基性化合物を用いてアニオン性基を中和させ水性媒体中に再溶解させる方法である。転相法は、アニオン性基含有樹脂の有機溶媒中で顔料を分散し、塩基性化合物を添加した後、超音波を照射しながら水を加え転相乳化を行い、その後、溶剤を留去させる方法である。ミニエマルション重合法は、水に対する溶解度がモノマーより低いハイドロホーブを加えた顔料分散体を水中に乳化し、そのままラジカル重合することにより顔料を樹脂中に含有したカプセル化顔料とするものである。
The encapsulated pigment of the present invention is characterized in that it is coated with a resin containing at least a carboxyl group and a sulfate ester base.
As a method for producing an encapsulated pigment, an acid precipitation re-dissolution method, a phase inversion method, or a miniemulsion polymerization method is known. In the acid precipitation re-dissolution method, the anionic group-containing resin is neutralized, the pigment is dispersed in an aqueous medium, the pH is acidified to precipitate the resin and the pigment, the resin is fixed to the pigment, and then the base is fixed. In this method, the anionic group is neutralized by using a functional compound and redissolved in an aqueous medium. In the phase inversion method, a pigment is dispersed in an organic solvent of an anionic group-containing resin, a basic compound is added, water is added while irradiating ultrasonic waves, phase inversion emulsification is performed, and then the solvent is distilled off. Is the method. In the miniemulsion polymerization method, an encapsulated pigment containing a pigment in a resin is obtained by emulsifying a pigment dispersion to which a hydrophobe having a lower solubility in water than that of a monomer is added in water, and performing radical polymerization as it is.
本発明のカプセル化顔料はカプセル樹脂中にカルボキシル基と硫酸エステル塩基を含有するように作製されれば、上記のいずれの作製方法で作製してもよいが、カルボキシル基が中和されない状態とする必要があるため、カルボキシル基と硫酸エステル塩基の導入が比較的容易であるミニエマルション重合法が好ましい。カルボキシル基が中和されていると前処理液に含有されるオキサゾリンとの反応が抑制されるため、捺染印刷に使用した場合に定着性が非常に悪くなる。カルボキシル基が中和されない状態とはインク（あるいは後述するカプセル化顔料の水分散体）においてはｐＨを７以下にすることが必要である。より好ましくは６以下である。 The encapsulated pigment of the present invention may be produced by any of the above production methods as long as the encapsulated pigment contains a carboxyl group and a sulfate ester base in the capsule resin, but the carboxyl group is not neutralized. Since it is necessary, a miniemulsion polymerization method in which introduction of a carboxyl group and a sulfate ester base is relatively easy is preferable. When the carboxyl group is neutralized, the reaction with the oxazoline contained in the pretreatment liquid is suppressed, so that the fixability becomes very poor when used for textile printing. The state in which the carboxyl group is not neutralized requires that the pH of the ink (or an encapsulated pigment aqueous dispersion described later) be 7 or less. More preferably, it is 6 or less.
ｐＨが７よりも高くなると、ほとんどのカルボキシル基は電離している状態と考えられる。通常、カプセル化顔料の安定性を確保するためには顔料表面の電荷を高めることが必要であるため、インクのｐＨはカルボキシル基が電離した状態となるｐＨ７よりも高い方が好ましい。従って、ｐＨ７以下にすることはカプセル化顔料の安定性という側面からはマイナスとなるが、本発明ではカプセル化顔料の電荷はカルボキシル基の他に硫酸エステル塩基によって補われるため、ｐＨが７以下でも十分なマイナス電荷を保持することが可能となりカプセル化顔料全体としての安定性を確保することができる。 When the pH is higher than 7, most of the carboxyl groups are considered to be ionized. Usually, in order to ensure the stability of the encapsulated pigment, it is necessary to increase the charge on the surface of the pigment. Therefore, the pH of the ink is preferably higher than pH 7 at which the carboxyl group is ionized. Accordingly, the pH of 7 or less is negative from the viewpoint of the stability of the encapsulated pigment, but in the present invention, the charge of the encapsulated pigment is supplemented by a sulfate ester base in addition to the carboxyl group. A sufficient negative charge can be retained, and the stability of the encapsulated pigment as a whole can be ensured.
ミニエマルション重合法では、ハイドロホーブ（モノマーと相溶性の良い水難溶性物質）を入れることでミニエマルションからモノマーが抜けることを防ぐことができる。ミニエマルションからモノマーが抜けていくと顔料を充分に樹脂で被覆することができず、重合時顔料の凝集が多く発生する。また抜けたモノマーが、系中の反応性乳化剤のミセル中でモノマーだけで乳化重合を始めるため、カプセル顔料以外に樹脂の微粒子が多数生成する。ハイドロホーブとしては通常よく使用されているヘキサデカンの他、モノマーと相溶性がよく水難溶性のものであれば多くの物が使用できるが、その中でもモノマーより分子量が大きくモノマーと相溶性のよい、１分子中にアクリロイル基またはメタクリロイル基を２つ以上有するラジカル重合性オリゴマーを使用することが好ましい。ラジカル重合性オリゴマーによって、重合時のエマルションが安定化するため、カプセル化顔料の粒子径の増大化や凝集を抑制することができる。以下、この場合を例にとって説明する。 In the miniemulsion polymerization method, it is possible to prevent the monomer from escaping from the miniemulsion by adding a hydrophobe (a poorly water-soluble substance that is compatible with the monomer). When the monomer escapes from the mini-emulsion, the pigment cannot be sufficiently covered with the resin, and agglomeration of the pigment occurs during polymerization. Further, since the lost monomer starts emulsion polymerization only with the monomer in the micelle of the reactive emulsifier in the system, a large number of resin fine particles are generated in addition to the capsule pigment. In addition to hexadecane, which is commonly used as a hydrophobe, many substances can be used as long as they are compatible with monomers and poorly water-soluble. Among them, molecular weight is higher than monomers and compatibility with monomers is good. It is preferable to use a radically polymerizable oligomer having two or more acryloyl groups or methacryloyl groups in the molecule. Since the emulsion at the time of polymerization is stabilized by the radically polymerizable oligomer, increase in the particle diameter and aggregation of the encapsulated pigment can be suppressed. Hereinafter, this case will be described as an example.
ミニエマルション重合法によるカプセル化顔料の製造工程は、（１）顔料分散体の調製工程、（２）Ｏ／Ｗ型エマルションの調製工程、（３）Ｏ／Ｗ型エマルションの重合工程を備え、必要に応じて、（４）溶媒の除去工程を備えてもよい。 The manufacturing process of encapsulated pigment by the mini-emulsion polymerization method includes (1) preparation process of pigment dispersion, (2) preparation process of O / W type emulsion, and (3) polymerization process of O / W type emulsion. Depending on (4), you may provide the removal process of a solvent.
（１）顔料分散体の調製工程
顔料分散体の調製工程は、顔料を油性溶媒中に分散することにより行う。
顔料としては、無機顔料および有機顔料の何れも使用できる。具体的には、カーボンブラック、カドミウムレッド、クロムイエロー、カドミウムイエロー、酸化クロム、ビリジアン、チタンコバルトグリーン、ウルトラマリンブルー、プルシアンブルー、コバルトブルー、アゾ系顔料、フタロシアニン系顔料、キナクリドン系顔料、イソインドリノン系顔料、ジオキサジン系顔料、スレン系顔料、ペリレン系顔料、チオインジゴ系顔料、キノフタロン系顔料、金属錯体顔料などが好適に使用できる。これらの顔料は単独で用いてもよいし、適宜組み合わせて使用してもよい。なお、上記顔料は、下記油性溶媒に親和性を有することが好ましく、すなわち、疎水性の表面を備えることが好ましい。
顔料の配合量は、顔料が油性溶媒中に分散すれば特に制限はないが、顔料分散体全量に対して１０〜５０質量％であることが好ましい。顔料の粒子径は６０〜１５０ｎｍであることが好ましい。
(1) Pigment Dispersion Preparation Step The pigment dispersion preparation step is performed by dispersing the pigment in an oily solvent.
As the pigment, any of inorganic pigments and organic pigments can be used. Specifically, carbon black, cadmium red, chrome yellow, cadmium yellow, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindo Rinone pigments, dioxazine pigments, selenium pigments, perylene pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments and the like can be suitably used. These pigments may be used alone or in appropriate combination. The pigment preferably has an affinity for the following oily solvent, that is, preferably has a hydrophobic surface.
The blending amount of the pigment is not particularly limited as long as the pigment is dispersed in the oily solvent, but is preferably 10 to 50% by mass with respect to the total amount of the pigment dispersion. The particle diameter of the pigment is preferably 60 to 150 nm.
油性溶媒は、カルボキシル基を含むラジカル重合性モノマーと好ましくは油溶性のラジカル重合性モノマーを含み、下記（２）の工程においてＯ／Ｗ型エマルションの油相粒子を形成できる必要がある。
カルボキシル基を含むラジカル重合性モノマーとしてはアクリル酸、メタクリル酸、クロトン酸、マレイン酸等を好ましく挙げることができる。
The oil-based solvent contains a radically polymerizable monomer containing a carboxyl group and preferably an oil-soluble radically polymerizable monomer, and it is necessary to be able to form oil phase particles of an O / W emulsion in the following step (2).
Preferable examples of the radical polymerizable monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid and the like.
１分子中にアクリロイル基またはメタクリロイル基を２つ以上有するラジカル重合性オリゴマーとしては、例えば、ウレタンアクリレート、エポキシアクリレートおよびポリエステルアクリレートからなる群より選ばれた少なくとも１種が挙げられる。ウレタンアクリレートオリゴマーとしては、ビームセット５０５Ａ−６（荒川化学製）、フォトマー６２１０（サンノプコ製）、Ｅｂｅｃｒｙｌ２７０（ダイセル製）、ＵＶ３２００Ｂ、ＵＶ６３００Ｂ、ＵＶ７５５０Ｂ（日本合成化学製）などが挙げられる。エポキシアクリレートとしては、バンビーム２２Ｃ（ハリマ化成製）、ＬａｒｏｍｅｒＬＲ８７６５（ＢＡＳＦ製）、フォトマー３００５（サンノプコ製）、Ｅｂｅｃｒｙｌ３５００（ダイセル製）などが挙げられる。ポリエステルアクリレートとしては、アロニックスＭ７１００、Ｍ６１００（東亞合成製）、Ｅｂｅｃｒｙｌ８０（ダイセル製）などが挙げられる。 Examples of the radical polymerizable oligomer having two or more acryloyl groups or methacryloyl groups in one molecule include at least one selected from the group consisting of urethane acrylate, epoxy acrylate and polyester acrylate. Examples of the urethane acrylate oligomer include Beamset 505A-6 (manufactured by Arakawa Chemical), Photomer 6210 (manufactured by Sannopco), Ebecryl 270 (manufactured by Daicel), UV3200B, UV6300B, and UV7550B (manufactured by Nippon Synthetic Chemical). Examples of the epoxy acrylate include Van Beam 22C (manufactured by Harima Kasei), Laromar LR8765 (manufactured by BASF), Photomer 3005 (manufactured by San Nopco), Ebecryl 3500 (manufactured by Daicel), and the like. Examples of the polyester acrylate include Aronix M7100, M6100 (manufactured by Toagosei), Ebecryl 80 (manufactured by Daicel), and the like.
油性溶媒は顔料分散体の粘度調整のために、さらに、ラジカル重合性を有しない有機溶剤を含有してもよい。かかる有機溶剤は水に溶解せず、上記モノマーおよびオリゴマーと混和できるものであれば特に限定されないが、重合後の除去を容易にするために、低沸点非水溶性有機溶剤であることが好ましい。低沸点非水溶性有機溶剤としては、沸点が１００℃以下のものが好ましい。具体例としては、ケトン系溶剤、エステル系溶剤（例えば酢酸エチル）が挙げられる。かかる有機溶剤は、上記オリゴマー、モノマーおよび顔料からなる顔料分散体が低粘度であれば入れる必要はない。しかし、溶液の粘度が低いほど顔料の分散性が向上し、下記（２）の工程におけるＯ／Ｗ型エマルションの油相粒子の粒径を小さくできるので、かかる有機溶剤の添加は有用である。かかる有機溶剤の配合量は、顔料分散体全量に対し０〜８０質量％であることが好ましい。 The oily solvent may further contain an organic solvent having no radical polymerizability for adjusting the viscosity of the pigment dispersion. Such an organic solvent is not particularly limited as long as it does not dissolve in water and is miscible with the above-mentioned monomer and oligomer, but is preferably a low-boiling water-insoluble organic solvent in order to facilitate removal after polymerization. As the low-boiling water-insoluble organic solvent, those having a boiling point of 100 ° C. or less are preferable. Specific examples include ketone solvents and ester solvents (for example, ethyl acetate). Such an organic solvent is not necessary if the pigment dispersion composed of the oligomer, monomer and pigment has a low viscosity. However, as the viscosity of the solution is lower, the dispersibility of the pigment is improved, and the particle size of the oil phase particles of the O / W type emulsion in the following step (2) can be reduced. Therefore, addition of such an organic solvent is useful. It is preferable that the compounding quantity of this organic solvent is 0-80 mass% with respect to the pigment dispersion whole quantity.
油性溶媒は、顔料分散体における顔料の分散性を改善するために、さらに、顔料分散剤を含有してもよい。顔料分散剤としては、使用する顔料や溶媒に相応しいものであれば特に限定されない。
顔料分散体は、上記油性溶媒に顔料を添加して、公知の分散機を用いて混合することにより調製できる。分散機としては、例えば、ビーズミル、超音波分散機等を使用することができる。
The oily solvent may further contain a pigment dispersant in order to improve the dispersibility of the pigment in the pigment dispersion. The pigment dispersant is not particularly limited as long as it is suitable for the pigment and solvent to be used.
The pigment dispersion can be prepared by adding a pigment to the oily solvent and mixing using a known disperser. As the disperser, for example, a bead mill, an ultrasonic disperser, or the like can be used.
（２）Ｏ／Ｗ型エマルションの調製工程
Ｏ／Ｗ型エマルションの調製工程は、上記（１）の工程で得られた顔料分散体を水中に添加してホモジナイズ処理することにより行うことができる。
(2) Preparation process of O / W type emulsion The preparation process of the O / W type emulsion can be performed by adding the pigment dispersion obtained in the above step (1) to water and homogenizing it.
乳化剤は、硫酸エステル塩基を含むモノマーが好ましく、硫酸エステル塩基を含むモノマーとしては硫酸エステル塩基を含むアニオン性反応性乳化剤等が挙げられる。具体的には、アクアロンＫＨ０５、アクアロンＫＨ１０、アクアロンＢＣ１０、アクアロンＢＣ２０（第一工業製薬製）、アデカリアソープＳＥ１０Ｎ、ＳＥ２０Ｎ、ＳＲ１０、ＳＲ２０（株式会社ＡＤＥＫＡ製）等が挙げられる。 The emulsifier is preferably a monomer containing a sulfate ester base, and examples of the monomer containing a sulfate ester base include an anionic reactive emulsifier containing a sulfate ester base. Specific examples include Aqualon KH05, Aqualon KH10, Aqualon BC10, Aqualon BC20 (Daiichi Kogyo Seiyaku), Adekaria Soap SE10N, SE20N, SR10, SR20 (manufactured by ADEKA Corporation).
カプセル化顔料の安定性をより高めるためには、カプセル化顔料の樹脂はポリオキシエチレン鎖基を有していることが好ましい。ポリオキシエチレン鎖基の立体障害により、カプセル化顔料をより安定化させることができる。
ポリオキシエチレン鎖基を含むモノマーとしてはノニオン性反応性乳化剤等が挙げられる。具体的には、アクアロンＲＮ２０、ＲＮ３０、ＲＮ５０（第一工業製薬製）、アデカリアソープＮＥ１０、ＮＥ２０、ＮＥ３０、ＮＥ４０、ＮＥ５０、ＥＲ１０、ＥＲ２０、ＥＲ３０、ＥＲ４０、ＥＲ５０（株式会社ＡＤＥＫＡ製）等が挙げられる。その他のモノマーとしてはブレンマーＰＥ２００、ＰＥ３５０、ＡＥ２００、ＡＥ４００（日本油脂製）等が挙げられる。
In order to further enhance the stability of the encapsulated pigment, the encapsulated pigment resin preferably has a polyoxyethylene chain group. The encapsulated pigment can be further stabilized by the steric hindrance of the polyoxyethylene chain group.
Examples of the monomer containing a polyoxyethylene chain group include nonionic reactive emulsifiers. Specifically, Aqualon RN20, RN30, RN50 (Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap NE10, NE20, NE30, NE40, NE50, ER10, ER20, ER30, ER40, ER50 (manufactured by ADEKA Corporation) and the like can be mentioned. It is done. Examples of other monomers include Bremer PE200, PE350, AE200, AE400 (manufactured by NOF Corporation).
下記（３）の重合工程を容易にするために、下記（３）の工程以前の段階で、上記顔料分散体に、ラジカル重合開始剤を添加しておくことが好ましい。上記顔料分散体に添加するラジカル重合開始剤としては、具体的には、２，２’−アゾビスイソブチロニトリル、２，２’− アゾビス−（２−メチルプロパンニトリル） 、２，２’−アゾビス−（２，４−ジメチルペンタンニトリル）、２，２’−アゾビス−（２−メチルブタンニトリル）、１，１’−アゾビス−（シクロヘキサンカルボニトリル）、２，２’−アゾビス−（２，４−ジメチル−４−メトキシバレロニトリル）、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビス−（２−アミジノプロパン）ヒドロクロリド等のアゾ（アゾビスニトリル）タイプの開始剤、過酸化ベンゾイル、クメンヒドロペルオキシド、過酸化水素、過酸化アセチル、過酸化ラウロイル、過硫酸塩（例えば過硫酸アンモニウム）、過酸エステル（例えばｔ−ブチルペルオクテート、α−クミルペルオキシピバレートおよびｔ−ブチルペルオクテート）等の過酸化物タイプの開始剤などが挙げられる。 In order to facilitate the polymerization step (3) below, it is preferable to add a radical polymerization initiator to the pigment dispersion at a stage prior to the step (3) below. Specific examples of the radical polymerization initiator added to the pigment dispersion include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2-methylpropanenitrile), 2,2 ′. -Azobis- (2,4-dimethylpentanenitrile), 2,2'-azobis- (2-methylbutanenitrile), 1,1'-azobis- (cyclohexanecarbonitrile), 2,2'-azobis- (2 , 4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (2-amidinopropane) hydrochloride, etc. Nitrile) type initiators, benzoyl peroxide, cumene hydroperoxide, hydrogen peroxide, acetyl peroxide, lauroyl peroxide, persulfates (eg ammonium persulfate) Arm), peresters (e.g., t- butyl peroxide octoate, etc. α- cumyl peroxypivalate and t- butyl peroxide octoate) peroxide type initiators and the like.
このＯ／Ｗ型エマルションの調製工程のホモジナイズ処理は、通常の乳化機、例えば、ホモミキサー、超音波分散機などを用いて行うことができる。
この工程において、水および顔料分散体の配合量は、両者全量に対して、水１０〜９０質量％、顔料分散体９０〜１０質量％である。
The homogenization treatment in the preparation process of the O / W emulsion can be performed using a normal emulsifier, for example, a homomixer or an ultrasonic disperser.
In this step, the blending amounts of water and the pigment dispersion are 10 to 90% by mass of water and 90 to 10% by mass of the pigment dispersion with respect to the total amount of both.
（３）Ｏ／Ｗ型エマルションの重合工程
Ｏ／Ｗ型エマルションの重合工程は、上記（２）の工程で得られたＯ／Ｗ型エマルションを加熱攪拌することにより行うことができる。この重合は、窒素雰囲気下で行うことが好ましい。また、反応系にラジカル重合開始剤が未だ添加されていない場合は、この時点で、ラジカル重合開始剤を添加して重合を行うことが好ましい。重合温度は４０〜９０℃が好ましく、重合開始剤の種類によって温度および重合時間を調整する必要がある。
このようにして、Ｏ／Ｗ型エマルション中に分散していた油相粒子が重合したカプセル化顔料の微粒子が水中に分散した分散体が得られる。微粒子の粒径は６０〜２００ｎｍであることが好ましい。
(3) O / W emulsion polymerization step The O / W emulsion polymerization step can be performed by heating and stirring the O / W emulsion obtained in the step (2). This polymerization is preferably performed in a nitrogen atmosphere. Moreover, when the radical polymerization initiator has not yet been added to the reaction system, it is preferable to perform polymerization by adding a radical polymerization initiator at this point. The polymerization temperature is preferably 40 to 90 ° C., and it is necessary to adjust the temperature and the polymerization time depending on the kind of the polymerization initiator.
In this way, a dispersion is obtained in which the encapsulated pigment fine particles obtained by polymerizing the oil phase particles dispersed in the O / W emulsion are dispersed in water. The particle diameter of the fine particles is preferably 60 to 200 nm.
（４）溶媒の除去工程
上記（２）の工程で油性溶媒として低沸点非水溶性有機溶剤を用いた場合は、この有機溶剤を除去するために、上記（３）の工程で得られたカプセル化顔料の水分散体をエバポレーターで加熱減圧することが好ましい。低沸点非水溶性有機溶剤を使用しない場合は、この溶媒の除去工程は行わなくてもよい。
(4) Solvent removal step When a low-boiling water-insoluble organic solvent is used as the oily solvent in the step (2), the capsule obtained in the step (3) is used to remove the organic solvent. It is preferable to heat and depressurize the aqueous dispersion of the fluorinated pigment with an evaporator. In the case where a low boiling water-insoluble organic solvent is not used, the solvent removal step may not be performed.
上記のようにして得られたカプセル化顔料の水分散体は、そのまま水性インクとして使用することもできるが、インクジェットインクとして使用する場合は、水分散体に含まれる粗粒や重合中に生成したエマルション粒子の凝集物を除く必要がある。従って、上記のようにして得られたカプセル化顔料の水分散体を、遠心分離機やフィルター等にかけることによって、インクジェットインクを調製することができる。 The encapsulated pigment aqueous dispersion obtained as described above can be used as an aqueous ink as it is, but when used as an ink-jet ink, it is produced during the coarse particles contained in the aqueous dispersion or during polymerization. It is necessary to remove aggregates of emulsion particles. Therefore, an inkjet ink can be prepared by subjecting the aqueous dispersion of the encapsulated pigment obtained as described above to a centrifuge or a filter.
また、インクジェットインクの表面張力をインクの吐出に適した４０ｍＮ／ｍ以下に調整するために、上記のようにして得られたカプセル化顔料の水分散体に、界面活性剤や追加の溶剤を添加することもできる。特に、インクジェットインクの保存安定性や機上安定性を向上させるため、あるいは、インク粘度を調整するために、水溶性有機溶剤を加えてもよい。 In addition, in order to adjust the surface tension of the inkjet ink to 40 mN / m or less suitable for ink ejection, a surfactant or an additional solvent is added to the aqueous dispersion of the encapsulated pigment obtained as described above. You can also In particular, a water-soluble organic solvent may be added in order to improve the storage stability and on-machine stability of the ink-jet ink, or to adjust the ink viscosity.
水溶性有機溶剤としては、具体的には、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、などのグリコール類、グリセリン、アセチン類、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノメチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテルなどのグリコール誘導体、トリエタノールアミン、１−メチル−２−ピロリドン、β−チオグリコール、スルホランなどを用いることができる。これらの水溶性有機溶剤は単独で、または２種類以上を組み合わせて使用することができる。水溶性有機溶剤は、インク全量に対し１〜８０質量％の範囲であることが好ましく、１０〜６０質量％の範囲であることがより好ましい。 Specific examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and other glycols, glycerin, acetins, Glycol derivatives such as triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, triethanolamine, 1-methyl-2-pyrrolidone, β-thioglycol, Sulfolane and the like can be used. These water-soluble organic solvents can be used alone or in combination of two or more. The water-soluble organic solvent is preferably in the range of 1 to 80% by mass and more preferably in the range of 10 to 60% by mass with respect to the total amount of the ink.
水性インクには、必要に応じて、本発明の目的を阻害しない範囲内で、当該分野において通常用いられている各種添加剤を含ませることができる。具体的には、顔料分散剤、消泡剤、表面張力低下剤等として、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、または高分子系、シリコーン系、フッ素系の界面活性剤をインクに含有させることができる。 If necessary, the water-based ink may contain various additives that are usually used in the art as long as the object of the present invention is not impaired. Specifically, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a polymer, silicone, fluorine, as a pigment dispersant, an antifoaming agent, a surface tension reducing agent, etc. System surfactants can be included in the ink.
水性インクは、例えばビーズミル等の公知の分散機に全成分を一括または分割して投入して分散させ、所望により、メンブレンフィルター等の公知のろ過機を通すことにより調製できる。例えば、予め溶剤の一部と顔料の全量を均一に混合させた混合液を調製して分散機にて分散させた後、この分散液に残りの成分を添加してろ過機を通すことにより調製することができる。 The water-based ink can be prepared by, for example, supplying all components into a known disperser such as a bead mill in a batch or divided and dispersing it, and if desired, passing it through a known filter such as a membrane filter. For example, after preparing a mixed liquid in which a part of the solvent and the whole amount of the pigment are uniformly mixed in advance and dispersing with a disperser, the remaining components are added to this dispersion and the mixture is passed through a filter. can do.
本発明の水性インクは、前処理液を記録媒体へ塗布した後、この記録媒体上へ吐出させることにより良好な洗濯堅牢性を確保することができる。前処理液は、オキサゾリン基を含む重合体と記録媒体との定着性を上げるために、カチオン性物質を含むものである。カチオン性物質はカチオン性水性樹脂エマルションであることが好ましい。 The water-based ink of the present invention can ensure good washing fastness by applying a pretreatment liquid to a recording medium and then discharging the pretreatment liquid onto the recording medium. The pretreatment liquid contains a cationic substance in order to improve the fixability between the polymer containing an oxazoline group and the recording medium. The cationic substance is preferably a cationic aqueous resin emulsion.
オキサゾリン基を有する重合体としては、下記一般式（Ｉ）で表される付加重合性オキサゾリンを必須成分として含む単量体成分を重合してなる水溶性または水分散性のオキサゾリニル基含有重合体が、安定性、反応後の密着性に優れているため好ましい。
上記付加重合性オキサゾリン単量体には、オキサゾリンとは反応しない付加重合性単量体、具体的には（メタ）アクリル酸エステル、（メタ）アクリルニトリル、（メタ）アクリルアミド、ビニルエステル、ビニルエーテル等を組み合わせることが可能であるが、この場合付加重合性オキサゾリン単量体の含有量はオキサゾリニル基含有重合体全量に対して５質量％以上が硬化性の点から好ましい。 The above addition polymerizable oxazoline monomer includes an addition polymerizable monomer that does not react with oxazoline, specifically (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, vinyl ester, vinyl ether, etc. In this case, the content of the addition polymerizable oxazoline monomer is preferably 5% by mass or more based on the total amount of the oxazolinyl group-containing polymer from the viewpoint of curability.
オキサゾリン重合体としては、水溶性オキサゾリン重合体 エポクロスＷＳ−５００、７００、水分散性オキサゾリン重合体 エポクロスＫ−１０１０、１０２０、１０３０Ｅ、エポクロスＫ−２０１０、２０２０、２０３０（エポクロスは登録商標：日本触媒）等を好ましく挙げることができる。前処理液中のオキサゾリン重合体の含有量は安定性と硬化程度を考慮して適宜変更することができ、０．１〜２０質量％の範囲が好ましい。 As the oxazoline polymer, water-soluble oxazoline polymer Epocros WS-500, 700, water dispersible oxazoline polymer Epocros K-1010, 1020, 1030E, Epocros K-2010, 2020, 2030 (Epocross is a registered trademark: Nippon Shokubai) Etc. can be mentioned preferably. The content of the oxazoline polymer in the pretreatment liquid can be appropriately changed in consideration of the stability and the degree of curing, and is preferably in the range of 0.1 to 20% by mass.
カチオン性物質としては、ポリビニルアミン、ポリアリルスルホンおよびその塩、ポリアリルアミンおよびその塩、アクリルアミドの共重合体のカチオン性重合体の他、酸性領域でカチオン性を示す各種両性界面活性剤（アミノ酸型、カルボン酸型、硫酸エステル型、リン酸エステル型等）がある。カチオン性水性樹脂エマルションとしてはウレタン系、アクリル系、酢酸ビニル系等が使用できる。スーパーフレックス６２０、６５０（第一工業製薬）、ハイドランＣＰ７６１０，ＣＰ７０５０（ＤＩＣ）等が挙げられる。前処理液中の含有量は５〜５０質量％の範囲が好ましい。 Examples of cationic substances include polyvinylamine, polyallylsulfone and salts thereof, polyallylamine and salts thereof, and cationic polymers of acrylamide copolymers, as well as various amphoteric surfactants that exhibit cationic properties in the acidic region (amino acid type). Carboxylic acid type, sulfuric acid ester type, phosphoric acid ester type, etc.). As the cationic aqueous resin emulsion, urethane, acrylic, vinyl acetate and the like can be used. Superflex 620, 650 (Daiichi Kogyo Seiyaku), Hydran CP7610, CP7050 (DIC), etc. are mentioned. The content in the pretreatment liquid is preferably in the range of 5 to 50% by mass.
前処理液の記録媒体への塗布は、刷毛、ローラー、バーコーター等を使用して記録媒体の表面を均一にコーティングすることによって行ってもよく、または、インクジェット印刷およびグラビア印刷などの印刷手段によって画像を印刷することで行ってもよい。 The pretreatment liquid may be applied to the recording medium by uniformly coating the surface of the recording medium using a brush, roller, bar coater or the like, or by printing means such as inkjet printing and gravure printing. This may be done by printing an image.
また、インクジェット印刷方法を容易に実施できるように、上記前処理液と水性インクとを少なくとも含むインクセットを構成して販売すると好都合である。ここでインクセットとは、前処理液カートリッジとインクカートリッジが複数一体になっているインクカートリッジ自体はもちろんのこと、単独の前処理液カートリッジとインクカートリッジを複数組み合わせて使用する場合も含み、さらに、前処理液カートリッジとインクカートリッジと記録ヘッドを一体としたものも含まれる。 Moreover, it is convenient to constitute and sell an ink set including at least the pretreatment liquid and the water-based ink so that the ink jet printing method can be easily performed. Here, the ink set includes not only an ink cartridge itself in which a plurality of pretreatment liquid cartridges and ink cartridges are integrated, but also a case where a plurality of single pretreatment liquid cartridges and ink cartridges are used in combination. A unit in which a pretreatment liquid cartridge, an ink cartridge, and a recording head are integrated is also included.
印刷工程後に、記録媒体に対し１００〜１８０℃、好ましくは１５０℃〜１７０℃程度で３０秒〜１分程度の熱処理を行うことにより、インクを乾燥させるとともに、インク中のカプセル化顔料のカルボキシル基を有する樹脂と、前処理液のオキサゾリン基を含む重合体とが記録媒体上で架橋反応し、記録媒体にインクを強固に付着させることができる。
以下、実施例により本発明をさらに詳細に説明する。
After the printing process, the recording medium is subjected to a heat treatment at 100 to 180 ° C., preferably about 150 to 170 ° C. for about 30 seconds to 1 minute, whereby the ink is dried and the carboxyl group of the encapsulated pigment in the ink And a polymer containing an oxazoline group in the pretreatment liquid undergo a crosslinking reaction on the recording medium, so that the ink can be firmly attached to the recording medium.
Hereinafter, the present invention will be described in more detail with reference to examples.
（実施例１）
（顔料分散体の作製）
顔料 カーボンブラック ＭＡ８（三菱化学製） ７部
分散剤 ソルスパース３２０００（ルーブリゾール製） ２部
モノマー ライトアクリレート１，９ＮＤ−Ａ（共栄社化学製） ２部
メタクリル酸（和光純薬製） １部
オリゴマー ＵＶ３２００（日本合成製） ２部
溶剤 酢酸エチル（和光純薬製） ３０部
上記を混合し、ビーズミルにて顔料を分散して、顔料分散体を作製した。
Example 1
(Preparation of pigment dispersion)
Pigment Carbon black MA8 (Mitsubishi Chemical) 7 parts Dispersant Solsperse 32000 (Lubrisol) 2 parts Monomer light acrylate 1,9ND-A (Kyoeisha Chemical) 2 parts
Methacrylic acid (manufactured by Wako Pure Chemical Industries) 1 part Oligomer UV3200 (manufactured by Nippon Gosei Co., Ltd.) 2 parts Solvent Ethyl acetate (manufactured by Wako Pure Chemical Industries) 30 parts The above was mixed, and the pigment was dispersed with a bead mill to prepare a pigment dispersion. .
（ミニエマルションの作製）
上記で作製した顔料分散体４４部中にラジカル重合開始剤ＡＩＢＮ（２，２’−アゾビスイソブチロニトリル）を０．１部添加した後、水（蒸留水）５２部、乳化剤アクアロンＫＨ−１０（第一工業製薬製）１部、ブレンマーＰＥ−２００（日本油脂製）２部と混合し、超音波乳化機で乳化しミニエマルションを作製した。
(Production of mini-emulsion)
After adding 0.1 part of radical polymerization initiator AIBN (2,2′-azobisisobutyronitrile) to 44 parts of the pigment dispersion prepared above, 52 parts of water (distilled water), emulsifier Aqualon KH— 10 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 2 parts of Bremer PE-200 (manufactured by NOF Corporation) were mixed and emulsified with an ultrasonic emulsifier to prepare a miniemulsion.
（重合、溶剤除去、粗粒除去）
作製したミニエマルションを窒素雰囲気下で攪拌しながら７０℃に加熱し４時間反応させた。重合反応させた後、エバポレーターで溶剤（酢酸エチル）を除去した。遠心分離機２００００Ｇで６分かけて粗粒を除き、カプセル化顔料を作製した。
(Polymerization, solvent removal, coarse particle removal)
The produced mini-emulsion was heated to 70 ° C. with stirring under a nitrogen atmosphere and reacted for 4 hours. After the polymerization reaction, the solvent (ethyl acetate) was removed with an evaporator. The coarse particles were removed over 6 minutes with a centrifugal separator 20000G to prepare an encapsulated pigment.
（インクの調製）
カプセル化顔料８０部、ジエチレングリコール１９部、サーフィノール４６５ （エアープロダクツジャパン製）１部をミックスし、その後、得られた分散液をメンブレンフィルター（開口径３μｍ）でろ過し、水性インクを得た。堀場製作所製 コンパクトｐＨメーターＢ−２１２でｐＨを測定したところ、４．０であった。
(Preparation of ink)
80 parts of encapsulated pigment, 19 parts of diethylene glycol and 1 part of Surfynol 465 (manufactured by Air Products Japan) were mixed, and then the resulting dispersion was filtered with a membrane filter (opening diameter: 3 μm) to obtain an aqueous ink. When the pH was measured with a compact pH meter B-212 manufactured by Horiba, Ltd., it was 4.0.
（前処理と画像形成）
エポクロスＷＳ−７００（日本触媒製）１５部、ハイドランＣＰ−７６１０（大日本インキ製）６０部、水２５部を混合して前処理液を得た。布に前処理液を霧吹きでしめらせた後、乾燥した。乾燥後、前処理をした布の上に、作製したインクを市販のインクジェットプリンター（エプソン社製）に充填し、１４４０ｄｐｉ×１４４０ｄｐｉ、９０ｍｍ×９０ｍｍのベタ印刷を行って、印字後アイロンで１５０℃１分間加熱した。
(Preprocessing and image formation)
15 parts of Epocros WS-700 (manufactured by Nippon Shokubai), 60 parts of Hydran CP-7610 (manufactured by Dainippon Ink) and 25 parts of water were mixed to obtain a pretreatment liquid. The pretreatment liquid was sprayed on the cloth and then dried. After drying, the prepared ink is filled into a commercially available ink jet printer (manufactured by Epson Corp.) on a pretreated cloth, solid printing of 1440 dpi × 1440 dpi, 90 mm × 90 mm is performed, and after printing, the iron is 150 ° C. 1 Heated for minutes.
（実施例２）
実施例１の顔料分散体の原料のメタクリル酸をアクリル酸に変更した以外は実施例１と同様に顔料分散体を作製し、その後は実施例１と同様にして画像形成を行った。
(Example 2)
A pigment dispersion was prepared in the same manner as in Example 1 except that methacrylic acid as a raw material for the pigment dispersion in Example 1 was changed to acrylic acid, and thereafter, image formation was performed in the same manner as in Example 1.
（比較例１）
実施例１の顔料分散体作製時に、メタクリル酸を除いてカプセル化顔料分散体を作製した以外は実施例１と同様に顔料分散体を作製し、その後は実施例１と同様にして画像形成を行った。
(Comparative Example 1)
A pigment dispersion was prepared in the same manner as in Example 1 except that methacrylic acid was removed and an encapsulated pigment dispersion was prepared at the time of preparing the pigment dispersion of Example 1, and then image formation was performed in the same manner as in Example 1. went.
（比較例２）
実施例１でインク作製時にトリエタノールアミンを０．５ｇ添加した以外は実施例１と同様にして画像形成を行った。なお、インクのｐＨを測定したところ８．５であった。
(Comparative Example 2)
In Example 1, an image was formed in the same manner as Example 1 except that 0.5 g of triethanolamine was added at the time of ink preparation. The measured pH of the ink was 8.5.
（比較例３）
実施例１の前処理液でエポクロスＷＳ−７００を除いて前処理液を作製した以外は実施例１と同様にして画像形成を行った。
(Comparative Example 3)
Image formation was performed in the same manner as in Example 1 except that the pretreatment liquid was prepared by removing Epochros WS-700 from the pretreatment liquid of Example 1.
（比較例４）
実施例１の前処理液でハイドランＣＰ７６１０を除いて前処理液を作製した以外は実施例１と同様にして画像形成を行った。
(Comparative Example 4)
Image formation was performed in the same manner as in Example 1 except that the pretreatment liquid was prepared using the pretreatment liquid of Example 1 except for hydran CP7610.
（比較例５）
実施例１の前処理液でハイドランＣＰ７６１０に代えてスーパーフレックス４６０を使用して前処理液を作製した以外は実施例１と同様にして画像形成を行った。
(Comparative Example 5)
Image formation was performed in the same manner as in Example 1 except that the pretreatment liquid was prepared using Superflex 460 instead of the hydran CP7610 with the pretreatment liquid of Example 1.
（比較例６）
実施例１において前処理を全く行わなかった以外は実施例１と同様にして画像形成を行った。
(Comparative Example 6)
Image formation was performed in the same manner as in Example 1 except that no pre-processing was performed in Example 1.
（評価）
（滲み）
ベタ画像の境界部における滲みの有無を目視で観察した。
○：画像の滲みがなく鮮明である
△：境界線がやや鮮明性に欠ける
×：画像が滲み、鮮明ではない
(Evaluation)
(Bleed)
The presence or absence of bleeding at the boundary portion of the solid image was visually observed.
○: The image is not blurred and △: The boundary line is slightly unclear ×: The image is blurred and not clear
（洗濯堅牢度）
三洋電機（株）製全自動洗濯機ＡＳＷ−４５Ａ１型を用いて、各捺染物を冷水で４０分間洗濯して、色落ち度合いを目視で観察した。
○：色落ち全くしない
△：若干色落ちする
×：明らかに色落ちした
評価の結果を表１に示す。
(Washing fastness)
Using a fully automatic washing machine ASW-45A1 manufactured by Sanyo Electric Co., Ltd., each printed matter was washed with cold water for 40 minutes, and the degree of color fading was visually observed.
○: No color fading Δ: Some color fading ×: Clear color fading Evaluation results are shown in Table 1.
実施例１および２のカプセル化顔料はカルボキシル基が中和されていないので、前処理液に含まれるオキサゾリン基との反応性が良く、滲みがなく、洗濯堅牢性のある良好な定着性を実現することができた。比較例１はカプセル化顔料がカルボキシル基を有しておらず、比較例２はカプセル化顔料がカルボキシル基を有しているものの中和されているため、滲みは問題がなかったが、実施例と同じ加熱条件では洗濯堅牢性は得られなかった。 Since the encapsulated pigments of Examples 1 and 2 are not neutralized with carboxyl groups, they have good reactivity with the oxazoline groups contained in the pretreatment liquid, no bleeding, and good fixability with washing fastness. We were able to. In Comparative Example 1, the encapsulated pigment did not have a carboxyl group, and in Comparative Example 2, although the encapsulated pigment had a carboxyl group, it was neutralized. Washing fastness was not obtained under the same heating conditions.
また、カプセル化顔料がカルボキシル基を有していても、前処理液にオキサゾリン基を含む重合体が含まれていない比較例３では、滲みは問題がなかったが、洗濯堅牢性は得られなかった。また、前処理液にカチオン性物質が含まれていない比較例４では滲みが多少あり、洗濯堅牢性は得られなかった。カチオン性水性エマルション樹脂に代えてアニオン性水性エマルション樹脂（ポリウレタン水分散体）を含有させた比較例５は、滲みが多少ある上、洗濯堅牢性は実施例には及ばなかった。 Further, even though the encapsulated pigment has a carboxyl group, in Comparative Example 3 where the pretreatment liquid does not contain a polymer containing an oxazoline group, bleeding was not a problem, but washing fastness was not obtained. It was. Further, in Comparative Example 4 where the pretreatment liquid did not contain a cationic substance, there was some bleeding and washing fastness was not obtained. In Comparative Example 5 in which an anionic aqueous emulsion resin (polyurethane aqueous dispersion) was contained instead of the cationic aqueous emulsion resin, there was some bleeding and the fastness to washing did not reach that of the examples.
以上のように、本発明のカプセル化顔料およびこのカプセル化顔料を含むインクは、顔料がカルボキシル基と硫酸エステル塩基とを含む樹脂で被覆されているので、前処理液に含まれるオキサゾリン基との反応性が良く、滲みがなく、加熱時間が短くても洗濯堅牢性のある良好な定着性を実現することができる。 As described above, the encapsulated pigment of the present invention and the ink containing the encapsulated pigment are coated with a resin containing a carboxyl group and a sulfate ester base, so that the pigment is coated with an oxazoline group contained in the pretreatment liquid. Good fixability with good washing fastness can be realized even if the reactivity is good, there is no bleeding, and the heating time is short.
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