WO2022176228A1 - 水性インクジェット用インク組成物、印刷物、及びインクジェット印刷方法 - Google Patents
水性インクジェット用インク組成物、印刷物、及びインクジェット印刷方法 Download PDFInfo
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- WO2022176228A1 WO2022176228A1 PCT/JP2021/026311 JP2021026311W WO2022176228A1 WO 2022176228 A1 WO2022176228 A1 WO 2022176228A1 JP 2021026311 W JP2021026311 W JP 2021026311W WO 2022176228 A1 WO2022176228 A1 WO 2022176228A1
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- Prior art keywords
- water
- ink composition
- inkjet ink
- mass
- surfactant
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000002736 nonionic surfactant 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
- 125000000962 organic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 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
- 239000012466 permeate Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229940104573 pigment red 5 Drugs 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement 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
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Definitions
- the present invention relates to an aqueous inkjet ink composition, a printed matter, and an inkjet printing method.
- the inkjet printing/recording method is a printing/recording method in which droplets of a water-based inkjet ink composition are directly ejected from extremely fine nozzles onto a substrate for printing/recording and adhered to obtain characters and images.
- Patent Documents 5 to 11 disclose water-based inkjet ink compositions having good storage stability and ejection stability. Also known are aqueous inkjet ink compositions containing colloidal silica (Patent Documents 5 to 11).
- an ink composition containing colloidal silica is required to have mechanical stability so that the colloidal silica does not aggregate during use or storage.
- the present invention has been made in view of the above circumstances, and provides an aqueous inkjet ink composition having good storage stability, mechanical stability, ejection stability, coating film drying property, and repelling resistance. intended to
- the present invention provides an aqueous inkjet ink composition containing a pigment, an alkali-soluble resin, a surfactant, a water-soluble solvent, colloidal silica, and water, wherein the surfactant has an HLB value of 3 or more and 10 and a surfactant (B) having an HLB value of 10 or more and 20 or less, and the water-soluble solvent has a boiling point of 170° C. or more and 250° C. or less under 1 atmosphere,
- the proportion of the colloidal silica relates to the aqueous inkjet ink composition, which is 0.05% by mass or more and 2% by mass or less in the aqueous inkjet ink composition.
- the present invention also relates to a printed matter obtained by printing the water-based inkjet ink composition.
- the present invention also relates to an inkjet printing method for printing on a non-absorbent printing medium using the water-based inkjet ink composition.
- the aqueous inkjet ink composition of the present invention contains a pigment, an alkali-soluble resin, a surfactant, a water-soluble solvent, colloidal silica, and water, and the surfactant has an HLB value of 3 or more and less than 10.
- the proportion is 0.05% by mass or more and 1% by mass or less in the water-based inkjet ink composition.
- the surfactant (A) having a low HLB value By adding a surfactant (A) having a low HLB value, the surface tension of the ink is lowered, and entrapment of air bubbles from the nozzle surface is suppressed. good properties. Further, since the surfactant (B) having a high HLB value has the effect of making the surfactant (A) and water compatible, the water-based inkjet ink composition of the present invention has good storage stability and ejection stability. , and good drying properties of the coating film. In addition, containing a specific amount of colloidal silica improves the adsorptivity to the base material surface and suppresses aggregation of droplets, resulting in good cissing resistance. In addition, mechanical stability is also improved by including colloidal silica in a specific amount or less.
- the aqueous inkjet ink composition of the present invention contains a pigment, an alkali-soluble resin, a surfactant, a water-soluble solvent, colloidal silica, and water.
- organic pigments and inorganic pigments used in inkjet ink compositions can be used without particular limitation.
- the organic pigment include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindico pigments, perylene pigments, Perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, nitro pigments, nitroso pigments, lavanthrone pigments, quinophthalone pigments, pyranthrone pigments, indanthrone pigments, and the like.
- the inorganic pigments include carbon black, titanium oxide, zinc white, red iron oxide, graphite, iron black, chromium oxide green, and aluminum hydroxide.
- the pigment may be surface-treated with a known surface-treating agent.
- the pigments may be used alone or in combination of two or more.
- yellow pigments examples include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213 and the like.
- magenta pigment for example, C.I. I. Pigment Red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, C.I. I. Pigment Violet 19 and the like.
- cyan pigment for example, C.I. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, 60 and the like.
- Black pigments include, for example, carbon black (C.I. Pigment Black 7).
- white pigments include titanium oxide and aluminum oxide, which may be surface-treated with various materials such as alumina and silica.
- the alkali-soluble resin of the present invention is not particularly limited as long as it is an alkali-soluble resin that can be used for dispersing pigments in ordinary inks and paints or as a binder, and that can be dissolved in an aqueous medium in the presence of a basic compound.
- the alkali-soluble resin preferably further has a hydrophobic portion in its molecule, mainly for improving adsorption to pigments.
- Hydrophobic moieties to be introduced into the molecule include, for example, hydrophobic groups such as long-chain alkyl groups, alicyclic and aromatic cyclic hydrocarbon groups.
- the acid value of the alkali-soluble resin is preferably 40 mgKOH/g or more, more preferably 70 mgKOH/g or more, from the viewpoint of increasing the solubility in an aqueous medium. Moreover, the acid value of the alkali-soluble resin is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, from the viewpoint of improving the water resistance of printed matter.
- the acid value was obtained by arithmetically determining the number of mg of potassium hydroxide theoretically required to neutralize 1 g of the alkali-soluble resin, based on the composition of the monomers used for synthesizing the alkali-soluble resin. Theoretical acid number.
- the glass transition temperature of the alkali-soluble resin is preferably 0°C or higher, more preferably 10°C or higher, from the viewpoint of improving the blocking resistance of the printed matter.
- the glass transition temperature of the alkali-soluble resin is preferably 100° C. or lower, more preferably 80° C. or lower, from the viewpoint of improving the bending resistance of printed matter.
- the glass transition temperature of the alkali-soluble resin is the theoretical glass transition temperature obtained by thermal analysis when the alkali-soluble resin is other than an acrylic copolymer resin.
- a method of thermal analysis according to JIS K7121 (method for measuring the transition temperature of plastics), as an example, using a Pyris1 DSC manufactured by PerkinElmer, a temperature increase rate of 20 ° C./min and a nitrogen gas flow rate of 20 ml/min.
- the glass transition temperature can be measured at
- the weight-average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of improving the water resistance of printed matter.
- the weight-average molecular weight of the alkali-soluble resin is preferably 100,000 or less, more preferably 50,000 or less, from the viewpoint of enhancing solubility in aqueous media.
- the weight average molecular weight can be measured by a gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- Water 2690 manufactured by Waters
- PLgel 5 ⁇
- MIXED-D manufactured by Polymer Laboratories
- tetrahydrofuran as a developing solvent
- column temperature 25 ° C. flow rate 1 ml / min
- RI Chromatography is performed under the conditions of a detector, a sample injection concentration of 10 mg/ml, and an injection amount of 100 microliters, and the polystyrene equivalent weight average molecular weight can be determined.
- alkali-soluble resin examples include acrylic copolymer resins, maleic acid copolymer resins, polyester resins obtained by polycondensation reaction, and polyurethane resins. Materials for synthesizing such alkali-soluble resins are disclosed, for example, in Japanese Unexamined Patent Application Publication No. 2000-94825. Maleic acid-based copolymer resins, polyester-based resins, polyurethane-based resins, and the like can be used. Furthermore, resins obtained using materials other than these can also be used. The said alkali-soluble resin can be used individually or in combination of 2 or more types.
- acrylic copolymer resin for example, a mixture of an anionic group-containing monomer and another copolymerizable monomer may be mixed with a usual radical generator (for example, benzoyl peroxide, tertiary butyl peroxybenzoate, Azobisisobutyronitrile, etc.) can be used that is obtained by polymerization in a solvent.
- a radical generator for example, benzoyl peroxide, tertiary butyl peroxybenzoate, Azobisisobutyronitrile, etc.
- anionic group-containing monomer examples include monomers having at least one anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic acid group.
- Group-bearing monomers are particularly preferred.
- Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, anhydrous Maleic acid, fumaric anhydride, maleic acid half ester and the like can be mentioned.
- Examples of the monomer having a sulfonic acid group include sulfoethyl methacrylate.
- Examples of the monomer having a phosphonic acid group include phosphonoethyl methacrylate.
- the other monomer copolymerizable with the anionic group-containing monomer preferably contains a hydrophobic group-containing monomer from the viewpoint of improving the adsorptivity with the pigment.
- hydrophobic group-containing monomers examples include, for example, monomers having a long-chain alkyl group, alkyl esters having 8 or more carbon atoms of a radically polymerizable unsaturated carboxylic acid such as (meth)acrylic acid (e.g.
- monomers having an aromatic hydrocarbon group include styrene-based monomers such as benzyl (meth)acrylate, styrene, ⁇ -methylstyrene and vinyltoluene.
- the hydrophobic group-containing monomers may be used alone or in combination of two or more.
- Other monomers copolymerizable with the anionic group-containing monomer may include hydrophilic group-containing monomers from the viewpoint of suppressing aggregation of the alkali-soluble resin in the aqueous medium.
- hydrophilic group-containing monomer examples include monomers having a (poly)oxyalkylene chain, such as methoxypolyethylene glycol, methoxypolyethylenepolypropyleneglycol, ethoxypolyethyleneglycol, ethoxypolyethylenepolypropyleneglycol, propoxypolyethyleneglycol, and propoxypolyethylene.
- monomers having a (poly)oxyalkylene chain such as methoxypolyethylene glycol, methoxypolyethylenepolypropyleneglycol, ethoxypolyethyleneglycol, ethoxypolyethylenepolypropyleneglycol, propoxypolyethyleneglycol, and propoxypolyethylene.
- Esterification products of single-terminal alkyl-blocked (poly)alkylene glycols such as polypropylene glycol and radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, and radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid ethylene oxide adducts and/or propylene oxide adducts; basic group-containing monomers such as vinylpyrrolidones such as 1-vinyl-2-pyrrolidone and 1-vinyl-3-pyrrolidone; 2-vinylpyridine; -Vinylpyridines such as vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, vinylimidazoles such as 1-vinylimidazole, 1-vinyl-2-methylimidazole, 3-vinylpiperidine , vinyl biperidines such as N-methyl-3-vinylpiperidine, dimethylaminoethyl (me
- hydroxyl group for example, hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate;
- hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate;
- a monomer having an epoxy group for example, glycidyl (Meth)acrylate and the like.
- the hydrophilic group-containing monomers may be used alone or in combination of two or more.
- copolymerizable monomers other than the hydrophobic group-containing monomer and the hydrophilic group-containing monomer include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (meth) Examples include alkyl esters of (meth)acrylic acid having less than 8 carbon atoms, such as propyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate.
- the hydrophobic group-containing monomer and other copolymerizable monomers other than the hydrophilic group-containing monomer can be used alone or in combination of two or more.
- the surfactant of the present invention includes a surfactant (A) having an HLB value of 3 or more and less than 10 and a surfactant (B) having an HLB value of 10 or more and 20 or less.
- the HLB value is an index representing the degree of hydrophilicity and lipophilicity of a surfactant calculated by the Griffin method. The smaller the HLB value, the higher the lipophilicity, and the larger the HLB value, the higher the hydrophilicity. indicates that The surfactant (A) and the surfactant (B) can be used alone or in combination of two or more.
- surfactant (A) and the surfactant (B) known surfactants used in water-based inkjet ink compositions can be used without particular limitation as long as each HLB value described above is satisfied.
- examples include nonionic surfactants, cationic surfactants, anionic surfactants, and betaine surfactants.
- Specific examples of the surfactant include silicone-based surfactants, fluorine-based surfactants, acetylene-based surfactants, and the like. Among these, acetylenic surfactants are preferred from the viewpoint of improving ejection stability and repelling resistance.
- surfactant (A) examples include trade names: “Surfinol 104E”, “Surfinol 104H”, “Surfinol 104A”, “Surfinol 104BC”, “Surfinol 104DPM”, and “Surfinol 104PA”. , “Surfinol 104PG-50”, “Surfinol 420”, “Surfinol 440”, “OLFINE E1004” (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
- surfactant (B) examples include trade names: "Surfinol 465", “Surfinol 485", “OLFINE E1010", and “OLFINE E1020” (manufactured by Nissin Chemical Industry Co., Ltd.). .
- the water-soluble solvent of the present invention has a boiling point of 170° C. or higher and 250° C. or lower under 1 atmosphere.
- any known water-soluble solvent used in water-based inkjet ink compositions can be used without particular limitation, as long as the boiling point is 170° C. or higher and 250° C. or lower at 1 atm.
- Examples include polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, nitrogen-containing compounds, and the like.
- water-soluble solvent examples include 1-octanol (boiling point 195°C), 2-ethylhexanol (boiling point 184°C), propylene glycol (boiling point 188°C), 1,2-butanediol (boiling point 197°C), and ethylene glycol.
- the aqueous inkjet ink composition of the present invention may contain known solvents (other solvents) used in aqueous inkjet ink compositions other than the water-soluble solvent.
- the colloidal silica of the present invention is in a state in which silica particles represented by the chemical composition formula of SiO 2 are dispersed in a medium to form a colloid.
- the medium include water, methanol, ethanol, i-propyl alcohol, n-butanol, xylene, dimethylformamide, and the like.
- the colloidal silica may be obtained by modifying the surface of silica particles with a surface treatment agent such as a silane compound.
- the colloidal silica can be used alone or in combination of two or more.
- the colloidal silica preferably has an average particle size of 3 to 100 nm, more preferably 5 to 30 nm.
- the average particle size is the average primary particle size and is indicated by the median diameter (D50) of the volume-based particle size distribution measured by the dynamic light scattering method.
- the shape of the colloidal silica includes a particle shape, a chain shape, a pearl necklace shape, and the like.
- Examples of commercial products of the colloidal silica include trade names: “Snowtex XS”, “Snowtex S”, “Snowtex 30", “Snowtex 50T”, “Snowtex 30L”, “Snowtex YL”, “Snowtex ZL”, “Snowtex MP1040”, “Snowtex UP”, “Snowtex PS-S”, “Snowtex PS-M”, “Snowtex OXS”, “Snowtex OS”, “Snowtex O” ”, “Snowtex O-40”, “Snowtex OL”, “Snowtex OYL”, “Snowtex OUP”, “Snowtex PS-SO”, “Snowtex PS-MO”, “Snowtex NXS”, “Snowtex NS”, “Snowtex N”, “Snowtex N-40”, “Snowtex CXS”, “Snowtex C”, “Snowtex C”, “Snowtex CM”, “Snowtex AK”, “Snowtex AK-L” ”, “Snowtex AK-Y”, “Organo Silica Sol EG-
- the water of the present invention includes water as an aqueous medium contained in the pigment dispersion described below, and water added to adjust the concentration of the water-based inkjet ink composition of the present invention.
- Examples of the water include ion-exchanged water, pure water, distilled water, and industrial water.
- the said water can be used individually or in combination of 2 or more types.
- the proportion of the pigment in the water-based inkjet ink composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of improving the print density of printed matter. From the viewpoint of improving ejection stability, the content is preferably 10% by mass or less, more preferably 8% by mass or less. However, when the pigment is a white pigment, the proportion of the white pigment in the water-based inkjet ink composition of the present invention is preferably 4% by mass or more, more preferably 8% by mass or more. The content is preferably 30% by mass or less, more preferably 20% by mass or less.
- the content of the alkali-soluble resin is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, relative to 100 parts by mass of the pigment.
- the content of the alkali-soluble resin is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, relative to 100 parts by mass of the pigment. It is preferably 60 parts by mass or less, and more preferably 60 parts by mass or less.
- the proportion of the surfactant (A) in the water-based inkjet ink composition of the present invention is preferably 0.1% by mass or more, and 0.2% by mass or more. more preferably 0.4% by mass or more, and from the viewpoint of improving storage stability, it is preferably 3% by mass or less, more preferably 2% by mass or less. .
- the proportion of the surfactant (B) in the water-based inkjet ink composition of the present invention is preferably 0.1% by mass or more, and 0.2% by mass. It is more preferably 0.4% by mass or more, more preferably 0.4% by mass or more, and from the viewpoint of improving storage stability, it is preferably 3% by mass or less, and 2% by mass or less. is more preferable.
- the proportion of the water-soluble solvent in the water-based inkjet ink composition of the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving ejection stability. From the viewpoint of improving the drying property of the coating film, the content is preferably 60% by mass or less, more preferably 50% by mass or less.
- the proportion of the colloidal silica in the water-based inkjet ink composition of the present invention is 0.05% by mass or more and 2% by mass or less.
- the proportion of colloidal silica in the water-based inkjet ink composition of the present invention is preferably 0.1% by mass or more from the viewpoint of improving storage stability, ejection stability, and repelling resistance. It is more preferably 3% by mass or more, and preferably 1.5% by mass or less from the viewpoint of improving storage stability, mechanical stability, ejection stability, and cissing resistance. It is more preferably 0% by mass or less, and even more preferably 0.8% by mass or less.
- the proportion of water (including water contained in each component) in the water-based inkjet ink composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass, from the viewpoint of improving the drying property of the coating film. From the viewpoint of improving ejection stability, the content is preferably 70% by mass or less, and more preferably 60% by mass or less.
- the water-based inkjet ink composition of the present invention preferably contains a resin emulsion from the viewpoint of improving coating film drying properties and repelling resistance.
- a resin emulsion known resin emulsions used in aqueous inkjet ink compositions can be used. Examples include acrylic resin emulsion, styrene-acrylic resin emulsion, polyester resin emulsion, polyurethane resin emulsion, and polyvinyl acetate. system resin emulsion, polyvinyl chloride system resin emulsion, polybutadiene system resin emulsion, polyolefin system resin emulsion, and the like.
- the resin emulsion preferably has a glass transition temperature of 20° C. or less from the viewpoint of improving the drying property of the coating film of the printed matter and the adhesion to the substrate.
- the glass transition temperature can be referred to the manufacturer's catalog value, but if this is not available, it is obtained by differential scanning calorimetry (DSC) and is usually calculated from the midpoint of the temperature range where the glass transition occurs.
- DSC differential scanning calorimetry
- the resin emulsions may be used alone or in combination of two or more.
- the (resin) solid content of the resin emulsion is preferably 1% by mass or more, more preferably 2% by mass or more, in the water-based inkjet ink composition from the viewpoint of improving print image quality and scratch resistance. is preferable, and from the viewpoint of improving print quality and storage stability, it is preferably 10% by mass or less, more preferably 5% by mass or less.
- the aqueous inkjet ink composition of the present invention preferably contains a basic compound.
- the basic compound include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; ammonia, methylamine, ethylamine, monoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, organic basic compounds such as N,N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine;
- the said basic compound can be used individually or in combination of 2 or more types.
- the proportion of the basic compound in the water-based inkjet ink composition of the present invention may be an amount that dissolves the alkali-soluble resin in the medium. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of increasing the water resistance of printed matter, it is preferably 1% by mass or less, and 0.5% by mass. % or less.
- the water-based inkjet ink composition of the present invention may further contain known resins, resin emulsions, wax emulsions, pigment dispersants, anti-mold agents, anti-rust agents, thickeners, antioxidants, and ultraviolet absorbers, depending on the purpose. Additives such as agents, preservability improvers, antifoaming agents, and pH adjusters can be added.
- the method for preparing (manufacturing) the aqueous inkjet ink composition of the present invention is not particularly limited, and the above components may be added in order or simultaneously and mixed.
- various dispersing machines such as ball mills, attritors, roll mills, sand mills, agitator mills, etc.
- a resin-coated pigment is obtained by depositing an alkali-soluble resin on the pigment surface by a precipitation method or an ion exchange means described in Republished Patent WO2005/116147, and then the obtained resin-coated pigment is neutralized with a basic compound. and redispersing in water using various dispersing machines (such as a high-speed stirrer), and then adding the remaining materials to prepare an aqueous inkjet ink composition.
- the aqueous inkjet ink composition of the present invention has an initial viscosity after production of 2.0 to 15.0 mPa ⁇ s, preferably 3.0 to 12.0 mPa ⁇ s.
- the viscosity can be measured, for example, with an E-type viscometer (trade name “RE100L type viscometer”, manufactured by Toki Sangyo Co., Ltd.).
- the printed matter of the present invention is obtained by printing with the water-based inkjet ink composition. Specifically, it is obtained by coating (printing) the aqueous inkjet ink composition on a substrate using an inkjet printer.
- the substrate examples include coated paper such as art paper, inkjet paper, and inkjet glossy paper; non-absorbent printing media such as plastic substrates such as polypropylene film and polyvinyl chloride sheet; plain paper and offset paper. uncoated paper such as; fabric such as cotton; and the like.
- the water-based inkjet ink composition of the present invention is excellent in cissing resistance, so it is suitable for plastic-based substrates among non-absorbent printing media.
- Inkjet printing method of the present invention conventionally known conditions can be appropriately employed. , and a method of ink-jet printing by jetting from a nozzle onto a substrate.
- Alkali-soluble resin acrylic acid/n-but
- ⁇ Production of aqueous inkjet ink composition The black pigment dispersion (black ink base), propylene glycol as a water-soluble solvent, and an acetylenic surfactant (trade name “OLFINE E1004” as a surfactant (A)) were used so that the mass proportions shown in Table 1 were obtained.
- black pigment dispersion black ink base
- propylene glycol as a water-soluble solvent
- an acetylenic surfactant trade name “OLFINE E1004” as a surfactant (A)
- Examples 2 to 26 Comparative Examples 1 to 9> ⁇ Production of aqueous inkjet ink composition>
- the same method as in Example 1 was used to prepare the water-based inkjet ink of each example and each comparative example. An ink composition for was manufactured.
- ⁇ Storage stability> Each of the aqueous inkjet ink compositions produced above was placed in a glass bottle, and the viscosity (mPa ⁇ s) at 25° C. was measured using a viscometer (“RE100L model” manufactured by Toki Sangyo Co., Ltd.). Then, it was sealed and stored at 60°C for 1 month, and the viscosity (25°C) after storage was measured with a viscometer. Storage stability was evaluated by viscosity change rate (60° C., (viscosity after 1 month ⁇ viscosity before storage)/viscosity before storage). [Evaluation Criteria for Storage Stability] ⁇ : Viscosity change rate is less than 5%. ⁇ : Viscosity change rate is 5% or more and less than 10%. x: Viscosity change rate is 10% or more.
- ⁇ Paint film drying property> The water-based inkjet ink composition produced above is packed in a cartridge of an inkjet printer (“PX105”, manufactured by Epson), printed on OK top-coated paper (manufactured by Oji Paper Co., Ltd.), and printed at 80 ° C. for 3 minutes. The ink was allowed to stand to dry, and the printed area was rubbed with a cotton swab to evaluate the drying property of the coating film.
- Evaluation Criteria for Drying of Coating Film ⁇ : No ink adheres to the cotton swab. ⁇ : A small amount of ink adheres to the cotton swab. x: A large amount of ink adheres to the cotton swab.
- ⁇ Repellency resistance> The water-based inkjet ink composition produced above was applied onto an OPP film (P2161, 25 ⁇ m, manufactured by Toyobo Co., Ltd.) using a 0.15 mm bar coater, and the repelling resistance was evaluated by visual observation.
- OPP film P2161, 25 ⁇ m, manufactured by Toyobo Co., Ltd.
- x Repelling occurs and uniform application is clearly impossible.
- propylene glycol has a boiling point of 188°C; Dipropylene glycol dimethyl ether has a boiling point of 175°C; Diethylene glycol monobutyl ether has a boiling point of 231°C; Ethylene glycol monomethyl ether has a boiling point of 124°C; Tripropylene glycol monobutyl ether has a boiling point of 274°C.
- Olfine E1004 is an acetylenic surfactant (solid content (active ingredient): 100%, HLB: 8, manufactured by Nissin Chemical Industry Co., Ltd.); Surfynol 104E is an acetylenic surfactant (solid content (active ingredient): 50%, HLB: 4, manufactured by Nissin Chemical Industry Co., Ltd.); Olfine E1010 is an acetylenic surfactant (solid content (active ingredient): 100%, HLB: 13, manufactured by Nissin Chemical Industry Co., Ltd.); Surfynol 485 is an acetylenic surfactant (solid content (active ingredient): 100%, HLB: 17, manufactured by Nissin Chemical Industry Co., Ltd.); Snowtex 30 is colloidal silica (solid content: 30%, particle size: 12 nm, Na + stable alkaline sol, manufactured by Nissan Chemical Industries, Ltd.); Snowtex XS is colloidal silica (solid content: 20%, particle size: 5 nm, Na
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Abstract
Description
本発明の顔料は、インクジェット用インク組成物に使用される有機顔料や無機顔料を特に制限なく使用することができる。前記有機顔料としては、例えば、染料レーキ顔料、アゾ系顔料、ベンズイミダゾロン系顔料、フタロシアニン系顔料、キナクリドン系顔料、アントラキノン系顔料、ジオキサジン系顔料、インジゴ系顔料、チオインジコ系顔料、ペリレン系顔料、ペリノン系顔料、ジケトピロロピロール系顔料、イソインドリノン系顔料、ニトロ系顔料、ニトロソ系顔料、ラバンスロン系顔料、キノフタロン系顔料、ピランスロン系顔料、インダンスロン系顔料等が挙げられる。また、前記無機顔料としては、例えば、カーボンブラック、酸化チタン、亜鉛華、ベンガラ、黒鉛、鉄黒、酸化クロムグリーン、水酸化アルミニウム等が挙げられる。前記顔料は、公知の表面処理剤により表面処理されたものであってもよい。前記顔料は単独で、又は2種以上を組み合わせて使用することができる。
本発明のアルカリ可溶性樹脂は、通常のインクや塗料の顔料分散用やバインダーとして利用できるアルカリ可溶性樹脂であって、塩基性化合物の存在下で水性媒体中に溶解できるものであれば特に制限はないが、カルボキシル基、スルホン酸基、ホスホン酸基(-P(=O)(OH2))等のアニオン性基の1種又は2種以上を含有する樹脂が好ましい。
Woodの式:1/Tg=W1/Tg1+W2/Tg2+W3/Tg3+・・・・・+Wx/Tgx
[式中、Tg1~Tgxはアルカリ可溶性樹脂を構成する単量体1、2、3・・・xのそれぞれの単独重合体のガラス転移温度、W1~Wxは単量体1、2、3・・・xのそれぞれの重合分率、Tgは理論ガラス転移温度を表す。ただし、woodの式におけるガラス転移温度は絶対温度である。]
本発明の界面活性剤は、HLB値が3以上10未満である界面活性剤(A)と、HLB値が10以上20以下である界面活性剤(B)を含む。ここで、HLB値とは、グリフィン法によって算出される界面活性剤の親水性と親油性の程度を表す指標であり、HLB値が小さいほど親油性が高く、HLB値が大きいほど親水性が高いことを示す。前記界面活性剤(A)及び前記界面活性剤(B)は単独で、又は2種以上を組み合わせて使用することができる。
本発明の水溶性溶剤は、沸点が1気圧下で170℃以上250℃以下である。
本発明のコロイダルシリカは、SiO2の化学組成式で示されるシリカ粒子が、媒体に分散してコロイドを形成した状態のものである。媒体としては、例えば、水、メタノ-ル、エタノ-ル、i-プロピルアルコ-ル、n-ブタノ-ル、キシレン、ジメチルホルムアミド、等が挙げられる。また、前記コロイダルシリカは、シリカ粒子の表面が、シラン化合物等の表面処理剤で修飾されたものであってもよい。前記コロイダルシリカは、単独で、又は2種以上を組み合わせて使用することができる。
本発明の水は、後述する顔料分散液中に含有する水性媒体としての水、及び本発明の水性インクジェット用インク組成物の濃度調製のために加える水、等を含むものである。前記水としては、例えば、イオン交換水、純水、蒸留水、工業用水等が挙げられる。前記水は単独で、又は2種以上を組み合わせて使用することができる。
本発明の水性インクジェット用インク組成物は、塗膜乾燥性及び耐ハジキ性を向上させる観点から、樹脂エマルジョンを含むことが好ましい。前記樹脂エマルジョンは、水性インクジェット用インク組成物に使用される公知の樹脂エマルジョンが使用でき、例えば、アクリル系樹脂エマルジョン、スチレン-アクリル系樹脂エマルジョン、ポリエステル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン、ポリ酢酸ビニル系樹脂エマルジョン、ポリ塩化ビニル系樹脂エマルジョン、ポリブタジエン系樹脂エマルジョン、ポリオレフィン系樹脂エマルジョン等が挙げられる。前記樹脂エマルジョンは、印刷物の塗膜の乾燥性や基材への密着性を向上させる観点から、樹脂のガラス転移温度が20℃以下であることが好ましい。なお、ガラス転移温度は、製造元のカタログ値が参考となるが、これが入手できない場合、示差走査熱量測定(DSC)によって求められ、通常、ガラス転移が起こる温度範囲の中点により算出される。前記樹脂エマルジョンは単独で、又は2種以上を組み合わせて使用することができる。
本発明の水性インクジェット用インク組成物には、アルカリ可溶性樹脂を溶解させる観点から、塩基性化合物を含むことが好ましい。前記塩基性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム等の無機塩基性化合物;アンモニア、メチルアミン、エチルアミン、モノエタノールアミン、N、N-ジメチルエタノールアミン、N、N-ジエチルエタノールアミン、N、N-ジブチルエタノールアミン、ジエタノールアミン、N-メチルジエタノールアミン、トリエタノールアミン、モルホリン、N-メチルモルホリン、N-エチルモルホリン等の有機塩基性化合物等が挙げられる。前記塩基性化合物は単独で、又は2種以上を組み合わせて使用することができる。
本発明の水性インクジェット用インク組成物を調製(製造)する方法としては、特に限定されず、上記の成分を順番に、あるいは同時に添加して、混合すればよいが、例えば、(1)前記塩基性化合物の存在下にアルカリ可溶性樹脂を水に溶解した水性樹脂ワニス、顔料、必要に応じて顔料分散剤等を混合した後、各種分散機、例えばボールミル、アトライター、ロールミル、サンドミル、アジテーターミル等を利用して顔料分散液(インクベース)を調製し、さらに残りの材料を添加して、水性インクジェット用インク組成物を調製する方法や、(2)上記の方法で顔料を分散した後、酸析法や再公表特許WO2005/116147号公報に記載のイオン交換手段等により、顔料表面にアルカリ可溶性樹脂を析出させた樹脂被覆顔料を得、次いで得られた樹脂被覆顔料を塩基性化合物で中和し、各種分散機(高速攪拌装置等)を用いて水に再分散し、さらに残りの材料を添加して、水性インクジェット用インク組成物を調製する方法等が挙げられる。
本発明の印刷物は、前記水性インクジェット用インク組成物を印刷して得られる。具体的には、前記水性インクジェット用インク組成物を、基材にインクジェット印刷機を用いて塗工(印刷)して得られる。
本発明のインクジェット印刷方法は、従来公知の条件が適宜採用できるが、例えば、前記水性インクジェット用インク組成物をインクカートリッジに収容し、該インクカートリッジをシングルパス方式等のインクジェット記録装置に装着して、ノズルから基材へ噴射することによりインクジェット印刷をする方法が挙げられる。
<顔料分散液(ブラックインクベース)の製造>
アルカリ可溶性樹脂(アクリル酸/n-ブチルアクリレート/ベンジルメタクリレート/スチレン共重合体)、重量平均分子量30,000、酸価185mgKOH/g、ガラス転移温度40℃)20質量部を、水酸化カリウム2.5質量部と水77.5質量部との混合溶液に溶解させて、アルカリ可溶性樹脂の固形分が20質量%の水性樹脂ワニスを得た。次に、上記水性樹脂ワニス23.7質量部に水64.3質量部を加え混合し、顔料分散用樹脂ワニスを調製した。この顔料分散用樹脂ワニスに、更に顔料としてカーボンブラック(商品名「プリンテックス90」、デグサ社製)12質量部を加え、攪拌混合後、湿式サーキュレーションミルで練肉を行い、製造例1のブラック顔料分散液(ブラックインクベース)を製造した。
<顔料分散液(イエロー、マゼンダ、及びシアンインクベース)の製造>
製造例1に記載のカーボンブラック(商品名「プリンテックス90」、デグサ社製)の替わりに、イエロー顔料(商品名「ノバパームイエロー4G01」、クラリアント社製)、マゼンタ顔料(商品名「インクジェットマゼンタE5B02」、クラリアント社製)、又はシアン顔料(商品名「ヘリオゲンブルーL7101F」、BASF社製)を使用したこと以外は、製造例1と同様の方法を行い、製造例2のイエロー顔料分散液(イエローインクベース)、製造例3のマゼンダ顔料分散液(マゼンダインクベース)、及び製造例4のシアン顔料分散液(シアンインクベース)を製造した。
<顔料分散液(ホワイトインクベース)の製造>
製造例1に記載の水性樹脂ワニス40.0質量部に水20.0質量部を加え混合し、顔料分散用樹脂ワニスを調製した。この顔料分散用樹脂ワニスに、更に顔料として酸化チタン(商品名「R-960」、デュポン社製)40質量部を加え、攪拌混合後、湿式サーキュレーションミルで練肉を行い、製造例5のホワイト顔料分散液(ホワイトインクベース)を製造した。
<水性インクジェット用インク組成物の製造>
表1の質量割合になるように、前記ブラック顔料分散液(ブラックインクベース)、水溶性溶剤としてプロピレングリコール、界面活性剤(A)としてアセチレン系界面活性剤(商品名「オルフィンE1004」、固形分(有効成分)100%、HLB8、日信化学工業社製)、界面活性剤(B)としてアセチレン系界面活性剤(商品名「オルフィンE1010」、固形分(有効成分)100%、HLB13、日信化学工業社製)、コロイダルシリカとしてコロイダルシリカ(商品名「スノーテックス30」、固形分30%、粒子径12nm、Na+安定型アルカリ性ゾル、日産化学工業社製)、樹脂エマルジョンとしてスチレン-アクリル系樹脂エマルジョン(商品名「Neocryl A-1092」、固形分48.5%、ガラス転移温度6℃、DSM社製)、及び水を攪拌混合し、実施例1の水性インクジェット用インク組成物を製造した。
<水性インクジェット用インク組成物の製造>
各実施例及び各比較例において、使用する原料及びその量を、表1-4に示すように変更したこと以外は、実施例1と同様の方法により、各実施例及び各比較例の水性インクジェット用インク組成物を製造した。
以下の方法により評価し、それらの結果を表1-4に示す。なお、以下の評価において、1つでも×があるインク組成物は不合格とする。
上記で製造した水性インクジェット用インク組成物をそれぞれガラス瓶にとり、25℃の粘度(mPa・s)を、粘度計(東機産業社製、「RE100L型」)を用いて測定した。その後、密栓し60℃、1ヵ月保存し、保存後の粘度(25℃)を粘度計により測定した。保存安定性は、粘度変化率(60℃、(1ヵ月後の粘度-保存前の粘度)/保存前の粘度)で評価した。
[保存安定性の評価基準]
○:粘度変化率が5%未満である。
△:粘度変化率が5%以上、10%未満である。
×:粘度変化率が10%以上である。
上記で製造した水性インクジェット用インク組成物について、それぞれポリ容器にとり、25℃の水浴中でダイヤフラムポンプ(KNF社製、NF60)を用いて500サイクル循環送液した。循環後のインクを目開き150のポリエステルメッシュでろ過し、残差を目視評価した。
[機械的安定性の評価基準]
○:残差がないもの。
△:わずかに残差がみられるもの。
×:多量に残差がみられるもの。
上記で製造した水性インクジェット用インク組成物をインクジェットプリンター(「PX105」、エプソン社製)のカートリッジに詰めて、写真用紙(「GL-101A450」、キャノン社製)に印字を行い、吐出安定性の評価を行った。
[吐出安定性の評価基準]
○:印字の乱れがほとんどなく、安定して吐出できる。
△:多少の印字の乱れがあるものの、吐出はできる。
×:印字の乱れがあり、安定して吐出できない。
上記で製造した水性インクジェット用インク組成物をインクジェットプリンター(「PX105」、エプソン社製)のカートリッジに詰めて、OKトップコート紙(王子製紙社製)に印字を行い、印刷物を80℃で3分放置してインクを乾燥させ、印字部を綿棒でこすって、塗膜乾燥性を評価した。
[塗膜乾燥性の評価基準]
○:綿棒にインクが全く付着しない。
△:綿棒にインクが少量付着する。
×:綿棒にインクが多量に付着する。
上記で製造した水性インクジェット用インク組成物を、0.15mmバーコーターによりOPPフィルム(P2161、25μm、東洋紡社製)上に塗布し、目視観察することにより、耐ハジキ性を評価した。
[耐ハジキ性の評価基準]
○:ハジキがなく均一に塗布できる。
△:僅かにハジキがあるものの塗布できる。
×:ハジキが発生し明らかに均一塗布できない。
ジプロピレングリコールジメチルエーテルは、沸点:175℃;
ジエチレングリコールモノブチルエーテルは、沸点:231℃;
エチレングリコールモノメチルエーテルは、沸点:124℃;
トリプロピレングリコールモノブチルエーテルは、沸点:274℃;を示す。
オルフィンE1004は、アセチレン系界面活性剤(固形分(有効成分):100%、HLB:8、日信化学工業社製);
サーフィノール104Eは、アセチレン系界面活性剤(固形分(有効成分):50%、HLB:4、日信化学工業社製);
オルフィンE1010は、アセチレン系界面活性剤(固形分(有効成分):100%、HLB:13、日信化学工業社製);
サーフィノール485は、アセチレン系界面活性剤(固形分(有効成分):100%、HLB:17、日信化学工業社製);
スノーテックス30は、コロイダルシリカ(固形分:30%、粒子径:12nm、Na+安定型アルカリ性ゾル、日産化学社製);
スノーテックスXSは、コロイダルシリカ(固形分:20%、粒子径:5nm、Na+安定型アルカリ性ゾル、日産化学社製);
スノーテックスOは、コロイダルシリカ(固形分:20%、粒子径:12nm、酸性ゾル、日産化学社製);
スノーテックスNは、コロイダルシリカ(固形分:20%、粒子径:12nm、NH4 +安定型アルカリ性ゾル、日産化学社製);
スノーテックスCは、コロイダルシリカ(固形分:20%、粒子径:12nm、中性域安定型ゾル、日産化学社製);
Levasil CC151は、コロイダルシリカ(固形分:15%、粒子径:5nm、シラン改質コロイダルシリカ、Nouryon社製);
Levasil CC301は、コロイダルシリカ(固形分:28%、粒子径:7nm、シラン改質コロイダルシリカ、Nouryon社製);
Levasil CC401は、コロイダルシリカ(固形分:37%、粒子径:12nm、シラン改質コロイダルシリカ、Nouryon社製);
Levasil CC503は、コロイダルシリカ(固形分:50%、粒子径:34nm、シラン改質コロイダルシリカ、Nouryon社製);
Neocryl A-1092(固形分:48.5%、スチレン-アクリル系エマルジョン、DSM社製、ガラス転移温度:6℃);を示す。
Claims (6)
- 顔料、アルカリ可溶性樹脂、界面活性剤、水溶性溶剤、コロイダルシリカ、及び水を含有する水性インクジェット用インク組成物であって、
前記界面活性剤は、HLB値が3以上10未満である界面活性剤(A)と、HLB値が10以上20以下である界面活性剤(B)を含み、
前記水溶性溶剤は、沸点が1気圧下で170℃以上250℃以下であり、
前記コロイダルシリカの割合は、前記水性インクジェット用インク組成物中、0.05質量%以上2質量%以下であることを特徴とする水性インクジェット用インク組成物。 - 前記水溶性溶剤の割合が、前記水性インクジェット用インク組成物中、15質量%以上60質量%以下であることを特徴とする請求項1に記載の水性インクジェット用インク組成物。
- 前記水溶性溶剤が、モノアルコール類、多価アルコール類、多価アルコールの低級アルキルエーテル類、及び窒素含有化合物類からなる群より選ばれる1つ以上である溶剤であることを特徴とする請求項1又は2に記載の水性インクジェット用インク組成物。
- 樹脂エマルジョンを含有することを特徴とする請求項1~3のいずれかに記載の水性インクジェット用インク組成物。
- 請求項1~4のいずれかに記載の水性インクジェット用インク組成物を印刷して得られることを特徴とする印刷物。
- 請求項1~4のいずれかに記載の水性インクジェット用インク組成物を用いて、非吸収性印刷媒体に印刷することを特徴とするインクジェット印刷方法。
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