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
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
  • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
• • 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
  • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

• the present invention is an aqueous pigment type that has excellent storage stability and has good printability such as bleeding and a high color gamut even when printed on absorbent media such as plain paper and low-absorbent media such as offset coated paper.
• the present invention relates to an inkjet ink composition.
• the ink jet printing method is a printing / recording method in which ink droplets are directly ejected from a very fine nozzle onto a printing / recording substrate and adhered to obtain characters and images.
• the water-based inkjet printing method was once considered unsuitable for the production of a large amount of printed matter due to problems such as a long print time due to the printing head being a scanning type and slow drying of an aqueous medium.
• it does not require a plate making process like a normal printing method, and even if it includes an electrophotographic method, it has the advantage that it can be printed with a very simple device configuration. It was mostly used at home.
• aqueous pigment dispersion obtained by dispersing and crosslinking a pigment, a (meth) acrylic acid ester copolymer, and an organic compound containing a glycidyl group in an aqueous medium. It is disclosed (for example, see Patent Document 1).
• the aqueous pigment ink containing the above pigment dispersion is not satisfactory in terms of storage stability and color gamut.
• a crosslinked polymer particle containing a colorant wherein the crosslinked polymer particle is a polymer particle obtained by crosslinking a polymer with a crosslinking agent having two or more epoxy groups.
• a water-based inkjet recording ink composition containing crosslinked polymer particles for inkjet recording containing a structural unit derived from a linear or branched alkyl group or alkenyl group-containing monomer having 6 to 22 carbon atoms.
• the ink composition for aqueous inkjet recording containing the crosslinked polymer particles containing 10% of the structural unit derived from stearyl methacrylate described in the Examples of Patent Document 2 is a polymer containing the structural unit derived from lauryl methacrylate. It is described that the stability is worse than that of an aqueous ink jet recording ink composition containing 10% of crosslinked polymer particles.
• the aqueous ink jet recording ink composition containing crosslinked polymer particles containing 10% of a structural unit derived from lauryl methacrylate in the polymer has not been satisfactory in terms of stability.
• the present invention is a water-based inkjet ink composition having excellent printability and high color gamut even when printed on low-absorbent media (coated paper, etc.) or absorbent media (uncoated paper). The issue is to provide goods.
• aqueous ink-jet ink composition A resin layer obtained by crosslinking an alkali-soluble resin having an acid value of 40 to 300 KOH mg / g and neutralizing 50 to 90% of acid groups with a basic compound with a bifunctional or higher functional crosslinking agent,
• the alkali-soluble resin contains, as a structural unit, lauryl (meth) acrylate in the alkali-soluble resin in a total monomer amount of 20 to An aqueous pigment-type inkjet ink composition containing 40% by mass.
• the ink composition itself is excellent in storage stability and printed on an absorbent medium (plain paper) and a low-absorbent medium (coated paper, etc.) A remarkable effect of having good printability without bleeding and a high color gamut can be exhibited.
• the present inventors can solve the above-mentioned problems by using an aqueous pigment-type inkjet ink composition containing a coating pigment obtained by crosslinking a pigment coated with a specific alkali-soluble resin with a bifunctional or higher functional crosslinking agent.
• the present invention has been found to solve the present invention.
• the aqueous pigment-type inkjet ink composition of the present invention will be described.
• the pigment used for the pigment coated with the alkali-soluble resin examples include various inorganic pigments and organic pigments generally used in ink jet inks.
• the inorganic pigment includes colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, ultramarine blue, bitumen, carbon black, graphite, and the like (including achromatic pigments such as white and black).
• extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc.
• organic pigment examples include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. These may be used alone or in combination of two or more. Further, as the above-mentioned pigment, in particular, from the viewpoint that a clear hue can be expressed, C.I. I. Red pigments such as CI Pigment Red 5, 7, 12, 57: 1, 122, 146, 202, 242 and 282; I. Blue pigments such as CI Pigment Blue 1, 2, 15: 3, 15: 4, 16, 17, 60; I. Purple pigments such as Pigment Violet 19, 23; I.
• Red pigments such as CI Pigment Red 5, 7, 12, 57: 1, 122, 146, 202, 242 and 282
• Blue pigments such as CI Pigment Blue 1, 2, 15: 3, 15: 4, 16, 17, 60
• I. Purple pigments such as Pigment Violet 19, 23; I.
• alkali-soluble resins satisfying the following (a) to (c) can be used.
• the acid value of the alkali-soluble resin is 40 to 300 KOH mg / g.
• B 50 to 90% of the acid groups of the alkali-soluble resin are neutralized with a basic compound.
• C the alkali-soluble resin contains 20 to 40% by mass of lauryl (meth) acrylate in the alkali-soluble resin as a monomer of the constituent unit, and further has a monomer having an aromatic ring, Preferably, a styrenic monomer is contained.
• an alkali-soluble resin for example, a monomer having a carboxyl group as a constituent unit, and further a monomer having lauryl (meth) acrylate and an aromatic ring in order to improve the adsorptivity with the pigment Or a copolymer obtained by reacting these monomers with other polymerizable monomers as required.
• Examples of the monomer having a carboxyl group for alkali-soluble resin include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2- Examples thereof include carboxypropyl (meth) acrylate, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, citraconic acid monoalkyl ester, and the like.
• the monomer containing a hydrophobic group for improving the adsorptivity with the pigment examples include lauryl (meth) acrylate and a monomer having an aromatic ring such as styrene, ⁇ -styrene, vinyltoluene, and the like. Examples thereof include styrene monomers and benzyl (meth) acrylate.
• the styrene monomer refers to a compound having styrene as a basic skeleton and optionally having a substituent.
• the alkali-soluble resin preferably contains a monomer having an aromatic ring, preferably 30 to 60% by mass of a styrene monomer.
• the alkali-soluble resin preferably contains 20 to 40% by mass of lauryl (meth) acrylate. It is not necessary to use stearyl (meth) acrylate, but together with the use of lauryl (meth) acrylate, stearyl (meth) acrylate should be used in combination as long as the effects of using lauryl (meth) acrylate are not impaired. Is also possible.
• (Meth) acrylic acid such as isopropyl acid, butyl (meth) acrylate, hexyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-methylolacrylamide, 2-ethylhexyl (meth) acrylate, octyl (meth) ) Acrylate, stearyl (meth) acrylate, 2-hydroxystearyl (meth) acrylate, dodecyl vinyl ether, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. All It is.
• the acid value of the alkali-soluble resin is preferably 40 to 300 KOH mg / g, more preferably 70 to 250 KOH mg / g. If the acid value of the alkali-soluble resin is lower than 40 KOHmg / g, the dispersion stability of the aqueous dispersion of the pigment coated with the resulting alkali-soluble resin may be lowered. On the other hand, if the acid value is higher than 300 KOHmg / g, the hydrophilicity Is too high, storage stability and water resistance may decrease. It is preferable that 50 to 90% of the acid groups of the alkali-soluble resin are neutralized with a basic compound.
• the molecular weight of the alkali-soluble resin is preferably 3,000 to 100,000, more preferably 10,000 to 50,000.
• the weight average molecular weight of the alkali-soluble resin is less than 3,000, the dispersion stability of the pigment and the scratch resistance of the obtained printed matter tend to be lowered.
• the weight average molecular weight exceeds 100,000, the viscosity is preferably increased. Absent.
• Acid value is calculated from the number of mg of potassium hydroxide theoretically required to neutralize 1 g of the alkali-soluble resin, based on the composition of the monomer used to synthesize the alkali-soluble resin. The calculated theoretical acid value.
• Weight average molecular weight The weight average molecular weight can be measured by gel permeation chromatography (GPC). As an example, chromatography can be performed using Waters 2690 (manufactured by Waters) as a GPC apparatus and PLgel 5 ⁇ m MIXED-D (manufactured by Polymer Laboratories) as a column, and the weight average molecular weight in terms of polystyrene can be obtained.
• GPC gel permeation chromatography
• Basic compounds that neutralize the acid groups of alkali-soluble resins include inorganic basic compounds such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, ethylamine, monoethanolamine, N, N-dimethylethanolamine.
• Organic basic compounds such as N, N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. . These basic compounds can be used alone or in admixture of two or more.
• alkanolamines such as monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine are preferable from the viewpoint of pigment dispersion. Is preferred.
• the bifunctional or higher functional crosslinking agent used for the production of the coated pigment is used for appropriately crosslinking the alkali-soluble resin.
• the cross-linking agent of the present invention is a cross-linking agent having two or more reactive functional groups, and the molecular weight of the cross-linking agent is in the range of 100 to 2000 from the viewpoint of ease of reaction and storage stability. It is preferable.
• the reactive functional group one or more selected from the group consisting of an epoxy group, a hydroxyl group, and an aridine group are preferably exemplified. Of these, an epoxy group is preferable from the viewpoint of viscosity and tolerance, and a bifunctional epoxy compound is more preferable.
• epoxy compound having two or more functions examples include Epolite 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-201, EX-211 , EX-212, EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614, EX-614B, EX -622 (manufactured by Nagase ChemteX Corporation).
• the coated pigment in the present invention is insolubilized by dissolving or dispersing an alkali-soluble resin in which an acid group is neutralized with a basic compound and the pigment in an aqueous solvent, and then salting out the alkali-soluble resin. And is attached to the pigment surface. 50 to 90% of the acid groups of the insolubilized resin thus adhered were neutralized. Obtaining a dispersion dispersed from the pigment coated with the obtained alkali-soluble resin, adding a cross-linking agent to the dispersion, and then heating this to cross-link the alkali-soluble resin covering the pigment surface And insolubilized to produce a coated pigment.
• the obtained cross-linked alkali-soluble resin has a cross-linking rate of 10 to 90%, preferably 20 to 80%, more preferably 30 to 70%, more preferably the theoretical acid value of the alkali-soluble resin. 35-50%. If the crosslinking rate is less than 10%, the coating strength to the pigment may not be sufficient, and if it exceeds 90%, the dispersion stability of the pigment may be inhibited.
• the water-soluble organic solvent used in the aqueous pigment-type inkjet ink composition of the present invention is used as an aqueous medium together with water.
• the water is preferably ion-exchanged water or distilled water from which metal ions or the like have been removed.
• a water-soluble organic solvent it may be possible to impart more excellent ink jet printing suitability in terms of storage stability, ejection stability, ink flying property, and the like.
• Examples of such water-soluble organic solvents include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, nitrogen-containing compounds, and the like. These may be used alone or in combination of two or more.
• the monoalcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or these Isomers, cyclopentanol, cyclohexanol and the like, and preferably an alcohol having an alkyl group with 1 to 6 carbon atoms.
• polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1 , 2-hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol , Dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol and the like.
• lower alkyl ethers of the polyhydric alcohol include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether.
• Specific examples of the ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
• ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
• esters include propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate, and ⁇ -caprolactone, ⁇ -Cyclic esters such as caprolactam.
• nitrogen-containing compounds examples include urea, pyrrolidone, N-methyl-2-pyrrolidone, octyl pyrrolidone and the like.
• the content of the water-soluble organic solvent is preferably 20 to 40% by mass in the aqueous pigment-type inkjet ink composition.
• the medium is a low-absorbency medium (coated paper or the like)
• Examples of the surfactant used in the present invention include an acetylene glycol compound represented by the formula (1), an HLB 4-14 compound obtained by adding ethylene oxide to an acetylenic diol compound, a silicon surfactant, and At least one selected from fluorine-based surfactants can be used.
• Formula (1) Specific examples of the acetylene glycol compound represented by the formula (1) include Surfynol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG- manufactured by Air Products. 50 etc. are mentioned.
• HLB4-14 compounds obtained by adding ethylene oxide to acetylenic diol compounds include Surfynol 420 and Surfynol 440 manufactured by Air Products.
• silicon-based surfactant and the fluorine-based surfactant known ones conventionally used in water-based inkjet ink compositions can be used.
• the content of the surfactant is preferably 0.1 to 3.0% by mass in the aqueous pigment-type inkjet ink composition. If the surfactant content is less than 0.1% by mass, the dot expandability and the solid uniformity of the printed matter tend to be reduced. On the other hand, if it exceeds 3.0% by mass, the storage stability of the ink is deteriorated. It is not preferable because it is in a tendency.
• the HLB represents a balance between a hydrophilic part and a hydrophobic part of a molecule used in the field of surfactants (hydrophile-lipophile balance), and has a value from 0 to 20, The larger the value, the higher the hydrophilicity.
• the water-based pigment-type inkjet ink composition of the present invention includes a known resin emulsion, pigment dispersant, antifungal agent, rust inhibitor, thickener, antioxidant, ultraviolet absorber, storage according to the purpose. Additives such as property improvers, antifoaming agents, and pH adjusters can also be added.
• resin emulsions include acrylic resin emulsions having a glass transition temperature of 20 ° C. or less, styrene-acrylic resin emulsions, polyester resin emulsions, polyurethane resin emulsions, polyvinyl acetate resin emulsions, polyvinyl chloride resin emulsions, polybutadiene resins.
• resin emulsions include resin emulsions and polyethylene resin emulsions. Of these, a styrene-acrylic resin emulsion is preferred because the printed matter obtained is excellent in appearance and various resistances.
• the content of the resin emulsion is preferably 1 to 10% by mass, more preferably 2 to 5% by mass as a solid content in the aqueous pigment ink-jet ink composition.
• the content of the resin emulsion is less than 1% by mass as the solid content, the appearance and various resistances of the obtained printed matter tend to be reduced.
• it exceeds 10% by mass the ink ejection tends to be unstable. This is not preferable.
• the glass transition temperature of the resin emulsion is a theoretical glass transition temperature determined by the following wood equation.
• Wood formula: 1 / Tg W1 / Tg1 + W2 / Tg2 + W3 / Tg3 +... + Wx / Tgx (Wherein Tg1 to Tgx are the glass transition temperatures of the respective homopolymers of monomers 1, 2, 3,... X constituting the alkali-soluble resin, and W1 to Wx are the monomers 1, 2, 3,.
• Each of x polymerization fractions and Tg represents a theoretical glass transition temperature (however, the glass transition temperature in the wood equation is an absolute temperature).
• an aqueous resin varnish obtained by dissolving an alkali-soluble resin in water in the presence of a pigment, a basic compound, and a pigment dispersant as required And the like, and after dispersing the pigment using various dispersers such as a ball mill, an attritor, a roll mill, a sand mill, an agitator mill, etc., the acid precipitation method or the ion exchange means described in the republished WO 2005/116147 Or a phase inversion emulsification method or the like to obtain a pigment having an alkali-soluble resin precipitated on the surface of the pigment, and then the pigment obtained by precipitating the alkali-soluble resin on the obtained pigment surface has 50 to 90% of the acid groups of the alkali-soluble resin.
• aqueous pigment-type inkjet ink composition of the present invention has an initial viscosity after production of 2.0 to 10.0 mPa ⁇ s, preferably 3.0 to 9.0 mPa ⁇ s.
• the target surface tension is in the range of 25 to 40 mN / m.
• the aqueous pigment ink jet ink composition of the present invention As the printing medium of the aqueous pigment-type inkjet ink composition of the present invention, art paper, ink-jet exclusive paper, coated paper such as inkjet glossy paper, and the like can be used. It can also be used for uncoated paper such as plain paper and offset paper.
• the water-based pigment-type ink-jet ink composition of the present invention is contained in an ink cartridge, and the ink cartridge is mounted on a single-pass ink-jet recording apparatus and ejected from the nozzle onto the printing substrate. By doing so, inkjet printing can be performed.
• ⁇ Water-based resin varnish E> 25 parts by mass of a copolymer of acrylic acid / stearyl acrylate (SA) / styrene 25/30/45 having a weight average molecular weight of 23,000 and an acid value of 185 KOH mg / g was added to 4.9 parts by mass of potassium hydroxide and 70.
• ⁇ Water-based resin varnish H> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) / styrene 4/30/66 having a weight average molecular weight of 23,000 and an acid value of 30 KOH mg / g, 0.8 parts by mass of potassium hydroxide and 74.
• ⁇ Water-based resin varnish I> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) /styrene 44.6/30/25.4 having a weight average molecular weight of 23,000 and an acid value of 330 KOH mg / g was added to 8.7 parts by mass of potassium hydroxide. And an aqueous resin varnish I with a solid content of 25% was obtained.
• ⁇ Water-based resin varnish J> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) / styrene 25/30/45 having a weight average molecular weight of 20,000 and an acid value of 185 KOH mg / g was added to 4.9 parts by mass of potassium hydroxide and 70.
• ⁇ Water-based resin varnish K> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) / styrene 25/30/45 having a weight average molecular weight of 30,000 and an acid value of 185 KOH mg / g was added to 4.9 parts by mass of potassium hydroxide and 70.
• ⁇ Water Resin Varnish L> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) / styrene 25/30/45 having a weight average molecular weight of 40,000 and an acid value of 185 KOH mg / g was added to 4.9 parts by mass of potassium hydroxide and 70.
• ⁇ Water Resin Varnish M> 25 parts by mass of a copolymer of acrylic acid / lauryl acrylate (LA) / benzylmethyl acrylate 25/30/45 having a weight average molecular weight of 23,000 and an acid value of 185 KOH mg / g was added to 4.9 parts by mass of potassium hydroxide and water.
• aqueous black base ink 2 Mw 23,000, acid value 185, LA 20% 48 parts by mass of water was added to 32 parts by mass of the aqueous resin varnish B (solid content: 25%), and mixed to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, An aqueous black base ink 2 was prepared.
• aqueous black base ink 3 Mw 23,000, acid value 185, LA 40% 48 parts by mass of water was added to and mixed with 32 parts by mass of the aqueous resin varnish C (solid content: 25%) to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, An aqueous black base ink 3 was prepared.
• aqueous black base ink 4 Mw 23,000, acid value 150, LA 30% 48 parts by mass of water was added to and mixed with 32 parts by mass of the aqueous resin varnish D (solid content: 25%) to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 4 was prepared.
• aqueous black base ink 5 Mw 23,000, acid value 185, SA 30% 48 parts by mass of water was added to and mixed with 32 parts by mass of the aqueous resin varnish E (solid content: 25%) to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 5 was prepared.
• aqueous black base ink 7 Mw 23,000, acid value 185, LA 15% 48 parts by mass of water was added to and mixed with 32 parts by mass of the aqueous resin varnish G (solid content 25%) to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 7 was prepared.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 8 was prepared.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 12 was prepared.
• aqueous black base ink 13 Mw 23,000, acid value 185, LA 30% 48 parts by mass of water was added to and mixed with 32 parts by mass of the aqueous resin varnish M (solid content: 25%) to prepare a resin varnish for pigment dispersion.
• 20 parts by mass of carbon black (trade name Printex 90, manufactured by Degusa (currently Orion Engineered Carbons, hereinafter the same)) is added, and after stirring and mixing, the mixture is kneaded with a wet circulation mill, A water-based black base ink 13 was prepared.
• a magenta pigment trade name Inkjet Magenta E5B02, manufactured by Clariant
• a cyan pigment trade name Heliogen Blue L7101F, manufactured by BASF
• Aqueous pigment dispersion 1 (aqueous black base ink 1, Mw 23,000, acid value 185, LA 30%, neutralization degree 45%)
• Aqueous pigment dispersion 2 (aqueous black base ink 1, Mw 23,000, acid value 185, LA 30%, neutralization degree 55%)
• Aqueous pigment dispersion 3 (aqueous black base ink 1, Mw 23,000, acid value 185, LA 30%, neutralization degree 65%)
• Aqueous pigment dispersion 4 (aqueous black base ink 1, Mw 23,000, acid value 185, LA 30%, neutralization degree 75%)
• Aqueous pigment dispersion 5 (aqueous black base ink 1, Mw 23,000, acid value 185, LA 30%, neutralization degree 95%)
• Aqueous pigment dispersion 6 (aqueous black base ink 2, Mw 23,000, acid value 185, LA 20%, neutralization degree 65%)
• Aqueous pigment dispersion 7 (aqueous black base ink 3, Mw 23,000, acid value 185, LA 40%
• aqueous pigment dispersions 1 to 22 As shown in Table 1, aqueous pigment dispersions 1 to 22, a bifunctional or higher functional crosslinking agent (Epolite 1600, Chemite DZ-22E, Denacol EX-614) and water are added and heated at 60 ° C. for 24 hours to form crosslinked particles. Aqueous dispersions 1 to 21 were obtained.
• Optical density The aqueous pigment-type inkjet ink compositions of Examples 1 to 19 and Comparative Examples 1 to 9 were developed on a sheet of paper (manufactured by Fuji Xerox Co., Ltd.) using a 0.1 mm wire bar, and the optical density of the developed surface was adjusted. Measurement was performed using a spectroeye (manufactured by X-Rite). Evaluation criteria ⁇ : Optical density is in the following range (Yellow> 0.9, Magenta > 1.0, Cyan> 1.0, Black> 1.1)
• X Optical density within the following range (Yellow ⁇ 0.9, Magenta ⁇ 1.0, Cyan ⁇ 1.0, Black ⁇ 1.1)
• the water-based pigment-type ink jet ink composition of the present invention has excellent storage stability, has excellent solidification properties when used on plain paper and coated paper, and exhibits high optical density even when used on plain paper. When used for paper, the coating film was excellent in drying property.
• Comparative Examples 1, 2, 11 and 12 whose degree of neutralization is outside the scope of the present invention
• Comparative Examples 3 and 13 containing stearyl acrylate, and the content of lauryl acrylate in all monomers is According to Comparative Examples 4, 5, 14 and 15, which are outside the scope of the invention, and Comparative Examples 6, 7, 16 and 17 where the acid value is outside the scope of the present invention, the storage stability and the solidification were inferior. .

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