WO2015111645A1 - Ink composition for aqueous ink jet - Google Patents

Ink composition for aqueous ink jet Download PDF

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Publication number
WO2015111645A1
WO2015111645A1 PCT/JP2015/051621 JP2015051621W WO2015111645A1 WO 2015111645 A1 WO2015111645 A1 WO 2015111645A1 JP 2015051621 W JP2015051621 W JP 2015051621W WO 2015111645 A1 WO2015111645 A1 WO 2015111645A1
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Prior art keywords
surfactant
ink composition
mass
aqueous
inkjet ink
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PCT/JP2015/051621
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French (fr)
Japanese (ja)
Inventor
佐藤　洋一
廣幸 小西
員揮 森安
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サカタインクス株式会社
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Publication of WO2015111645A1 publication Critical patent/WO2015111645A1/en

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    • 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
    • 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 that is excellent in dot expandability, solid uniformity, and storage stability even when printed on non-absorbent media such as coated paper and polyvinyl chloride sheet.
  • 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.
  • non-absorbent media such as coated paper and polyvinyl chloride sheets as well as uncoated paper such as inexpensive plain paper and ordinary offset paper is also being considered as a printing substrate.
  • uncoated paper such as inexpensive plain paper and ordinary offset paper
  • the contact angle of ink droplets with the media is large, and when ink droplets land, they are difficult to wet and spread on the media. Does not expand sufficiently, resulting in a printed matter lacking in density.
  • water-based inks tend to wet and spread non-absorbent media unevenly, and a mottled pattern is generated in a solid image portion having a uniform density.
  • a surfactant may be introduced into the ink.
  • acetylenic diol surfactants are superior to other types of surfactants in reducing the surface tension of an aqueous inkjet ink composition and also having the ability to form an ink liquid film uniformly on a medium. It is out. Examples of such techniques are listed in Patent Documents 1 and 2. However, even if such a technique is used, since the dot expandability and the uniformity of the solid portion are insufficient, the required print quality level that has been increasing in recent years has not been reached.
  • the acetylenic diol surfactant has a high effect of reducing the surface tension of the aqueous inkjet ink composition, but has a strong tendency to separate from the aqueous inkjet ink composition, and an adverse effect on storage stability is recognized.
  • non-absorbent media such as coated paper and polyvinyl chloride sheet
  • it has excellent dot expandability, excellent uniformity of solid parts, and stable storage
  • it is difficult to obtain a water-based inkjet ink composition having good properties.
  • the present invention is an aqueous ink-jet ink composition having excellent storage stability and excellent dot expansion even when printed on non-absorptive media (coated paper, polyvinyl chloride sheet, etc.) and excellent uniformity of solid portions.
  • non-absorptive media coated paper, polyvinyl chloride sheet, etc.
  • the issue is to provide goods.
  • a water-based inkjet ink composition containing a pigment, an alkali-soluble resin, a basic compound, a water-soluble organic solvent, a surfactant A, and a surfactant B, wherein the surfactant A is HLB 4-9.
  • An acetylenic diol-based surfactant having a surfactant A content of 0.1 to 10% by mass in an aqueous inkjet ink composition and a surfactant B of HLB 13 to 16
  • An aqueous inkjet ink composition which is an activator and the content of surfactant B is 0.1 to 10% by mass in the aqueous inkjet ink composition.
  • aqueous inkjet ink composition according to any one of (1) to (3), wherein the content of the water-soluble organic solvent is 20 to 30% by mass in the aqueous inkjet ink composition.
  • the ink composition itself is excellent in storage stability and excellent in dot expandability even when printed on non-absorbent media (coated paper, polyvinyl chloride sheet, etc.). And the remarkable effect that it is excellent also in the uniformity of a solid part can be exhibited.
  • the inventors of the present invention have made it possible to add a novel acetylenic diol surfactant having a low HLB of 4 to 9 and an acetylenic diol surfactant having a high HLB of 13 to 16 to the aqueous inkjet ink.
  • a water-based inkjet ink composition was developed.
  • the contact angle of the ink droplet with respect to the medium surface is reduced, reflecting the surface tension of the ink that has been reduced by the acetylenic diol surfactant having a low HLB.
  • the acetylene diol surfactant having a high HLB causes the ink droplets to uniformly spread on the medium and form a uniform solid in the solid image portion.
  • the acetylene diol surfactant having a high HLB has a function of making the acetylene diol surfactant having a low HLB compatible with the aqueous inkjet ink composition, and suppresses the separation of the two.
  • 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, It can be said that the larger the value, the higher the hydrophilicity.
  • the water-based inkjet ink composition of the present invention will be specifically described for each component.
  • the pigment include various inorganic pigments and organic pigments that are 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, and graphite (achromatic colored pigments such as white and black).
  • extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc.
  • the 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, 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; I. Pigment Yellow 12, 13, 14, 17, 74, 83, 93, 128, 139, 151, 154, 155, 180, 185, 213 and the like yellow pigments; C.I. I. Black 7 (carbon black) and the like are preferable.
  • Red pigments such as CI Pigment Red 5, 7, 12, 57: 1, 122, 146,
  • self-dispersed pigments in which polar functional groups are introduced by chemical reaction on the surface of the pigment particles, and coated pigment particles in which the pigment is coated with polymer particles can also be used as the pigment.
  • an alkali-soluble resin and a basic compound, which will be described later may be used as a pigment dispersion resin, and the pigment may be dispersed in an aqueous medium.
  • the content of the pigment in the aqueous inkjet ink composition of the present invention is preferably 1 to 10% by mass, and more preferably 2 to 6% by mass.
  • Alkali-soluble resin As the alkali-soluble resin, a copolymer resin that is used for dispersing pigments in ordinary inks and paints and is soluble in an aqueous medium in the presence of a basic compound can be used.
  • a monomer having a carboxyl group preferably a copolymer with a monomer containing a hydrophobic group for improving the adsorptivity with a pigment, or these A copolymer obtained by reacting the monomer with other polymerizable monomer as required can be used.
  • 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, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, citraconic acid monoalkyl ester and the like can be mentioned.
  • a radical polymerizable unsaturated such as (meth) acrylic acid Alkyl esters having 8 or more carbon atoms of carboxylic acid (for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxystearyl (meth) acrylate, etc.) ), Alkyl vinyl ethers having 8 or more carbon atoms (for example, dodecyl vinyl ether), vinyl esters of fatty acids having 8 or more carbon atoms (for example, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, etc.)
  • cyclohexyl (meth) acrylic acid Alkyl esters having 8 or more carbon atoms of carboxylic acid (for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, la
  • polymerizable monomers used as necessary include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) (Meth) acrylic acid such as butyl acrylate and hexyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-methylolacrylamide and the like.
  • the alkali-soluble resin obtained by copolymerizing the above monomers when considering improvement of the solubility of the resin in an aqueous medium and prevention of reduction in water resistance of the printed matter, a glass transition temperature of 10 to 50 ° C.,
  • the acid value is 100 to 300 mg KOH / g, and the weight average molecular weight is 10,000 to 50,000.
  • the acid value of the alkali-soluble resin is less than 100 mgKOH / g, the solubility of the resin in an aqueous medium tends to decrease, whereas when it exceeds 300 mgKOH / g, the water resistance of the obtained printed matter tends to decrease.
  • the glass transition temperature of the alkali-soluble resin is preferably 10 to 50 ° C., more preferably 20 to 45 ° C.
  • the glass transition temperature of the alkali-soluble resin is less than 10 ° C., the blocking resistance of the obtained printed matter tends to be lowered, whereas when it exceeds 50 ° C., the bending resistance tends to be lowered.
  • the alkali-soluble resin preferably has a weight average molecular weight of 10,000 to 50,000, preferably 20,000 to More preferably, it is 30,000.
  • the weight average molecular weight of the alkali-soluble resin is less than 10,000, the dispersion stability of the pigment and the scratch resistance of the resulting printed matter tend to be reduced.
  • the weight average molecular weight exceeds 50,000, the viscosity is preferably increased. Absent.
  • the content of the alkali-soluble resin is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the aqueous inkjet ink composition.
  • the content of the alkali-soluble resin is less than the above range, the dispersibility of the pigment in the aqueous medium tends to decrease.
  • exceeding the above range is not preferable because the viscosity increases.
  • the glass transition temperature, acid value, and weight average molecular weight of the alkali-soluble resin described above can be determined by the following method.
  • the acid value is a theoretical acid value 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 monomer used for synthesizing the alkali-soluble resin. It is.
  • the weight average molecular weight can be measured by a gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • chromatography is performed using Water 2690 (manufactured by Waters) as a GPC apparatus and PLgel 5 ⁇ MIXED-D (manufactured by Polymer Laboratories) as a column, and the weight average molecular weight in terms of polystyrene can be obtained.
  • Basic compound Specific examples of the basic compound used in the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, methylamine, ethylamine, monoethanolamine, N, N-dimethylethanolamine, N, Examples thereof include organic basic compounds such as N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. These may be used alone or in combination of two or more.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • methylamine, ethylamine monoethanolamine
  • N N-dimethylethanolamine
  • organic basic compounds such as N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine.
  • aqueous medium examples of the aqueous medium used in the aqueous inkjet ink composition of the present invention include an aqueous medium composed of water and a water-soluble organic solvent.
  • 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.
  • 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 alcohol examples 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, Examples include dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and thiodiglycol.
  • 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.
  • 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 examples 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, and cyclic esters such as ⁇ -caprolactam.
  • the nitrogen-containing compound include urea, pyrrolidone, N-methyl-2-pyrrolidone, octyl pyrrolidone and the like.
  • the content of the water-soluble organic solvent is preferably 20 to 30% by mass in the aqueous inkjet ink composition.
  • Surfactant A used in the present invention includes Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfynol manufactured by Air Products. Nord 420, Surfynol 440, Orphine E1004 manufactured by Nissin Chemical Industry Co., Ltd. and the like.
  • the content of the surfactant A is preferably 0.1 to 10% by mass, more preferably 0.2 to 3% by mass, and more preferably 0.4 to 3% by mass in the aqueous inkjet ink composition. % Is more preferable. When the content of the surfactant A is less than 0.1% by mass, the dot expandability tends to deteriorate, whereas when it exceeds 10% by mass, the storage stability of the ink tends to deteriorate, such being undesirable.
  • Examples of the surfactant B used in the present invention include Surfynol 465 manufactured by Air Products, Olphine E1010, Olphine E1020 manufactured by Nissin Chemical Industry, and the like.
  • the content of the surfactant B is preferably 0.1 to 10% by mass, more preferably 0.2 to 3% by mass, and more preferably 0.4 to 3% by mass in the aqueous inkjet ink composition. % Is more preferable.
  • the content of the surfactant B is less than 0.1% by mass, the storage stability of the ink and the solid uniformity of the printed matter tend to be reduced. On the other hand, when the content exceeds 10% by mass, the storage stability of the ink is deteriorated. This is not preferable.
  • the resin emulsion examples include acrylic resin emulsion, styrene-acrylic resin emulsion, polyester resin emulsion, polyurethane resin emulsion, polyvinyl acetate resin emulsion, polyvinyl chloride resin emulsion, polybutadiene resin emulsion, polyethylene Resin emulsions and the like. 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 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. On the other hand, when it exceeds 10% by mass, the ink ejection tends to be unstable. This is not preferable.
  • the water-based inkjet ink composition of the present invention includes known pigment dispersants, antifungal agents, rust preventives, thickeners, antioxidants, ultraviolet absorbers, preservability improvers, antiseptics depending on the purpose. Additives such as foaming agents and pH adjusting agents can also be added.
  • Method for producing aqueous ink-jet ink composition As a method for producing the aqueous inkjet ink composition of the present invention using the above components, (1) An aqueous resin varnish in which an alkali-soluble resin is dissolved in water in the presence of a pigment and a basic compound, and a pigment dispersant as necessary are mixed, and then various dispersing machines such as a ball mill, an attritor, a roll mill, and a sand mill.
  • a method of dispersing a pigment using an agitator mill or the like, and further adding the remaining materials to prepare an aqueous inkjet ink composition (hereinafter referred to as production method 1), (2) After dispersing the pigment by the above-described method, a resin-coated pigment in which an alkali-soluble resin is precipitated on the pigment surface is obtained by an acid precipitation method or ion exchange means described in the republished WO 2005/116147, The resulting resin-coated pigment is neutralized with a basic compound, re-dispersed in water using various dispersers (such as a high-speed stirring device), and the remaining materials are added to prepare an aqueous ink-jet ink composition.
  • production method 1 A method of dispersing a pigment using an agitator mill or the like, and further adding the remaining materials to prepare an aqueous inkjet ink composition.
  • the production method (2) is preferable because the storage stability of the aqueous inkjet ink composition is further improved.
  • the thus obtained aqueous inkjet ink composition of the present invention has an initial viscosity after production of 2.0 to 10.0 mmPa ⁇ s, preferably 3.0 to 7.0 mmPa ⁇ s.
  • the printing medium for the aqueous ink-jet ink composition of the present invention include art paper, ink-jet exclusive paper, coated paper such as ink-jet glossy paper, plastic base materials such as polyvinyl chloride sheets, plain paper, and offset. Uncoated paper such as paper can also be used.
  • the water-based inkjet ink composition of the present invention is accommodated in an ink cartridge, the ink cartridge is mounted on a single-pass inkjet recording apparatus, and ejected from the nozzle onto the printing substrate.
  • inkjet printing can be performed.
  • Water-based resin varnish 20 parts by mass of an acrylic acid / n-butyl acrylate / benzyl methacrylate / styrene copolymer having a glass transition temperature of 40 ° C., a weight average molecular weight of 30,000 and an acid value of 185 mg KOH / g, 2.5 parts by mass of potassium hydroxide and 77% water It was dissolved in a mixed solution with 5 parts by mass to obtain an aqueous resin varnish having a solid content of 20%.
  • carbon black trade name Printex 90, manufactured by Degussa
  • a yellow pigment trade name Nova Palm Yellow 4G01, manufactured by Clariant
  • a magenta pigment trade name Inkjet Magenta E5B02, manufactured by Clariant
  • a cyan pigment trade name Heliogen Blue L7101F, manufactured by BASF
  • Neocryl A-1091 45% solids, styrene-acrylic emulsion, manufactured by DSM Neoresins
  • Examples 1 to 11 and Comparative Examples 1 to 7 were prepared by stirring and mixing the water-based color ink base, the surfactant, the emulsion, propylene glycol as a water-soluble organic solvent, and water so that the mass ratios shown in Table 1 were obtained. 1 to 7 aqueous inkjet ink compositions were obtained.
  • the water-based inkjet ink composition of the present invention has good storage stability, dot expandability, and solid uniformity, and has stable properties regardless of the type of pigment. I understand that.
  • Comparative Example 1 when only Surfynol 420 was used as the surfactant A, dot expandability and solid uniformity were insufficient. Therefore, as Comparative Example 2, when the amount of Surfynol 420 was increased in Comparative Example 1, the storage stability was impaired.
  • Comparative Example 3 when only Olfine E1004 was used as the surfactant A, the dot expandability and the solid uniformity were insufficient as in Comparative Example 1.
  • Comparative Example 4 when only Olfine E1010 was used as surfactant B, the storage stability and solid uniformity were good, but the dots did not expand.
  • Comparative Example 5 when Surfynol 420 and Olphine E1004 were used in combination as surfactant A, the storage stability and dot expandability were good, but the solid uniformity was insufficient.
  • Comparative Examples 6 and 7 when the surfactant A or B was excessively contained, the storage stability was impaired in any case.

Abstract

　Provided is an ink composition for an aqueous ink jet having superior storage stability, dot extendability and uniformity, even when printing on non-absorbent media. The ink composition for an aqueous ink jet contains a pigment, an alkali-soluble resin, a basic compound, a water-soluble organic solvent, a surfactant (A) and a surfactant (B), and is characterized in that: the surfactant (A) is an acetylenic diol surfactant with a hydrophile-lipophile balance (HLB) of 4 to 9, and the content of the surfactant (A) in the ink composition for an aqueous ink jet is 0.1 to 10 mass%; and the surfactant (B) is is an acetylenic diol surfactant with an HLB of 13 to 16, and the content of the surfactant (B) in the ink composition for an aqueous ink jet is 0.1 to 10 mass%.

Description

水性インクジェット用インク組成物Water-based inkjet ink composition
　本発明は、コート紙や、ポリ塩化ビニルシートなどの非吸収性メディアに印刷しても、ドット拡張性、ベタ均一性、及び保存安定性に優れる水性インクジェット用インク組成物に関する。 The present invention relates to an aqueous inkjet ink composition that is excellent in dot expandability, solid uniformity, and storage stability even when printed on non-absorbent media such as coated paper and polyvinyl chloride sheet.
　インクジェット印刷方式は、非常に微細なノズルからインク液滴を印刷・記録用基材に直接吐出し、付着させて文字や画像を得る印刷・記録方式である。
　水性インクジェット印刷方式は、かつて、印刷ヘッドが走査型であるために印刷に時間がかかる、水性媒体の乾燥が遅いなどの問題から、多量の印刷物の製造に適さないとされていた。
　しかし、一方で、通常の印刷方式のような製版工程を必要とせず、また、電子写真方式を含めても、非常に簡単な装置の構成で印刷が可能であるなどの利点があるため、個人や家庭で利用されることがほとんどであった。 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.
However, on the other hand, 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.
　そのため、上記の印刷や乾燥にかかる時間などの問題を解決できれば、オフィスや商業印刷等の産業用途においても、他の印刷方式と競合してなお利用する価値は十分にあると考えられる。このような理由から、インクジェット印刷方式を産業用途で利用するために、最近は印刷装置とインクの両面から、積極的に印刷の高速化と低価格の印刷用紙を適用する技術が検討されている。 Therefore, if problems such as the time required for printing and drying can be solved, it is considered that there is sufficient value in competing with other printing methods in industrial applications such as office and commercial printing. For these reasons, in order to use the inkjet printing method for industrial purposes, recently, a technology for actively applying high-speed printing and low-cost printing paper from both the printing apparatus and ink has been studied. .
　また、産業用途では、安価な普通紙や通常のオフセット紙のような未コート紙だけでなく、コート紙やポリ塩化ビニルシート等の非吸収性メディアの利用も、印刷用基材として検討されている。このようなメディアは、未コート紙等のメディアに比べて表面張力が低いため、インク液滴のメディアに対する接触角が大きくなり、インク液滴が着弾した際にメディア上で濡れ広がりにくく、そのためドットが十分に拡張せず、濃度感に欠ける印刷物となる。
　また、水性インクは非吸収性メディアに対して不均一に濡れ広がる傾向があり、均一な濃度のベタ画像部分で、まだら状の模様が発生する。 In industrial applications, the use of non-absorbent media such as coated paper and polyvinyl chloride sheets as well as uncoated paper such as inexpensive plain paper and ordinary offset paper is also being considered as a printing substrate. Yes. Since such media has a lower surface tension than media such as uncoated paper, the contact angle of ink droplets with the media is large, and when ink droplets land, they are difficult to wet and spread on the media. Does not expand sufficiently, resulting in a printed matter lacking in density.
In addition, water-based inks tend to wet and spread non-absorbent media unevenly, and a mottled pattern is generated in a solid image portion having a uniform density.
　このような不具合は印刷物の価値を損なうため、対策が求められている。加えて、本来のインクジェット印刷方式で要求されるインク性能である、保存安定性、ノズル詰りを起こさずに安定して吐出できる吐出安定性、液滴の飛翔性なども備えていなければならない。 Measures are required for such defects to damage the value of printed materials. In addition, the ink performance required in the original ink jet printing method, such as storage stability, ejection stability that allows stable ejection without causing nozzle clogging, and droplet flightability must also be provided.
　非吸収性メディアに対する水性インクの濡れを改善する技術として、インク中に界面活性剤を導入する事が挙げられる。とりわけ、アセチレンジオール系界面活性剤は、他種の界面活性剤と比較して、水性インクジェット用インク組成物の表面張力を低下させ、また、インク液膜をメディア上に均一に形成させる能力に秀でている。このような技術の例は特許文献１、２に挙げられている。
　しかしながら、このような技術を利用しても、ドット拡張性及びベタ部の均一性は不十分であるため、近年更に高まっている印刷品質の要求レベルに達していない。
　また、アセチレンジオール系界面活性剤は、水性インクジェット用インク組成物の表面張力を低下させる効果が高い一方で、水性インクジェット用インク組成物から分離する傾向が強く、保存安定性に対する悪影響が認められる。 As a technique for improving the wetness of the water-based ink with respect to the non-absorbent medium, a surfactant may be introduced into the ink. In particular, acetylenic diol surfactants are superior to other types of surfactants in reducing the surface tension of an aqueous inkjet ink composition and also having the ability to form an ink liquid film uniformly on a medium. It is out. Examples of such techniques are listed in Patent Documents 1 and 2.
However, even if such a technique is used, since the dot expandability and the uniformity of the solid portion are insufficient, the required print quality level that has been increasing in recent years has not been reached.
The acetylenic diol surfactant has a high effect of reducing the surface tension of the aqueous inkjet ink composition, but has a strong tendency to separate from the aqueous inkjet ink composition, and an adverse effect on storage stability is recognized.
　以上のように、水性インクジェット印刷方式で、コート紙やポリ塩化ビニルシート等の非吸収性メディアの利用が検討される中、ドット拡張性に優れ、かつベタ部の均一性に優れ、さらに保存安定性が良好な水性インクジェット用インク組成物を得ることは困難というのが現状である。 As described above, while the use of non-absorbent media such as coated paper and polyvinyl chloride sheet is being studied in the water-based inkjet printing method, it has excellent dot expandability, excellent uniformity of solid parts, and stable storage Under the present circumstances, it is difficult to obtain a water-based inkjet ink composition having good properties.
特開２０１０－８９３７０号JP 2010-89370 A 特開２０１３－１２９７１１号JP 2013-129711 A
　本発明は、保存安定性に優れ、かつ非吸収性メディア（コート紙、ポリ塩化ビニルシート等）に印刷しても、ドット拡張性に優れ、及びベタ部の均一性に優れる水性インクジェット用インク組成物を提供することを課題とする。 The present invention is an aqueous ink-jet ink composition having excellent storage stability and excellent dot expansion even when printed on non-absorptive media (coated paper, polyvinyl chloride sheet, etc.) and excellent uniformity of solid portions. The issue is to provide goods.
　本発明者等は、上記の課題を解決するために鋭意検討した結果、以下の水性インクジェット用インク組成物を発明した。
（１）顔料、アルカリ可溶性樹脂、塩基性化合物、水溶性有機溶剤、界面活性剤Ａ、及び、界面活性剤Ｂ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、界面活性剤ＡがＨＬＢ４～９のアセチレンジオール系界面活性剤であり、界面活性剤Ａの含有量が、水性インクジェット用インク組成物中に０．１～１０質量％であり、界面活性剤ＢがＨＬＢ１３～１６のアセチレンジオール系界面活性剤であり、界面活性剤Ｂの含有量が、水性インクジェット用インク組成物中に０．１～１０質量％である水性インクジェット用インク組成物。
（２）界面活性剤Ａの含有量が、水性インクジェット用インク組成物中に０．２～３質量％である（１）記載のインクジェット用インク組成物。
（３）界面活性剤Ｂの含有量が、水性インクジェット用インク組成物中に０．２～３質量％である（１）又は（２）記載のインクジェット用インク組成物。
（４）水溶性有機溶剤の含有量が、水性インクジェット用インク組成物中に２０～３０質量％である請求項（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。
（５）樹脂エマルションを含んでなる（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。 As a result of intensive studies to solve the above problems, the present inventors have invented the following aqueous ink-jet ink composition.
(1) A water-based inkjet ink composition containing a pigment, an alkali-soluble resin, a basic compound, a water-soluble organic solvent, a surfactant A, and a surfactant B, wherein the surfactant A is HLB 4-9. An acetylenic diol-based surfactant having a surfactant A content of 0.1 to 10% by mass in an aqueous inkjet ink composition and a surfactant B of HLB 13 to 16 An aqueous inkjet ink composition which is an activator and the content of surfactant B is 0.1 to 10% by mass in the aqueous inkjet ink composition.
(2) The inkjet ink composition according to (1), wherein the content of the surfactant A is 0.2 to 3% by mass in the aqueous inkjet ink composition.
(3) The inkjet ink composition according to (1) or (2), wherein the content of the surfactant B is 0.2 to 3% by mass in the aqueous inkjet ink composition.
(4) The aqueous inkjet ink composition according to any one of (1) to (3), wherein the content of the water-soluble organic solvent is 20 to 30% by mass in the aqueous inkjet ink composition.
(5) The aqueous inkjet ink composition according to any one of (1) to (4), comprising a resin emulsion.
　本発明の水性インクジェット用インク組成物によれば、インク組成物自体の保存安定性に優れると共に、非吸収性メディア（コート紙、ポリ塩化ビニルシート等）に印刷しても、ドット拡張性に優れ、かつベタ部の均一性にも優れるという顕著な効果を発揮することができる。 According to the aqueous inkjet ink composition of the present invention, the ink composition itself is excellent in storage stability and excellent in dot expandability even when printed on non-absorbent media (coated paper, polyvinyl chloride sheet, etc.). And the remarkable effect that it is excellent also in the uniformity of a solid part can be exhibited.
　本発明者等は、特にＨＬＢが４～９と低いアセチレンジオール系界面活性剤、及びＨＬＢが１３～１６と高いアセチレンジオール系界面活性剤の双方を水性インクジェット用インクに含有させることにより、新規の水性インクジェット用インク組成物を開発した。 The inventors of the present invention have made it possible to add a novel acetylenic diol surfactant having a low HLB of 4 to 9 and an acetylenic diol surfactant having a high HLB of 13 to 16 to the aqueous inkjet ink. A water-based inkjet ink composition was developed.
　本発明によると、印刷時においてインクがメディアの表面に着弾後、ＨＬＢが低いアセチレンジオール系界面活性剤により低下されたインクの表面張力を反映して、インク液滴のメディア表面に対する接触角を低下させてメディア表面への濡れを促進し、ドットを十分に拡張させる。さらに、ＨＬＢが高いアセチレンジオール系界面活性剤により、インク液滴をメディア上で均一に濡れ広がらせ、ベタ画像部分で均一なベタを形成する。
　さらに、ＨＬＢが高いアセチレンジオール系界面活性剤は、ＨＬＢが低いアセチレンジオール系界面活性剤と水性インクジェット用インク組成物を相溶させる機能を持ち、両者が分離することを抑制する。
　このような機構により、上記課題を解決し得ることを見出し、本発明を完成するに至ったものである。 According to the present invention, after the ink has landed on the surface of the medium during printing, the contact angle of the ink droplet with respect to the medium surface is reduced, reflecting the surface tension of the ink that has been reduced by the acetylenic diol surfactant having a low HLB. To promote wetting on the media surface and to fully expand the dots. Further, the acetylene diol surfactant having a high HLB causes the ink droplets to uniformly spread on the medium and form a uniform solid in the solid image portion.
Furthermore, the acetylene diol surfactant having a high HLB has a function of making the acetylene diol surfactant having a low HLB compatible with the aqueous inkjet ink composition, and suppresses the separation of the two.
The inventors have found that the above-described problems can be solved by such a mechanism, and have completed the present invention.
　上記ＨＬＢは、界面活性剤の分野で利用されている分子の親水性部分と疎水性部分のバランス（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ  Ｂａｌａｎｃｅ）を表すものであり、０から２０までの値を有し、ＨＬＢの数値が大きいものほど親水性が高いと言える。本発明では、以下のグリフィンの式により定義されるＨＬＢ値を用いている。
［グリフィンの式］
ＨＬＢ＝２０×界面活性剤中の親水部の式量の総和／界面活性剤の分子量 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, It can be said that the larger the value, the higher the hydrophilicity. In the present invention, the HLB value defined by the following Griffin equation is used.
[Griffin formula]
HLB = 20 × total formula weight of hydrophilic part in surfactant / molecular weight of surfactant
　以下、本発明の水性インクジェット用インク組成物について、その成分毎に具体的に説明する。
（顔料）
　上記顔料としては、一般にインクジェット用インクで使用される各種の無機顔料や有機顔料を挙げることができる。具体的には、上記無機顔料としては、酸化チタン、ベンガラ、アンチモンレッド、カドミニウムイエロー、コバルトブルー、群青、紺青、カーボンブラック、黒鉛等の有色顔料（白色、黒色等の無彩色の着色顔料も含める）、及び、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルク等の体質顔料を挙げることができる。上記有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。これらは単独で用いてもよく、２種以上を併用してもよい。
　また、上記顔料としては、特に、鮮明な色相の表現を可能とする点から、具体的には、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ  Ｒｅｄ　５、７、１２、５７：１、１２２、１４６、２０２、２８２等の赤色系顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ  Ｂｌｕｅ  １、２、１５：３、１５：４、１６、１７、６０等の青色系顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ  Ｖｉｏｌｅｔ  １９等の紫色系顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ  Ｙｅｌｌｏｗ　１２、１３、１４、１７、７４、８３、９３、１２８、１３９、１５１、１５４、１５５、１８０、１８５、２１３等の黄色系顔料；Ｃ．Ｉ．Ｂｌａｃｋ  ７（カーボンブラック）等が好ましい。 Hereinafter, the water-based inkjet ink composition of the present invention will be specifically described for each component.
(Pigment)
Examples of the pigment include various inorganic pigments and organic pigments that are generally used in ink jet inks. Specifically, the inorganic pigment includes colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, ultramarine blue, bitumen, carbon black, and graphite (achromatic colored pigments such as white and black). And extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. Examples of the organic pigment 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, 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; I. Pigment Yellow 12, 13, 14, 17, 74, 83, 93, 128, 139, 151, 154, 155, 180, 185, 213 and the like yellow pigments; C.I. I. Black 7 (carbon black) and the like are preferable.
　なお、本発明においては、顔料として、顔料粒子の表面に極性官能基を化学反応で導入した自己分散顔料、顔料をポリマー粒子で被覆した被覆型顔料粒子も使用可能である。尚、上記自己分散顔料、被覆型顔料粒子以外の顔料を使用する場合は、後述するアルカリ可溶性樹脂及び塩基性化合物を使用して顔料分散用樹脂とし、水性媒体中に顔料を分散させるとよい。
　本発明の水性インクジェット用インク組成物中の上記顔料の含有量は、１～１０質量％であることが好ましく、２～６質量％であることがより好ましい。 In the present invention, self-dispersed pigments in which polar functional groups are introduced by chemical reaction on the surface of the pigment particles, and coated pigment particles in which the pigment is coated with polymer particles can also be used as the pigment. In the case of using a pigment other than the self-dispersed pigment and the coated pigment particles, an alkali-soluble resin and a basic compound, which will be described later, may be used as a pigment dispersion resin, and the pigment may be dispersed in an aqueous medium.
The content of the pigment in the aqueous inkjet ink composition of the present invention is preferably 1 to 10% by mass, and more preferably 2 to 6% by mass.
（アルカリ可溶性樹脂）
　上記アルカリ可溶性樹脂としては、通常のインクや塗料の顔料分散用として使用されている、塩基性化合物の存在下で水性媒体に可溶の共重合体樹脂が利用できる。
　このようなアルカリ可溶性樹脂としては、例えば、カルボキシル基を有する単量体、好ましくは、顔料との吸着性を向上させるための疎水性基を含有する単量体との共重合体、あるいはこれらの単量体と必要に応じて他の重合可能な単量体と共に反応させて得られる共重合体を利用できる。
　上記カルボキシル基を有する単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマール酸、２－カルボキシエチル（メタ）アクリレート、２－カルボキシプロピル（メタ）アクリレート、無水マレイン酸、マレイン酸モノアルキルエステル、シトラコン酸、無水シトラコン酸、シトラコン酸モノアルキルエステル等が挙げられる。 (Alkali-soluble resin)
As the alkali-soluble resin, a copolymer resin that is used for dispersing pigments in ordinary inks and paints and is soluble in an aqueous medium in the presence of a basic compound can be used.
As such an alkali-soluble resin, for example, a monomer having a carboxyl group, preferably a copolymer with a monomer containing a hydrophobic group for improving the adsorptivity with a pigment, or these A copolymer obtained by reacting the monomer with other polymerizable monomer as required can be used.
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, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, citraconic acid monoalkyl ester and the like can be mentioned.
　また、上記顔料との吸着性を向上させるための疎水性基を含有する単量体としては、例えば、長鎖アルキル基を有する単量体として、（メタ）アクリル酸等のラジカル重合性不飽和カルボン酸の炭素数が８以上のアルキルエステル類（例えば、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシステアリル（メタ）アクリレート等）、炭素数が８以上のアルキルビニルエーテル類（例えば、ドデシルビニルエーテルなど）、炭素数が８以上の脂肪酸のビニルエステル類（例えば、ビニル２－エチルヘキサノエート、ビニルラウレート、ビニルステアレートなど）、脂環族炭化水素基を有する単量体として、シクロヘキシル(メタ)アクリレート等、芳香族炭化水素基を有する単量体として、ベンジル（メタ）アクリレート、スチレン、α－スチレン、ビニルトルエン等のスチレン系単量体等が挙げられる。 Moreover, as a monomer containing a hydrophobic group for improving the adsorptivity with the pigment, for example, as a monomer having a long chain alkyl group, a radical polymerizable unsaturated such as (meth) acrylic acid Alkyl esters having 8 or more carbon atoms of carboxylic acid (for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxystearyl (meth) acrylate, etc.) ), Alkyl vinyl ethers having 8 or more carbon atoms (for example, dodecyl vinyl ether), vinyl esters of fatty acids having 8 or more carbon atoms (for example, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, etc.) As a monomer having an alicyclic hydrocarbon group, cyclohexyl (meth) Acrylate and the like, as the monomer having an aromatic hydrocarbon group, benzyl (meth) acrylate, styrene, alpha-styrene, and a styrene monomer such as vinyltoluene.
　また、上記必要に応じて使用する他の重合可能な単量体としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシルなどの（メタ）アクリル酸、（メタ）アクリル酸ヒドロキシエチル、アクリルアミド、Ｎ－メチロールアクリルアミド等が挙げられる。
  上記の単量体を共重合して得られるアルカリ可溶性樹脂において、水性媒体中への樹脂の溶解性向上及び印刷物の耐水性の低下防止を考慮する場合には、ガラス転移温度１０～５０℃、酸価１００～３００ｍｇＫＯＨ／ｇ、重量平均分子量が１０，０００～５０，０００である。アルカリ可溶性樹脂の酸価が１００ｍｇＫＯＨ／ｇ未満の場合は水性媒体中への樹脂の溶解性が低下する傾向があり、一方３００ｍｇＫＯＨ／ｇを超えると得られる印刷物の耐水性が低下する傾向がある。 In addition, other polymerizable monomers used as necessary include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) (Meth) acrylic acid such as butyl acrylate and hexyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-methylolacrylamide and the like.
In the alkali-soluble resin obtained by copolymerizing the above monomers, when considering improvement of the solubility of the resin in an aqueous medium and prevention of reduction in water resistance of the printed matter, a glass transition temperature of 10 to 50 ° C., The acid value is 100 to 300 mg KOH / g, and the weight average molecular weight is 10,000 to 50,000. When the acid value of the alkali-soluble resin is less than 100 mgKOH / g, the solubility of the resin in an aqueous medium tends to decrease, whereas when it exceeds 300 mgKOH / g, the water resistance of the obtained printed matter tends to decrease.
　また、印刷物の耐ブロッキング性の向上及び耐折り曲げ性の向上を図る場合には、アルカリ可溶性樹脂のガラス転移温度が１０～５０℃であることが好ましく、２０～４５℃であることがさらに好ましい。アルカリ可溶性樹脂のガラス転移温度が１０℃未満の場合は得られる印刷物の耐ブロッキング性が低下する傾向があり、一方５０℃を超えると耐折り曲げ性が低下する傾向がある。 In order to improve the blocking resistance and the bending resistance of the printed matter, the glass transition temperature of the alkali-soluble resin is preferably 10 to 50 ° C., more preferably 20 to 45 ° C. When the glass transition temperature of the alkali-soluble resin is less than 10 ° C., the blocking resistance of the obtained printed matter tends to be lowered, whereas when it exceeds 50 ° C., the bending resistance tends to be lowered.
　さらに、印刷物の耐擦過性をさらに向上させ、かつ顔料の分散性の向上を図る場合には、アルカリ可溶性樹脂の重量平均分子量を１０，０００～５０，０００とすることが好ましく、２０，０００～３０，０００とすることがさらに好ましい。
　アルカリ可溶性樹脂の重量平均分子量が１０，０００未満の場合には顔料の分散安定性や得られる印刷物の耐擦過性が低下する傾向にあり、一方５０，０００を超えると、粘度が高くなるため好ましくない。
　上記アルカリ可溶性樹脂の含有量は、水性インクジェット用インク組成物に含まれる顔料１００質量部に対して１０～６０質量部であることが好ましく、１５～５０質量部であることがさらに好ましい。アルカリ可溶性樹脂の含有量が上記の範囲より少ない場合は、水性媒体への顔料の分散性が低下する傾向にある。一方、上記の範囲を超える場合は、粘度が高くなるため好ましくない。 Furthermore, in order to further improve the scratch resistance of the printed matter and improve the dispersibility of the pigment, the alkali-soluble resin preferably has a weight average molecular weight of 10,000 to 50,000, preferably 20,000 to More preferably, it is 30,000.
When the weight average molecular weight of the alkali-soluble resin is less than 10,000, the dispersion stability of the pigment and the scratch resistance of the resulting printed matter tend to be reduced. On the other hand, when the weight average molecular weight exceeds 50,000, the viscosity is preferably increased. Absent.
The content of the alkali-soluble resin is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the aqueous inkjet ink composition. When the content of the alkali-soluble resin is less than the above range, the dispersibility of the pigment in the aqueous medium tends to decrease. On the other hand, exceeding the above range is not preferable because the viscosity increases.
　ここで、上記したアルカリ可溶性樹脂のガラス転移温度、酸価、及び重量平均分子量は、以下の方法により求めることができる。
＜ガラス転移温度＞
　ガラス転移温度は、下記のＷｏｏｄの式により求めた理論上のガラス転移温度である。
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。） Here, the glass transition temperature, acid value, and weight average molecular weight of the alkali-soluble resin described above can be determined by the following method.
<Glass transition temperature>
The glass transition temperature is a theoretical glass transition temperature obtained by the following Wood formula.
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 Wood's formula is an absolute temperature).
＜酸価＞
　酸価は、アルカリ可溶性樹脂を合成するために用いる単量体の組成に基づいて、アルカリ可溶性樹脂１ｇを中和するのに理論上要する水酸化カリウムのｍｇ数を算術的に求めた理論酸価である。 <Acid value>
The acid value is a theoretical acid value 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 monomer used for synthesizing the alkali-soluble resin. It is.
＜重量平均分子量＞
　重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）法によって測定することができる。一例として、ＧＰＣ装置としてＷａｔｅｒ  ２６９０（ウォーターズ社製）、カラムとしてＰＬｇｅｌ  ５μ  ＭＩＸＥＤ－Ｄ（Ｐｏｌｙｍｅｒ　Ｌａｂｏｒａｔｏｒｉｅｓ社製）を使用してクロマトグラフィーを行ない、ポリスチレン換算の重量平均分子量として求めることができる。 <Weight average molecular weight>
The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. As an example, chromatography is performed using Water 2690 (manufactured by Waters) as a GPC apparatus and PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) as a column, and the weight average molecular weight in terms of polystyrene can be obtained.
（塩基性化合物）
　本発明にて使用される塩基性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、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を挙げることができる。これらは単独で用いてもよく、２種以上を併用してもよい。 (Basic compound)
Specific examples of the basic compound used in the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, methylamine, ethylamine, monoethanolamine, N, N-dimethylethanolamine, N, Examples thereof include organic basic compounds such as N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. These may be used alone or in combination of two or more.
（水性媒体）
　本発明の水性インクジェット用インク組成物で使用する水性媒体としては、水及び水溶性有機溶剤から構成される水性媒体を挙げることができる。
　上記水としては、金属イオン等を除去したイオン交換水ないし蒸留水が好ましい。
　また、水溶性有機溶剤を含有させることにより、保存安定性、吐出安定性、インクの飛翔性等で、より優れたインクジェット印刷適性を付与することができる場合がある。このような水溶性有機溶剤としては、例えば、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、ケトン類、エーテル類、エステル類、窒素含有化合物類等を挙げることができる。これらは単独で用いてもよく、２種以上を併用してもよい。 (Aqueous medium)
Examples of the aqueous medium used in the aqueous inkjet ink composition of the present invention include an aqueous medium composed of water and a water-soluble organic solvent.
The water is preferably ion-exchanged water or distilled water from which metal ions or the like have been removed.
Further, by including 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.
　上記モノアルコール類の具体例としては、メタノール、エタノール、ｎ－プロパノール、ｎ－ブタノール、ｎ－ペンタノール、ｎ－ヘキサノール、ｎ－ヘプタノール、ｎ－オクタノール、ｎ－ノニルアルコール、ｎ－デカノール、またはこれらの異性体、シクロペンタノール、シクロヘキサノール等が挙げられ、好ましくはアルキル基の炭素数が１～６のアルコールである。 Specific examples of 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.
　上記多価アルコールの具体例としては、エチレングリコール、プロピレングリコール、１，３－ブチレングリコール、１，４－ブチレングリコール、１，２－ペンタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、１，２－シクロヘキサンジオール、ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、グリセリン、ペンタエリスリトール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール等が挙げられる。 Specific examples of the polyhydric alcohol 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, Examples include dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and thiodiglycol.
　上記多価アルコールの低級アルキルエーテル類の具体例としては、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル等が挙げられる。 Specific examples of the 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. , Ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropiate Glycol mono -n- butyl ether.
　上記ケトン類の具体例としては、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、ジイソプロピルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
　上記エーテル類の具体例としては、イソプロピルエーテル、ｎ－ブチルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン等が挙げられる。
　上記エステル類の例としては、プロピレンカルボネート、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル、乳酸エチル、酪酸エチル、ジブチルフタレート、ジオクチルフタレート、及びε－カプロラクトン、ε－カプロラクタム等の環状エステル等が挙げられる。
　上記窒素含有化合物の例としては、尿素、ピロリドン、Ｎ－メチル－２－ピロリドン、オクチルピロリドン等が挙げられる。
　上記水溶性有機溶剤の含有量は、水性インクジェット用インク組成物中２０～３０質量％が好ましい。 Specific examples of the ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
Specific examples of the ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
Examples of the 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 ε-caprolactone, and cyclic esters such as ε-caprolactam.
Examples of the nitrogen-containing compound include urea, pyrrolidone, N-methyl-2-pyrrolidone, octyl pyrrolidone and the like.
The content of the water-soluble organic solvent is preferably 20 to 30% by mass in the aqueous inkjet ink composition.
（界面活性剤）
　本発明にて使用される界面活性剤Ａとしては、エアープロダクツ社製のサーフィノール１０４Ｅ、サーフィノール１０４Ｈ、サーフィノール１０４Ａ、サーフィノール１０４ＢＣ、サーフィノール１０４ＤＰＭ、サーフィノール１０４ＰＡ、サーフィノール１０４ＰＧ－５０、サーフィノール４２０、サーフィノール４４０、日信化学工業社製のオルフィンＥ１００４等が挙げられる。
　上記界面活性剤Ａの含有量は、水性インクジェット用インク組成物中０．１～１０質量％であることが好ましく、０．２～３質量％であることがさらに好ましく、０．４～３質量％であることがより好ましい。界面活性剤Ａの含有量が０．１質量％未満の場合はドット拡張性が悪化する傾向にあり、一方１０質量％を超える場合はインクの保存安定性が悪化する傾向にあるので好ましくない。 (Surfactant)
Surfactant A used in the present invention includes Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfynol manufactured by Air Products. Nord 420, Surfynol 440, Orphine E1004 manufactured by Nissin Chemical Industry Co., Ltd. and the like.
The content of the surfactant A is preferably 0.1 to 10% by mass, more preferably 0.2 to 3% by mass, and more preferably 0.4 to 3% by mass in the aqueous inkjet ink composition. % Is more preferable. When the content of the surfactant A is less than 0.1% by mass, the dot expandability tends to deteriorate, whereas when it exceeds 10% by mass, the storage stability of the ink tends to deteriorate, such being undesirable.
　本発明にて使用される界面活性剤Ｂの例としては、エアープロダクツ社製のサーフィノール４６５、日信化学工業社製のオルフィンＥ１０１０、オルフィンＥ１０２０等が挙げられる。
　上記界面活性剤Ｂの含有量は、水性インクジェット用インク組成物中０．１～１０質量％であることが好ましく、０．２～３質量％であることがさらに好ましく、０．４～３質量％であることがより好ましい。界面活性剤Ｂの含有量が０．１質量％未満の場合はインクの保存安定性及び印刷物のベタ均一性が低下する傾向にあり、一方１０質量％を超える場合はインクの保存安定性が悪化する傾向にあるので好ましくない。 Examples of the surfactant B used in the present invention include Surfynol 465 manufactured by Air Products, Olphine E1010, Olphine E1020 manufactured by Nissin Chemical Industry, and the like.
The content of the surfactant B is preferably 0.1 to 10% by mass, more preferably 0.2 to 3% by mass, and more preferably 0.4 to 3% by mass in the aqueous inkjet ink composition. % Is more preferable. When the content of the surfactant B is less than 0.1% by mass, the storage stability of the ink and the solid uniformity of the printed matter tend to be reduced. On the other hand, when the content exceeds 10% by mass, the storage stability of the ink is deteriorated. This is not preferable.
（樹脂エマルション）
　上記樹脂エマルションの例としては、アクリル系樹脂エマルション、スチレン－アクリル系樹脂エマルション、ポリエステル系樹脂エマルション、ポリウレタン系樹脂エマルション、ポリ酢酸ビニル系樹脂エマルション、ポリ塩化ビニル系樹脂エマルション、ポリブタジエン系樹脂エマルション、ポリエチレン系樹脂エマルション等が挙げられる。中でも、得られる印刷物の外観及び各種耐性に優れる事から、スチレン－アクリル系樹脂エマルションが好ましい。
　上記樹脂エマルションの含有量は、インクジェット用インク組成物中、固形分として１～１０質量％であることが好ましく、２～５質量％であることがさらに好ましい。
　樹脂エマルションの含有量が固形分として１質量％未満の場合は、得られる印刷物の外観及び各種耐性が低下する傾向にあり、一方１０質量％を超える場合はインクの吐出が不安定になる傾向にあるので好ましくない。 (Resin emulsion)
Examples of the resin emulsion include acrylic resin emulsion, styrene-acrylic resin emulsion, polyester resin emulsion, polyurethane resin emulsion, polyvinyl acetate resin emulsion, polyvinyl chloride resin emulsion, polybutadiene resin emulsion, polyethylene Resin emulsions and the like. 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 ink-jet ink composition.
When 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. On the other hand, when it exceeds 10% by mass, the ink ejection tends to be unstable. This is not preferable.
（添加剤）
　さらに、本発明の水性インクジェット用インク組成物には、目的に応じて公知の顔料分散剤、防黴剤、防錆剤、増粘剤、酸化防止剤、紫外線吸収剤、保存性向上剤、消泡剤、ＰＨ調整剤等の添加剤も添加することもできる。 (Additive)
Furthermore, the water-based inkjet ink composition of the present invention includes known pigment dispersants, antifungal agents, rust preventives, thickeners, antioxidants, ultraviolet absorbers, preservability improvers, antiseptics depending on the purpose. Additives such as foaming agents and pH adjusting agents can also be added.
［水性インクジェット用インク組成物の製造方法］
　以上の構成成分を用いて本発明の水性インクジェット用インク組成物を製造する方法としては、
（１）顔料、塩基性化合物の存在下にアルカリ可溶性樹脂を水中に溶解した水性樹脂ワニス、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を分散し、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（以下、製造方法１と記載する）、
（２）上記の方法で顔料を分散した後、酸析法や再公表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（以下、製造方法２と記載する）等を挙げることができる。
　中でも、水性インクジェット用インク組成物の保存安定性が更に良好になることから製造方法（２）が好ましい。
　このようにして得られた本発明の水性インクジェット用インク組成物は製造後の初期粘度が２．０～１０．０ｍｍＰａ・ｓ、好ましくは３．０～７．０ｍｍＰａ・ｓの範囲とする。 [Method for producing aqueous ink-jet ink composition]
As a method for producing the aqueous inkjet ink composition of the present invention using the above components,
(1) An aqueous resin varnish in which an alkali-soluble resin is dissolved in water in the presence of a pigment and a basic compound, and a pigment dispersant as necessary are mixed, and then various dispersing machines such as a ball mill, an attritor, a roll mill, and a sand mill. , A method of dispersing a pigment using an agitator mill or the like, and further adding the remaining materials to prepare an aqueous inkjet ink composition (hereinafter referred to as production method 1),
(2) After dispersing the pigment by the above-described method, a resin-coated pigment in which an alkali-soluble resin is precipitated on the pigment surface is obtained by an acid precipitation method or ion exchange means described in the republished WO 2005/116147, The resulting resin-coated pigment is neutralized with a basic compound, re-dispersed in water using various dispersers (such as a high-speed stirring device), and the remaining materials are added to prepare an aqueous ink-jet ink composition. And the like (hereinafter referred to as production method 2).
Among these, the production method (2) is preferable because the storage stability of the aqueous inkjet ink composition is further improved.
The thus obtained aqueous inkjet ink composition of the present invention has an initial viscosity after production of 2.0 to 10.0 mmPa · s, preferably 3.0 to 7.0 mmPa · s.
［印刷方法］
　次に、本発明の水性インクジェット用インク組成物を用いた印刷方法について説明する。
　本発明の水性インクジェット用インク組成物の印刷用メディアとしては、アート紙、インクジェット専用紙、インクジェット光沢紙等のコート紙、ポリ塩化ビニルシートのようなプラスチック系基材等の他、普通紙やオフセット紙等の未コート紙も利用できる。
　そして、例えば、本発明の上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、ノズルから上記印刷用基材へ噴射することによりインクジェット印刷をすることができる。 [Printing method]
Next, a printing method using the aqueous inkjet ink composition of the present invention will be described.
Examples of the printing medium for the aqueous ink-jet ink composition of the present invention include art paper, ink-jet exclusive paper, coated paper such as ink-jet glossy paper, plastic base materials such as polyvinyl chloride sheets, plain paper, and offset. Uncoated paper such as paper can also be used.
Then, for example, the water-based inkjet ink composition of the present invention is accommodated in an ink cartridge, the ink cartridge is mounted on a single-pass inkjet recording apparatus, and ejected from the nozzle onto the printing substrate. Thus, inkjet printing can be performed.
　以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味する
ものである。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples. Note that “%” means “mass%” unless otherwise specified.
＜水性樹脂ワニス＞
　ガラス転移温度４０℃、重量平均分子量３０，０００、酸価１８５ｍｇＫＯＨ／ｇの、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、固形分２０％の水性樹脂ワニスを得た。 <Water-based resin varnish>
20 parts by mass of an acrylic acid / n-butyl acrylate / benzyl methacrylate / styrene copolymer having a glass transition temperature of 40 ° C., a weight average molecular weight of 30,000 and an acid value of 185 mg KOH / g, 2.5 parts by mass of potassium hydroxide and 77% water It was dissolved in a mixed solution with 5 parts by mass to obtain an aqueous resin varnish having a solid content of 20%.
＜水性ブラックインクベースの調製＞
　上記水性樹脂ワニスの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。このワニスに、更にカーボンブラック（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、水性ブラックインクベースを調製した。 <Preparation of aqueous black ink base>
64.3 parts by mass of water was added to 23.7 parts by mass of the aqueous resin varnish and mixed to prepare a resin varnish for pigment dispersion. To this varnish, 12 parts by mass of carbon black (trade name Printex 90, manufactured by Degussa) was added, mixed with stirring, and then kneaded with a wet circulation mill to prepare an aqueous black ink base.
＜水性イエローインクベースの調製＞
　上記水性樹脂ワニスの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。このワニスに、更にイエロー顔料（商品名ノバパームイエロー４Ｇ０１、クラリアント社製）の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、水性イエローインクベースを調製した。 <Preparation of aqueous yellow ink base>
64.3 parts by mass of water was added to 23.7 parts by mass of the aqueous resin varnish and mixed to prepare a resin varnish for pigment dispersion. To this varnish, 12 parts by mass of a yellow pigment (trade name Nova Palm Yellow 4G01, manufactured by Clariant) was further added, stirred and mixed, and then kneaded with a wet circulation mill to prepare an aqueous yellow ink base.
＜水性マゼンタインクベースの調製＞
　上記水性樹脂ワニスの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。このワニスに、更にマゼンタ顔料（商品名インクジェットマゼンタＥ５Ｂ０２、クラリアント社製）の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、水性マゼンタインクベースを調製した。 <Preparation of aqueous magenta ink base>
64.3 parts by mass of water was added to 23.7 parts by mass of the aqueous resin varnish and mixed to prepare a resin varnish for pigment dispersion. To this varnish was further added 12 parts by mass of a magenta pigment (trade name Inkjet Magenta E5B02, manufactured by Clariant), mixed with stirring, and then kneaded with a wet circulation mill to prepare an aqueous magenta ink base.
＜水性シアンインクベースの調製＞
　上記水性樹脂ワニスの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。このワニスに、更にシアン顔料（商品名ヘリオゲンブルーＬ７１０１Ｆ、ＢＡＳＦ社製）の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、水性シアンインクベースを調製した。 <Preparation of aqueous cyan ink base>
64.3 parts by mass of water was added to 23.7 parts by mass of the aqueous resin varnish and mixed to prepare a resin varnish for pigment dispersion. To this varnish, 12 parts by mass of a cyan pigment (trade name Heliogen Blue L7101F, manufactured by BASF) was further added, stirred and mixed, and then kneaded with a wet circulation mill to prepare an aqueous cyan ink base.
＜界面活性剤Ａ＞
　サーフィノール４２０（固形分１００％、ＨＬＢ４、エアープロダクツ社製）
　オルフィンＥ１００４（固形分１００％、ＨＬＢ７～９、日信化学社製） <Surfactant A>
Surfynol 420 (solid content 100%, HLB4, manufactured by Air Products)
Orphin E1004 (100% solids, HLB7-9, manufactured by Nissin Chemical)
＜界面活性剤Ｂ＞
　オルフィンＥ１０１０（固形分１００％、ＨＬＢ１３～１４、日信化学社製）
　オルフィンＥ１０２０（固形分１００％、ＨＬＢ１５～１６、日信化学社製） <Surfactant B>
Orphin E1010 (solid content 100%, HLB13-14, manufactured by Nissin Chemical)
Olfine E1020 (100% solid content, HLB15-16, manufactured by Nissin Chemical)
＜樹脂エマルション＞
　ネオクリルＡ－１０９１（固形分４５％、スチレン－アクリル系エマルション、ＤＳＭ　Ｎｅｏｒｅｓｉｎｓ社製） <Resin emulsion>
Neocryl A-1091 (45% solids, styrene-acrylic emulsion, manufactured by DSM Neoresins)
＜実施例１～１１、比較例１～７の水性インクジェット用インク組成物＞
　表１の質量割合となるように、上記水性各色インクベース、上記界面活性剤、上記エマルション、水溶性有機溶剤としてのプロピレングリコール、及び、水を攪拌混合して、実施例１～１１、比較例１～７の水性インクジェット用インク組成物を得た。 <Water-based inkjet ink compositions of Examples 1 to 11 and Comparative Examples 1 to 7>
Examples 1 to 11 and Comparative Examples were prepared by stirring and mixing the water-based color ink base, the surfactant, the emulsion, propylene glycol as a water-soluble organic solvent, and water so that the mass ratios shown in Table 1 were obtained. 1 to 7 aqueous inkjet ink compositions were obtained.
＜水性インクジェット用インク組成物の印刷評価＞
　以下の評価方法により評価し、それらの結果を表１に示す。
（保存安定性）
　実施例１～１１、比較例１～７の水性インクジェット用インク組成物をガラス瓶に充填し、２３℃で１日間静置した後、水性インクジェット用インク組成物の分離状態を観察して、保存安定性を評価した。
　評価基準
　○：液相の分離がなく、均一であるもの
　×：液相の分離が認められる、不均一なもの <Printing evaluation of water-based inkjet ink composition>
Evaluation was performed by the following evaluation methods, and the results are shown in Table 1.
(Storage stability)
The water-based inkjet ink compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were filled in a glass bottle and allowed to stand at 23 ° C. for 1 day. Sex was evaluated.
Evaluation criteria ○: There is no separation of the liquid phase and it is uniform. ×: The separation of the liquid phase is observed and it is non-uniform.
（ドット拡張性）
　実施例１～１１、比較例１～７の水性インクジェット用インク組成物の２μＬをＯＫトップコート＋紙（王子製紙社製）の上に滴下して、２３℃において接触角計ＤＭ７０１（協和界面科学社製）を用いて接触角を測定して、ドット拡張性を評価した。
　評価基準
　○：接触角が１６°以下のもの
　△：接触角が１６°を超えるが２０°以下のもの
　×：接触角が２０°を超えるもの (Dot extensibility)
2 μL of the aqueous ink-jet ink compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were dropped on an OK top coat + paper (manufactured by Oji Paper Co., Ltd.) and contact angle meter DM701 (Kyowa Interface Science) at 23 ° C. The contact angle was measured using a product manufactured by Kogyo Co., Ltd. to evaluate dot expandability.
Evaluation criteria ○: Contact angle of 16 ° or less △: Contact angle exceeding 16 ° but 20 ° or less ×: Contact angle exceeding 20 °
（ベタ均一性）
　実施例１～１１、比較例１～７の水性インクジェット用インク組成物を、０．１ｍｍワイヤーバーを用いてＯＫトップコート紙（王子製紙社製）に展色して、展色面の均一性を評価した。
　評価基準
　○：展色面が均一なもの
　△：展色面がやや不均一なもの
　×：展色面が不均一であり、まだら模様が認められるもの (Solid uniformity)
The aqueous ink-jet ink compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were developed on OK top coat paper (manufactured by Oji Paper Co., Ltd.) using a 0.1 mm wire bar, and the uniformity of the color development surface Evaluated.
Evaluation criteria ○: Uniform color surface △: Non-uniform color surface ×: Non-uniform color surface and mottled pattern
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
　実施例１～１１の結果によると、本発明の水性インクジェット用インク組成物は、保存安定性、ドット拡張性、及びベタ均一性が良好であり、顔料の種類に影響されず安定した性質を有することが分かる。
　比較例１では、界面活性剤Ａとしてサーフィノール４２０のみを使用した場合には、ドット拡張性及びベタ均一性が不十分であった。
　そこで、比較例２として、比較例１においてサーフィノール４２０を増量すると、かえって保存安定性が損なわれた。
　比較例３では、界面活性剤ＡとしてオルフィンＥ１００４のみを使用した場合、比較例１と同様にドット拡張性及びベタ均一性が不十分であった。
　比較例４では、界面活性剤ＢとしてオルフィンＥ１０１０のみを使用した場合、保存安定性とベタ均一性が良好であるが、ドットが拡張しない結果であった。
　比較例５では、界面活性剤Ａとしてサーフィノール４２０とオルフィンＥ１００４を併用した場合には、保存安定性とドット拡張性が良好であるが、ベタ均一性が不十分であった。
　比較例６及び７では、界面活性剤ＡまたはＢを過剰に含有すると、いずれの場合でも保存安定性が損なわれた。 According to the results of Examples 1 to 11, the water-based inkjet ink composition of the present invention has good storage stability, dot expandability, and solid uniformity, and has stable properties regardless of the type of pigment. I understand that.
In Comparative Example 1, when only Surfynol 420 was used as the surfactant A, dot expandability and solid uniformity were insufficient.
Therefore, as Comparative Example 2, when the amount of Surfynol 420 was increased in Comparative Example 1, the storage stability was impaired.
In Comparative Example 3, when only Olfine E1004 was used as the surfactant A, the dot expandability and the solid uniformity were insufficient as in Comparative Example 1.
In Comparative Example 4, when only Olfine E1010 was used as surfactant B, the storage stability and solid uniformity were good, but the dots did not expand.
In Comparative Example 5, when Surfynol 420 and Olphine E1004 were used in combination as surfactant A, the storage stability and dot expandability were good, but the solid uniformity was insufficient.
In Comparative Examples 6 and 7, when the surfactant A or B was excessively contained, the storage stability was impaired in any case.

Claims (5)

  1. 　顔料、アルカリ可溶性樹脂、塩基性化合物、水溶性有機溶剤、界面活性剤Ａ、及び、界面活性剤Ｂ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、界面活性剤ＡがＨＬＢ４～９のアセチレンジオール系界面活性剤であり、界面活性剤Ａの含有量が、水性インクジェット用インク組成物中に０．１～１０質量％であり、界面活性剤ＢがＨＬＢ１３～１６のアセチレンジオール系界面活性剤であり、界面活性剤Ｂの含有量が、水性インクジェット用インク組成物中に０．１～１０質量％である水性インクジェット用インク組成物。 Aqueous inkjet ink composition comprising a pigment, an alkali-soluble resin, a basic compound, a water-soluble organic solvent, a surfactant A, and a surfactant B, wherein the surfactant A is acetylene diol having HLB 4 to 9 Is an acetylenic diol surfactant having an HLB of 13 to 16 and a surfactant B of 0.1 to 10% by mass in the aqueous inkjet ink composition. A water-based inkjet ink composition having a surfactant B content of 0.1 to 10% by mass in the water-based inkjet ink composition.
  2. 　界面活性剤Ａの含有量が、水性インクジェット用インク組成物中に０．２～３質量％である請求項１記載のインクジェット用インク組成物。 The inkjet ink composition according to claim 1, wherein the content of the surfactant A is 0.2 to 3% by mass in the aqueous inkjet ink composition.
  3. 　界面活性剤Ｂの含有量が、水性インクジェット用インク組成物中に０．２～３質量％である請求項１又は２記載のインクジェット用インク組成物。 The inkjet ink composition according to claim 1 or 2, wherein the content of the surfactant B is 0.2 to 3% by mass in the aqueous inkjet ink composition.
  4. 　水溶性有機溶剤の含有量が、水性インクジェット用インク組成物中に２０～３０質量％である請求項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。 4. The aqueous inkjet ink composition according to claim 1, wherein the content of the water-soluble organic solvent is 20 to 30% by mass in the aqueous inkjet ink composition.
  5. 　樹脂エマルションを含んでなる請求項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。 The water-based inkjet ink composition according to any one of claims 1 to 4, comprising a resin emulsion.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131479A1 (en) * 2017-12-28 2019-07-04 花王株式会社 Aqueous ink for inkjet recording
CN112739783A (en) * 2018-10-15 2021-04-30 Dic株式会社 Water-based ink, ink for inkjet recording, printed matter, and method for producing printed matter

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6952208B1 (en) * 2020-09-28 2021-10-20 サカタインクス株式会社 Aqueous inkjet ink compositions, printed matter, and inkjet printing methods
JP2023019633A (en) * 2021-07-29 2023-02-09 株式会社Ｓｃｒｅｅｎホールディングス Aqueous ink composition for inkjet

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033602A1 (en) * 2001-10-18 2003-04-24 Seiko Epson Corporation Water-based ink, water-based ink set, and process for producing dispersion
JP2004074434A (en) * 2002-08-09 2004-03-11 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004074433A (en) * 2002-08-09 2004-03-11 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004098402A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004098401A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder using it
JP2004098403A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004306441A (en) * 2003-04-07 2004-11-04 Seiko Epson Corp Ink cartridge and inkjet recorder
JP2007277287A (en) * 2006-04-03 2007-10-25 Seiko Epson Corp Ink composition for margin-less printing and inkjet printer
JP2008101043A (en) * 2006-10-17 2008-05-01 Seiko Epson Corp Ink composition for borderless printing, and inkjet printer
JP2008138064A (en) * 2006-12-01 2008-06-19 Seiko Epson Corp Ink for ink jet recording
JP2009235387A (en) * 2008-03-06 2009-10-15 Seiko Epson Corp Pigment dispersion, method for producing pigment dispersion, water-based ink composition comprising pigment dispersion, and ink jet recording method and ink jet recorded matter using water-based ink composition
JP2013170198A (en) * 2012-02-20 2013-09-02 Sakata Corp Black ink composition for aqueous inkjet

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033602A1 (en) * 2001-10-18 2003-04-24 Seiko Epson Corporation Water-based ink, water-based ink set, and process for producing dispersion
JP2004074434A (en) * 2002-08-09 2004-03-11 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004074433A (en) * 2002-08-09 2004-03-11 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004098402A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004098401A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder using it
JP2004098403A (en) * 2002-09-06 2004-04-02 Seiko Epson Corp Ink cartridge and inkjet recorder employing it
JP2004306441A (en) * 2003-04-07 2004-11-04 Seiko Epson Corp Ink cartridge and inkjet recorder
JP2007277287A (en) * 2006-04-03 2007-10-25 Seiko Epson Corp Ink composition for margin-less printing and inkjet printer
JP2008101043A (en) * 2006-10-17 2008-05-01 Seiko Epson Corp Ink composition for borderless printing, and inkjet printer
JP2008138064A (en) * 2006-12-01 2008-06-19 Seiko Epson Corp Ink for ink jet recording
JP2009235387A (en) * 2008-03-06 2009-10-15 Seiko Epson Corp Pigment dispersion, method for producing pigment dispersion, water-based ink composition comprising pigment dispersion, and ink jet recording method and ink jet recorded matter using water-based ink composition
JP2013170198A (en) * 2012-02-20 2013-09-02 Sakata Corp Black ink composition for aqueous inkjet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131479A1 (en) * 2017-12-28 2019-07-04 花王株式会社 Aqueous ink for inkjet recording
JP2019119787A (en) * 2017-12-28 2019-07-22 花王株式会社 Water-based ink for inkjet recording
JP7191512B2 (en) 2017-12-28 2022-12-19 花王株式会社 Water-based ink for inkjet recording
CN112739783A (en) * 2018-10-15 2021-04-30 Dic株式会社 Water-based ink, ink for inkjet recording, printed matter, and method for producing printed matter

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