WO2022124249A1 - Ink, ink set, ink medium set, and printing medium - Google Patents

Ink, ink set, ink medium set, and printing medium Download PDF

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Publication number
WO2022124249A1
WO2022124249A1 PCT/JP2021/044634 JP2021044634W WO2022124249A1 WO 2022124249 A1 WO2022124249 A1 WO 2022124249A1 JP 2021044634 W JP2021044634 W JP 2021044634W WO 2022124249 A1 WO2022124249 A1 WO 2022124249A1
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Prior art keywords
ink
sol
water
examples
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PCT/JP2021/044634
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French (fr)
Japanese (ja)
Inventor
博俊 高橋
彩 段
波 崔
径明 武田
勇気 田中
俊太 三澤
勇之介 笠
正悟 戸田
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日本化薬株式会社
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Priority to JP2022568256A priority Critical patent/JPWO2022124249A1/ja
Publication of WO2022124249A1 publication Critical patent/WO2022124249A1/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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • 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
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to an ink, an ink set including the ink, an ink media set including the ink or the ink set and a print medium, and a print medium to which each ink of the ink or the ink set is attached.
  • the printing method using an inkjet printer is one of the typical methods.
  • small droplets of ink are generated and attached to a printing medium such as paper for printing.
  • the inkjet printing method has come to be used in the field of high-definition printing realized by silver salt photography and offset printing.
  • ink-resistant print media such as coated paper are often used as print media.
  • the ink coating is pressed only on the scratched portion and the surface becomes smooth, resulting in stronger light. It is mirror-reflected and glare occurs. Then, only the scratched portion is glaring, so that the appearance of the entire printed matter is deteriorated and the print quality is deteriorated. For this reason, there is a strong demand for an ink that has little change in the glare of the ink coating film even if scratches such as nails are formed.
  • the present invention is an ink having little change in glare of an ink coating film even if scratch marks such as nails are formed on a print medium having poor ink absorption, particularly a printed matter obtained by printing on offset coated paper. It is an object of the present invention to provide an ink set including the ink, an ink media set including the ink or the ink set and a printing medium, and a printing medium to which each ink of the ink or the ink set is attached.
  • a water-insoluble colorant selected from the group consisting of pigments, disperse dyes, and solvent dyes, a resin dispersant having a weight average molecular weight of less than 50,000, and a solid content of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C.
  • a resin emulsion, a sol having an average particle size of 3 nm or more and less than 22 nm, and water are contained.
  • An ink having a sol content of 1.0 to 5.0% by mass.
  • An ink set comprising the ink according to any one of 1) to 8) and another ink different from the ink.
  • An ink media set comprising the ink according to any one of 1) to 8), or the ink set according to 9) and a printing medium.
  • the ink has little change in glare of the ink coating film. It is possible to provide an ink set including the ink, an ink media set including the ink or the ink set and a printing medium, and a printing medium to which each ink included in the ink or the ink set is attached.
  • CI means "color index”.
  • alkylene means "propylene”, and “alkyl” are used in the sense of including both linear and branched structures unless otherwise specified.
  • mass% is described as a value having a decimal point
  • numerical value of the second decimal place is rounded off and the value up to the first decimal place is described.
  • the ink according to this embodiment is a water-insoluble colorant selected from the group consisting of pigments, disperse dyes, and solvent dyes, a resin dispersant having a weight average molecular weight of less than 50,000, and a solid content of 100 g of methyl ethyl ketone at 25 ° C. It contains a resin emulsion having a solubility in 10 g or less, a sol having an average particle size of 3 nm or more and less than 22 nm, and water, and the content of the sol is 1.0 to 5.0% by mass. ..
  • the water-insoluble colorant means a colorant having a solubility in water at 25 ° C. of usually 5 g / L or less, preferably 3 g / L or less, more preferably 1 g / L or less, still more preferably 0.5 g / L or less. ..
  • the lower limit of solubility includes 0 g / L.
  • the water-insoluble colorant is selected from the group consisting of pigments, disperse dyes, and solvent dyes, and can be appropriately selected from known pigments, disperse dyes, and solvent dyes. Among these, pigments are preferable. Examples of the pigment include inorganic pigments and organic pigments.
  • inorganic pigment examples include carbon black, metal oxide, metal hydroxide, metal sulfide, metal ferrocyanide, metal chloride and the like.
  • organic pigments include various pigments such as azo, disazo, phthalocyanine, quinacridone, isoindole, dioxazine, perylene, perinone, thioindigo, antholaquinone, and quinophthalone.
  • organic pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, Yellow pigments such as 139, 150, 151, 154, 180, 185, 193, 199, 202, 213; C.I. I.
  • disperse dye examples include C.I. I. Dyes selected from Dispers are preferred. Specific examples thereof include, for example, C.I. I. Dispers Yellow 9, 23, 33, 42, 49, 54, 58, 60, 64, 66, 71, 76, 79, 83, 86, 90, 93, 99, 114, 116, 119, 122, 126, 149, Yellow dyes such as 160, 163, 165, 180, 183, 186, 198, 200, 211, 224, 226, 227, 231 and 237; C.I. I.
  • Red dyes such as Dispers Red 60, 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 167, 179, 191, 192, 206, 221, 258, 283;
  • Orange dyes such as Dispers Orange 9, 25, 29, 30, 31, 32, 37, 38, 42, 44, 45, 53, 54, 55, 56, 61, 71, 73, 76, 80, 96, 97;
  • solvent dye for example, C.I. I. Dyes selected from Solvent are preferred.
  • the color ink refers to colored inks other than black inks (for example, inks of each color such as yellow, magenta, cyan, red, orange, brown, violet, blue, and green).
  • carbon black such as thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black is preferable.
  • carbon black include, for example, the Raven series manufactured by Columbia Carbon Co., Ltd .; the Monarch series, Regal series, and Mogul series manufactured by Cabot Corporation; the Printex series, Color Black series, and Special Black manufactured by Orion Engineered Carbons Co., Ltd. Series, HIBLACK series, NIPex series, and NEROX series; MA series, MCF series, No. 25, No. 33, No. 40, No. 47, No. 52, No. 900 and No. 2300; and the like.
  • those having a BET specific surface area of 180 m 2 / g or more are preferable, and those having a BET specific surface area of 220 m 2 / g or more are more preferable, and 260 m 2 is more preferable, from the viewpoint of improving the print density on coated paper and plain paper. It is more preferable that it is / g or more.
  • the DBP oil absorption amount of carbon black is, for example, preferably 40 to 150 mL / 100 g, preferably 70 mL / 100 g or more, and preferably 90 mL / 100 g or more from the viewpoint of improving color development on plain paper. More preferred.
  • the DBP oil absorption amount indicates the amount of DBP (dibutyl phthalate) absorbed by 100 g of carbon black in cm3 units, and can be measured according to, for example, JIS K 6221.
  • the average particle size of the water-insoluble colorant is usually 50 to 250 nm, preferably 60 to 200 nm.
  • the average particle size means the average particle size of particles measured by a laser light scattering method.
  • the content of the water-insoluble colorant is usually 1 to 30% by mass, preferably 1 to 10% by mass, and more preferably 2 to 7% by mass with respect to the total mass of the ink according to the present embodiment.
  • resin dispersant examples include styrene and its derivatives; vinylnaphthalene and its derivatives; aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids; (meth) acrylic acids and their derivatives; maleic acid and its derivatives. At least two types of monomers (preferably at least one of them) selected from monomers such as; itaconic acid and its derivatives; carboxylic acid and its derivatives; vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof; Examples thereof include copolymers composed of (hydrophilic monomers).
  • Examples of such a copolymer include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, and (meth) acrylic acid ester- (meth).
  • examples thereof include acrylic acid copolymers, polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymers, and styrene-maleic acid copolymers.
  • styrene- (meth) acrylic acid copolymer styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, and Polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymers are preferred, styrene- (meth) acrylic acid copolymers, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymers, and (meth) acrylic acid copolymers.
  • Acrylic acid ester- (meth) acrylic acid copolymer is more preferable, (meth) acrylic acid ester- (meth) acrylic acid copolymer is further preferable, and methacrylic acid ester-methacrylic acid copolymer is particularly preferable.
  • Examples of the type of copolymer include block copolymers, random copolymers, graft copolymers and the like. These copolymers may be in the form of salts.
  • (meth) acrylic is used to mean both “acrylic” and “methacrylic”. The same applies to “(meth) acrylate” and the like.
  • the resin dispersant can be synthesized or obtained as a commercial product.
  • Examples of the resin dispersant obtained by synthesis include AB block polymers disclosed in International Publication No. 2013/115071.
  • the monomers constituting the A block of the AB block polymer disclosed in WO 2013/115071 are selected from (meth) acrylic acid and linear or branched C4 alkyl (meth) acrylates. It is at least one kind of monomer, and at least one kind of monomer selected from methacrylic acid and n-butyl methacrylate is preferable, and it is more preferable to use these two kinds of monomers together.
  • 2013/115071 is at least one kind of monomer selected from benzyl methacrylate and benzyl acrylate, and benzyl methacrylate is preferable.
  • Specific examples of the AB block polymer include the block copolymer disclosed in Synthesis Examples 3 to 8 of International Publication No. 2013/115071.
  • Examples of the resin dispersant available as a commercially available product include Joncill 62, 67, 68, 678, 687 (styrene-acrylic copolymer manufactured by BASF); Movinyl S-100A (manufactured by Japan Coating Resin Co., Ltd.). Modified vinyl acetate copolymer); Julima AT-210 (polyacrylic acid ester copolymer manufactured by Toa Synthetic Co., Ltd.); and the like.
  • the weight average molecular weight (MW) of the resin dispersant is less than 50,000, preferably 3,000 or more and less than 50,000, and more preferably 7,000 to 25,000.
  • the weight average molecular weight of the resin dispersant can be measured by a gel permeation chromatograph method (GPC method). Specifically, HLC-8320GPC (manufactured by Tosoh Corporation) is used as the GPC device, and two TSK gel Super MultiIpore HZ-H (manufactured by Tosoh Co., Ltd., inner diameter 4.6 mm ⁇ 15 cm) are used as columns for elution. Measurement can be performed using tetrahydrofuran as a liquid and TSK Standard (manufactured by Tosoh Corporation) as a standard sample.
  • the acid value of the resin dispersant is, for example, preferably 50 to 300 mgKOH / g, more preferably 80 to 275 mgKOH / g, and even more preferably 80 to 250 mgKOH / g.
  • the resin dispersant can be used in a state of being mixed with a water-insoluble colorant. Further, it can be used in a state where a part or all of the surface of the water-insoluble colorant is covered with the resin dispersant. Alternatively, both of these states may be used together.
  • the ratio of the total mass of the resin dispersant to the total mass of the water-insoluble colorant is usually 0.1 to 1.0, preferably 0.1 to 0.6, and more preferably 0.2 to 0.5.
  • the resin emulsion contains a solid content (resin) having a dissolution amount of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C.
  • the dissolved amount is preferably 8 g or less, more preferably 5 g or less, and further preferably 2 g or less.
  • a solid content (resin) having a dissolution amount of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C. usually has a weight average molecular weight of 50,000 or more.
  • the amount of dissolution in the present specification shall be measured as follows. That is, the resin emulsion is completely dried in an environment of 35 ° C. to obtain a solid content. Then, the obtained solid content is gradually added to 100 g of methyl ethyl ketone, and the upper limit at which complete dissolution can be visually confirmed is defined as the "dissolution amount”.
  • the resin emulsion preferably contains at least one of a polymer emulsion and a wax emulsion.
  • each polymer such as urethane-based, polyester, acrylic-based, vinyl acetate-based, vinyl chloride-based, styrene-acrylic, acrylic-silicone-based, and styrene-butadiene-based is dispersed in water or a water-soluble organic solvent.
  • the emulsion which has been made is mentioned.
  • an emulsion of a polymer selected from urethane-based, acrylic-based, and styrene-butadiene-based is preferable, and an acrylic polymer emulsion is more preferable.
  • Polymer emulsions can be synthesized or obtained as commercial products.
  • Examples of the polymer emulsion obtained by synthesis include the polymer emulsion disclosed in International Publication No. 2015/147192.
  • the polymers contained in the polymer emulsion disclosed in International Publication No. 2015/147192 0.5 to 3.5 parts by mass (preferably 1 to 3 parts by mass) of methacrylic acid and 41 to 59 parts by mass (preferably) of methacrylic acid.
  • a polymer obtained by polymerizing methacrylic acid (up to 2 parts by mass) without containing other monomers is preferable.
  • polymer emulsions available on the market include Superflex 126, 130, 150, 170, 210, 420, 470, 820, 830, 890 (above, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • Hydran HW-350, HW-178, HW-163, HW-171, AP-20, AP-30, WLS-201, WLS-210 (above, urethane resin emulsion manufactured by DIC Co., Ltd.); 0569, 0850Z , 2108 (above, styrene-butadiene resin emulsion manufactured by JSR Co., Ltd.); AE980, AE981A, AE982, AE986B, AE104 (above, acrylic resin emulsion manufactured by E-Tech Co., Ltd.), NeoCryl A-1105, A-1125, A-1127 (above, acrylic resin emulsion manufactured by Kusumoto Kasei Co., Ltd.); and the like.
  • wax emulsion an emulsion in which natural wax or synthetic wax is dispersed in water or a water-soluble organic solvent can be used.
  • Examples of the natural wax emulsion include petroleum waxes such as paraffin wax and microcrystallin wax; brown charcoal waxes such as montan wax; plant waxes such as carnauba wax and canderia wax; animal and plant waxes such as beeswax and lanolin; Emulsion of each wax of.
  • Examples of the synthetic wax emulsion include emulsions such as polyalkylene wax (preferably poly C2-C4 alkylene wax), oxide polyalkylene wax (preferably poly oxide C2-C4 alkylene wax), and paraffin wax.
  • emulsions such as polyalkylene wax (preferably poly C2-C4 alkylene wax), oxide polyalkylene wax (preferably poly oxide C2-C4 alkylene wax), and paraffin wax.
  • a wax emulsion selected from polyethylene wax, polypropylene wax, polyethylene oxide wax, polypropylene oxide wax, and paraffin wax is preferable, and polyethylene oxide wax emulsion is more preferable.
  • wax emulsions available as commercially available products include CERAFLOUR 925, 929, 950, 991, AQUACER 498, 515, 526, 513, 537, 537, 552, 1547, AQUAMAT 208, 263, 272, MINERPOL 221 (or more).
  • the acrylic resin emulsion and the polyethylene oxide wax emulsion it is preferable to include both.
  • the average particle size of the wax is preferably 50 nm to 5 ⁇ m, more preferably 100 nm to 1 ⁇ m in order to prevent clogging of the inkjet head.
  • the content of the resin emulsion as a solid content is usually 0. It is 6 to 6.0% by mass, preferably 1.0 to 5.0% by mass.
  • a sol is a liquid in which colloidal particles are dispersed.
  • the sol preferably contains at least one of a silica sol and a zirconium oxide sol from the viewpoint of ink storage stability, and more preferably contains a silica sol from the viewpoint of improving the printing density on coated paper and plain paper. It is more preferable to contain at least one of a silica sol and an organosilica sol.
  • the sol can be obtained as a commercial product.
  • Commercially available colloidal silica sol includes, for example, Snowtex series manufactured by Nissan Chemical Industries, Ltd., SI series manufactured by JGC Catalysts and Chemicals Co., Ltd., silica doll series manufactured by Nippon Chemical Industrial Co., Ltd., and Fuso Chemical Industries, Ltd. PL series and the like.
  • Examples of commercially available organosilica sol include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, EG-ST, NPC-ST-30, PGM-ST, NMP-ST and the like.
  • Examples of commercially available zirconium oxide sol products include the SZR series manufactured by Sakai Chemical Industry Co., Ltd.
  • the average particle size of the sol is preferably 3 nm or more and less than 22 nm, preferably 5 to 20 nm, from the viewpoint that scratch marks are less likely to glare.
  • the content of the sol is 1.0 to 5.0% by mass and 1.0 to 3.5% by mass from the viewpoint of making scratch marks less likely to glare and the storage stability of the ink. preferable.
  • water water having few impurities (metal ions, etc.) such as ion-exchanged water and distilled water is preferable.
  • the ink according to the present embodiment may further contain an ink preparation agent in addition to the above-mentioned components.
  • the ink preparation agent include organic solvents, surfactants, fungicides, preservatives, pH adjusters, rust preventives, defoamers and the like.
  • organic solvent examples include C1-C6 alkanols such as methanol, ethanol, propanol, texanol, isopropanol, butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • Carous acid amides such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2-one, 1,3-dimethylhexahydropyrimido Cyclic ureas such as -2-one; acetone, 2-methyl-2-hydroxypentane-4-one, ketones such as ethylene carbonate, keto alcohol, or carbonates; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, diethylene glycol.
  • mono, oligos, or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as polypropylene glycol, thiodiglycol, dithiodiglycol; glycerin, diglycerin, hexane -C3-C9 polyol (triol) such as 1,2,6-triol and trimethylpropane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, prolen glycol monobutyl ether, dipropylene glycol
  • Glycol ethers preferably glycol ethers selected from C3-C10 mono, di, or triethylene glycol ethers, and C4-C13 mono, di, or tripropylene glycol ethers); 1,2-Pen. Tandiol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-diol Examples thereof include C5-C9 alkanediol such as -1,5-pentanediol; ⁇ -butyrolactone, dimethyl sulfoxide; and the like. Of these, 1,2-hexanediol and texanol are preferred.
  • surfactant examples include anion-based, nonionic, silicone-based, and fluorine-based surfactants.
  • a silicone-based surfactant and a fluorine-based surfactant are preferable, and a silicone-based surfactant is more preferable from the viewpoint of safety to the living body and the environment.
  • anionic surfactant examples include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acylamino acids or salts thereof, and N-acylmethyl.
  • nonionic surfactant examples include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxy.
  • Ethers such as ethylene distyrene phenyl ether; polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate , Polyoxyethylene stearate and other ester systems; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3, Examples thereof include acetylene glycol (alcohol) type such as 5-dimethyl-1-hexin-3-ol; polyglycol ether type and the like.
  • silicone-based surfactant examples include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like.
  • Dynol 960, 980 manufactured by Air Products Co., Ltd . Silface SAG001, SAG002, SAG003, SAG005, SAG503A, SAG008, SAG090, SAG010 manufactured by Nisshin Chemical Co., Ltd .
  • BYK-345 manufactured by BYK Co., Ltd.
  • fluorosurfactant examples include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group as side chains.
  • fluorosurfactant examples include polyoxyalkylene ether polymer compounds having.
  • Antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof.
  • preservative examples include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloarylsulfone-based, iodopropagil-based, haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzothiazole-based.
  • examples thereof include acetate-based and inorganic salt-based compounds.
  • Specific examples of the organic halogen-based compound include sodium pentachlorophenol and the like.
  • Specific examples of the pyridine oxide compound include 2-pyridinethiol-1-oxide sodium and the like.
  • isothiazolinone compound examples include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one.
  • 5-chloro-2-methyl-4-isothiazolin-3-onmagnesium chloride 5-chloro-2-methyl-4-isothiazolin-3-oncalc chloride, 2-methyl-4-isothiazolin-3-oncalcium Chloride and the like can be mentioned.
  • antiseptic and antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, Proxel GXL (S), LV, XL-2 (S) manufactured by Ronza, and the like.
  • pH adjuster examples include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water).
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate; and the like.
  • rust preventive examples include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
  • Examples of the defoaming agent include silicone-based, silica-mineral oil-based, olefin-based, and acetylene-based compounds.
  • Examples of commercially available products include Surfinol DF37, DF58, DF110D, DF220, MD-20, and Olefin SK-14 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Ink preparation method, etc. For the ink according to the present embodiment, prepare an aqueous dispersion containing a water-insoluble colorant and a resin dispersant, and add a resin emulsion, a sol, and an ink preparation if necessary to the aqueous dispersion and mix them. Can be prepared by.
  • Examples of the method for preparing the aqueous dispersion include a phase inversion emulsification method, an acid analysis method, an interfacial polymerization method, an in-situ polymerization method, an in-liquid curing coating method, a core selvation (phase separation) method, and an in-liquid drying method.
  • Examples thereof include a melt dispersion cooling method, an air suspension coating method, and a spray drying method.
  • the phase inversion emulsification method, the acid analysis method, and the interfacial polymerization method are preferable, and the phase inversion emulsification method is more preferable.
  • a resin dispersant is dissolved in an organic solvent such as 2-butanone, and an aqueous solution of a neutralizing agent is added to prepare an emulsion.
  • a water-insoluble colorant is added to the obtained emulsion to carry out a dispersion treatment.
  • the dispersion treatment can be performed using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like.
  • a sand mill bead mill
  • beads having a particle diameter of about 0.01 to 1 mm can be used, and the filling rate of the beads can be appropriately set to perform the dispersion treatment.
  • the particle size of the particles contained in the aqueous dispersion can be made uniform.
  • foaming occurs during the preparation of the aqueous dispersion, a very small amount of a known silicone-based or acetylene glycol-based defoaming agent can be added.
  • the average particle size (D50) of the water-insoluble colorant in the aqueous dispersion is usually 300 nm or less, preferably 30 to 280 nm, more preferably 40 to 270 nm, and further preferably 50 to 250 nm.
  • D90 is usually 400 nm or less, preferably 350 nm or less, and more preferably 300 nm or less.
  • the lower limit of D90 is preferably 100 nm or more.
  • D10 is usually 10 nm or more, preferably 20 nm or more, and more preferably 30 nm or more.
  • the upper limit of D10 is preferably 100 nm or less.
  • the average particle size of the water-insoluble colorant can be measured by using laser light scattering.
  • the content of inorganic impurities such as metal cation chloride (for example, sodium chloride) and metal cation sulfate (for example, sodium sulfate) may be low. preferable.
  • metal cation chloride for example, sodium chloride
  • metal cation sulfate for example, sodium sulfate
  • Such inorganic impurities are often contained in commercially available water-insoluble colorants.
  • the guideline for the content of inorganic impurities is about 1% by mass or less with respect to the total amount of the water-insoluble colorant, and the lower limit is ideally below the detection limit of the analytical instrument, that is, 0%.
  • a method for obtaining a water-insoluble colorant having few inorganic impurities for example, a method using a reverse osmosis membrane; a solid water-insoluble colorant is suspended and stirred in a mixed solvent of C1-C4 alcohol such as methanol and water.
  • a mixed solvent of C1-C4 alcohol such as methanol and water.
  • examples thereof include a method of filtering and separating a water-insoluble colored substance and drying it; a method of exchanging and adsorbing inorganic impurities with an ion exchange resin; and the like.
  • the ink according to the present embodiment is used as an inkjet ink, it is preferable to microfilter the ink.
  • a membrane filter, glass filter paper, or the like can be used.
  • the pore size of the filter or the like when performing microfiltration is usually 0.5 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m.
  • the ink according to this embodiment can be used in various printing fields such as writing, printing, information printing, and printing, and is particularly preferably used for inkjet printing.
  • the ink set according to the present embodiment includes the above-mentioned ink according to the present embodiment and other inks different from the ink.
  • the other ink is not particularly limited as long as it has a structure different from that of the ink according to the present embodiment, but an ink having a hue different from that of the ink according to the present embodiment is preferable.
  • the ink set according to the present embodiment includes the ink or the ink set according to the above-mentioned embodiment and a print medium.
  • print media examples include paper, film, fibers and cloths (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. These recording media can be roughly classified into those having an ink receiving layer and those having no ink receiving layer.
  • Examples of the recording medium having an ink receiving layer include those using paper, synthetic paper, film, or the like as a base material and providing an ink receiving layer on the base material.
  • the ink receiving layer is, for example, a method of impregnating or coating a base material with a cationic polymer; inorganic fine particles such as porous silica, alumina sol, and special ceramics are placed on the surface of the base material together with hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone. It is provided by a method of coating; etc.
  • Such recording media are usually referred to as inkjet paper, inkjet film, glossy paper, or the like.
  • Specific examples of commercially available products include, for example, product names manufactured by Canon Co., Ltd .: professional photo paper, super photo paper, glossy gold, and matte photo paper; product names manufactured by Seiko Epson Co., Ltd .: photo paper crispia (high). Glossy), photo paper (glossy), photo matte paper; product name made by Nippon Hulett Packard Co., Ltd .: advanced photo paper (glossy); product name made by Fujifilm Co., Ltd .: painting photo finishing Pro; etc. Can be mentioned.
  • examples of recording media having no ink receiving layer include various types of paper such as coated paper and art paper used for gravure printing and offset printing; cast coated paper used for label printing, and the like.
  • Specific examples of commercially available products include, for example, trade name: OK Top Coat + manufactured by Oji Paper Co., Ltd.
  • ⁇ Inkjet printing method In the inkjet printing method according to the present embodiment, droplets of the ink according to the present embodiment described above or the ink droplets of each ink provided in the ink set according to the above-mentioned embodiment are ejected according to a print signal and adhered to the print media. It is a method of printing by making the ink. There are no particular restrictions on the ink nozzles and the like of the inkjet printer that ejects ink, and the ink nozzles and the like can be appropriately selected according to the purpose.
  • a large number of inks having a low content of water-insoluble colorant in the ink are ejected in a small volume to improve the image quality; the ink has substantially the same hue and is water-insoluble in the ink.
  • a method of improving image quality by using a plurality of inks having different colorant contents; by using a colorless transparent ink and an ink containing a water-insoluble colorant in combination, the fixability of the water-insoluble colorant to a print medium Methods to improve; etc. are also included.
  • the inkjet printing method a known method can be adopted. Examples thereof include a charge control method, a drop-on-demand method (pressure pulse method), an acoustic inkjet method, a thermal inkjet method, and the like.
  • a container (ink tank) containing ink is loaded in a predetermined position of an inkjet printer, and printing is performed on the print media by the above printing method. It is also possible to realize full-color printing by loading a container containing ink of each color into a predetermined position of an inkjet printer and printing on a printing medium by the above printing method.
  • the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable.
  • Preparation Example 1 Preparation of dispersion liquid DP1>
  • the block copolymer of Synthesis Example 3 was prepared by retesting Synthesis Example 3 of International Publication No. 2013/115071.
  • the acid value of the obtained block copolymer was 105 mgKOH / g, and the weight average molecular weight was 25,000.
  • Neurox605 carbon black manufactured by Orion Engineered Carbons Co., Ltd. (20 parts) was added to the obtained emulsified liquid, and a sand grinder was used to disperse the liquid under the condition of 1500 rpm for 15 hours to obtain a liquid.
  • Ion-exchanged water 120 parts was added to the obtained liquid, and the beads for dispersion were separated by filtration to obtain a filtrate.
  • 2-Butanone and a part of water were distilled off from the obtained filtrate under reduced pressure by an evaporator to obtain a dispersion liquid DP1 having a solid content of 12% as a colorant.
  • Preparation Example 2 Preparation of Dispersion Liquid DP2> Instead of Neox605, C.I. I. A dispersion liquid DP2 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 1 except that Pigment Yellow 74 (HANSA YELLOW 5GX01-JP manufactured by Clariant AG) was used.
  • Pigment Yellow 74 HANSA YELLOW 5GX01-JP manufactured by Clariant AG
  • ⁇ Preparation Example 3 Preparation of Resin Emulsion A> Water (100 parts), ammonium persulfate (0.3 parts), and a reactive emulsifier (1 part) were added to a glass reaction vessel (capacity 3 L) to obtain a liquid. After replacing the air inside the reaction vessel with nitrogen, the temperature of the liquid was raised to 70 ° C. In this solution, water (120 parts), reactive emulsifier (0.9 parts), methacrylic acid (2 parts), methyl methacrylate (37 parts), 2-ethylhexyl acrylate (59 parts), and allyl methacrylate (59 parts). The liquid consisting of 2 parts) was added dropwise over 3 hours.
  • Examples 1 to 15 Ink preparation> After mixing each component shown in Tables 1 and 2 below, the inks of Examples 1 to 15 were obtained by filtering with a membrane filter having a pore size of 3 ⁇ m.
  • Comparative Examples 1 to 6 Preparation of ink for comparison> After mixing each component shown in Table 3 below, the inks of Comparative Examples 1 to 6 were obtained by filtering with a membrane filter having a pore size of 3 ⁇ m. The ink of Comparative Example 5 had extremely poor storage stability, and could not be evaluated for scratch resistance and the like, which will be described later.
  • the printed matter obtained by using each of the inks of the examples has little change in the glare of the ink coating film even if scratches are made by the nails on the offset coated paper, and the scratch resistance is improved. It was excellent.
  • Inkjet printing is performed on the print media by a single pass (1 pass) method using the inks of Examples 1 to 6, 13 to 15, and Comparative Examples 1 to 4, 6, and a 100% Duty print image is obtained. Obtained.
  • As the printing media offset coated paper "OK Top Coat +" manufactured by Oji Paper Co., Ltd. and plain paper “Npi Foam 70NEXT-IL” manufactured by Nippon Paper Industries Co., Ltd. were used.
  • As the inkjet head a 600 dpi head manufactured by Kyocera Corporation was used, and the head temperature was 32 ° C. The appropriate amount of ink to be ejected was 12 pL. After inkjet printing, the obtained printed image was dried.
  • the printed image after drying was color-measured using a spectrocolorimeter (eXact, manufactured by X-Rite). Color measurement was performed under the conditions of density standard: ANSI T, light source: D65, and viewing angle: 2 °. Then, the print density was evaluated according to the evaluation criteria shown in Table 6 below. The results are shown in Table 7 below.
  • ⁇ Preparation Example 4 Preparation of dispersion DP3>
  • the block copolymer of Synthesis Example 3 was prepared by retesting Synthesis Example 3 of International Publication No. 2013/115071.
  • the acid value of the obtained block copolymer was 105 mgKOH / g, and the weight average molecular weight was 25,000.
  • HIBLACK890 carbon black manufactured by Orion Engineered Carbons Co., Ltd. (20 parts) was added to the obtained emulsion, and a dispersion treatment was carried out for 15 hours with a sand grinder under the condition of 1500 rpm to obtain a liquid.
  • Ion-exchanged water 120 parts was added to the obtained liquid, and the beads for dispersion were separated by filtration to obtain a filtrate.
  • 2-Butanone and a part of water were distilled off from the obtained filtrate under reduced pressure by an evaporator to obtain a dispersion liquid DP3 having a solid content of a colorant of 12%.
  • Preparation Example 5 Preparation of Dispersion Liquid DP4> A dispersion DP4 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 4 except that NIPex90 (carbon black manufactured by Orion Engineered Carbons) was used instead of HIBLACK890.
  • NIPex90 carbon black manufactured by Orion Engineered Carbons
  • Preparation of dispersion liquid DP5> A dispersion DP5 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 4 except that Printex80 (carbon black manufactured by Orion Engineered Carbons) was used instead of HIBLACK890.
  • Printex80 carbon black manufactured by Orion Engineered Carbons
  • ⁇ Preparation Example 7 Preparation of Dispersion Liquid DP6> A dispersion liquid DP6 having a solid content of 12% of a colorant was obtained in the same manner as in Preparation Example 4 except that HIBLACK 50L (carbon black manufactured by Orion Engineered Carbons Co., Ltd.) was used instead of HIBLACK 890.
  • HIBLACK 50L carbon black manufactured by Orion Engineered Carbons Co., Ltd.
  • Examples 16 to 25 Ink preparation> After mixing each component shown in Tables 9 to 10 below, the inks of Examples 16 to 25 were obtained by filtering with a membrane filter having a pore size of 3 ⁇ m.
  • Comparative Examples 7 to 11 Preparation of ink for comparison> After mixing each component shown in Table 11 below, the inks of Comparative Examples 7 to 11 were obtained by filtering with a membrane filter having a pore size of 3 ⁇ m.
  • Resin emulsion D AQUACER531 manufactured by BYK (solid content: 45%, solid content dissolved in 100 g of methyl ethyl ketone at 25 ° C.: 5 g or less)
  • ST30 Nissan Chemical Industries, Ltd., Snowtex 30 (coloidal silica sol, solid content: 30%)
  • STXS Nissan Chemical Industries, Ltd., Snowtex XS (coloidal silica sol, solid content: 20%) SD40: Made by Nippon Chemical Industrial Co., Ltd., Silica Doll 40 (coloidal silica sol, solid content: 40%)
  • ST50T Nissan Chemical Industries, Ltd., Snowtex 50T (coloidal silica sol, solid content: 50%)
  • ST30L Nissan Chemical Industries, Ltd., Snowtex 30L (coloidal silica sol, solid content: 30%)
  • SZRCW Made by Sakai Chemical Industry Co
  • Bar coater No. 3 (Yasuda Machinery Works Co., Ltd.) was used to apply the inks of Examples 11 to 25 and Comparative Examples 7 to 11 to the print media.
  • As the printing media offset coated paper "OK Top Coat +” manufactured by Oji Paper Co., Ltd. and plain paper “Npi Foam 70NEXT-IL” manufactured by Nippon Paper Industries Co., Ltd. were used. The obtained image was dried at 70 ° C. for 2 minutes to obtain a test piece.
  • the obtained test piece was measured with optical densities (OD values) at five points using a spectrocolorimeter (eXact, manufactured by X-Rite), and the average value was taken as the OD value of the test piece.
  • Color measurement was performed under the conditions of density standard: ANSI T, light source: D65, and viewing angle: 2 °. Then, the print density was evaluated according to the following evaluation criteria. The results are shown in Table 12 below.
  • OD value is 2.3 or more
  • B OD value is 2.0 or more and less than 2.3 C: OD value is 1.7 or more and less than 2.0 D: OD value is less than 1.7-evaluation criteria (Npi form) 70NEXT-IJ)-

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Abstract

The present invention provides an ink which contains: a water-insoluble coloring agent that is selected from the group consisting of a pigment, a disperse dye and a solvent dye; a resin dispersant that has a weight average molecular weight of less than 50,000; a resin emulsion wherein the dissolution amount of the solid content in 100 g of methyl ethyl ketone at 25°C is 10 g or less; a sol that has an average particle diameter of 3 nm or more but less than 22 nm; and water. With respect to this ink, the content of the sol is from 1.0% by mass to 5.0% by mass. The present invention also provides: an ink set which comprises this ink; an ink medium set which comprises this ink or ink set, and a printing medium; and a printing medium to which this ink or each ink in the ink set adheres.

Description

インク、インクセット、インクメディアセット、及び印刷メディアInks, ink sets, ink media sets, and print media
　本発明は、インク、そのインクを備えるインクセット、そのインク又はインクセットと印刷メディアとを備えるインクメディアセット、及びそのインク又はインクセットが備える各インクが付着した印刷メディアに関する。 The present invention relates to an ink, an ink set including the ink, an ink media set including the ink or the ink set and a print medium, and a print medium to which each ink of the ink or the ink set is attached.
　各種のカラー印刷方法の中で、インクジェットプリンタを用いる印刷方法（インクジェット印刷方法）は、代表的な方法の１つである。この方法は、インクの小滴を発生させ、これを紙等の印刷メディアに付着させ印刷を行うものである。インクジェット印刷技術の進歩により、銀塩写真やオフセット印刷によって実現されてきた高精細な印刷の分野においても、インクジェット印刷方法が用いられるようになってきた。そのような分野においては、印刷メディアとして、コート紙のようなインク難吸収性の印刷メディアが多用されている。 Among various color printing methods, the printing method using an inkjet printer (inkjet printing method) is one of the typical methods. In this method, small droplets of ink are generated and attached to a printing medium such as paper for printing. With the progress of inkjet printing technology, the inkjet printing method has come to be used in the field of high-definition printing realized by silver salt photography and offset printing. In such fields, ink-resistant print media such as coated paper are often used as print media.
　また、近年では産業用インクジェット印刷の需要が高まり、これまでとは異なる特性が要求されるようになっている。そのような特性の１つとして、印刷メディアに付着したインクの耐擦性の向上が強く要望されている。 Also, in recent years, the demand for industrial inkjet printing has increased, and different characteristics are required. As one of such characteristics, there is a strong demand for improving the abrasion resistance of the ink adhering to the print media.
　例えば、インクジェットプリンタを用いてコート紙に印刷し、得られた印字物を爪等で線擦過すると、線擦過した箇所のみ、インク塗膜が押し付けられて表面が平滑になる結果、光がより強く鏡面反射され、ぎらつきが生じる。そして、線擦過した箇所のみがぎらついてしまうことで、印字物全体の見栄えが悪くなり、印刷品質が低下してしまう。このため、爪等の擦過痕がついたとしても、インク塗膜のぎらつきの変化が少ないインクが強く要望されている。 For example, when printing on coated paper using an inkjet printer and scratching the obtained printed matter with a nail or the like, the ink coating is pressed only on the scratched portion and the surface becomes smooth, resulting in stronger light. It is mirror-reflected and glare occurs. Then, only the scratched portion is glaring, so that the appearance of the entire printed matter is deteriorated and the print quality is deteriorated. For this reason, there is a strong demand for an ink that has little change in the glare of the ink coating film even if scratches such as nails are formed.
　インク塗膜のぎらつきを抑制する手法としては、印刷前のコート紙に前処理剤を塗布することや、印刷後のコート紙にオーバーコート剤を塗布することが考えられる。しかし、印刷コスト抑制や印刷スピード向上、工程追加による装置の大型化を考慮すると、前処理剤やオーバーコート剤を利用することなく、先に述べた耐擦性が得られることが望ましい。 As a method for suppressing the glare of the ink coating film, it is conceivable to apply a pretreatment agent to the coated paper before printing or to apply an overcoating agent to the coated paper after printing. However, considering the reduction of printing cost, the improvement of printing speed, and the increase in size of the apparatus due to the addition of processes, it is desirable that the above-mentioned abrasion resistance can be obtained without using a pretreatment agent or an overcoat agent.
特許５２７３４３４号公報Japanese Patent No. 5273434 特許４６７９３２２号公報Japanese Patent No. 4679322 国際公開第２０１６／０３５７８７号International Publication No. 2016/035877
　本発明は、インク難吸収性の印刷メディア、特にオフセットコート紙に印刷して得られた印字物に爪等の擦過痕がついたとしても、インク塗膜のぎらつきの変化が少ないインク、そのインクを備えるインクセット、そのインク又はインクセットと印刷メディアとを備えるインクメディアセット、及びそのインク又はインクセットが備える各インクが付着した印刷メディアを提供することを課題とする。 INDUSTRIAL APPLICABILITY The present invention is an ink having little change in glare of an ink coating film even if scratch marks such as nails are formed on a print medium having poor ink absorption, particularly a printed matter obtained by printing on offset coated paper. It is an object of the present invention to provide an ink set including the ink, an ink media set including the ink or the ink set and a printing medium, and a printing medium to which each ink of the ink or the ink set is attached.
　上記課題を解決するための具体的な手段には、以下の実施態様が含まれる。
１）
　顔料、分散染料、及び溶剤染料からなる群より選択される水不溶性着色剤と、重量平均分子量が５００００未満である樹脂分散剤と、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量が１０ｇ以下である樹脂エマルションと、平均粒子径が３ｎｍ以上２２ｎｍ未満であるゾルと、水と、を含有し、
　前記ゾルの含有率が１．０～５．０質量％であるインク。 Specific means for solving the above problems include the following embodiments.
1)
A water-insoluble colorant selected from the group consisting of pigments, disperse dyes, and solvent dyes, a resin dispersant having a weight average molecular weight of less than 50,000, and a solid content of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C. A resin emulsion, a sol having an average particle size of 3 nm or more and less than 22 nm, and water are contained.
An ink having a sol content of 1.0 to 5.0% by mass.
２）
　前記ゾルが、シリカゾル及び酸化ジルコニウムゾルの少なくとも一方を含む、１）に記載のインク。 2)
The ink according to 1), wherein the sol contains at least one of a silica sol and a zirconium oxide sol.
３）
　前記ゾルが、シリカゾルを含む、２）に記載のインク。 3)
The ink according to 2), wherein the sol contains a silica sol.
４）
　前記ゾルが、コロイダルシリカゾル及びオルガノシリカゾルの少なくとも一方を含む、３）に記載のインク。 4)
The ink according to 3), wherein the sol contains at least one of a colloidal silica sol and an organosilica sol.
５）
　前記樹脂エマルションが、アクリル樹脂エマルション及び酸化ポリエチレンワックスエマルションの少なくとも一方を含む、１）～４）のいずれか１項に記載のインク。 5)
The ink according to any one of 1) to 4), wherein the resin emulsion contains at least one of an acrylic resin emulsion and a polyethylene oxide wax emulsion.
６）
　前記樹脂エマルションが、アクリル樹脂エマルション及び酸化ポリエチレンワックスエマルションを含む、５）に記載のインク。 6)
The ink according to 5), wherein the resin emulsion contains an acrylic resin emulsion and a polyethylene oxide wax emulsion.
７）
　前記樹脂エマルションの含有率が、固形分として０．６～６．０質量％である、１）～６）のいずれか１項に記載のインク。 7)
The ink according to any one of 1) to 6), wherein the content of the resin emulsion is 0.6 to 6.0% by mass as a solid content.
８）
　前記水不溶性着色剤が、ＢＥＴ比表面積が１８０ｍ２／ｇ以上のカーボンブラックを含む、１）～７）のいずれか１項に記載のインク。 8)
The ink according to any one of 1) to 7), wherein the water-insoluble colorant contains carbon black having a BET specific surface area of 180 m 2 / g or more.
９）
　１）～８）のいずれか１項に記載のインクと、該インクとは異なる他のインクと、を備えるインクセット。 9)
An ink set comprising the ink according to any one of 1) to 8) and another ink different from the ink.
１０）
　１）～８）のいずれか１項に記載のインク、又は９）に記載のインクセットと、印刷メディアと、を備えるインクメディアセット。 10)
An ink media set comprising the ink according to any one of 1) to 8), or the ink set according to 9) and a printing medium.
１１）
　１）～８）のいずれか１項に記載のインク、又は９）に記載のインクセットが備える各インクが付着した印刷メディア。 11)
A print medium to which the ink according to any one of 1) to 8) or each ink provided in the ink set according to 9) is attached.
　本発明によれば、インク難吸収性の印刷メディア、特にオフセットコート紙に印刷して得られた印字物に爪等の擦過痕がついたとしても、インク塗膜のぎらつきの変化が少ないインク、そのインクを備えるインクセット、そのインク又はインクセットと印刷メディアとを備えるインクメディアセット、及びそのインク又はインクセットが備える各インクが付着した印刷メディアを提供することができる。 According to the present invention, even if a print medium having poor ink absorption, particularly a printed matter obtained by printing on offset coated paper, has scratch marks such as claws, the ink has little change in glare of the ink coating film. It is possible to provide an ink set including the ink, an ink media set including the ink or the ink set and a printing medium, and a printing medium to which each ink included in the ink or the ink set is attached.
　以下、本発明を適用した具体的な実施形態について詳細に説明する。
　本明細書において、「Ｃ．Ｉ．」とは、「カラーインデックス」を意味する。
　また、本明細書において、「アルキレン」、「プロピレン」、「アルキル」の用語は、特に断りのない限り、直鎖状及び分岐鎖状の両方の構造を包含する意味で使用する。
　また、本明細書において、質量％の値で小数点を有する値で記載しているものは、小数点以下２桁目の数値を四捨五入し、小数点以下１桁目までを記載する。 Hereinafter, specific embodiments to which the present invention is applied will be described in detail.
As used herein, "CI" means "color index".
Further, in the present specification, the terms "alkylene", "propylene", and "alkyl" are used in the sense of including both linear and branched structures unless otherwise specified.
Further, in the present specification, when the value of mass% is described as a value having a decimal point, the numerical value of the second decimal place is rounded off and the value up to the first decimal place is described.
＜インク＞
　本実施形態に係るインクは、顔料、分散染料、及び溶剤染料からなる群より選択される水不溶性着色剤と、重量平均分子量が５００００未満である樹脂分散剤と、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量が１０ｇ以下である樹脂エマルションと、平均粒子径が３ｎｍ以上２２ｎｍ未満であるゾルと、水と、を含有し、上記ゾルの含有率が１．０～５．０質量％である。 <Ink>
The ink according to this embodiment is a water-insoluble colorant selected from the group consisting of pigments, disperse dyes, and solvent dyes, a resin dispersant having a weight average molecular weight of less than 50,000, and a solid content of 100 g of methyl ethyl ketone at 25 ° C. It contains a resin emulsion having a solubility in 10 g or less, a sol having an average particle size of 3 nm or more and less than 22 nm, and water, and the content of the sol is 1.0 to 5.0% by mass. ..
　以下、本実施形態に係るインクに含有される成分について詳細に説明する。なお、以下に説明する各成分は、そのうちの１種類を単独で使用してもよく、２種類以上を併用してもよい。 Hereinafter, the components contained in the ink according to the present embodiment will be described in detail. As for each component described below, one of them may be used alone, or two or more of them may be used in combination.
［水不溶性着色剤］
　水不溶性着色剤とは、２５℃の水に対する溶解度が通常５ｇ／Ｌ以下、好ましくは３ｇ／Ｌ以下、より好ましくは１ｇ／Ｌ以下、さらに好ましくは０．５ｇ／Ｌ以下の着色剤を意味する。溶解度の下限は０ｇ／Ｌを含む。 [Water-insoluble colorant]
The water-insoluble colorant means a colorant having a solubility in water at 25 ° C. of usually 5 g / L or less, preferably 3 g / L or less, more preferably 1 g / L or less, still more preferably 0.5 g / L or less. .. The lower limit of solubility includes 0 g / L.
　水不溶性着色剤は、顔料、分散染料、及び溶剤染料からなる群より選択されるものであり、公知の顔料、分散染料、及び溶剤染料の中から適宜選択することができる。これらの中でも、顔料が好ましい。顔料としては、無機顔料、有機顔料等が挙げられる。 The water-insoluble colorant is selected from the group consisting of pigments, disperse dyes, and solvent dyes, and can be appropriately selected from known pigments, disperse dyes, and solvent dyes. Among these, pigments are preferable. Examples of the pigment include inorganic pigments and organic pigments.
　無機顔料としては、例えば、カーボンブラック、金属酸化物、金属水酸化物、金属硫化物、金属フェロシアン化物、金属塩化物等が挙げられる。 Examples of the inorganic pigment include carbon black, metal oxide, metal hydroxide, metal sulfide, metal ferrocyanide, metal chloride and the like.
　有機顔料としては、例えば、アゾ、ジスアゾ、フタロシアニン、キナクリドン、イソインドリノン、ジオキサジン、ペリレン、ペリノン、チオインジゴ、アンソラキノン、キノフタロン等の各種の顔料が挙げられる。 Examples of organic pigments include various pigments such as azo, disazo, phthalocyanine, quinacridone, isoindole, dioxazine, perylene, perinone, thioindigo, antholaquinone, and quinophthalone.
　有機顔料の具体例としては、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１、２、３、１２、１３、１４、１６、１７、２４、５５、７３、７４、７５、８３、９３、９４、９５、９７、９８、１０８、１１４、１２８、１２９、１３８、１３９、１５０、１５１、１５４、１８０、１８５、１９３、１９９、２０２、２１３等のイエロー顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　５、７、１２、４８、４８：１、５７、８８、１１２、１２２、１２３、１４６、１４９、１５０、１６６、１６８、１７７、１７８、１７９、１８４、１８５、２０２、２０６、２０７、２５４、２５５、２５７、２６０、２６４、２６９、２７２等のレッド顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１、２、３、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、２２、２５、６０、６６、８０等のブルー顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、２３、２９、３７、３８、５０等のバイオレット顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１３、１６、４３、６８、６９、７１、７３等のオレンジ顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、３６、５４等のグリーン顔料；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１等のブラック顔料；などが挙げられる。 Specific examples of organic pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, Yellow pigments such as 139, 150, 151, 154, 180, 185, 193, 199, 202, 213; C.I. I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 150, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, Red pigments such as 254, 255, 257, 260, 264, 269, 272; C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 25, 60, 66, 80 and other blue pigments; C.I. I. Pigment Violet 19, 23, 29, 37, 38, 50 and other violet pigments; C.I. I. Pigment Orange 13, 16, 43, 68, 69, 71, 73 and other orange pigments; C.I. I. Green pigments such as Pigment Green 7, 36, 54; C.I. I. Black pigments such as Pigment Black 1; and the like.
　分散染料としては、例えば、Ｃ．Ｉ．Ｄｉｓｐｅｒｓから選択される染料が好ましい。その具体例としては、例えば、Ｃ．Ｉ．Ｄｉｓｐｅｒｓ　Ｙｅｌｌｏｗ　９、２３、３３、４２、４９、５４、５８、６０、６４、６６、７１、７６、７９、８３、８６、９０、９３、９９、１１４、１１６、１１９、１２２、１２６、１４９、１６０、１６３、１６５、１８０、１８３、１８６、１９８、２００、２１１、２２４、２２６、２２７、２３１、２３７等のイエロー染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓ　Ｒｅｄ　６０、７３、８８、９１、９２，１１１、１２７、１３１、１４３、１４５、１４６、１５２、１５３、１５４、１６７、１７９、１９１、１９２、２０６、２２１、２５８、２８３等のレッド染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓ　Ｏｒａｎｇｅ　９、２５、２９、３０、３１、３２、３７、３８、４２、４４、４５、５３、５４、５５、５６、６１、７１、７３、７６、８０、９６、９７等のオレンジ染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓ　Ｖｉｏｌｅｔ　２５、２７、２８、５４、５７、６０、７３、７７、７９、７９：１等のバイオレット染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓ　Ｂｌｕｅ　２７、５６、６０、７９：１、８７、１４３、１６５、１６５：１、１６５：２、１８１、１８５、１９７、２０２、２２５、２５７、２６６、２６７、２８１、３４１、３５３、３５４、３５８、３６４、３６５、３６８等のブルー染料；などが挙げられる。 Examples of the disperse dye include C.I. I. Dyes selected from Dispers are preferred. Specific examples thereof include, for example, C.I. I. Dispers Yellow 9, 23, 33, 42, 49, 54, 58, 60, 64, 66, 71, 76, 79, 83, 86, 90, 93, 99, 114, 116, 119, 122, 126, 149, Yellow dyes such as 160, 163, 165, 180, 183, 186, 198, 200, 211, 224, 226, 227, 231 and 237; C.I. I. Red dyes such as Dispers Red 60, 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 167, 179, 191, 192, 206, 221, 258, 283; C. I. Orange dyes such as Dispers Orange 9, 25, 29, 30, 31, 32, 37, 38, 42, 44, 45, 53, 54, 55, 56, 61, 71, 73, 76, 80, 96, 97; C. I. Dispers Violet 25, 27, 28, 54, 57, 60, 73, 77, 79, 79: 1 and other violet dyes; C.I. I. Dispers Blue 27, 56, 60, 79: 1, 87, 143, 165, 165: 1, 165: 2, 181 185, 197, 202, 225, 257, 266, 267, 281, 341, 353, 354, Blue dyes such as 358, 364, 365, 368; and the like.
　溶剤染料としては、例えば、Ｃ．Ｉ．Ｓｏｌｖｅｎｔから選択される染料が好ましい。 As the solvent dye, for example, C.I. I. Dyes selected from Solvent are preferred.
　色調を調整するため、２種類以上の水不溶性着色剤を配合することも可能である。例えば、ブラックインクの場合には、３～５種類の水不溶性着色剤を併用することが好ましく、ブラックインク以外のカラーインクの場合には、２種類以上の水不溶性着色剤を併用することが好ましい。但し、ブラックインクが水不溶性着色剤としてカーボンブラックを含有する場合、水不溶性着色剤の種類は２種類又は１種類が好ましい。なお、本明細書において、カラーインクとは、ブラックインク以外の有色インク（例えば、イエロー、マゼンタ、シアン、レッド、オレンジ、ブラウン、バイオレット、ブルー、グリーン等の各色のインク）を指す。 It is also possible to mix two or more types of water-insoluble colorants to adjust the color tone. For example, in the case of black ink, it is preferable to use 3 to 5 kinds of water-insoluble colorants in combination, and in the case of color inks other than black ink, it is preferable to use two or more kinds of water-insoluble colorants in combination. .. However, when the black ink contains carbon black as a water-insoluble colorant, the type of the water-insoluble colorant is preferably two or one. In the present specification, the color ink refers to colored inks other than black inks (for example, inks of each color such as yellow, magenta, cyan, red, orange, brown, violet, blue, and green).
　ブラックインクが含有する水不溶性着色剤としては、例えば、サーマルブラック、アセチレンブラック、オイルファーネスブラック、ガスファーネスブラック、ランプブラック、ガスブラック、チャンネルブラック等のカーボンブラックが好ましい。カーボンブラックの具体例としては、例えば、コロンビア・カーボン社製のＲａｖｅｎシリーズ；キャボット社製のＭｏｎａｒｃｈシリーズ、Ｒｅｇａｌシリーズ、及びＭｏｇｕｌシリーズ；オリオンエンジニアドカーボンズ社製のＰｒｉｎｔｅｘシリーズ、Ｃｏｌｏｕｒ　Ｂｌａｃｋシリーズ、Ｓｐｅｃｉａｌ　Ｂｌａｃｋシリーズ、ＨＩＢＬＡＣＫシリーズ、ＮＩＰｅｘシリーズ、及びＮＥＲＯＸシリーズ；三菱ケミカル（株）製のＭＡシリーズ、ＭＣＦシリーズ、Ｎｏ．２５、Ｎｏ．３３、Ｎｏ．４０、Ｎｏ．４７、Ｎｏ．５２、Ｎｏ．９００、及びＮｏ．２３００；等が挙げられる。 As the water-insoluble colorant contained in the black ink, for example, carbon black such as thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black is preferable. Specific examples of carbon black include, for example, the Raven series manufactured by Columbia Carbon Co., Ltd .; the Monarch series, Regal series, and Mogul series manufactured by Cabot Corporation; the Printex series, Color Black series, and Special Black manufactured by Orion Engineered Carbons Co., Ltd. Series, HIBLACK series, NIPex series, and NEROX series; MA series, MCF series, No. 25, No. 33, No. 40, No. 47, No. 52, No. 900 and No. 2300; and the like.
　これらのカーボンブラックの中でも、コート紙上及び普通紙上における印刷濃度を向上させる観点から、ＢＥＴ比表面積が１８０ｍ２／ｇ以上であるものが好ましく、２２０ｍ２／ｇ以上であるものがより好ましく、２６０ｍ２／ｇ以上であるものがさらに好ましい。具体例としては、Ｒａｖｅｎ　２０００、２３５０ＵＬＴＲＡ、２５００ＵＬＴＲＡ、２８００ＵＬＴＲＡ、２９００ＵＬＴＲＡ、３０００ＵＬＴＲＡ、３５００、５０００ＵＬＴＲＡ（以上、コロンビア・カーボン社製）；Ｍｏｎａｒｃｈ７００、８８０、９００、１０００、１３００（以上、キャボット社製）；Ｐｒｉｎｔｅｘ７５、８０、８５、９５、Ｌ６、Ｃｏｌｏｕｒ　Ｂｌａｃｋ　Ｓ１６０Ｓ、Ｓ１７０、ＦＷ１８、ＦＷ１８２、ＦＷ１、ＦＷ２、ＦＷ１７１、ＦＷ２００、ＦＷ２８５、Ｓｐｅｃｉａｌ　Ｂｌａｃｋ　５、６、ＨＩＢＬＡＣＫ５０Ｌ、６００Ｌ、８９０、９３０Ｌ、９７０ＬＢ、ＮＩＰｅｘ９０、１６０ＩＱ、１７０ＩＱ、１８０ＩＱ（以上、オリオンエンジニアドカーボンズ社製）；などが挙げられる。カーボンブラックのＢＥＴ比表面積は、例えば、ＡＳＴＭ　Ｄ　６５５６に準拠して測定することができる。 Among these carbon blacks, those having a BET specific surface area of 180 m 2 / g or more are preferable, and those having a BET specific surface area of 220 m 2 / g or more are more preferable, and 260 m 2 is more preferable, from the viewpoint of improving the print density on coated paper and plain paper. It is more preferable that it is / g or more. Specific examples include Raven 2000, 2350ULTRA, 2500ULTRA, 2800ULTRA, 2900ULTRA, 3000ULTRA, 3500, 5000ULTRA (above, Columbia Carbon); Monarch 700, 880, 900, 1000, 1300 (above, Cabot); 80, 85, 95, L6, Color Black S160S, S170, FW18, FW182, FW1, FW2, FW171, FW200, FW285, Special Black 5, 6, HIBLACK50L, 600L, 890, 930L, 970LB, NIPex 180 IQ (all manufactured by Orion Engineered Carbons Co., Ltd.); etc. The BET specific surface area of carbon black can be measured, for example, according to ASTM D 6556.
　カーボンブラックのＤＢＰ吸油量は、例えば、４０～１５０ｍＬ／１００ｇであることが好ましく、普通紙上における発色性を向上させる観点から、７０ｍＬ／１００ｇ以上であることが好ましく、９０ｍＬ／１００ｇ以上であることがより好ましい。ＤＢＰ吸油量とは、カーボンブラック１００ｇが吸収するＤＢＰ（ジブチルフタレート）の量をｃｍ３単位で示すものであり、例えば、ＪＩＳ　Ｋ　６２２１に準拠して測定することができる。 The DBP oil absorption amount of carbon black is, for example, preferably 40 to 150 mL / 100 g, preferably 70 mL / 100 g or more, and preferably 90 mL / 100 g or more from the viewpoint of improving color development on plain paper. More preferred. The DBP oil absorption amount indicates the amount of DBP (dibutyl phthalate) absorbed by 100 g of carbon black in cm3 units, and can be measured according to, for example, JIS K 6221.
　水不溶性着色剤の平均粒径は、通常５０～２５０ｎｍ、好ましくは６０～２００ｎｍである。本明細書において平均粒径とは、レーザ光散乱法を用いて測定した粒子の平均粒径をいう。 The average particle size of the water-insoluble colorant is usually 50 to 250 nm, preferably 60 to 200 nm. In the present specification, the average particle size means the average particle size of particles measured by a laser light scattering method.
　水不溶性着色剤の含有率は、本実施形態に係るインクの総質量に対して、通常１～３０質量％、好ましくは１～１０質量％、より好ましくは２～７質量％である。 The content of the water-insoluble colorant is usually 1 to 30% by mass, preferably 1 to 10% by mass, and more preferably 2 to 7% by mass with respect to the total mass of the ink according to the present embodiment.
［樹脂分散剤］
　樹脂分散剤としては、例えば、スチレン及びその誘導体；ビニルナフタレン及びその誘導体；α，β－エチレン性不飽和性カルボン酸の脂肪族アルコールエステル；（メタ）アクリル酸及びその誘導体；マレイン酸及びその誘導体；イタコン酸及びその誘導体；ファール酸及びその誘導体；酢酸ビニル、ビニルアルコール、ビニルピロリドン、アクリルアミド、及びそれらの誘導体；等のモノマーから選択される少なくとも２種類のモノマー（好ましくは、このうち少なくとも１種類が親水性のモノマー）から構成される共重合体が挙げられる。 [Resin dispersant]
Examples of the resin dispersant include styrene and its derivatives; vinylnaphthalene and its derivatives; aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids; (meth) acrylic acids and their derivatives; maleic acid and its derivatives. At least two types of monomers (preferably at least one of them) selected from monomers such as; itaconic acid and its derivatives; carboxylic acid and its derivatives; vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof; Examples thereof include copolymers composed of (hydrophilic monomers).
　そのような共重合体としては、例えば、スチレン－（メタ）アクリル酸共重合体、スチレン－（メタ）アクリル酸－（メタ）アクリル酸エステル共重合体、（メタ）アクリル酸エステル－（メタ）アクリル酸共重合体、ポリエチレングリコール（メタ）アクリレート－（メタ）アクリル酸共重合体、スチレン－マレイン酸共重合体等が挙げられる。これらの中でも、スチレン－（メタ）アクリル酸共重合体、スチレン－（メタ）アクリル酸－（メタ）アクリル酸エステル共重合体、（メタ）アクリル酸エステル－（メタ）アクリル酸共重合体、及びポリエチレングリコール（メタ）アクリレート－（メタ）アクリル酸共重合体が好ましく、スチレン－（メタ）アクリル酸共重合体、スチレン－（メタ）アクリル酸－（メタ）アクリル酸エステル共重合体、及び（メタ）アクリル酸エステル－（メタ）アクリル酸共重合体がより好ましく、（メタ）アクリル酸エステル－（メタ）アクリル酸共重合体がさらに好ましく、メタクリル酸エステル－メタクリル酸共重合体が特に好ましい。共重合体の種類としては、例えば、ブロック共重合体、ランダム共重合体、グラフト共重合体等が挙げられる。これらの共重合体は、塩の形態であってもよい。 Examples of such a copolymer include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, and (meth) acrylic acid ester- (meth). Examples thereof include acrylic acid copolymers, polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymers, and styrene-maleic acid copolymers. Among these, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, and Polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymers are preferred, styrene- (meth) acrylic acid copolymers, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymers, and (meth) acrylic acid copolymers. ) Acrylic acid ester- (meth) acrylic acid copolymer is more preferable, (meth) acrylic acid ester- (meth) acrylic acid copolymer is further preferable, and methacrylic acid ester-methacrylic acid copolymer is particularly preferable. Examples of the type of copolymer include block copolymers, random copolymers, graft copolymers and the like. These copolymers may be in the form of salts.
　なお、本明細書において「（メタ）アクリル」の用語は、「アクリル」と「メタクリル」の両方を含む意味で用いる。「（メタ）アクリレート」等も同様である。 In this specification, the term "(meth) acrylic" is used to mean both "acrylic" and "methacrylic". The same applies to "(meth) acrylate" and the like.
　樹脂分散剤は、合成することも市販品として入手することもできる。 The resin dispersant can be synthesized or obtained as a commercial product.
　合成により得られる樹脂分散剤としては、例えば、国際公開第２０１３／１１５０７１号に開示されたＡ－Ｂブロックポリマーが挙げられる。国際公開第２０１３／１１５０７１号に開示されたＡ－ＢブロックポリマーのＡブロックを構成するモノマーは、（メタ）アクリル酸、及び直鎖状又は分岐鎖状のＣ４アルキル（メタ）アクリレートから選択される少なくとも１種類のモノマーであり、メタクリル酸及びｎ－ブチルメタクリレートから選択される少なくとも１種類のモノマーが好ましく、これら２種類のモノマーを併用するのがより好ましい。また、国際公開第２０１３／１１５０７１号に開示されたＡ－ＢブロックポリマーのＢブロックを構成するモノマーは、ベンジルメタクリレート及びベンジルアクリレートから選択される少なくとも１種類のモノマーであり、ベンジルメタクリレートが好ましい。Ａ－Ｂブロックポリマーの具体例としては、国際公開第２０１３／１１５０７１号の合成例３～８に開示されたブロック共重合体が挙げられる。 Examples of the resin dispersant obtained by synthesis include AB block polymers disclosed in International Publication No. 2013/115071. The monomers constituting the A block of the AB block polymer disclosed in WO 2013/115071 are selected from (meth) acrylic acid and linear or branched C4 alkyl (meth) acrylates. It is at least one kind of monomer, and at least one kind of monomer selected from methacrylic acid and n-butyl methacrylate is preferable, and it is more preferable to use these two kinds of monomers together. Further, the monomer constituting the B block of the AB block polymer disclosed in International Publication No. 2013/115071 is at least one kind of monomer selected from benzyl methacrylate and benzyl acrylate, and benzyl methacrylate is preferable. Specific examples of the AB block polymer include the block copolymer disclosed in Synthesis Examples 3 to 8 of International Publication No. 2013/115071.
　市販品として入手可能な樹脂分散剤としては、例えば、Ｊｏｎｃｙｒｌ　６２、６７、６８、６７８、６８７（ＢＡＳＦ社製のスチレン－アクリル系共重合体）；モビニールＳ－１００Ａ（ジャパンコーティングレジン（株）製の変性酢酸ビニル共重合体）；ジュリマーＡＴ－２１０（東亜合成（株）製のポリアクリル酸エステル共重合体）；等が挙げられる。 Examples of the resin dispersant available as a commercially available product include Joncill 62, 67, 68, 678, 687 (styrene-acrylic copolymer manufactured by BASF); Movinyl S-100A (manufactured by Japan Coating Resin Co., Ltd.). Modified vinyl acetate copolymer); Julima AT-210 (polyacrylic acid ester copolymer manufactured by Toa Synthetic Co., Ltd.); and the like.
　樹脂分散剤の重量平均分子量（ＭＷ）は、５００００未満であり、３０００以上５００００未満であることが好ましく、７０００～２５０００であることがより好ましい。樹脂分散剤の重量平均分子量は、ゲルパーミュエーションクロマトグラフ法（ＧＰＣ法）により測定することができる。具体的には、ＧＰＣ装置としてＨＬＣ－８３２０ＧＰＣ（東ソー（株）製）を用い、カラムとしてＴＳＫ　ｇｅｌ　Ｓｕｐｅｒ　ＭｕｌｔＩｐｏｒｅ　ＨＺ－Ｈ（東ソー（株）製、内径４．６ｍｍ×１５ｃｍ）を２本用い、溶離液としてテトラヒドロフランを用い、標準試料としてＴＳＫ　Ｓｔａｎｄａｒｄ（東ソー（株）製）を用いて測定することができる。 The weight average molecular weight (MW) of the resin dispersant is less than 50,000, preferably 3,000 or more and less than 50,000, and more preferably 7,000 to 25,000. The weight average molecular weight of the resin dispersant can be measured by a gel permeation chromatograph method (GPC method). Specifically, HLC-8320GPC (manufactured by Tosoh Corporation) is used as the GPC device, and two TSK gel Super MultiIpore HZ-H (manufactured by Tosoh Co., Ltd., inner diameter 4.6 mm × 15 cm) are used as columns for elution. Measurement can be performed using tetrahydrofuran as a liquid and TSK Standard (manufactured by Tosoh Corporation) as a standard sample.
　樹脂分散剤の酸価は、例えば、５０～３００ｍｇＫＯＨ／ｇであることが好ましく、８０～２７５ｍｇＫＯＨ／ｇであることがより好ましく、８０～２５０ｍｇＫＯＨ／ｇであることがさらに好ましい。 The acid value of the resin dispersant is, for example, preferably 50 to 300 mgKOH / g, more preferably 80 to 275 mgKOH / g, and even more preferably 80 to 250 mgKOH / g.
　樹脂分散剤は、水不溶性着色剤と混合した状態で使用することができる。また、水不溶性着色剤の表面の一部又は全部を樹脂分散剤で被覆した状態で使用することもできる。あるいは、これらの両方の状態を併用してもよい。 The resin dispersant can be used in a state of being mixed with a water-insoluble colorant. Further, it can be used in a state where a part or all of the surface of the water-insoluble colorant is covered with the resin dispersant. Alternatively, both of these states may be used together.
　水不溶性着色剤の総質量に対する樹脂分散剤の総質量の比は、通常０．１～１．０、好ましくは０．１～０．６、より好ましくは０．２～０．５である。 The ratio of the total mass of the resin dispersant to the total mass of the water-insoluble colorant is usually 0.1 to 1.0, preferably 0.1 to 0.6, and more preferably 0.2 to 0.5.
［樹脂エマルション］
　樹脂エマルションは、２５℃のメチルエチルケトン１００ｇへの溶解量が１０ｇ以下である固形分（樹脂）を含むものである。当該溶解量は、８ｇ以下であることが好ましく、５ｇ以下であることがより好ましく、２ｇ以下であることがさらに好ましい。２５℃のメチルエチルケトン１００ｇへの溶解量が１０ｇ以下である固形分（樹脂）は、通常、重量平均分子量が５００００以上となる。 [Resin emulsion]
The resin emulsion contains a solid content (resin) having a dissolution amount of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C. The dissolved amount is preferably 8 g or less, more preferably 5 g or less, and further preferably 2 g or less. A solid content (resin) having a dissolution amount of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C. usually has a weight average molecular weight of 50,000 or more.
　なお、本明細書における溶解量は、以下のようにして測定するものとする。すなわち、樹脂エマルションを３５℃の環境下で完全に乾燥させて固形分を得る。そして、得られた固形分をメチルエチルケトン１００ｇ中に徐々に添加し、目視で完全溶解を確認できた上限を「溶解量」とする。 The amount of dissolution in the present specification shall be measured as follows. That is, the resin emulsion is completely dried in an environment of 35 ° C. to obtain a solid content. Then, the obtained solid content is gradually added to 100 g of methyl ethyl ketone, and the upper limit at which complete dissolution can be visually confirmed is defined as the "dissolution amount".
　樹脂エマルションとしては、ポリマーエマルション及びワックスエマルションの少なくとも一方を含むことが好ましい。 The resin emulsion preferably contains at least one of a polymer emulsion and a wax emulsion.
　ポリマーエマルションとしては、例えば、ウレタン系、ポリエステル、アクリル系、酢酸ビニル系、塩化ビニル系、スチレン－アクリル系、アクリル－シリコーン系、スチレン－ブタジエン系等の各ポリマーを水又は水溶性有機溶剤に分散させたエマルションが挙げられる。これらの中でも、ウレタン系、アクリル系、及びスチレン－ブタジエン系から選択されるポリマーのエマルションが好ましく、アクリル系ポリマーのエマルションがより好ましい。 As the polymer emulsion, for example, each polymer such as urethane-based, polyester, acrylic-based, vinyl acetate-based, vinyl chloride-based, styrene-acrylic, acrylic-silicone-based, and styrene-butadiene-based is dispersed in water or a water-soluble organic solvent. The emulsion which has been made is mentioned. Among these, an emulsion of a polymer selected from urethane-based, acrylic-based, and styrene-butadiene-based is preferable, and an acrylic polymer emulsion is more preferable.
　ポリマーエマルションは、合成することも市販品として入手することもできる。 Polymer emulsions can be synthesized or obtained as commercial products.
　合成により得られるポリマーエマルションとしては、例えば、国際公開第２０１５／１４７１９２号に開示されたポリマーエマルションが挙げられる。国際公開第２０１５／１４７１９２号に開示されたポリマーエマルションに含まれるポリマーの中でも、０．５～３．５質量部（好ましくは１～３質量部）のメタクリル酸と、４１～５９質量部（好ましくは４２～５８質量部）のメタクリル酸メチルと、４１～５９質量部（好ましくは４２～５８質量部）のアクリル酸２－エチルへキシルと、０．２～３質量部（好ましくは０．５～２質量部）のメタクリル酸とを、他のモノマーを含まないで重合することにより得られるポリマーが好ましい。 Examples of the polymer emulsion obtained by synthesis include the polymer emulsion disclosed in International Publication No. 2015/147192. Among the polymers contained in the polymer emulsion disclosed in International Publication No. 2015/147192, 0.5 to 3.5 parts by mass (preferably 1 to 3 parts by mass) of methacrylic acid and 41 to 59 parts by mass (preferably) of methacrylic acid. 42-58 parts by mass of methyl methacrylate, 41-59 parts by mass (preferably 42-58 parts by mass) of 2-ethylhexyl acrylate, and 0.2-3 parts by mass (preferably 0.5). A polymer obtained by polymerizing methacrylic acid (up to 2 parts by mass) without containing other monomers is preferable.
　市販品として入手可能なポリマーエマルションとしては、例えば、スーパーフレックス　１２６、１３０、１５０、１７０、２１０、４２０、４７０、８２０、８３０、８９０（以上、第一工業製薬（株）製のウレタン樹脂エマルション）；ハイドラン　ＨＷ－３５０、ＨＷ－１７８、ＨＷ－１６３、ＨＷ－１７１、ＡＰ－２０、ＡＰ－３０、ＷＬＳ－２０１、ＷＬＳ－２１０（以上、ＤＩＣ（株）製のウレタン樹脂エマルション）；０５６９、０８５０Ｚ、２１０８（以上、ＪＳＲ（株）製のスチレン－ブタジエン樹脂エマルション）；ＡＥ９８０、ＡＥ９８１Ａ、ＡＥ９８２、ＡＥ９８６Ｂ、ＡＥ１０４（以上、（株）イーテック製のアクリル樹脂エマルション）、ＮｅｏＣｒｙｌ　Ａ－１１０５、Ａ－１１２５、Ａ－１１２７（以上、楠本化成（株）製のアクリル樹脂エマルション）；等が挙げられる。 Examples of polymer emulsions available on the market include Superflex 126, 130, 150, 170, 210, 420, 470, 820, 830, 890 (above, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Hydran HW-350, HW-178, HW-163, HW-171, AP-20, AP-30, WLS-201, WLS-210 (above, urethane resin emulsion manufactured by DIC Co., Ltd.); 0569, 0850Z , 2108 (above, styrene-butadiene resin emulsion manufactured by JSR Co., Ltd.); AE980, AE981A, AE982, AE986B, AE104 (above, acrylic resin emulsion manufactured by E-Tech Co., Ltd.), NeoCryl A-1105, A-1125, A-1127 (above, acrylic resin emulsion manufactured by Kusumoto Kasei Co., Ltd.); and the like.
　ワックスエマルションとしては、天然ワックス又は合成ワックスを水又は水溶性有機溶剤に分散させたエマルションを用いることができる。 As the wax emulsion, an emulsion in which natural wax or synthetic wax is dispersed in water or a water-soluble organic solvent can be used.
　天然ワックスエマルションとしては、例えば、パラフィンワックス、マイクロクリスタリンワックス等の石油系ワックス；モンタンワックス等の褐炭系ワックス；カルナバワックス、キャンデリアワックス等の植物系ワックス；蜜蝋、ラノリン等の動植物系ワックス；などの各ワックスのエマルションが挙げられる。 Examples of the natural wax emulsion include petroleum waxes such as paraffin wax and microcrystallin wax; brown charcoal waxes such as montan wax; plant waxes such as carnauba wax and canderia wax; animal and plant waxes such as beeswax and lanolin; Emulsion of each wax of.
　合成ワックスエマルションとしては、例えば、ポリアルキレンワックス（好ましくは、ポリＣ２－Ｃ４アルキレンワックス）、酸化ポリアルキレンワックス（好ましくは、酸化ポリＣ２－Ｃ４アルキレンワックス）、パラフィンワックス等のエマルションが挙げられる。これらの中でも、ポリエチレンワックス、ポリプロピレンワックス、酸化ポリエチレンワックス、酸化ポリプロピレンワックス、及びパラフィンワックスから選択されるワックスのエマルションが好ましく、酸化ポリエチレンワックスエマルションがより好ましい。 Examples of the synthetic wax emulsion include emulsions such as polyalkylene wax (preferably poly C2-C4 alkylene wax), oxide polyalkylene wax (preferably poly oxide C2-C4 alkylene wax), and paraffin wax. Among these, a wax emulsion selected from polyethylene wax, polypropylene wax, polyethylene oxide wax, polypropylene oxide wax, and paraffin wax is preferable, and polyethylene oxide wax emulsion is more preferable.
　市販品として入手可能なワックスエマルションとしては、例えば、ＣＥＲＡＦＬＯＵＲ　９２５、９２９、９５０、９９１、ＡＱＵＡＣＥＲ　４９８、５１５、５２６、５３１、５３７、５３９、５５２、１５４７、ＡＱＵＡＭＡＴ　２０８、２６３、２７２、ＭＩＮＥＲＰＯＬ　２２１（以上、ＢＹＫ社製）；三井ハイワックス　ＮＬ１００、ＮＬ２００、ＮＬ５００、４２０２Ｅ、１１０５Ａ、２２０３Ａ、ＮＰ５５０、ＮＰ０５５、ＮＰ５０５（以上、三井化学（株）製）；ＫＵＥ－１００、１１（以上、三洋化学工業（株）製）；ＨＹＴＥＣ　Ｅ－６５００、９０１５、６４００（以上、東邦化学工業（株）製）；等が挙げられる。 Examples of wax emulsions available as commercially available products include CERAFLOUR 925, 929, 950, 991, AQUACER 498, 515, 526, 513, 537, 537, 552, 1547, AQUAMAT 208, 263, 272, MINERPOL 221 (or more). , BYK); Mitsui High Wax NL100, NL200, NL500, 4202E, 1105A, 2203A, NP550, NP055, NP505 (above, Mitsui Chemicals, Inc.); KUE-100, 11 (above, Sanyo Chemicals, Inc.) ); HYTEC E-6500, 9015, 6400 (all manufactured by Toho Kagaku Kogyo Co., Ltd.); and the like.
　以上の樹脂エマルションの中でも、アクリル樹脂エマルション及び酸化ポリエチレンワックスエマルションの少なくとも一方を含むことが好ましく、両方を含むことがより好ましい。 Among the above resin emulsions, it is preferable to include at least one of the acrylic resin emulsion and the polyethylene oxide wax emulsion, and it is more preferable to include both.
　ワックスの平均粒径は、インクジェットヘッドの目詰まりを防止するため、５０ｎｍ～５μｍであることが好ましく、１００ｎｍ～１μｍであることがより好ましい。 The average particle size of the wax is preferably 50 nm to 5 μm, more preferably 100 nm to 1 μm in order to prevent clogging of the inkjet head.
　樹脂エマルションの固形分としての含有率は、インクの紙への定着性、インクの吐出性、及びインクの保存安定性の観点から、本実施形態に係るインクの総質量に対して、通常０．６～６．０質量％、好ましくは１．０～５．０質量％である。 The content of the resin emulsion as a solid content is usually 0. It is 6 to 6.0% by mass, preferably 1.0 to 5.0% by mass.
［ゾル］
　ゾルは、液体中にコロイド粒子が分散しているものである。ゾルとしては、インクの保存安定性の観点から、シリカゾル及び酸化ジルコニウムゾルの少なくとも一方を含むことが好ましく、コート紙上及び普通紙上における印刷濃度を向上させる観点から、シリカゾルを含むことがより好ましく、コロイダルシリカゾル及びオルガノシリカゾルの少なくとも一方を含むことがさらに好ましい。特に、ブラックインクとしたときのコート紙上及び普通紙上における印刷濃度を向上させるためには、ＢＥＴ比表面積が１８０ｍ２／ｇ以上のカーボンブラックと、コロイダルシリカゾルとを組み合わせることが好ましい。 [Sol]
A sol is a liquid in which colloidal particles are dispersed. The sol preferably contains at least one of a silica sol and a zirconium oxide sol from the viewpoint of ink storage stability, and more preferably contains a silica sol from the viewpoint of improving the printing density on coated paper and plain paper. It is more preferable to contain at least one of a silica sol and an organosilica sol. In particular, in order to improve the print density on coated paper and plain paper when black ink is used, it is preferable to combine carbon black having a BET specific surface area of 180 m 2 / g or more with colloidal silica sol.
　ゾルは、市販品として入手することができる。コロイダルシリカゾルの市販品としては、例えば、日産化学（株）製のスノーテックスシリーズ、日揮触媒化成（株）製のＳＩシリーズ、日本化学工業（株）製のシリカドールシリーズ、扶桑化学工業（株）製のＰＬシリーズ等が挙げられる。オルガノシリカゾルの市販品としては、日産化学（株）製のメタノールシリカゾル、ＩＰＡ－ＳＴ、ＥＧ－ＳＴ、ＮＰＣ－ＳＴ－３０、ＰＧＭ－ＳＴ、ＮＭＰ－ＳＴ等が挙げられる。酸化ジルコニウムゾルの市販品としては、堺化学工業（株）製のＳＺＲシリーズ等が挙げられる。 The sol can be obtained as a commercial product. Commercially available colloidal silica sol includes, for example, Snowtex series manufactured by Nissan Chemical Industries, Ltd., SI series manufactured by JGC Catalysts and Chemicals Co., Ltd., silica doll series manufactured by Nippon Chemical Industrial Co., Ltd., and Fuso Chemical Industries, Ltd. PL series and the like. Examples of commercially available organosilica sol include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, EG-ST, NPC-ST-30, PGM-ST, NMP-ST and the like. Examples of commercially available zirconium oxide sol products include the SZR series manufactured by Sakai Chemical Industry Co., Ltd.
　ゾルの平均粒子径は、擦過痕がぎらつきにくくなる観点から、３ｎｍ以上２２ｎｍ未満であり、５～２０ｎｍであることが好ましい。 The average particle size of the sol is preferably 3 nm or more and less than 22 nm, preferably 5 to 20 nm, from the viewpoint that scratch marks are less likely to glare.
　ゾルの含有率は、擦過痕がぎらつきにくくなる観点、及びインクの保存安定性の観点から、１．０～５．０質量％であり、１．０～３．５質量％であることが好ましい。
［水］
　水としては、イオン交換水、蒸留水等の不純物（金属イオン等）の少ないものが好ましい。 The content of the sol is 1.0 to 5.0% by mass and 1.0 to 3.5% by mass from the viewpoint of making scratch marks less likely to glare and the storage stability of the ink. preferable.
[water]
As the water, water having few impurities (metal ions, etc.) such as ion-exchanged water and distilled water is preferable.
［インク調製剤］
　本実施形態に係るインクは、上述した成分以外に、インク調製剤をさらに含有していてもよい。インク調製剤としては、例えば、有機溶剤、界面活性剤、防黴剤、防腐剤、ｐＨ調整剤、防錆剤、消泡剤等が挙げられる。 [Ink preparation]
The ink according to the present embodiment may further contain an ink preparation agent in addition to the above-mentioned components. Examples of the ink preparation agent include organic solvents, surfactants, fungicides, preservatives, pH adjusters, rust preventives, defoamers and the like.
（有機溶剤）
　有機溶剤としては、例えば、メタノール、エタノール、プロパノール、テキサノール、イソプロパノール、ブタノール、イソブタノール、第二ブタノール、第三ブタノール等のＣ１－Ｃ６アルカノール；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のカルボン酸アミド；２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－メチルピロリジン－２－オン等のラクタム；１，３－ジメチルイミダゾリジン－２－オン、１，３－ジメチルヘキサヒドロピリミド－２－オン等の環式尿素類；アセトン、２－メチル－２－ヒドロキシペンタン－４－オン、エチレンカーボネート等のケトン、ケトアルコール、又はカーボネート；テトラヒドロフラン、ジオキサン等の環状エーテル；エチレングリコール、ジエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブチレングリコール、１，４－ブチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、ポリエチレングリコール（好ましくは、分子量４００、８００、１５４０、又はそれ以上のもの）、ポリプロピレングリコール、チオジグリコール、ジチオジグリコール等のＣ２－Ｃ６アルキレン単位を有するモノ、オリゴ、若しくはポリアルキレングリコール又はチオグリコール；グリセリン、ジグリセリン、ヘキサン－１，２，６－トリオール、トリメチロールプロパン等のＣ３－Ｃ９ポリオール（トリオール）；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モノエチルエーテル、エチレングリコールモノアリルエーテル、エチレングリコールモノイソプロピルエーテル、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、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、プロレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコールエーテル（好ましくは、Ｃ３－Ｃ１０のモノ、ジ、又はトリエチレングリコールエーテル、及びＣ４－Ｃ１３のモノ、ジ、又はトリプロピレングリコールエーテルから選択されるグリコールエーテル）；１，２－ペンタンジオール、１，５－ペンタンジオール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，４－ジエチル－１，５－ペンタンジオール等のＣ５－Ｃ９アルカンジオール；γ－ブチロラクトン、ジメチルスルホキシド；などが挙げられる。これらの中でも、１，２－ヘキサンジオール及びテキサノールが好ましい。 (Organic solvent)
Examples of the organic solvent include C1-C6 alkanols such as methanol, ethanol, propanol, texanol, isopropanol, butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, N, N-dimethylacetamide and the like. Carous acid amides; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2-one, 1,3-dimethylhexahydropyrimido Cyclic ureas such as -2-one; acetone, 2-methyl-2-hydroxypentane-4-one, ketones such as ethylene carbonate, keto alcohol, or carbonates; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, diethylene glycol. , 1,2-Propanediol, 1,3-Propanediol, 1,2-butylene glycol, 1,4-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol (preferably molecular weight). 400, 800, 1540, or more), mono, oligos, or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as polypropylene glycol, thiodiglycol, dithiodiglycol; glycerin, diglycerin, hexane -C3-C9 polyol (triol) such as 1,2,6-triol and trimethylpropane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, prolen glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. Glycol ethers (preferably glycol ethers selected from C3-C10 mono, di, or triethylene glycol ethers, and C4-C13 mono, di, or tripropylene glycol ethers); 1,2-Pen. Tandiol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-diol Examples thereof include C5-C9 alkanediol such as -1,5-pentanediol; γ-butyrolactone, dimethyl sulfoxide; and the like. Of these, 1,2-hexanediol and texanol are preferred.
（界面活性剤）
　界面活性剤としては、アニオン、ノニオン、シリコーン系、及びフッ素系の各界面活性剤が挙げられる。これらの中でも、シリコーン系及びフッ素系から選択される界面活性剤が好ましく、生体や環境への安全性の観点から、シリコーン系界面活性剤がより好ましい。 (Surfactant)
Examples of the surfactant include anion-based, nonionic, silicone-based, and fluorine-based surfactants. Among these, a silicone-based surfactant and a fluorine-based surfactant are preferable, and a silicone-based surfactant is more preferable from the viewpoint of safety to the living body and the environment.
　アニオン界面活性剤としては、例えば、アルキルスルホカルボン酸塩、α－オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、Ｎ－アシルアミノ酸又はその塩、Ｎ－アシルメチルタウリン塩、アルキル硫酸塩ポリオキシアルキルエーテル硫酸塩、アルキル硫酸塩ポリオキシエチレンアルキルエーテル燐酸塩、ロジン酸石鹸、ヒマシ油硫酸エステル塩、ラウリルアルコール硫酸エステル塩、アルキルフェノール型燐酸エステル、アルキル型燐酸エステル、アルキルアリールスルホン酸塩、ジエチルスルホ琥珀酸塩、ジエチルヘキシルスルホ琥珀酸塩、ジオクチルスルホ琥珀酸塩等が挙げられる。 Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acylamino acids or salts thereof, and N-acylmethyl. Taurine salt, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, loginate soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, Examples thereof include alkylaryl sulfonate, diethyl sulfo sulphate, diethyl hexyl sulfo sulphate, dioctyl sulfo sulphate and the like.
　ノニオン界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル等のエーテル系；ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系；２，４，７，９－テトラメチル－５－デシン－４，７－ジオール、３，６－ジメチル－４－オクチン－３，６－ジオール、３，５－ジメチル－１－ヘキシン－３－オール等のアセチレングリコール（アルコール）系；ポリグリコールエーテル系等が挙げられる。市販品としては、例えば、日信化学（株）製のサーフィノール　１０４、１０４ＰＧ５０、８２、４２０、４４０、４６５、４８５、オルフィン　ＳＴＧ；花王（株）製のエマルゲン　Ａ－６０、Ａ－９０、Ａ－５００；等が挙げられる。 Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxy. Ethers such as ethylene distyrene phenyl ether; polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate , Polyoxyethylene stearate and other ester systems; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3, Examples thereof include acetylene glycol (alcohol) type such as 5-dimethyl-1-hexin-3-ol; polyglycol ether type and the like. Commercially available products include, for example, Surfinol 104, 104PG50, 82, 420, 440, 465, 485, Orfin STG manufactured by Nisshin Kagaku Co., Ltd .; Emargen A-60, A-90, A manufactured by Kao Corporation. -500; and the like.
　シリコーン系界面活性剤としては、例えば、ポリエーテル変性シロキサン、ポリエーテル変性ポリジメチルシロキサン等が挙げられる。市販品としては、例えば、エアープロダクツ社製のダイノール　９６０、９８０；日信化学（株）製のシルフェイス　ＳＡＧ００１、ＳＡＧ００２、ＳＡＧ００３、ＳＡＧ００５、ＳＡＧ５０３Ａ、ＳＡＧ００８、ＳＡＧ００９、ＳＡＧ０１０；ＢＹＫ社製のＢＹＫ－３４５、３４７、３４８、３４９、３４５５、ＬＰ－Ｘ２３２８８、ＬＰ－Ｘ２３２８９、ＬＰ－Ｘ２３３４７；Ｅｖｏｎｉｃ　Ｔｅｇｏ　Ｃｈｅｍｉｅ社製のＴＥＧＯ　Ｔｗｉｎ　４０００、ＴＥＧＯ　Ｗｅｔ　ＫＬ　２４５、２５０、２６０、２６５、２７０、２８０；等が挙げられる。 Examples of the silicone-based surfactant include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. As commercial products, for example, Dynol 960, 980 manufactured by Air Products Co., Ltd .; Silface SAG001, SAG002, SAG003, SAG005, SAG503A, SAG008, SAG090, SAG010 manufactured by Nisshin Chemical Co., Ltd .; BYK-345 manufactured by BYK Co., Ltd. , 347, 348, 349, 3455, LP-X23288, LP-X23289, LP-X23347; TEGO Twin 4000, TEGO Wet KL 245, 250, 260, 265, 270, 280; manufactured by Evonik Tego Chemie, etc. ..
　フッ素系界面活性剤としては、例えば、パーフルオロアルキルスルホン酸化合物、パーフルオロアルキルカルボン酸系化合物、パーフルオロアルキルリン酸エステル化合物、パーフルオロアルキルエチレンオキサイド付加物、パーフルオロアルキルエーテル基を側鎖に有するポリオキシアルキレンエーテルポリマー化合物等が挙げられる。 Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group as side chains. Examples thereof include polyoxyalkylene ether polymer compounds having.
（防黴剤）
　防黴剤としては、例えば、デヒドロ酢酸ナトリウム、安息香酸ナトリウム、ナトリウムピリジンチオン－１－オキシド、ｐ－ヒドロキシ安息香酸エチルエステル、１，２－ベンズイソチアゾリン－３－オン及びその塩等が挙げられる。 (Antifungal agent)
Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof.
（防腐剤）
　防腐剤としては、例えば、有機硫黄系、有機窒素硫黄系、有機ハロゲン系、ハロアリールスルホン系、ヨードプロパギル系、ハロアルキルチオ系、ニトリル系、ピリジン系、８－オキシキノリン系、ベンゾチアゾール系、イソチアゾリン系、ジチオール系、ピリジンオキシド系、ニトロプロパン系、有機スズ系、フェノール系、第４アンモニウム塩系、トリアジン系、チアジン系、アニリド系、アダマンタン系、ジチオカーバメイト系、ブロム化インダノン系、ベンジルブロムアセテート系、無機塩系等の化合物が挙げられる。有機ハロゲン系化合物の具体例としては、例えば、ペンタクロロフェノールナトリウム等が挙げられる。ピリジンオキシド系化合物の具体例としては、例えば、２－ピリジンチオール－１－オキサイドナトリウム等が挙げられる。イソチアゾリン系化合物の具体例としては、例えば、１，２－ベンズイソチアゾリン－３－オン、２－ｎ－オクチル－４－イソチアゾリン－３－オン、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、５－クロロ－２－メチル－４－イソチアゾリン－３－オンマグネシウムクロライド、５－クロロ－２－メチル－４－イソチアゾリン－３－オンカルシウムクロライド、２－メチル－４－イソチアゾリン－３－オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤の具体例としては、無水酢酸ナトリウム、ソルビン酸ナトリウム、安息香酸ナトリウム、ロンザ社製のプロキセルＧＸＬ（Ｓ）、ＬＶ、ＸＬ－２（Ｓ）等が挙げられる。 (Preservative)
Examples of the preservative include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloarylsulfone-based, iodopropagil-based, haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzothiazole-based. Isothiazolin-based, dithiol-based, pyridine oxide-based, nitropropane-based, organic tin-based, phenol-based, tetraammonium salt-based, triazine-based, thiadine-based, anilide-based, adamantan-based, dithiocarbamate-based, brominated indanone-based, benzyl brom Examples thereof include acetate-based and inorganic salt-based compounds. Specific examples of the organic halogen-based compound include sodium pentachlorophenol and the like. Specific examples of the pyridine oxide compound include 2-pyridinethiol-1-oxide sodium and the like. Specific examples of the isothiazolinone compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one. On, 5-chloro-2-methyl-4-isothiazolin-3-onmagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-oncalc chloride, 2-methyl-4-isothiazolin-3-oncalcium Chloride and the like can be mentioned. Specific examples of other antiseptic and antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, Proxel GXL (S), LV, XL-2 (S) manufactured by Ronza, and the like.
（ｐＨ調整剤）
　ｐＨ調整剤としては、例えば、ジエタノールアミン、トリエタノールアミン、Ｎ－メチルジエタノールアミン等のアルカノールアミン；水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物；水酸化アンモニウム（アンモニア水）；炭酸リチウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩；ケイ酸ナトリウム、酢酸カリウム等の有機酸のアルカリ金属塩；リン酸二ナトリウム等の無機塩基；などが挙げられる。 (PH regulator)
Examples of the pH adjuster include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water). Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate; and the like.
（防錆剤）
　防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグリコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムナイトライト等が挙げられる。 (anti-rust)
Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
（消泡剤）
　消泡剤としては、例えば、シリコーン系、シリカ鉱物油系、オレフィン系、アセチレン系等の化合物が挙げられる。市販品としては、例えば、信越化学工業（株）製のサーフィノールＤＦ３７、ＤＦ５８、ＤＦ１１０Ｄ、ＤＦ２２０、ＭＤ－２０、オレフィンＳＫ－１４等が挙げられる。 (Defoamer)
Examples of the defoaming agent include silicone-based, silica-mineral oil-based, olefin-based, and acetylene-based compounds. Examples of commercially available products include Surfinol DF37, DF58, DF110D, DF220, MD-20, and Olefin SK-14 manufactured by Shin-Etsu Chemical Co., Ltd.
［インクの調製方法等］
　本実施形態に係るインクは、水不溶性着色剤及び樹脂分散剤を含有する水性分散液を調製し、この水性分散液に樹脂エマルション、ゾル、及び必要に応じてインク調製剤を加えて混合することにより調製することができる。 [Ink preparation method, etc.]
For the ink according to the present embodiment, prepare an aqueous dispersion containing a water-insoluble colorant and a resin dispersant, and add a resin emulsion, a sol, and an ink preparation if necessary to the aqueous dispersion and mix them. Can be prepared by.
　水性分散液の調製方法としては、例えば、転相乳化法、酸析法、界面重合法、ｉｎ－ｓｉｔｕ重合法、液中硬化被膜法、コアセルベーション（相分離）法、液中乾燥法、融解分散冷却法、気中懸濁被覆法、スプレードライング法等が挙げられる。これらの中でも、転相乳化法、酸析法、及び界面重合法が好ましく、転相乳化法がより好ましい。 Examples of the method for preparing the aqueous dispersion include a phase inversion emulsification method, an acid analysis method, an interfacial polymerization method, an in-situ polymerization method, an in-liquid curing coating method, a core selvation (phase separation) method, and an in-liquid drying method. Examples thereof include a melt dispersion cooling method, an air suspension coating method, and a spray drying method. Among these, the phase inversion emulsification method, the acid analysis method, and the interfacial polymerization method are preferable, and the phase inversion emulsification method is more preferable.
　転相乳化法により水性分散液を調製する場合、例えば、２－ブタノン等の有機溶剤に樹脂分散剤を溶解し、中和剤の水溶液を加えて乳化液を調製する。得られた乳化液に水不溶性着色剤を加えて分散処理を行う。このようにして得られた液から有機溶剤と一部の水とを減圧留去することにより、目的とする水性分散液を得ることができる。 When preparing an aqueous dispersion by the phase inversion emulsification method, for example, a resin dispersant is dissolved in an organic solvent such as 2-butanone, and an aqueous solution of a neutralizing agent is added to prepare an emulsion. A water-insoluble colorant is added to the obtained emulsion to carry out a dispersion treatment. By distilling off the organic solvent and a part of water under reduced pressure from the liquid thus obtained, the desired aqueous dispersion can be obtained.
　分散処理は、サンドミル（ビーズミル）、ロールミル、ボールミル、ペイントシェーカー、超音波分散機、マイクロフルイダイザー等を用いて行うことができる。例えば、サンドミルを用いるときは、粒子径０．０１～１ｍｍ程度のビーズを使用し、ビーズの充填率を適宜設定して分散処理を行うことができる。上記のようにして得られた水性分散液に対して、濾過、遠心分離等の操作を行うことにより、水性分散液に含有される粒子の粒子径を揃えることができる。水性分散液の調製中に泡立ちが生じるときは、公知のシリコーン系、アセチレングリコール系等の消泡剤を極微量加えることができる。 The dispersion treatment can be performed using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like. For example, when a sand mill is used, beads having a particle diameter of about 0.01 to 1 mm can be used, and the filling rate of the beads can be appropriately set to perform the dispersion treatment. By performing operations such as filtration and centrifugation on the aqueous dispersion obtained as described above, the particle size of the particles contained in the aqueous dispersion can be made uniform. When foaming occurs during the preparation of the aqueous dispersion, a very small amount of a known silicone-based or acetylene glycol-based defoaming agent can be added.
　水性分散液中における水不溶性着色剤の平均粒子径（Ｄ５０）は、通常３００ｎｍ以下、好ましくは３０～２８０ｎｍ、より好ましくは４０～２７０ｎｍ、さらに好ましくは５０～２５０ｎｍである。同様にＤ９０は、通常４００ｎｍ以下、好ましくは３５０ｎｍ以下、より好ましくは３００ｎｍ以下である。Ｄ９０の下限は１００ｎｍ以上が好ましい。同様にＤ１０は、通常１０ｎｍ以上、好ましくは２０ｎｍ以上、より好ましくは３０ｎｍ以上である。Ｄ１０の上限は１００ｎｍ以下が好ましい。なお、水不溶性着色剤の平均粒子径は、レーザ光散乱を用いて測定することができる。 The average particle size (D50) of the water-insoluble colorant in the aqueous dispersion is usually 300 nm or less, preferably 30 to 280 nm, more preferably 40 to 270 nm, and further preferably 50 to 250 nm. Similarly, D90 is usually 400 nm or less, preferably 350 nm or less, and more preferably 300 nm or less. The lower limit of D90 is preferably 100 nm or more. Similarly, D10 is usually 10 nm or more, preferably 20 nm or more, and more preferably 30 nm or more. The upper limit of D10 is preferably 100 nm or less. The average particle size of the water-insoluble colorant can be measured by using laser light scattering.
　本実施形態に係るインクをインクジェットインクとして使用する場合、金属陽イオンの塩化物（例えば、塩化ナトリウム）、金属陽イオンの硫酸塩（例えば、硫酸ナトリウム）等の無機不純物の含有量が少ないことが好ましい。このような無機不純物は、市販品の水不溶性着色剤に含まれることが多い。無機不純物の含有率の目安は、おおよそ水不溶性着色剤の総量に対して１質量％以下程度であり、下限は分析機器の検出限界以下、すなわち０％が理想である。無機不純物の少ない水不溶性着色剤を得る方法としては、例えば、逆浸透膜を用いる方法；水不溶性着色剤の固体をメタノール等のＣ１－Ｃ４アルコールと水との混合溶媒中で懸濁撹拌し、水不溶性着色体を濾過分離して、乾燥する方法；イオン交換樹脂で無機不純物を交換吸着する方法；等が挙げられる。 When the ink according to this embodiment is used as an inkjet ink, the content of inorganic impurities such as metal cation chloride (for example, sodium chloride) and metal cation sulfate (for example, sodium sulfate) may be low. preferable. Such inorganic impurities are often contained in commercially available water-insoluble colorants. The guideline for the content of inorganic impurities is about 1% by mass or less with respect to the total amount of the water-insoluble colorant, and the lower limit is ideally below the detection limit of the analytical instrument, that is, 0%. As a method for obtaining a water-insoluble colorant having few inorganic impurities, for example, a method using a reverse osmosis membrane; a solid water-insoluble colorant is suspended and stirred in a mixed solvent of C1-C4 alcohol such as methanol and water. Examples thereof include a method of filtering and separating a water-insoluble colored substance and drying it; a method of exchanging and adsorbing inorganic impurities with an ion exchange resin; and the like.
　また、本実施形態に係るインクをインクジェットインクとして使用する場合、インクを精密濾過することが好ましい。精密濾過には、メンブランフィルター、ガラス濾紙等を用いることができる。精密濾過を行うときのフィルター等の孔径は、通常０．５～２０μｍ、好ましくは０．５～１０μｍである。 Further, when the ink according to the present embodiment is used as an inkjet ink, it is preferable to microfilter the ink. For microfiltration, a membrane filter, glass filter paper, or the like can be used. The pore size of the filter or the like when performing microfiltration is usually 0.5 to 20 μm, preferably 0.5 to 10 μm.
　本実施形態に係るインクは、筆記、印刷、情報印刷、捺染等の各種の印刷分野に使用することができ、特に、インクジェット印刷に用いることが好ましい。 The ink according to this embodiment can be used in various printing fields such as writing, printing, information printing, and printing, and is particularly preferably used for inkjet printing.
＜インクセット、インクメディアセット＞
　本実施形態に係るインクセットは、上述した本実施形態に係るインクと、該インクとは異なる他のインクとを備えるものである。他のインクとしては、本実施形態に係るインクと構成が異なるものであれば特に限定されないが、本実施形態に係るインクと色相が異なるものが好ましい。 <Ink set, ink media set>
The ink set according to the present embodiment includes the above-mentioned ink according to the present embodiment and other inks different from the ink. The other ink is not particularly limited as long as it has a structure different from that of the ink according to the present embodiment, but an ink having a hue different from that of the ink according to the present embodiment is preferable.
　また、本実施形態に係るインクセットは、上述した本実施形態に係るインク又はインクセットと、印刷メディアとを備えるものである。 Further, the ink set according to the present embodiment includes the ink or the ink set according to the above-mentioned embodiment and a print medium.
　印刷メディアとしては、例えば、紙、フィルム、繊維や布（セルロース、ナイロン、羊毛等）、皮革、カラーフィルター用基材等が挙げられる。これらの記録メディアは、インク受容層を有するものと有しないものとに大別することができる。 Examples of print media include paper, film, fibers and cloths (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. These recording media can be roughly classified into those having an ink receiving layer and those having no ink receiving layer.
　インク受容層を有する記録メディアとしては、例えば、紙、合成紙、フィルム等を基材とし、これにインク受容層を設けたものが挙げられる。インク受容層は、例えば、基材にカチオン系ポリマーを含浸又は塗工する方法；多孔質シリカ、アルミナゾル、特殊セラミックス等の無機微粒子を、ポリビニルアルコール、ポリビニルピロリドン等の親水性ポリマーとともに基材表面に塗工する方法；等により設けられる。このような記録メディアは、通常、インクジェット専用紙、インクジェット専用フィルム、光沢紙等と呼ばれる。市販品の具体例としては、例えば、キヤノン（株）製の商品名：プロフェッショナルフォトペーパー、スーパーフォトペーパー、光沢ゴールド、及びマットフォトペーパー；セイコーエプソン（株）製の商品名：写真用紙クリスピア（高光沢）、写真用紙（光沢）、フォトマット紙；日本ヒューレット・パッカード（株）製の商品名：アドバンスフォト用紙（光沢）；富士フイルム（株）製の商品名：画彩写真仕上げＰｒｏ；等が挙げられる。 Examples of the recording medium having an ink receiving layer include those using paper, synthetic paper, film, or the like as a base material and providing an ink receiving layer on the base material. The ink receiving layer is, for example, a method of impregnating or coating a base material with a cationic polymer; inorganic fine particles such as porous silica, alumina sol, and special ceramics are placed on the surface of the base material together with hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone. It is provided by a method of coating; etc. Such recording media are usually referred to as inkjet paper, inkjet film, glossy paper, or the like. Specific examples of commercially available products include, for example, product names manufactured by Canon Co., Ltd .: professional photo paper, super photo paper, glossy gold, and matte photo paper; product names manufactured by Seiko Epson Co., Ltd .: photo paper crispia (high). Glossy), photo paper (glossy), photo matte paper; product name made by Nippon Hulett Packard Co., Ltd .: advanced photo paper (glossy); product name made by Fujifilm Co., Ltd .: painting photo finishing Pro; etc. Can be mentioned.
　一方、インク受容層を有しない記録メディアとしては、グラビア印刷、オフセット印刷等の用途に用いられるコート紙、アート紙等の各種の用紙；ラベル印刷用途に用いられるキャストコート紙；等が挙げられる。市販品の具体例としては、例えば、王子製紙（株）製の商品名：ＯＫトップコート＋等が挙げられる。 On the other hand, examples of recording media having no ink receiving layer include various types of paper such as coated paper and art paper used for gravure printing and offset printing; cast coated paper used for label printing, and the like. Specific examples of commercially available products include, for example, trade name: OK Top Coat + manufactured by Oji Paper Co., Ltd.
＜インクジェット印刷方法＞
　本実施形態に係るインクジェット印刷方法は、上述した本実施形態に係るインク、或いは上述した本実施形態に係るインクセットが備える各インクの液滴を印刷信号に応じて吐出させて、印刷メディアに付着させることにより印刷を行う方法である。インクの吐出を行うインクジェットプリンタのインクノズル等については特に制限はなく、目的に応じて適宜選択することができる。 <Inkjet printing method>
In the inkjet printing method according to the present embodiment, droplets of the ink according to the present embodiment described above or the ink droplets of each ink provided in the ink set according to the above-mentioned embodiment are ejected according to a print signal and adhered to the print media. It is a method of printing by making the ink. There are no particular restrictions on the ink nozzles and the like of the inkjet printer that ejects ink, and the ink nozzles and the like can be appropriately selected according to the purpose.
　本実施形態に係るインクジェット印刷方法には、インク中の水不溶性着色剤の含有率の低いインクを小さい体積で多数射出して画質を改良する方法；実質的に同じ色相で、インク中の水不溶性着色剤の含有率が異なる複数のインクを用いて画質を改良する方法；無色透明のインクと、水不溶性着色剤を含有するインクとを併用することにより、印刷メディアに対する水不溶性着色剤の定着性を向上させる方法；等も含まれる。 In the inkjet printing method according to the present embodiment, a large number of inks having a low content of water-insoluble colorant in the ink are ejected in a small volume to improve the image quality; the ink has substantially the same hue and is water-insoluble in the ink. A method of improving image quality by using a plurality of inks having different colorant contents; by using a colorless transparent ink and an ink containing a water-insoluble colorant in combination, the fixability of the water-insoluble colorant to a print medium Methods to improve; etc. are also included.
　インクジェット印刷方式としては、公知の方式を採用することができる。その一例としては、例えば、電荷制御方式、ドロップオンデマンド方式（圧力パルス方式）、音響インクジェット方式、サーマルインクジェット方式等が挙げられる。 As the inkjet printing method, a known method can be adopted. Examples thereof include a charge control method, a drop-on-demand method (pressure pulse method), an acoustic inkjet method, a thermal inkjet method, and the like.
　印刷メディアに印刷するときは、例えば、インクを含有する容器（インクタンク）をインクジェットプリンタの所定の位置に装填し、上記の印刷方法で印刷メディアに印刷する。なお、各色のインクを含有する容器をインクジェットプリンタの所定の位置に装填し、上記の印刷方法で印刷メディアに印刷することにより、フルカラーの印刷を実現することもできる。 When printing on print media, for example, a container (ink tank) containing ink is loaded in a predetermined position of an inkjet printer, and printing is performed on the print media by the above printing method. It is also possible to realize full-color printing by loading a container containing ink of each color into a predetermined position of an inkjet printer and printing on a printing medium by the above printing method.
　上記した全ての内容について、好ましいもの同士の組み合わせはより好ましく、より好ましいもの同士の組み合わせはさらに好ましい。好ましいものとより好ましいものとの組み合わせ、より好ましいものとさらに好ましいものとの組み合わせ等についても同様である。 For all the above-mentioned contents, the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable. The same applies to the combination of a preferable one and a more preferable one, a combination of a more preferable one and a more preferable one, and the like.
　以下、実施例により本発明をさらに詳細に説明するが、本発明は、以下の実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
　実施例においては、特に断りのない限り、「部」は質量部を、「％」は質量％をそれぞれ意味する。実施例における各種の合成、調製等の操作は、特に断りのない限り、いずれも撹拌下に行った。また、水性分散液中の着色剤の固形分の定量が必要な場合には、（株）エイ・アンド・デイ製のＭＳ－７０を用いて、乾燥重量法により、着色剤のみの換算値として算出した。 In the examples, unless otherwise specified, "part" means parts by mass and "%" means mass%. Unless otherwise specified, all the operations such as synthesis and preparation in the examples were carried out under stirring. When it is necessary to quantify the solid content of the colorant in the aqueous dispersion, MS-70 manufactured by A & D Co., Ltd. is used as a conversion value of the colorant only by the dry weight method. Calculated.
＜調製例１：分散液ＤＰ１の調製＞
　国際公開第２０１３／１１５０７１号の合成例３を追試することにより、合成例３のブロック共重合体を調製した。得られたブロック共重合体の酸価は１０５ｍｇＫＯＨ／ｇ、重量平均分子量は２５０００であった。得られたブロック共重合体（６．６部）を２－ブタノン（２０部）に溶解し、これに水酸化ナトリウム（０．３６部）をイオン交換水（５０部）に溶解させた液を加え、３０分間撹拌して乳化液とした。得られた乳化液にＮｅｒｏｘ６０５（オリオンエンジニアドカーボンズ社製のカーボンブラック）（２０部）を加え、サンドグラインダーで１５００ｒｐｍの条件下、１５時間分散処理を行って液を得た。得られた液にイオン交換水（１２０部）を加え、分散用ビーズを濾過分離して濾液を得た。得られた濾液からエバポレーターで２－ブタノン及び水の一部を減圧留去することにより、着色剤の固形分含有率が１２％の分散液ＤＰ１を得た。 <Preparation Example 1: Preparation of dispersion liquid DP1>
The block copolymer of Synthesis Example 3 was prepared by retesting Synthesis Example 3 of International Publication No. 2013/115071. The acid value of the obtained block copolymer was 105 mgKOH / g, and the weight average molecular weight was 25,000. A solution prepared by dissolving the obtained block copolymer (6.6 parts) in 2-butanone (20 parts) and dissolving sodium hydroxide (0.36 parts) in ion-exchanged water (50 parts) was added thereto. In addition, the mixture was stirred for 30 minutes to prepare an emulsion. Neurox605 (carbon black manufactured by Orion Engineered Carbons Co., Ltd.) (20 parts) was added to the obtained emulsified liquid, and a sand grinder was used to disperse the liquid under the condition of 1500 rpm for 15 hours to obtain a liquid. Ion-exchanged water (120 parts) was added to the obtained liquid, and the beads for dispersion were separated by filtration to obtain a filtrate. 2-Butanone and a part of water were distilled off from the obtained filtrate under reduced pressure by an evaporator to obtain a dispersion liquid DP1 having a solid content of 12% as a colorant.
＜調製例２：分散液ＤＰ２の調製＞
　Ｎｅｒｏｘ６０５の代わりにＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　７４（クラリアント社製、ＨＡＮＳＡ　ＹＥＬＬＯＷ　５ＧＸ０１－ＪＰ）を用いる以外は調製例１と同様にして、着色剤の固形分含有率が１２％の分散液ＤＰ２を得た。 <Preparation Example 2: Preparation of Dispersion Liquid DP2>
Instead of Neox605, C.I. I. A dispersion liquid DP2 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 1 except that Pigment Yellow 74 (HANSA YELLOW 5GX01-JP manufactured by Clariant AG) was used.
＜調製例３：樹脂エマルションＡの調製＞
　ガラス製反応容器（容量３Ｌ）に水（１００部）、過硫酸アンモニウム（０．３部）、及び反応性乳化剤（１部）を加えて液を得た。反応容器内部の空気を窒素で置換した後、液の温度を７０℃に昇温した。この液に、水（１２０部）、反応性乳化剤（０．９部）、メタクリル酸（２部）、メタクリル酸メチル（３７部）、アクリル酸２－エチルヘキシル（５９部）、及びメタクリル酸アリル（２部）からなる液を３時間かけて滴下した。液の滴下中は、窒素を導入しながら７０℃の液温を維持して反応を行った。液の滴下終了後、さらに７０℃で２時間反応させた後、４０℃に冷却した。得られた液にトリエタノールアミン（３．１部）を加えることにより、固形分２５％の白色懸濁液として樹脂エマルションＡを得た。樹脂エマルションＡに含まれる固形分（樹脂）の２５℃のメチルエチルケトン１００ｇへの溶解量は５ｇ以下、酸価は１３ｍｇＫＯＨ／ｇ、ガラス転移温度（Ｔｇ）は－１０℃であった。 <Preparation Example 3: Preparation of Resin Emulsion A>
Water (100 parts), ammonium persulfate (0.3 parts), and a reactive emulsifier (1 part) were added to a glass reaction vessel (capacity 3 L) to obtain a liquid. After replacing the air inside the reaction vessel with nitrogen, the temperature of the liquid was raised to 70 ° C. In this solution, water (120 parts), reactive emulsifier (0.9 parts), methacrylic acid (2 parts), methyl methacrylate (37 parts), 2-ethylhexyl acrylate (59 parts), and allyl methacrylate (59 parts). The liquid consisting of 2 parts) was added dropwise over 3 hours. During the dropping of the liquid, the reaction was carried out while maintaining the liquid temperature at 70 ° C. while introducing nitrogen. After the dropping of the liquid was completed, the mixture was further reacted at 70 ° C. for 2 hours and then cooled to 40 ° C. By adding triethanolamine (3.1 parts) to the obtained liquid, a resin emulsion A was obtained as a white suspension having a solid content of 25%. The amount of the solid content (resin) contained in the resin emulsion A dissolved in 100 g of methyl ethyl ketone at 25 ° C. was 5 g or less, the acid value was 13 mgKOH / g, and the glass transition temperature (Tg) was −10 ° C.
＜実施例１～１５：インクの調製＞
　下記表１～２に記載の各成分を混合した後、孔径３μｍのメンブランフィルターで濾過することにより、実施例１～１５のインクをそれぞれ得た。 <Examples 1 to 15: Ink preparation>
After mixing each component shown in Tables 1 and 2 below, the inks of Examples 1 to 15 were obtained by filtering with a membrane filter having a pore size of 3 μm.
＜比較例１～６：比較用のインクの調製＞
　下記表３に記載の各成分を混合した後、孔径３μｍのメンブランフィルターで濾過することにより、比較例１～６のインクをそれぞれ得た。なお、比較例５のインクは、保存安定性が極めて悪く、後述する耐擦性等の評価を行うことができなかった。 <Comparative Examples 1 to 6: Preparation of ink for comparison>
After mixing each component shown in Table 3 below, the inks of Comparative Examples 1 to 6 were obtained by filtering with a membrane filter having a pore size of 3 μm. The ink of Comparative Example 5 had extremely poor storage stability, and could not be evaluated for scratch resistance and the like, which will be described later.
　表１～３中の略号等は、以下の意味を表す。
１２ＨＤ：１，２－ヘキサンジオール
ＰＧ：１，２－プロパンジオール
ＴＥＸ：テキサノール
ＴＥＡ：トリエタノールアミン
ＢＹＫ３４９：ＢＹＫ社製、ＢＹＫ－３４９
樹脂エマルションＢ：ＢＹＫ社製、ＡＱＵＡＣＥＲ５１５（固形分：３５％、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量：１ｇ以下）
ＳＴ３０：日産化学（株）製、スノーテックス３０（コロイダルシリカゾル、固形分：３０％）
ＳＴＸＳ：日産化学（株）製、スノーテックスＸＳ（コロイダルシリカゾル、固形分：２０％）
ＳＴＣ：日産化学（株）製、スノーテックスＣ（コロイダルシリカゾル、固形分：２０％）
ＳＤ４０：日本化学工業（株）製、シリカドール４０（コロイダルシリカゾル、固形分：４０％）
ＳＺＲＣＷ：堺化学工業（株）製、ＳＺＲ－ＣＷ（酸化ジルコニウムゾル、固形分：３０％）
ＳＺＲＧＣＷ：堺化学工業（株）製、ＳＺＲ－ＧＣＷ（酸化ジルコニウムゾル、固形分：３０％）
ＰＧＭＳＴ：日産化学（株）製、ＰＧＭ－ＳＴ（オルガノシリカゾル、固形分：３０％）
ＳＴ５０Ｔ：日産化学（株）製、スノーテックス５０Ｔ（コロイダルシリカゾル、固形分：５０％）
ＳＴ３０Ｌ：日産化学（株）製、スノーテックス３０Ｌ（コロイダルシリカゾル、固形分：３０％）
ＧＸＬ（Ｓ）：ロンザ社製、プロキセルＧＸＬ（Ｓ） The abbreviations and the like in Tables 1 to 3 have the following meanings.
12HD: 1,2-hexanediol PG: 1,2-propanediol TEX: texanol TEA: triethanolamine BYK349: BYK, BYK-349
Resin emulsion B: AQUACER515 manufactured by BYK (solid content: 35%, solid content dissolved in 100 g of methyl ethyl ketone at 25 ° C.: 1 g or less)
ST30: Nissan Chemical Industries, Ltd., Snowtex 30 (coloidal silica sol, solid content: 30%)
STXS: Nissan Chemical Industries, Ltd., Snowtex XS (coloidal silica sol, solid content: 20%)
STC: Nissan Chemical Industries, Ltd., Snowtex C (coloidal silica sol, solid content: 20%)
SD40: Made by Nippon Chemical Industrial Co., Ltd., Silica Doll 40 (coloidal silica sol, solid content: 40%)
SZRCW: Made by Sakai Chemical Industry Co., Ltd., SZR-CW (zirconium oxide sol, solid content: 30%)
SZRGCW: manufactured by Sakai Chemical Industry Co., Ltd., SZR-GCW (zirconium oxide sol, solid content: 30%)
PGMST: manufactured by Nissan Chemical Industries, Ltd., PGM-ST (organo silica sol, solid content: 30%)
ST50T: Nissan Chemical Industries, Ltd., Snowtex 50T (coloidal silica sol, solid content: 50%)
ST30L: Nissan Chemical Industries, Ltd., Snowtex 30L (coloidal silica sol, solid content: 30%)
GXL (S): Proxel GXL (S) manufactured by Lonza
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
＜評価＞
［耐擦性の評価］
　実施例１～１５、比較例１～４、６の各インクを用いて、印刷メディアに対してシングルパス（１パス）方式にてインクジェット印刷を行い、１００％Ｄｕｔｙの印刷画像を得た。印刷メディアとしては、王子製紙（株）製のオフセットコート紙「ＯＫトップコート＋」を使用した。インクジェットヘッドとしては、京セラ（株）製の６００ｄｐｉヘッドを使用し、ヘッド温度は３２℃とした。また、吐出するインクの液適量は１２ｐＬとした。インクジェット印刷後、得られた印刷画像を乾燥させた。 <Evaluation>
[Evaluation of abrasion resistance]
Using the inks of Examples 1 to 15 and Comparative Examples 1 to 4 and 6, inkjet printing was performed on the print media by a single pass (1 pass) method to obtain a 100% Duty print image. As the printing medium, offset coated paper "OK Top Coat +" manufactured by Oji Paper Co., Ltd. was used. As the inkjet head, a 600 dpi head manufactured by Kyocera Corporation was used, and the head temperature was 32 ° C. The appropriate amount of ink to be ejected was 12 pL. After inkjet printing, the obtained printed image was dried.
　乾燥後の印刷画像を爪で線擦過し、印刷画像を蛍光灯にかざした際の、擦過部とそれ以外の箇所とのぎらつきの差を観察し、以下の評価基準に従って耐擦性を評価した。評価結果を下記表４～５に示す。
－評価基準－
Ａ：「擦過部にぎらつきや光沢の変化がない」と観察者１０人中１０人全員が判定した。
Ｂ：「擦過部にぎらつきや光沢の変化がある」と観察者１０人中１０人全員が判定した。
Ｃ：線擦過時に擦過部のインクが紙からはがれてしまい、ぎらつきの差を観察できなかった。 When the printed image after drying was scratched with a nail and the printed image was held over a fluorescent lamp, the difference in glare between the scratched part and other parts was observed, and the scratch resistance was evaluated according to the following evaluation criteria. .. The evaluation results are shown in Tables 4 to 5 below.
-Evaluation criteria-
A: All 10 out of 10 observers judged that "there was no glare or change in gloss in the scratched part".
B: All 10 out of 10 observers judged that "the scratched part had glare or a change in gloss".
C: When the line was rubbed, the ink in the rubbed part was peeled off from the paper, and the difference in glare could not be observed.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表４～５に示すとおり、実施例の各インクを用いて得られた印刷物は、オフセットコート紙上で爪による擦過痕がついたとしても、インク塗膜のぎらつきの変化が少なく、耐擦過性に優れていた。 As shown in Tables 4 to 5, the printed matter obtained by using each of the inks of the examples has little change in the glare of the ink coating film even if scratches are made by the nails on the offset coated paper, and the scratch resistance is improved. It was excellent.
［印刷濃度の評価］
　実施例１～６、１３～１５、比較例１～４、６の各インクを用いて、印刷メディアに対してシングルパス（１パス）方式にてインクジェット印刷を行い、１００％Ｄｕｔｙの印刷画像を得た。印刷メディアとしては、王子製紙（株）製のオフセットコート紙「ＯＫトップコート＋」及び日本製紙（株）製の普通紙「Ｎｐｉフォーム７０ＮＥＸＴ－ＩＬ」を使用した。インクジェットヘッドとしては、京セラ（株）製の６００ｄｐｉヘッドを使用し、ヘッド温度は３２℃とした。また、吐出するインクの液適量は１２ｐＬとした。インクジェット印刷後、得られた印刷画像を乾燥させた。 [Evaluation of print density]
Inkjet printing is performed on the print media by a single pass (1 pass) method using the inks of Examples 1 to 6, 13 to 15, and Comparative Examples 1 to 4, 6, and a 100% Duty print image is obtained. Obtained. As the printing media, offset coated paper "OK Top Coat +" manufactured by Oji Paper Co., Ltd. and plain paper "Npi Foam 70NEXT-IL" manufactured by Nippon Paper Industries Co., Ltd. were used. As the inkjet head, a 600 dpi head manufactured by Kyocera Corporation was used, and the head temperature was 32 ° C. The appropriate amount of ink to be ejected was 12 pL. After inkjet printing, the obtained printed image was dried.
　乾燥後の印刷画像について、分光測色計（ｅＸａｃｔ、Ｘ－Ｒｉｔｅ社製）を用いて測色した。測色は、濃度基準：ＡＮＳＩ　Ｔ、光源：Ｄ６５、視野角：２°の条件で行った。そして、下記表６に示す評価基準に従って印刷濃度を評価した。結果を下記表７に示す。 The printed image after drying was color-measured using a spectrocolorimeter (eXact, manufactured by X-Rite). Color measurement was performed under the conditions of density standard: ANSI T, light source: D65, and viewing angle: 2 °. Then, the print density was evaluated according to the evaluation criteria shown in Table 6 below. The results are shown in Table 7 below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表７に示すとおり、実施例の各インクによれば、オフセットコート紙及び普通紙のいずれに印刷した場合にも、良好な印刷濃度を実現することができた。 As shown in Table 7, according to each ink of the example, good print density could be realized when printing on either offset coated paper or plain paper.
＜調製例４：分散液ＤＰ３の調製＞
　国際公開第２０１３／１１５０７１号の合成例３を追試することにより、合成例３のブロック共重合体を調製した。得られたブロック共重合体の酸価は１０５ｍｇＫＯＨ／ｇ、重量平均分子量は２５０００であった。得られたブロック共重合体（６．６部）を２－ブタノン（２０部）に溶解し、これに水酸化ナトリウム（０．３６部）をイオン交換水（５０部）に溶解させた液を加え、３０分間撹拌して乳化液とした。得られた乳化液にＨＩＢＬＡＣＫ８９０（オリオンエンジニアドカーボンズ社製のカーボンブラック）（２０部）を加え、サンドグラインダーで１５００ｒｐｍの条件下、１５時間分散処理を行って液を得た。得られた液にイオン交換水（１２０部）を加え、分散用ビーズを濾過分離して濾液を得た。得られた濾液からエバポレーターで２－ブタノン及び水の一部を減圧留去することにより、着色剤の固形分が１２％の分散液ＤＰ３を得た。 <Preparation Example 4: Preparation of dispersion DP3>
The block copolymer of Synthesis Example 3 was prepared by retesting Synthesis Example 3 of International Publication No. 2013/115071. The acid value of the obtained block copolymer was 105 mgKOH / g, and the weight average molecular weight was 25,000. A solution prepared by dissolving the obtained block copolymer (6.6 parts) in 2-butanone (20 parts) and dissolving sodium hydroxide (0.36 parts) in ion-exchanged water (50 parts) was added thereto. In addition, the mixture was stirred for 30 minutes to prepare an emulsion. HIBLACK890 (carbon black manufactured by Orion Engineered Carbons Co., Ltd.) (20 parts) was added to the obtained emulsion, and a dispersion treatment was carried out for 15 hours with a sand grinder under the condition of 1500 rpm to obtain a liquid. Ion-exchanged water (120 parts) was added to the obtained liquid, and the beads for dispersion were separated by filtration to obtain a filtrate. 2-Butanone and a part of water were distilled off from the obtained filtrate under reduced pressure by an evaporator to obtain a dispersion liquid DP3 having a solid content of a colorant of 12%.
＜調製例５：分散液ＤＰ４の調製＞
　ＨＩＢＬＡＣＫ８９０の代わりにＮＩＰｅｘ９０（オリオンエンジニアドカーボンズ社製のカーボンブラック）を用いる以外は調製例４と同様にして、着色剤の固形分が１２％の分散液ＤＰ４を得た。 <Preparation Example 5: Preparation of Dispersion Liquid DP4>
A dispersion DP4 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 4 except that NIPex90 (carbon black manufactured by Orion Engineered Carbons) was used instead of HIBLACK890.
＜調製例６：分散液ＤＰ５の調製＞
　ＨＩＢＬＡＣＫ８９０の代わりにＰｒｉｎｔｅｘ８０（オリオンエンジニアドカーボンズ社製のカーボンブラック）を用いる以外は調製例４と同様にして、着色剤の固形分が１２％の分散液ＤＰ５を得た。 <Preparation Example 6: Preparation of dispersion liquid DP5>
A dispersion DP5 having a solid content of 12% as a colorant was obtained in the same manner as in Preparation Example 4 except that Printex80 (carbon black manufactured by Orion Engineered Carbons) was used instead of HIBLACK890.
＜調製例７：分散液ＤＰ６の調製＞
　ＨＩＢＬＡＣＫ８９０の代わりにＨＩＢＬＡＣＫ５０Ｌ（オリオンエンジニアドカーボンズ社製のカーボンブラック）を用いる以外は調製例４と同様にして、着色剤の固形分が１２％の分散液ＤＰ６を得た。 <Preparation Example 7: Preparation of Dispersion Liquid DP6>
A dispersion liquid DP6 having a solid content of 12% of a colorant was obtained in the same manner as in Preparation Example 4 except that HIBLACK 50L (carbon black manufactured by Orion Engineered Carbons Co., Ltd.) was used instead of HIBLACK 890.
　上記の調製例４～７で使用したカーボンブラックの物性を下記表８に記載する。 The physical characteristics of the carbon black used in the above preparation examples 4 to 7 are shown in Table 8 below.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
＜実施例１６～２５：インクの調製＞
　下記表９～１０に記載の各成分を混合した後、孔径３μｍのメンブランフィルターで濾過することにより、実施例１６～２５のインクをそれぞれ得た。 <Examples 16 to 25: Ink preparation>
After mixing each component shown in Tables 9 to 10 below, the inks of Examples 16 to 25 were obtained by filtering with a membrane filter having a pore size of 3 μm.
＜比較例７～１１：比較用のインクの調製＞
　下記表１１に記載の各成分を混合した後、孔径３μｍのメンブランフィルターで濾過することにより、比較例７～１１のインクをそれぞれ得た。 <Comparative Examples 7 to 11: Preparation of ink for comparison>
After mixing each component shown in Table 11 below, the inks of Comparative Examples 7 to 11 were obtained by filtering with a membrane filter having a pore size of 3 μm.
　表９～１１中の略号等は、以下の意味を表す。
１２ＨＤ：１，２－ヘキサンジオール
ＰＧ：１，２－プロパンジオール
ＴＥＸ：テキサノール
ＴＥＡ：トリエタノールアミン
ＢＹＫ３４９：ＢＹＫ社製、ＢＹＫ－３４９
樹脂エマルションＣ：楠本化成（株）製、ＮｅｏＣｒｙｌ　Ａ－１１２７（固形分：４４％、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量：１ｇ以下）
樹脂エマルションＤ：ＢＹＫ社製、ＡＱＵＡＣＥＲ５３１（固形分：４５％、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量：５ｇ以下）
ＳＴ３０：日産化学（株）製、スノーテックス３０（コロイダルシリカゾル、固形分：３０％）
ＳＴＸＳ：日産化学（株）製、スノーテックスＸＳ（コロイダルシリカゾル、固形分：２０％）
ＳＤ４０：日本化学工業（株）製、シリカドール４０（コロイダルシリカゾル、固形分：４０％）
ＳＴ５０Ｔ：日産化学（株）製、スノーテックス５０Ｔ（コロイダルシリカゾル、固形分：５０％）
ＳＴ３０Ｌ：日産化学（株）製、スノーテックス３０Ｌ（コロイダルシリカゾル、固形分：３０％）
ＳＺＲＣＷ：堺化学工業（株）製、ＳＺＲ－ＣＷ（酸化ジルコニウムゾル、固形分：３０％）
ＳＺＲＧＣＷ：堺化学工業（株）製、ＳＺＲ－ＧＣＷ（酸化ジルコニウムゾル、固形分：３０％）
ＰＧＭＳＴ：日産化学（株）製、ＰＧＭ－ＳＴ（オルガノシリカゾル、固形分：３０％）
ＧＸＬ（Ｓ）：ロンザ社製、プロキセルＧＸＬ（Ｓ） The abbreviations and the like in Tables 9 to 11 have the following meanings.
12HD: 1,2-hexanediol PG: 1,2-propanediol TEX: texanol TEA: triethanolamine BYK349: BYK, BYK-349
Resin emulsion C: NeoCryl A-1127 manufactured by Kusumoto Kasei Co., Ltd. (solid content: 44%, solid content dissolved in 100 g of methyl ethyl ketone at 25 ° C.: 1 g or less)
Resin emulsion D: AQUACER531 manufactured by BYK (solid content: 45%, solid content dissolved in 100 g of methyl ethyl ketone at 25 ° C.: 5 g or less)
ST30: Nissan Chemical Industries, Ltd., Snowtex 30 (coloidal silica sol, solid content: 30%)
STXS: Nissan Chemical Industries, Ltd., Snowtex XS (coloidal silica sol, solid content: 20%)
SD40: Made by Nippon Chemical Industrial Co., Ltd., Silica Doll 40 (coloidal silica sol, solid content: 40%)
ST50T: Nissan Chemical Industries, Ltd., Snowtex 50T (coloidal silica sol, solid content: 50%)
ST30L: Nissan Chemical Industries, Ltd., Snowtex 30L (coloidal silica sol, solid content: 30%)
SZRCW: Made by Sakai Chemical Industry Co., Ltd., SZR-CW (zirconium oxide sol, solid content: 30%)
SZRGCW: manufactured by Sakai Chemical Industry Co., Ltd., SZR-GCW (zirconium oxide sol, solid content: 30%)
PGMST: manufactured by Nissan Chemical Industries, Ltd., PGM-ST (organo silica sol, solid content: 30%)
GXL (S): Proxel GXL (S) manufactured by Lonza
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
＜評価＞
［印刷濃度の評価］
　バーコーターＮｏ．３（（株）安田機械製作所）を用いて、実施例１１～２５、比較例７～１１の各インクを印刷メディアに塗布した。印刷メディアとしては、王子製紙（株）製のオフセットコート紙「ＯＫトップコート＋」及び日本製紙（株）製の普通紙「Ｎｐｉフォーム７０ＮＥＸＴ－ＩＬ」を使用した。得られた画像を７０℃で２分間乾燥させることにより、試験片を得た。 <Evaluation>
[Evaluation of print density]
Bar coater No. 3 (Yasuda Machinery Works Co., Ltd.) was used to apply the inks of Examples 11 to 25 and Comparative Examples 7 to 11 to the print media. As the printing media, offset coated paper "OK Top Coat +" manufactured by Oji Paper Co., Ltd. and plain paper "Npi Foam 70NEXT-IL" manufactured by Nippon Paper Industries Co., Ltd. were used. The obtained image was dried at 70 ° C. for 2 minutes to obtain a test piece.
　得られた試験片について、分光測色計（ｅＸａｃｔ、Ｘ－Ｒｉｔｅ社製）を用いて５箇所の光学濃度（ＯＤ値）を測定し、その平均値を試験片のＯＤ値とした。測色は、濃度基準：ＡＮＳＩ　Ｔ、光源：Ｄ６５、視野角：２°の条件で行った。そして、下記評価基準に従って印刷濃度を評価した。結果を下記表１２に示す。
－評価基準（ＯＫトップコート＋）－
Ａ：ＯＤ値が２．３以上
Ｂ：ＯＤ値が２．０以上２．３未満
Ｃ：ＯＤ値が１．７以上２．０未満
Ｄ：ＯＤ値が１．７未満
－評価基準（Ｎｐｉフォーム７０ＮＥＸＴ－ＩＪ）－
Ａ：ＯＤ値が１．３０以上
Ｂ：ＯＤ値が１．２５以上１．３０未満
Ｃ：ＯＤ値が１．２０以上１．２５未満
Ｄ：ＯＤ値が１．２０未満 The obtained test piece was measured with optical densities (OD values) at five points using a spectrocolorimeter (eXact, manufactured by X-Rite), and the average value was taken as the OD value of the test piece. Color measurement was performed under the conditions of density standard: ANSI T, light source: D65, and viewing angle: 2 °. Then, the print density was evaluated according to the following evaluation criteria. The results are shown in Table 12 below.
-Evaluation criteria (OK top coat +)-
A: OD value is 2.3 or more B: OD value is 2.0 or more and less than 2.3 C: OD value is 1.7 or more and less than 2.0 D: OD value is less than 1.7-evaluation criteria (Npi form) 70NEXT-IJ)-
A: OD value is 1.30 or more B: OD value is 1.25 or more and less than 1.30 C: OD value is 1.20 or more and less than 1.25 D: OD value is less than 1.20
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表１２に示すとおり、実施例の各インクによれば、オフセットコート紙及び普通紙のいずれに印刷した場合にも、良好な印刷濃度を実現することができた。 As shown in Table 12, according to each ink of the example, good print density could be realized when printing on either offset coated paper or plain paper.

Claims (11)

  1. 　顔料、分散染料、及び溶剤染料からなる群より選択される水不溶性着色剤と、重量平均分子量が５００００未満である樹脂分散剤と、固形分の２５℃のメチルエチルケトン１００ｇへの溶解量が１０ｇ以下である樹脂エマルションと、平均粒子径が３ｎｍ以上２２ｎｍ未満であるゾルと、水と、を含有し、
    　前記ゾルの含有率が１．０～５．０質量％であるインク。     A water-insoluble colorant selected from the group consisting of pigments, disperse dyes, and solvent dyes, a resin dispersant having a weight average molecular weight of less than 50,000, and a solid content of 10 g or less in 100 g of methyl ethyl ketone at 25 ° C. A resin emulsion, a sol having an average particle size of 3 nm or more and less than 22 nm, and water are contained.
    An ink having a sol content of 1.0 to 5.0% by mass.
  2. 　前記ゾルが、シリカゾル及び酸化ジルコニウムゾルの少なくとも一方を含む、請求項１に記載のインク。 The ink according to claim 1, wherein the sol contains at least one of a silica sol and a zirconium oxide sol.
  3. 　前記ゾルが、シリカゾルを含む、請求項２に記載のインク。 The ink according to claim 2, wherein the sol contains a silica sol.
  4. 　前記ゾルが、コロイダルシリカゾル及びオルガノシリカゾルの少なくとも一方を含む、請求項３に記載のインク。 The ink according to claim 3, wherein the sol contains at least one of a colloidal silica sol and an organosilica sol.
  5. 　前記樹脂エマルションが、アクリル樹脂エマルション及び酸化ポリエチレンワックスエマルションの少なくとも一方を含む、請求項１～４のいずれか１項に記載のインク。 The ink according to any one of claims 1 to 4, wherein the resin emulsion contains at least one of an acrylic resin emulsion and a polyethylene oxide wax emulsion.
  6. 　前記樹脂エマルションが、アクリル樹脂エマルション及び酸化ポリエチレンワックスエマルションを含む、請求項５に記載のインク。 The ink according to claim 5, wherein the resin emulsion contains an acrylic resin emulsion and a polyethylene oxide wax emulsion.
  7. 　前記樹脂エマルションの含有率が、固形分として０．６～６．０質量％である、請求項１～６のいずれか１項に記載のインク。 The ink according to any one of claims 1 to 6, wherein the content of the resin emulsion is 0.6 to 6.0% by mass as a solid content.
  8. 　前記水不溶性着色剤が、ＢＥＴ比表面積が１８０ｍ２／ｇ以上のカーボンブラックを含む、請求項１～７のいずれか１項に記載のインク。 The ink according to any one of claims 1 to 7, wherein the water-insoluble colorant contains carbon black having a BET specific surface area of 180 m 2 / g or more.
  9. 　請求項１～８のいずれか１項に記載のインクと、該インクとは異なる他のインクと、を備えるインクセット。 An ink set comprising the ink according to any one of claims 1 to 8 and another ink different from the ink.
  10. 　請求項１～８のいずれか１項に記載のインク、又は請求項９に記載のインクセットと、印刷メディアと、を備えるインクメディアセット。 An ink media set comprising the ink according to any one of claims 1 to 8 or the ink set according to claim 9 and a printing medium.
  11. 　請求項１～８のいずれか１項に記載のインク、又は請求項９に記載のインクセットが備える各インクが付着した印刷メディア。 A print medium to which the ink according to any one of claims 1 to 8 or each ink provided in the ink set according to claim 9 is attached.
PCT/JP2021/044634 2020-12-10 2021-12-06 Ink, ink set, ink medium set, and printing medium WO2022124249A1 (en)

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JPH09227812A (en) * 1996-02-26 1997-09-02 Toyo Ink Mfg Co Ltd Water-base ink jet recording liquid
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