WO2022124249A1 - Encre, ensemble d'encres, ensemble de supports d'encres et support d'impression - Google Patents

Encre, ensemble d'encres, ensemble de supports d'encres et support d'impression 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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ink
sol
water
examples
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PCT/JP2021/044634
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English (en)
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/fr

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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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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une encre qui contient : un agent colorant insoluble dans l'eau qui est sélectionné dans le groupe constitué par un pigment, d'un colorant dispersé et d'un colorant solvant ; un dispersant de résine qui a un poids moléculaire moyen en poids inférieur à 50 000 ; une émulsion de résine dans laquelle la quantité de dissolution de la teneur en solides dans 100 g de méthyléthylcétone à 25 °C est inférieure ou égale à 10 g ; un sol qui a un diamètre moyen de particule de 3 nm ou plus mais inférieur à 22 nm ; et de l'eau. Relativement à cette encre, la teneur en sol est de 1,0 % en masse à 5,0 % en masse La présente invention concerne également : un ensemble d'encres qui comprend cette encre ; un ensemble de supports d'encre qui comprend cette encre ou cet ensemble d'encres, et un support d'impression ; et un support d'impression sur lequel cette encre ou chaque encre dans l'ensemble d'encres adhère.
PCT/JP2021/044634 2020-12-10 2021-12-06 Encre, ensemble d'encres, ensemble de supports d'encres et support d'impression WO2022124249A1 (fr)

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JPH09227812A (ja) * 1996-02-26 1997-09-02 Toyo Ink Mfg Co Ltd 水性インクジェット用記録液
JPH09286941A (ja) * 1996-02-22 1997-11-04 Seiko Epson Corp インクジェット記録用インクおよび記録方法
JPH10195404A (ja) * 1996-09-27 1998-07-28 Seiko Epson Corp インクジェット記録方法
JP2011062999A (ja) * 2009-09-18 2011-03-31 Fujifilm Corp 画像形成方法及びインク組成物
JP2011063772A (ja) * 2009-09-18 2011-03-31 Fujifilm Corp インク組成物、インクセットおよびインクジェット画像形成方法
JP2012102247A (ja) * 2010-11-10 2012-05-31 Ricoh Co Ltd インクジェット記録用インク、インクカートリッジ、及びインクジェット記録装置
JP6952208B1 (ja) * 2020-09-28 2021-10-20 サカタインクス株式会社 水性インクジェット用インク組成物、印刷物、及びインクジェット印刷方法

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Publication number Priority date Publication date Assignee Title
JPH09286941A (ja) * 1996-02-22 1997-11-04 Seiko Epson Corp インクジェット記録用インクおよび記録方法
JPH09227812A (ja) * 1996-02-26 1997-09-02 Toyo Ink Mfg Co Ltd 水性インクジェット用記録液
JPH10195404A (ja) * 1996-09-27 1998-07-28 Seiko Epson Corp インクジェット記録方法
JP2011062999A (ja) * 2009-09-18 2011-03-31 Fujifilm Corp 画像形成方法及びインク組成物
JP2011063772A (ja) * 2009-09-18 2011-03-31 Fujifilm Corp インク組成物、インクセットおよびインクジェット画像形成方法
JP2012102247A (ja) * 2010-11-10 2012-05-31 Ricoh Co Ltd インクジェット記録用インク、インクカートリッジ、及びインクジェット記録装置
JP6952208B1 (ja) * 2020-09-28 2021-10-20 サカタインクス株式会社 水性インクジェット用インク組成物、印刷物、及びインクジェット印刷方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116330874A (zh) * 2023-03-10 2023-06-27 浙江卡游动漫有限公司 一种用于塑料文具表面的光变油墨印刷方法

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