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WO2022202045A1 - Composition d'encre aqueuse - Google Patents

Composition d'encre aqueuse Download PDF

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Publication number
WO2022202045A1
WO2022202045A1 PCT/JP2022/007084 JP2022007084W WO2022202045A1 WO 2022202045 A1 WO2022202045 A1 WO 2022202045A1 JP 2022007084 W JP2022007084 W JP 2022007084W WO 2022202045 A1 WO2022202045 A1 WO 2022202045A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
mass
water
pigment
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/007084
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English (en)
Japanese (ja)
Inventor
眞 岡村
清貴 藤原
正将 篠原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mimaki Engineering Co Ltd
Original Assignee
Mimaki Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021053312A external-priority patent/JP2022150628A/ja
Priority claimed from JP2021053313A external-priority patent/JP2022150629A/ja
Application filed by Mimaki Engineering Co Ltd filed Critical Mimaki Engineering Co Ltd
Publication of WO2022202045A1 publication Critical patent/WO2022202045A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment

Definitions

  • the present invention relates to a water-based ink composition used for printing.
  • the water-based ink composition generally contains pigments, binder resins, water-soluble organic solvents, etc. in addition to water.
  • water-based ink compositions containing pigment-encapsulating resin fine particles in which the pigment surface is coated with a resin have been proposed (see Patent Documents 1 to 4).
  • the water-based ink composition containing the pigment-encapsulating resin fine particles is likely to cause color fading or deterioration of the printed image due to lack of pigment due to friction caused when an external force is applied to the surface of the printed image. , there is a problem in the abrasion resistance of the printed image.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a water-based ink composition that provides excellent scratch resistance of printed images.
  • the present invention provides a water-based ink composition containing pigment-encapsulated resin particles, a diol-based organic solvent, and a fluorine-based surfactant, wherein the resin in the pigment-encapsulated resin particles is a hydrophobic resin.
  • a composition is provided.
  • the amount of the fluorosurfactant added is preferably 0.3% by mass or more and 3.0% by mass or less with respect to the total amount of the ink composition.
  • the water-based ink composition may contain an amine-based organic solvent.
  • the amount of the fluorine-based surfactant added is preferably 0.01% by mass or more and 0.50% by mass or less with respect to the total amount of the ink composition.
  • the amount of the amine-based organic solvent added is preferably 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the ink composition.
  • the average particle size of the pigment-encapsulating resin particles is preferably 30 nm or more and 200 nm or less.
  • the amount of the diol-based organic solvent added is preferably 10.0% by mass or more and 40.0% by mass or less with respect to the total amount of the ink composition.
  • the pigment-encapsulating resin particles are preferably synthesized batchwise in an emulsion containing a pigment, a hydrophobic monomer, an aqueous medium, a surfactant, and a polymerization initiator.
  • the polymerization initiator preferably has the action of reducing the ionic strength of the aqueous phase of the emulsion.
  • a water-based ink composition that reduces the load on the environment, is excellent in dispersion stability and storage stability, is less likely to cause clogging of nozzles in an inkjet printer, and is excellent in abrasion resistance of printed images. is provided.
  • 1 is an FE-SEM image of Dispersion A of Example 1 of the first embodiment (magnification of 100,000 times).
  • 1 is an image obtained by observing a coating film surface after coating film formation in Example 1 of the first embodiment (magnification of 200 times). It is the image which observed the coating-film surface after coating-film formation of the comparative example 1 of 1st Embodiment (magnification 200 times).
  • 10 is an FE-SEM image of the dispersion liquid A of Example 2 of the second embodiment (magnification of 100,000 times). It is the image which observed the coating-film surface after coating-film formation of Example 2 of 2nd Embodiment (magnification 200 times). It is the image which observed the coating-film surface after coating-film formation of Example 4 of 2nd Embodiment (magnification 200 times).
  • a water-based ink composition according to a first embodiment of the present invention is a water-based ink composition containing pigment-encapsulated resin particles, a diol-based organic solvent, a fluorine-based surfactant, and an amine-based organic solvent, wherein the pigment-encapsulated resin It is preferred that the resin in the particles is a hydrophobic resin.
  • Pigment-encapsulated resin particles are prepared by mixing a pigment insoluble in an aqueous medium, a hydrophobic monomer, an aqueous medium, and a surfactant to form an emulsion containing oil-in-water droplets, and using a polymerization initiator to produce a monomer.
  • Pigment-encapsulated resin particles containing a pigment inside are prepared by synthesizing in a batch system by emulsion polymerization in which the is polymerized.
  • batch type means that the process is performed in one facility. That is, in the first embodiment of the present invention, the synthesis by emulsion polymerization of the pigment-encapsulated resin particles containing the pigment therein can be performed in the reaction system in the same reaction vessel.
  • the average particle size of the pigment-encapsulating resin particles is in the range of 30 nm to 200 nm, preferably 50 nm to 180 nm, and more preferably 70 nm to 150 nm.
  • the average particle size of the pigment-encapsulating resin particles is less than 30 nm, the difference in particle size from the pigment particles having a normal particle size becomes small, making it difficult to sufficiently enclose the pigment in the resin particles. If the average particle diameter of the pigment-encapsulating resin particles exceeds 200 nm, ejection from the inkjet nozzle may be affected.
  • the particle size measurement of the pigment-encapsulating resin particles can be performed with a commercially available particle size measuring instrument using a light scattering method, an electrophoresis method, a laser Doppler method, or the like. Alternatively, the particle size can be measured by taking a particle image with a field emission scanning electron microscope or a transmission electron microscope. In the first embodiment of the present invention, the average particle size of the pigment-encapsulating resin particles is measured by dynamic light scattering (DLS), or measured from particle image photography with a field emission scanning electron microscope. preferably.
  • DLS dynamic light scattering
  • the pigment used for the pigment-encapsulated resin particles is not particularly limited as long as it does not dissolve in an aqueous medium, and known inorganic pigments and organic pigments can be used depending on the purpose.
  • inorganic pigments include titanium oxide, antimony red, iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite.
  • organic pigments include quinacridone-based pigments and quinacridonequinone-based pigments.
  • pigments dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, Anthraquinone-based pigments, thioindigo-based pigments, benzimidazolone-based pigments, azo-based pigments, and the like can be used.
  • Examples of pigments that can be used in the first embodiment of the invention are also described in The Color Index, 3rd Edition (The Society of Dyers and Colourists, 1982). Two or more of these pigments may be used in combination.
  • the ratio of the pigment to the resin in the pigment-encapsulating resin particles is 1.0% by mass or more and 15.0% by mass or less, preferably 6.0% by mass or more and 12.0% by mass, based on the total amount of monomers during emulsion polymerization. % or less. If it is less than 1.0% by mass, the color development of the pigment may be insufficient and high-quality images may not be obtained. there is a possibility.
  • the amount of the pigment added, excluding the resin content, in the pigment-encapsulated resin particles is 0.1% by mass or more and 15.0% by mass or less, preferably 0.5% by mass or more and 10.0% by mass or less, relative to the total amount of the ink composition. % by mass or less. If it is less than 0.1% by mass, the coloring may be insufficient and a high-quality image may not be obtained. If it is more than 15.0% by mass, the storage stability of the ink composition may be insufficient. have a nature.
  • the hydrophobic monomer used in the preparation of pigment-encapsulated resin particles using emulsion polymerization is not particularly limited as long as it has polymerizability and the resin after polymerization is a hydrophobic resin.
  • styrene-based monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc.
  • a styrenic monomer and a methacrylic acid ester are preferably used, and a combination of a styrenic monomer and a methacrylic acid ester is more preferably used.
  • the hydrophobic monomer means a monomer that becomes a resin with a water absorption rate of less than 1% in the state of homopolymerized resin. Therefore, it does not contain hydrophilic monomers such as (meth)acrylic acid, polyethylene glycol (meth)acrylate, hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, dimethylacrylamide and polyvinyl alcohol.
  • Hydrophobic monomers have a water absorption rate of less than 1% when turned into a resin, do not swell in an aqueous medium, and tend to have a high surface hardness. effective for
  • the amount of the monomer that forms the resin after polymerization is 2.0% by mass or more and 5.0% by mass or less, preferably 3.0% by mass or more and 4.0% by mass or less, relative to the total amount of the ink composition. more preferably 3.0% by mass or more and 3.5% by mass or less. If it is less than 2.0% by mass, the scratch resistance of printed images may be insufficient, and if it is more than 5.0% by mass, dispersion stability and ejection stability in an inkjet printer may be insufficient. have a nature.
  • Water eg, ion-exchanged water, distilled water, ultrapure water, etc.
  • water-soluble organic solvents or mixtures thereof can be used as the aqueous medium used in the preparation of pigment-encapsulated resin particles using emulsion polymerization.
  • water-soluble organic solvents include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; and alkyl ethers of polyalkylene glycol. and lactams such as N-methyl-2-pyrrolidone. From the viewpoint of safety and environmental impact, it is preferable to use water or a mixture of water and a water-soluble organic solvent.
  • Surfactants used in the preparation of pigment-encapsulated resin particles using emulsion polymerization are not particularly limited.
  • Nonionic surfactants such as oxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene/polyoxypropylene block copolymers, cationic interfaces such as alkylamine salts and quaternary ammonium salts
  • An active agent can be mentioned, and an anionic surfactant can be preferably used in particular. Among them, low CMC surfactants are preferred.
  • low CMC surfactant means a surfactant with a low critical micelle concentration (CMC) (for example, CMC is 0.1 to 0.001 mol/l).
  • CMC critical micelle concentration
  • anionic surfactant having a low critical micelle concentration (CMC) an anionic surfactant having a linear alkyl group or alkenyl group is preferred.
  • those having a linear alkyl group or alkenyl group having 11 to 25 carbon atoms, preferably 15 to 23 carbon atoms can be used, but it is preferable to use an anionic surfactant having a linear alkyl group.
  • anionic surfactant having a linear alkyl group having 15 to 23 carbon atoms It is more preferable to use an anionic surfactant having a linear alkyl group having 18 carbon atoms. more preferred.
  • the amount of the low-CMC surfactant added is 0.01% by mass or more and 0.50% by mass or less, preferably 0.03% by mass or more and 0.25% by mass or less, based on the total amount of the monomers.
  • the polymerization initiator used for synthesizing the pigment-encapsulating resin particles is not particularly limited. oxide, peroxides such as lauroyl peroxide and 2,2′-azobis ⁇ 2-methyl-N-[2-(1-hydroxybutyl)propionamide] ⁇ , 2,2′-azobis[(2-methylpropion amidine) dihydrochloride], 2,2′-azobis[N-(2-carboxyethyl)-2-methyl-propiondiamine] tetrahydrate, 2,2′-azobis(2,4-dimethylvaleronitrile),
  • organic polymerization initiators such as azo compounds such as azobisisobutyronitrile
  • inorganic polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate.
  • a so-called redox polymerization initiator which uses a reducing agent such as sodium bisulfite, ascorbic acid and salts thereof in combination with a polymerization initiator, can also be used.
  • a polymerization initiator having an effect of lowering the ionic strength of the emulsion polymerization reaction system (aqueous phase of the emulsion) is preferable.
  • persulfates such as ammonium persulfate and potassium persulfate are preferably used.
  • ammonium persulfate is preferably used.
  • the amount of the polymerization initiator added is 1.0% by mass or more and 30.0% by mass or less, preferably 5.0% by mass or more and 30.0% by mass or less, and more preferably It is 10.0 mass % or more and 20.0 mass % or less. If it is less than 1.0% by mass, the polymerization reaction of the monomer may not proceed sufficiently, and the resin may not sufficiently coat the pigment. If it is more than 30.0% by mass, the polymerization reaction of the monomer will accelerate. Too much, and foaming and cracks may occur in the resin.
  • Diol-based organic solvents used in the first embodiment of the present invention include 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol and the like can be used, preferably 1,2-butane Diols can be used.
  • the amount of the diol-based organic solvent added to the total amount of the ink composition is in the range of 10.0% by mass or more and 40.0% by mass or less, preferably in the range of 15.0% by mass or more and 30.0% by mass or less. If it is less than 10.0% by mass, the surface tension of the ink composition may not be sufficiently reduced and high-quality images may not be obtained. storage stability may be insufficient.
  • the fluorosurfactants used in the first embodiment of the present invention include Megafac F-114, F-410, F-493, F-494, F-443, F-444, F-445 and F-446.
  • the amount of the fluorosurfactant added to the total amount of the ink composition is in the range of 0.01% by mass or more and 0.50% by mass or less, preferably in the range of 0.02% by mass or more and 0.4% by mass or less. . If it is less than 0.01% by mass, the dispersion stability and ejection stability in an inkjet printer may become insufficient, and if it is more than 0.50% by mass, the storage stability of the ink composition becomes insufficient. there is a possibility.
  • the amine organic solvent used in the first embodiment of the present invention includes diethanolamine (bp 268° C.), N-methyldiethanolamine (bp 243° C.), N,N-dimethylmonoethanolamine (bp 139° C.), N-phenylethanolamine ( bp 282-287° C.), alkylamines such as diethylenediamine (bp 206° C.), triethylenetetramine (bp 267° C.), tetraethylenepentamine (bp 333° C.), and the like.
  • the amine-based organic solvent affects the dispersibility of the pigment-encapsulated resin particles by controlling the drying speed of the water-based ink composition during printing, thereby contributing to the improvement of the scratch resistance of the printed image. Therefore, an amine-based organic solvent having a boiling point (bp) of 200° C. or higher is preferably used, alcohol amines are more preferably used, and N-methyldiethanolamine is particularly preferably used.
  • the amount of the amine-based organic solvent added to the total amount of the ink composition is in the range of 0.1% by mass or more and 10.0% by mass or less, preferably in the range of 0.1% by mass or more and 5% by mass or less, and more preferably. is in the range of 0.2% by mass or more and 3% by mass or less. If it is less than 0.1% by mass, it may be difficult to obtain scratch resistance of the printed image, and if it is more than 10.0% by mass, odor may become a problem.
  • the water-based ink composition of the first embodiment of the present invention can contain other components, and is not particularly limited as long as it is a component that can be contained in a normal water-based ink.
  • it may contain components such as penetrating agents, antifungal agents, antirust agents, pH adjusters, wetting agents, antifoaming agents, additional surfactants, water-soluble ultraviolet absorbers, and water-soluble infrared absorbers. .
  • the water-based ink composition of the first embodiment of the present invention is prepared, for example, by adding pigment-encapsulating resin particles, a diol-based organic solvent, a fluorine-based surfactant, and an amine-based organic solvent into water and mixing and stirring. be able to. Other ingredients may be blended as needed.
  • the water-based ink composition of the first embodiment of the present invention does not particularly limit the substrate used for printing, and the substrate may be plain paper, coated paper, cardboard, wood, cloth, or a film using resin. or a sheet, etc., preferably a film or sheet using a resin, more preferably a film or sheet using at least one resin selected from vinyl chloride resin, polyolefin resin, acrylic resin, polyester resin and polystyrene resin is a sheet.
  • the water-based ink composition of the first embodiment of the present invention does not particularly limit the printing means and method, but is preferably used for inkjet printing because nozzle clogging in inkjet printers is less likely to occur.
  • Example 1 Preparation of pigment-encapsulating resin particles 200 ml of ion-exchanged water was added to 2.69 g of EMACOL SF CYAN AE2034F (manufactured by Sanyo Color Co., Ltd., pigment concentration 20%), which is a commercially available pigment dispersion, and ultrasonic waves were applied for 30 minutes to disperse the pigment in the ion-exchanged water. After that, 18.6 mg of sodium octadecyl sulfate was added.
  • EMACOL SF CYAN AE2034F manufactured by Sanyo Color Co., Ltd., pigment concentration 20%
  • the resulting aqueous solution (220 ml) was poured into a half-liter four-necked separate reactor (inner diameter: 7.5 cm) that had been preheated in a constant temperature bath at 70°C.
  • the four-necked separate reactor was equipped with an Areen condenser, a nitrogen gas inlet tube and a mechanical stirrer, and was further equipped with four baffles (0.7 cm wide) located 1 cm above the bottom and a four-blade pitch paddle impeller. (5 cm long). Nitrogen gas was bubbled through the aqueous solution for 30 minutes while stirring at 360 rpm.
  • the product is cooled to room temperature (25° C.), and the morphology is observed using a field emission scanning electron microscope (FE-SEM: JSM-7000F manufactured by JEOL Ltd.) to obtain a spherical pigment encapsulation. It was confirmed that resin particles were synthesized. Coarse particles were removed from the resulting product using a syringe filter (pore size: 1 ⁇ m) to obtain a sample.
  • FE-SEM field emission scanning electron microscope
  • FIG. 1 shows an image (magnification of 100,000 times) of dispersion liquid A observed using a field emission scanning electron microscope (FE-SEM: JSM-7000F manufactured by JEOL Ltd.). From FIG. 1, it can be seen that the dispersion liquid A is composed of spherical particles of pigment-encapsulating resin having uniform particle diameters.
  • Comparative Example 1 was prepared in the same manner as the water-based ink composition of Example 1 above, except that N-methyldiethanolamine was not blended.
  • FIGS. 2 Images of the coated surface of the performance evaluation samples using the water-based ink compositions of Example 1 and Comparative Example 1 observed using a digital microscope (VHX2000/1100 manufactured by Keyence Corporation) (magnification: 200) are shown in FIGS. 2 using the water-based ink composition of Example 1, compared to FIG. 3 using the water-based ink composition of Comparative Example 1, it can be seen that a uniform coating film surface is obtained.
  • Table 1 shows the results of performing the following performance evaluations (water resistance and alcohol resistance) using the performance evaluation samples.
  • the water-based ink composition according to the first embodiment of the invention has the following configuration.
  • (1-1) The water-based ink composition contains pigment-encapsulating resin particles, a diol-based organic solvent, a fluorine-based surfactant, and an amine-based organic solvent.
  • the resin in the pigment-encapsulating resin particles is a hydrophobic resin.
  • the water-based ink composition can be free of volatile organic solvents, reducing the burden on the environment.
  • the water-based ink composition is excellent in dispersion stability and storage stability, and not only does nozzle clogging of inkjet printers hardly occur, but also can improve the abrasion resistance of printed images.
  • the pigment-encapsulating resin particles may have an average particle size of 30 nm or more and 200 nm or less.
  • the average particle size of the pigment-encapsulating resin particles is less than 30 nm, the difference in particle size from the pigment particles having a normal particle size becomes small, making it difficult for the resin particles to sufficiently contain the pigment. If the average particle diameter of the pigment-encapsulating resin particles exceeds 200 nm, ejection from the inkjet nozzle may be affected.
  • the amount of the diol-based organic solvent added can be 10.0% by mass or more and 40.0% by mass or less with respect to the total amount of the ink composition.
  • the amount of the diol-based organic solvent added By setting the amount of the diol-based organic solvent added to 10.0% by mass or more, the surface tension of the ink composition can be lowered, and high-quality images can be obtained. By setting the amount to be added to 40.0% by mass or less, the storage stability of the ink composition can be improved.
  • the amount of the fluorosurfactant added can be 0.01% by mass or more and 0.50% by mass or less with respect to the total amount of the ink composition.
  • the addition amount of the fluorosurfactant By setting the addition amount of the fluorosurfactant to 0.01% by mass or more, it is possible to improve dispersion stability and ejection stability in an inkjet printer. By setting the amount of the fluorosurfactant added to 0.50% by mass or less, the storage stability of the ink composition can be improved.
  • the amount of the amine-based organic solvent added can be 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the ink composition.
  • the pigment-encapsulated resin particles are batch-synthesized in an emulsion containing a pigment, a hydrophobic monomer, an aqueous medium, a surfactant, and a polymerization initiator.
  • synthesis can be performed in a reaction system within the same reaction vessel.
  • the polymerization initiator can have the effect of lowering the ionic strength of the aqueous phase of the emulsion.
  • a water-based ink composition according to a second embodiment of the present invention is a water-based ink composition containing pigment-encapsulated resin particles, a diol-based organic solvent, and a fluorine-based surfactant, wherein the resin in the pigment-encapsulated resin particles is hydrophobic. Resin is preferred.
  • Pigment-encapsulated resin particles are prepared by mixing a pigment insoluble in an aqueous medium, a hydrophobic monomer, an aqueous medium, and a surfactant to form an emulsion containing oil-in-water droplets, and using a polymerization initiator to produce a monomer.
  • Pigment-encapsulated resin particles containing a pigment inside are prepared by synthesizing in a batch system by emulsion polymerization in which the is polymerized.
  • batch type means that the process is performed in one facility. That is, in the second embodiment of the present invention, synthesis by emulsion polymerization of the pigment-encapsulated resin particles containing the pigment therein can be performed in the reaction system in the same reaction vessel.
  • the average particle size of the pigment-encapsulating resin particles is in the range of 30 nm to 200 nm, preferably 50 nm to 180 nm, and more preferably 70 nm to 150 nm.
  • the particle size measurement of the pigment-encapsulating resin particles can be performed with a commercially available particle size measuring instrument using a light scattering method, an electrophoresis method, a laser Doppler method, or the like. Alternatively, the particle size can be measured by taking a particle image with a field emission scanning electron microscope or a transmission electron microscope. In the second embodiment of the present invention, the average particle size of the pigment-encapsulating resin particles is measured by dynamic light scattering (DLS), or measured from particle image photography with a field emission scanning electron microscope. preferably.
  • DLS dynamic light scattering
  • the pigment used for the pigment-encapsulated resin particles is not particularly limited as long as it does not dissolve in an aqueous medium, and known inorganic pigments and organic pigments can be used depending on the purpose.
  • inorganic pigments include titanium oxide, antimony red, iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite.
  • organic pigments include quinacridone-based pigments and quinacridonequinone-based pigments.
  • pigments dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, Anthraquinone-based pigments, thioindigo-based pigments, benzimidazolone-based pigments, azo-based pigments, and the like can be used.
  • Examples of pigments that can be used in the second embodiment of the invention are also described in The Color Index, 3rd Edition (The Society of Dyers and Colorists, 1982). Two or more of these pigments may be used in combination.
  • the ratio of the pigment to the resin in the pigment-encapsulating resin particles is 1.0% by mass or more and 15.0% by mass or less, preferably 6.0% by mass or more and 12.0% by mass, based on the total amount of monomers during emulsion polymerization. % or less. If it is less than 1.0% by mass, the color development of the pigment may be insufficient and high-quality images may not be obtained. there is a possibility.
  • the amount of the pigment added to the pigment-encapsulated resin particles excluding the resin content is 0.1% by mass or more and 15% by mass or less, preferably 0.5% by mass or more and 10% by mass or less, relative to the total amount of the ink composition. be. If it is less than 0.1% by mass, the coloring may be insufficient and a high-quality image may not be obtained. If it is more than 15% by mass, the storage stability of the ink composition may be insufficient. be.
  • the hydrophobic monomer used in the preparation of pigment-encapsulated resin particles using emulsion polymerization is not particularly limited as long as it has polymerizability and the resin after polymerization is a hydrophobic resin.
  • styrene-based monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc.
  • a styrenic monomer and a methacrylic acid ester are preferably used, and a combination of a styrenic monomer and a methacrylic acid ester is more preferably used.
  • the hydrophobic monomer means a monomer that becomes a resin with a water absorption rate of less than 1% in the state of homopolymerized resin. Therefore, it does not contain hydrophilic monomers such as (meth)acrylic acid, polyethylene glycol (meth)acrylate, hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, dimethylacrylamide and polyvinyl alcohol.
  • Hydrophobic monomers have a water absorption rate of less than 1% when turned into a resin, do not swell in an aqueous medium, and tend to have a high surface hardness. effective for
  • the amount of the monomer that forms the resin after polymerization is 2.0% by mass or more and 5.0% by mass or less, preferably 3.0% by mass or more and 4.0% by mass or less, relative to the total amount of the ink composition. more preferably 3.0% by mass or more and 3.5% by mass or less. If it is less than 2.0% by mass, the scratch resistance of printed images may be insufficient, and if it is more than 5.0% by mass, dispersion stability and ejection stability in an inkjet printer may be insufficient. have a nature.
  • Water eg, ion-exchanged water, distilled water, ultrapure water, etc.
  • water-soluble organic solvents or mixtures thereof can be used as the aqueous medium used in the preparation of pigment-encapsulated resin particles using emulsion polymerization.
  • water-soluble organic solvents include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; and alkyl ethers of polyalkylene glycol. and lactams such as N-methyl-2-pyrrolidone. From the viewpoint of safety and environmental impact, it is preferable to use water or a mixture of water and a water-soluble organic solvent.
  • Surfactants used in the preparation of pigment-encapsulated resin particles using emulsion polymerization are not particularly limited.
  • Nonionic surfactants such as oxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene/polyoxypropylene block copolymers, cationic interfaces such as alkylamine salts and quaternary ammonium salts
  • An active agent can be mentioned, and an anionic surfactant can be preferably used in particular. Among them, low CMC surfactants are preferred.
  • low CMC surfactant means a surfactant with a low critical micelle concentration (CMC) (for example, CMC is 0.1 to 0.001 mol/l).
  • CMC critical micelle concentration
  • anionic surfactant having a low critical micelle concentration (CMC) an anionic surfactant having a linear alkyl group or alkenyl group is preferred.
  • those having a linear alkyl group or alkenyl group having 11 to 25 carbon atoms, preferably 15 to 23 carbon atoms can be used, but it is preferable to use an anionic surfactant having a linear alkyl group.
  • anionic surfactant having a linear alkyl group having 15 to 23 carbon atoms It is more preferable to use an anionic surfactant having a linear alkyl group having 18 carbon atoms. more preferred.
  • the amount of the low-CMC surfactant added is 0.01% by mass or more and 0.5% by mass or less, preferably 0.03% by mass or more and 0.25% by mass or less, based on the total amount of the monomers.
  • the polymerization initiator used for synthesizing the pigment-encapsulating resin particles is not particularly limited. oxide, peroxides such as lauroyl peroxide and 2,2′-azobis ⁇ 2-methyl-N-[2-(1-hydroxybutyl)propionamide] ⁇ , 2,2′-azobis[(2-methylpropion amidine) dihydrochloride], 2,2′-azobis[N-(2-carboxyethyl)-2-methyl-propiondiamine] tetrahydrate, 2,2′-azobis(2,4-dimethylvaleronitrile),
  • organic polymerization initiators such as azo compounds such as azobisisobutyronitrile
  • inorganic polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate.
  • a so-called redox polymerization initiator which uses a reducing agent such as sodium bisulfite, ascorbic acid and salts thereof in combination with a polymerization initiator, can also be used.
  • a polymerization initiator having an effect of lowering the ionic strength of the emulsion polymerization reaction system (aqueous phase of the emulsion) is preferable.
  • persulfates such as ammonium persulfate and potassium persulfate are preferably used.
  • ammonium persulfate is preferably used.
  • the amount of the polymerization initiator added is 1.0% by mass or more and 30.0% by mass or less, preferably 5.0% by mass or more and 30.0% by mass or less, and more preferably It is 10.0 mass % or more and 20.0 mass % or less. If it is less than 1.0% by mass, the polymerization reaction of the monomer may not proceed sufficiently, and the resin may not sufficiently coat the pigment. If it is more than 30.0% by mass, the polymerization reaction of the monomer will accelerate. Too much, and foaming and cracks may occur in the resin.
  • Diol-based organic solvents used in the second embodiment of the present invention include 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol and the like can be used, preferably 1,2-butane Diols can be used.
  • the amount of the diol-based organic solvent added to the total amount of the ink composition is in the range of 10.0% by mass or more and 40.0% by mass or less, preferably in the range of 15.0% by mass or more and 30.0% by mass or less. If it is less than 10.0% by mass, the surface tension of the ink composition may not be sufficiently reduced and high-quality images may not be obtained. storage stability may be insufficient.
  • the fluorosurfactants used in the present invention include Megafac F-114, F-410, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F- 489, F-172D, F-178K, F-178RM, ESM-1, MCF-350SF, R-08, F-472SF, R-30, BL-20, R-61, R-90 (all trade names , manufactured by DIC Corporation), FC-430, FC-4432 (all trade names, manufactured by Sumitomo 3M), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (all trade names, manufactured by Du
  • the fluorosurfactant is a component with a lower surface tension than the diol-based organic solvent, it is unevenly distributed in the surface layer portion of the water-based ink composition, and by controlling the drying speed during printing, the pigment-encapsulating resin It is believed that it affects the dispersibility of the particles and contributes to the improvement of the scratch resistance of the printed image.
  • the amount of the fluorosurfactant added to the total amount of the ink composition is in the range of 0.3% by mass or more and 3.0% by mass or less, preferably in the range of 0.4% by mass or more and 2.5% by mass or less. . If it is less than 0.3% by mass, the printed image may not have sufficient scratch resistance, and if it is more than 3.0% by mass, the jetting property of the inkjet printer may be insufficient.
  • the water-based ink composition of the second embodiment of the present invention can contain other components, and is not particularly limited as long as it is a component that can be contained in a normal water-based ink.
  • it may contain components such as penetrating agents, antifungal agents, antirust agents, pH adjusters, wetting agents, antifoaming agents, additional surfactants, water-soluble ultraviolet absorbers, and water-soluble infrared absorbers. .
  • the water-based ink composition of the second embodiment of the present invention can be prepared, for example, by adding pigment-encapsulating resin particles, a diol-based organic solvent, and a fluorine-based surfactant into water and mixing and stirring. Other ingredients may be blended as needed.
  • the water-based ink composition of the second embodiment of the present invention does not particularly limit the substrate used for printing, and the substrate may be plain paper, coated paper, cardboard, wood, cloth, or a film using resin or a sheet, etc., preferably a film or sheet using a resin, more preferably a film or sheet using at least one resin selected from vinyl chloride resin, polyolefin resin, acrylic resin, polyester resin and polystyrene resin is a sheet.
  • the water-based ink composition of the second embodiment of the present invention is not particularly limited in terms of printing means and method, but is preferably used for inkjet printing because of its excellent ejection properties with an inkjet printer.
  • Example 2 Preparation of pigment-encapsulating resin particles 200 ml of ion-exchanged water was added to 2.69 g of EMACOL SF CYAN AE2034F (manufactured by Sanyo Color Co., Ltd., pigment concentration 20%), which is a commercially available pigment dispersion, and ultrasonic waves were applied for 30 minutes to disperse the pigment in the ion-exchanged water. After that, 18.6 mg of sodium octadecyl sulfate was added.
  • EMACOL SF CYAN AE2034F manufactured by Sanyo Color Co., Ltd., pigment concentration 20%
  • the resulting aqueous solution (220 ml) was poured into a half-liter four-necked separate reactor (inner diameter: 7.5 cm) that had been preheated in a constant temperature bath at 70°C.
  • the four-necked separate reactor was equipped with an Areen condenser, a nitrogen gas inlet tube and a mechanical stirrer, and was further equipped with four baffles (0.7 cm wide) located 1 cm above the bottom and a four-blade pitch paddle impeller. (5 cm long). Nitrogen gas was bubbled through the aqueous solution for 30 minutes while stirring at 360 rpm.
  • the product is cooled to room temperature (25° C.), and the morphology is observed using a field emission scanning electron microscope (FE-SEM: JSM-7000F manufactured by JEOL Ltd.) to obtain a spherical pigment encapsulation. It was confirmed that resin particles were synthesized. Coarse particles were removed from the resulting product using a syringe filter (pore size: 1 ⁇ m) to obtain a sample.
  • FE-SEM field emission scanning electron microscope
  • FIG. 4 shows an image (magnification of 100,000 times) of dispersion liquid A observed using a field emission scanning electron microscope (FE-SEM: JSM-7000F manufactured by JEOL Ltd.). It can be seen from FIG. 4 that the dispersion liquid A is composed of spherical pigment-encapsulating resin fine particles having uniform particle diameters.
  • Example 3 was prepared in the same manner as the water-based ink composition of Example 2 above, except that the amount of the fluorine-based surfactant was changed to 2.0 parts by weight.
  • Example 4 was prepared in the same manner as the water-based ink composition of Example 2 above, except that the amount of the fluorosurfactant was changed to 0.1 parts by weight.
  • Example 5 was prepared in the same manner as the water-based ink composition of Example 2 above, except that the amount of the fluorine-based surfactant was changed to 4.0 parts by weight.
  • FIGS. Table 2 shows the results of performing the following performance evaluations (water resistance and alcohol resistance) using the performance evaluation samples.
  • the water-based ink composition according to the second embodiment of the invention has the following configuration.
  • (2-1) The water-based ink composition contains pigment-encapsulating resin particles, a diol-based organic solvent, and a fluorine-based surfactant.
  • the resin in the pigment-encapsulating resin particles is a hydrophobic resin.
  • the water-based ink composition can be free of volatile organic solvents, reducing the burden on the environment.
  • the water-based ink composition is excellent in dispersion stability and storage stability, and not only does nozzle clogging of inkjet printers hardly occur, but also can improve the abrasion resistance of printed images.
  • the pigment-encapsulating resin particles may have an average particle size of 30 nm or more and 200 nm or less.
  • the average particle size of the pigment-encapsulating resin particles is less than 30 nm, the difference in particle size from the pigment particles having a normal particle size becomes small, making it difficult for the resin particles to sufficiently contain the pigment. If the average particle diameter of the pigment-encapsulating resin particles exceeds 200 nm, ejection from the inkjet nozzle may be affected.
  • the amount of the diol-based organic solvent added can be 10.0% by mass or more and 40.0% by mass or less with respect to the total amount of the ink composition.
  • the amount of the diol-based organic solvent added By setting the amount of the diol-based organic solvent added to 10.0% by mass or more, the surface tension of the ink composition can be lowered, and high-quality images can be obtained. By setting the amount to be added to 40.0% by mass or less, the storage stability of the ink composition can be improved.
  • the amount of the fluorosurfactant added can be 0.3% by mass or more and 3.0% by mass or less with respect to the total amount of the ink composition.
  • the addition amount of the fluorosurfactant By setting the addition amount of the fluorosurfactant to 0.3% by mass or more, it is possible to improve the abrasion resistance of the printed image. By setting the addition amount of the fluorosurfactant to 3.0% by mass or less, it is possible to improve the ejection property of an inkjet printer.
  • the pigment-encapsulated resin particles are batch-synthesized in an emulsion containing a pigment, a hydrophobic monomer, an aqueous medium, a surfactant, and a polymerization initiator. can be done.
  • synthesis can be performed in a reaction system within the same reaction vessel.
  • the polymerization initiator can act to lower the ionic strength of the aqueous phase of the emulsion.
  • the water-based ink composition of the present invention can be suitably used as a printing ink.
  • (Appendix 1) (1-1) A water-based ink composition containing pigment-encapsulated resin particles, a diol-based organic solvent, a fluorine-based surfactant, and an amine-based organic solvent, wherein the resin in the pigment-encapsulated resin particles is a hydrophobic resin.
  • a water-based ink composition characterized by: (1-2) The water-based ink composition described in (1-1) above, wherein the pigment-encapsulating resin particles have an average particle size of 30 nm or more and 200 nm or less.
  • the amount of the diol-based organic solvent added is 10.0% by mass or more and 40.0% by mass or less with respect to the total amount of the ink composition.
  • a water-based ink composition as described. (1-4) The above (1-1) to (1-3), wherein the amount of the fluorosurfactant added is 0.01% by mass or more and 0.50% by mass or less with respect to the total amount of the ink composition.
  • (1-5) The above (1-1) to (1-4), wherein the amount of the amine-based organic solvent added is 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the ink composition.
  • the pigment-encapsulated resin particles are synthesized batchwise in an emulsion containing a pigment, a hydrophobic monomer, an aqueous medium, a surfactant, and a polymerization initiator. ) to (1-5).
  • (1-7) The water-based ink composition described in (1-6) above, wherein the polymerization initiator has a function of reducing the ionic strength of the aqueous phase of the emulsion.
  • (Appendix 2) (2-1) A water-based ink composition containing pigment-encapsulated resin particles, a diol-based organic solvent, and a fluorine-based surfactant, wherein the resin in the pigment-encapsulated resin particles is a hydrophobic resin. ink composition. (2-2) The water-based ink composition described in (2-1) above, wherein the pigment-encapsulating resin particles have an average particle size of 30 nm or more and 200 nm or less. (2-3) The above (2-1) or the above (2-2), wherein the amount of the diol-based organic solvent added is 10.0% by mass or more and 40.0% by mass or less with respect to the total amount of the ink composition. The water-based ink composition described in .
  • the water-based ink composition according to any one of . (2-5) The pigment-encapsulated resin particles are synthesized batchwise in an emulsion containing a pigment, a hydrophobic monomer, an aqueous medium, a surfactant, and a polymerization initiator. ) to (2-4).
  • (2-6) The water-based ink composition according to any one of (2-1) to (2-5) above, wherein the polymerization initiator has an action of reducing the ionic strength of the aqueous phase of the emulsion. thing.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Le problème à résoudre par la présente invention est de fournir une composition d'encre aqueuse donnant des images imprimées ayant une excellente résistance à l'abrasion. La solution selon l'invention porte sur une composition d'encre aqueuse comprenant des particules de résine contenant un pigment encapsulé, un solvant organique à base de diol, un tensioactif fluorochimique et un solvant organique à base d'amine, caractérisé en ce que la résine des particules de résine contenant un pigment encapsulé est une résine hydrophobe.
PCT/JP2022/007084 2021-03-26 2022-02-22 Composition d'encre aqueuse Ceased WO2022202045A1 (fr)

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JP2021-053312 2021-03-26
JP2021-053313 2021-03-26
JP2021053312A JP2022150628A (ja) 2021-03-26 2021-03-26 水系インク組成物
JP2021053313A JP2022150629A (ja) 2021-03-26 2021-03-26 水系インク組成物

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140343A (ja) * 1997-11-12 1999-05-25 Nippon Paint Co Ltd 着色剤組成物、インクジェット記録用インク及びその製造方法
JP2001302708A (ja) * 2000-04-20 2001-10-31 Mitsubishi Chemicals Corp 着色剤含有重合体エマルジョン及びそれを用いた水性インク
JP2008163059A (ja) * 2006-12-26 2008-07-17 Dainippon Toryo Co Ltd 顔料含有ポリマー粒子水分散体の製造方法及び水系顔料インク組成物
JP2015101705A (ja) * 2013-11-27 2015-06-04 株式会社Ｄｎｐファインケミカル インクジェット記録用インク組成物、及びその製造方法、並びに、インクジェット記録方法
JP2018109094A (ja) * 2016-12-28 2018-07-12 花王株式会社 水系インク
JP2018123235A (ja) * 2017-01-31 2018-08-09 株式会社リコー インクジェット用捺染インク、インクジェット記録装置、及びインクジェット記録方法
JP2019196430A (ja) * 2018-05-08 2019-11-14 コニカミノルタ株式会社 水性インクジェットインク、記録液セット及びインクジェット記録方法
WO2021100443A1 (fr) * 2019-11-20 2021-05-27 株式会社ミマキエンジニアリング Encre à base d'eau

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140343A (ja) * 1997-11-12 1999-05-25 Nippon Paint Co Ltd 着色剤組成物、インクジェット記録用インク及びその製造方法
JP2001302708A (ja) * 2000-04-20 2001-10-31 Mitsubishi Chemicals Corp 着色剤含有重合体エマルジョン及びそれを用いた水性インク
JP2008163059A (ja) * 2006-12-26 2008-07-17 Dainippon Toryo Co Ltd 顔料含有ポリマー粒子水分散体の製造方法及び水系顔料インク組成物
JP2015101705A (ja) * 2013-11-27 2015-06-04 株式会社Ｄｎｐファインケミカル インクジェット記録用インク組成物、及びその製造方法、並びに、インクジェット記録方法
JP2018109094A (ja) * 2016-12-28 2018-07-12 花王株式会社 水系インク
JP2018123235A (ja) * 2017-01-31 2018-08-09 株式会社リコー インクジェット用捺染インク、インクジェット記録装置、及びインクジェット記録方法
JP2019196430A (ja) * 2018-05-08 2019-11-14 コニカミノルタ株式会社 水性インクジェットインク、記録液セット及びインクジェット記録方法
WO2021100443A1 (fr) * 2019-11-20 2021-05-27 株式会社ミマキエンジニアリング Encre à base d'eau

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