JP2019218435A - Inkjet ink, inkjet printed matter and method for producing inkjet printed matter - Google Patents

Abstract

To provide an inkjet ink that has excellent discharge stability, can impart various levels of matte properties, and can improve designability and productivity of printed matter, provide inkjet printed matter and provide a method for producing inkjet printed matter.SOLUTION: The inkjet ink contains particles with an average particle size of 0.4-2.5 μm, with a refractive index of 1.4-1.7, with a specific gravity of 2.1 or less.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet ink, an inkjet print, and a method for manufacturing an inkjet print. More specifically, the present invention relates to an inkjet ink, an inkjet print, and a method for manufacturing an inkjet print, which have excellent ejection stability and can impart various degrees of matting properties.

  2. Description of the Related Art Inkjet printing inks and printing methods for obtaining a printed matter having a matte property have been proposed (Patent Document 1). Patent Literature 1 discloses an ink jet printing ink and a printing method in which irregularities are formed by curing an ink containing a photocurable resin, thereby irregularly reflecting the surface of a printed material to exert a matte effect. I have.

JP 2014-101479 A

  The technology described in Patent Literature 1 uses a diffuse reflection of irregularities formed on the surface of a printed material to exhibit a matte effect. Therefore, each unevenness needs to be independent. As a result, the obtained mattability is limited, and the desired mattability may not be expressed. Further, since it is necessary to form each of the concavities and convexities independently, the design described in Patent Literature 1 tends to limit the designs that can be expressed. Furthermore, in order to form independent irregularities, the amount of one-time ejection is likely to be limited, and the inkjet device that can be used during inkjet printing is likely to be limited to a serial type or the like. As a result, the technology described in Patent Literature 1 tends to limit the designability and productivity of the obtained printed matter.

  The present invention has been made in view of such conventional inventions, has excellent ejection stability, can impart various degrees of matting properties, and improves the design and productivity of printed matter. It is an object of the present invention to provide an obtained inkjet ink, an inkjet print, and a method for producing an inkjet print.

  The inkjet ink, the inkjet print, and the method for manufacturing the inkjet print of the present invention that solve the above-mentioned problems mainly include the following configurations.

  (1) An inkjet ink containing particles having an average particle diameter of 0.4 to 2.5 μm, a refractive index of 1.4 to 1.7, and a specific gravity of 2.1 or less.

  According to such a configuration, the inkjet ink contains particles having the above-mentioned predetermined average particle diameter, refractive index and specific gravity. Such an ink-jet ink hardly causes clogging of nozzles and channels during ink-jet printing, and has excellent ejection stability. In addition, since the ink-jet ink contains the above-described particles, various degrees of matting can be imparted, and the design of printed matter can be improved. Further, since the ink-jet ink exhibits the matting property by containing the above particles, it is not essential to form the unevenness independently as in the related art. As a result, according to the ink-jet ink, the ink-jet device that can be used during the ink-jet printing is not easily limited, and it is possible to increase the discharge amount at one time or to apply the ink on the base material in a short time, Productivity can be improved.

  (2) The inkjet ink according to (1), wherein the content of the particles is 0.5 to 15% by mass.

  According to such a configuration, the inkjet ink is more likely to have excellent ejection stability and an excellent matting effect.

  (3) The inkjet ink according to (1) or (2), wherein the particles include true spherical crosslinkable polymer fine particles.

  According to such a configuration, the inkjet ink is less likely to cause nozzle clogging during inkjet printing, and has excellent ejection stability. Further, the spherical crosslinkable polymer fine particles hardly swell in the ink, and the obtained ink has excellent stability.

  (4) The inkjet ink according to (1) or (2), wherein the particles include melamine-based beads.

  According to such a configuration, the melamine-based beads hardly swell in the ink, and the stability of the obtained ink is more excellent.

  (5) The inkjet ink according to any one of (1) to (4), wherein the inkjet ink is a radical polymerization type ultraviolet curable ink.

  According to such a configuration, the inkjet ink has much room for material selection and cost merit, and it is easy to design a desired ink.

  (6) The inkjet ink according to (5), comprising (meth) acrylsilane.

  According to such a configuration, the inkjet ink has more excellent stability.

  (7) The particles according to (6), wherein the particles include melamine-based beads, and a mixing ratio (mass ratio) of the (meth) acrylsilane and the melamine-based beads is 1:10 to 1: 200. Inkjet ink.

  According to such a configuration, the compatibility of the melamine-based beads with, for example, an acrylic monomer is improved by the (meth) acrylsilane. As a result, the inkjet ink has better stability.

  (8) A method for producing a printed matter, comprising: a step of applying the inkjet ink according to any one of (1) to (4) on a substrate by an inkjet method, and a step of drying the substrate.

  According to such a configuration, by using the above-described inkjet ink, various degrees of matting properties are imparted, and an inkjet print having excellent design properties can be produced. In addition, according to such a method for manufacturing an ink-jet print, the ink-jet device to be used is not limited, and the discharge amount per discharge can be increased, or the ink can be applied onto the base material in a short time, The productivity of printed matter can be improved.

  (9) A step of applying the inkjet ink according to any one of (5) to (7) on a substrate by an inkjet method, and a step of irradiating the applied inkjet ink with ultraviolet rays to cure the inkjet ink. And a method for producing an ink-jet print.

  According to such a configuration, by using the above-described inkjet ink, various degrees of matting properties are imparted, and an inkjet print having excellent design properties can be produced. In addition, according to such a method for manufacturing an ink-jet print, the ink-jet device to be used is not limited, and the discharge amount per discharge can be increased, or the ink can be applied onto the base material in a short time, The productivity of printed matter can be improved.

  (10) An inkjet print, to which the inkjet ink according to any one of (1) to (7) is applied.

  According to such a configuration, the obtained printed matter is provided with various degrees of mattness by using the above-described inkjet ink, and is excellent in design. Printed matter is easily produced efficiently.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in discharge stability, can give various degrees of matting property, and can manufacture the inkjet ink which can improve the design property and productivity of a printed matter, an inkjet printed matter, and manufacture of an inkjet printed matter. A method can be provided.

<Inkjet ink>
The ink-jet ink according to one embodiment of the present invention (hereinafter also simply referred to as ink) has an average particle diameter of 0.4 to 2.5 μm, a refractive index of 1.4 to 1.7, and a specific gravity of 2. 1 or less. Since the ink of the present embodiment contains particles having a predetermined average particle diameter, a refractive index, and a specific gravity as described above, nozzles are less likely to be clogged during inkjet printing, and the ejection stability is excellent. In addition, since the ink contains the particles, various degrees of matting can be imparted, and the design of the printed matter can be improved. Furthermore, since the ink exhibits the matting property by containing the above-mentioned particles, it is not essential to form the unevenness independently as in the related art. As a result, according to the ink of the present embodiment, the inkjet device that can be used at the time of inkjet printing is not easily limited, and the amount of one ejection can be increased, or the ink can be applied to the base material in a short time, The productivity of printed matter can be improved. Hereinafter, each configuration will be described.

(particle)
The particles contained in the ink of the present embodiment have an average particle diameter of 0.4 to 2.5 μm, a refractive index of 1.4 to 1.7, and a specific gravity of 2.1 or less. I do. An ink containing such particles hardly clogs nozzles and flow paths during inkjet printing, and has excellent ink ejection stability. In addition, by providing such particles, the resulting coating film is unlikely to cause cloudiness or the like, and a desired matting property can be imparted to the substrate.

  The average particle size of the particles may be 0.4 μm or more, and preferably 0.8 μm or more. The average particle size of the particles may be 2.5 μm or less, and is preferably 2.0 μm or less. When the average particle size is less than 0.4 μm, the ink tends to have an insufficient matting effect obtained by providing particles. On the other hand, if the average particle size exceeds 2.5 μm, the ink may have particles clogged in nozzles and flow paths during inkjet printing, and the ejection stability may be reduced. In the present embodiment, the average particle diameter can be measured by, for example, a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. Examples of the particle size distribution measuring device include a particle size distribution meter (Microtrack UPA manufactured by Nikkiso Co., Ltd.) using a dynamic light scattering method as a measurement principle.

  The refractive index of the particles may be 1.40 or more, and preferably 1.45 or more. The refractive index of the particles may be 1.70 or less, and is preferably 1.65 or less. When the refractive index is less than 1.40, the ink tends to have a lower refractive index than a binder resin (for example, an acrylic monomer described later), and it is difficult to obtain a matting effect. On the other hand, when the refractive index exceeds 1.70, the coating film of the obtained printed matter tends to be cloudy. In the present embodiment, the refractive index of the particles can be measured by placing the particles on a prism using, for example, an Abbe refractometer (KPR-30A, manufactured by Shimadzu Corporation).

  The specific gravity of the particles may be 2.1 or less, preferably 2.0 or less. The lower limit of the specific gravity of the particles is not particularly limited. When the specific gravity of the particles exceeds 2.1, the particles tend to sink during the formation of the coating film, and the desired matting effect tends not to be obtained. In the present embodiment, the specific gravity of the particles represents a true specific gravity, and can be measured using a Geyrussack-type specific gravity bottle (pycnometer) method.

  The content of the particles is not particularly limited. As an example, the content of the particles in the ink is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. Further, the content of the particles in the ink is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less. When the content of the particles is within the above range, the ink can easily obtain a desired matte effect. In addition, the ink has excellent storage stability, and the resulting coating film hardly causes cloudiness.

  The particles of the present embodiment may be particles having the above-mentioned predetermined average particle diameter, refractive index and specific gravity, and the material of the particles is not particularly limited. For example, the particles may be various inorganic particles or organic particles (beads).

  The inorganic particles are oxides containing metal elements such as silicon, aluminum, zinc, titanium, zirconium, yttrium, indium, antimony, tin, and tungsten. Among these, silica beads (refractive index: 1.44, specific gravity: 2.44) are relatively small compared to binder resins (for example, acrylic monomers described below) and relatively small in specific gravity. 0), alumina beads (refractive index: 1.63, specific gravity: 4.0) and the like. Among these, the inorganic particles are preferably silica beads, since the specific gravity is relatively small. Inorganic particles may be used in combination. The composition may not be constant depending on the type of the inorganic particles. Therefore, the value of the refractive index is only a general value of the inorganic particles, like the inorganic particles used in Examples described later, the value is slightly different even for the same inorganic particles There are cases. The same applies to organic particles.

  Organic particles are polymethyl methacrylate beads (refractive index: 1.49, specific gravity: 1.2 to 1.4), acrylic beads (refractive index: 1.50, specific gravity: 1.2 to 1.4), acryl-styrene Copolymer beads (refractive index 1.54, specific gravity: 1.2 to 1.25), melamine beads (refractive index 1.57, specific gravity: 1.5 to 1.6), high refractive index melamine beads ( Refractive index 1.65, specific gravity: 1.5 to 1.6), polycarbonate beads (refractive index 1.57, specific gravity: 1.4 to 1.5), styrene beads (refractive index 1.60, specific gravity: 1.60) 05-1.1), cross-linked polystyrene beads (refractive index 1.61, specific gravity: 1.05-1.1), polyvinyl chloride beads (refractive index 1.60, specific gravity: 1.35-1.5), Benzoguanamine-melamine formaldehyde beads (refractive index 1.68, specific gravity: .4～1.5), silicone beads (refractive index 1.50, specific gravity: 1.3 to 1.4), and the like. Among these, the organic particles are hardly swelled in the ink, and the stability of the obtained ink is excellent, so that the crosslinked polymer fine particles such as acrylic beads, melamine beads, acrylic-styrene copolymer beads, etc. The particles are more preferably spherical cross-linkable polymer particles from the viewpoint that nozzles and flow paths are less likely to be clogged during ink jet printing and that the ejection stability of ink is improved. In the present embodiment, a true spherical shape refers to a smooth spherical shape with almost no irregularities or bumps on the bead surface. Further, the organic particles are preferably melamine-based beads, because they are particularly difficult to swell in the ink and the stability of the obtained ink is particularly excellent. The organic particles may be used in combination, or may be composite fine particles in which inorganic particles are coated on the surface of the organic particles.

(Other components)
The ink of the present embodiment only needs to contain the particles, and other components are not particularly limited. The ink may include, for example, a binder resin, a dispersant, a solvent, and various optional components.

(Binder resin)
The binder resin is contained, for example, in order to adjust the viscosity of the ink, to adjust the hardness of the obtained printed matter, and to control the shape.

  The type of the binder resin is not particularly limited. To give an example, the binder resin is an epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ethylene ethyl acrylate resin, acrylonitrile acrylate styrene Copolymer resin, acrylonitrile styrene resin, acrylonitrile chloride polyethylene styrene copolymer resin, ethylene acetate vinyl resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, acetic acid Cellulose resin, fluorine resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether Polyethersulfone resin, polyethersulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin Methacrylic resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formal resin, polyvinyl alcohol, polyvinylpyrrolidone, ethylcellulose, carboxymethylcellulose, gelatin, and copolymer resins thereof. The binder resin can be appropriately selected in consideration of film strength, viscosity, residual viscosity of the inkjet ink, dispersion stability of pigment, heat stability, non-coloring property, water resistance and chemical resistance. The binder resin may be used in combination.

-Fluororesin The fluororesin is not particularly limited. For example, the fluororesin is preferably a copolymer of various fluorine-containing monomers and a vinyl monomer. Further, among the vinyl monomers, the fluororesin is more preferably a copolymer with a vinyl ether monomer. Further, the fluororesin is more preferably a copolymer of fluoroethylene and a vinyl ether monomer.

  The weight average molecular weight (Mw) of the fluororesin is not particularly limited. For example, Mw is preferably 5000 or more, more preferably 8000 or more. Mw is preferably 50,000 or less, more preferably 40000 or less. When Mw is within the above range, the fluororesin is easily dissolved in a solvent. Further, the obtained ink has improved drying properties and excellent ejection stability at the time of inkjet printing. When Mw is less than 5000, the resulting printed matter tends to be sticky, and the anti-blocking property tends to decrease. On the other hand, when Mw exceeds 50,000, the solubility of the fluororesin tends to decrease, and the ejection stability of the ink during inkjet printing tends to decrease. In this specification, Mw and the number average molecular weight (Mn) described below are values measured by, for example, GPC (gel permeation chromatography), and are high-speed GPC devices (HLC-8120GPC, manufactured by Tosoh Corporation). Can be measured.

-Acrylic resin The acrylic resin is not particularly limited. As an example, the acrylic resin is exemplified by a polymer of an acrylate (acrylate) or a methacrylate (methacrylate). More specifically, acrylic resins include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, methacrylic Methacrylic acid alkyl esters such as ethyl acrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and the like Hydroxy group-containing acrylates; and polymers such as hydroxy group-containing methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. . These may be used in combination.

  The weight average molecular weight (Mw) of the acrylic resin is not particularly limited. As an example, Mw is preferably 5,000 or more, more preferably 10,000 or more. Mw is preferably 100,000 or less, more preferably 50,000 or less. When Mw is within the above range, the ink containing such an acrylic resin has excellent ejection stability during ink jet printing.

-Vinyl chloride resin The vinyl chloride resin is not particularly limited. As an example, the vinyl chloride resin is exemplified by a copolymer of vinyl chloride and another monomer such as vinyl acetate, vinylidene chloride, acrylic acid, maleic acid, and vinyl alcohol. Among these, the vinyl chloride resin is preferably a copolymer (vinyl chloride-vinyl acetate copolymer) containing structural units derived from vinyl chloride and vinyl acetate.

  The vinyl chloride-vinyl acetate copolymer can be obtained, for example, by suspension polymerization. The vinyl chloride-vinyl acetate copolymer preferably contains 70 to 90% by mass of a vinyl chloride unit. When the content is within the above range, the vinyl chloride-vinyl acetate copolymer is stably dissolved in the ink, so that the long-term storage stability is excellent. Further, the obtained ink has excellent ejection stability.

  The vinyl chloride-vinyl acetate copolymer may have other structural units as necessary in addition to the vinyl chloride unit and the vinyl acetate unit. As an example, examples of the other structural unit include a carboxylic acid unit, a vinyl alcohol unit, and a hydroxyalkyl acrylate unit. Among these, the other constituent units are preferably vinyl alcohol units.

  The number average molecular weight (Mn) of the vinyl chloride resin is not particularly limited. As an example, Mn of the vinyl chloride resin is preferably 10,000 or more, more preferably 12,000 or more. Further, Mn is preferably 50,000 or less, more preferably 42,000 or less. Note that Mn can be measured by GPC and can be obtained as a relative value in terms of polystyrene.

-Silicone resin The silicone resin is not particularly limited. For example, silicone resins include methyl-based straight silicone resin (polydimethylsiloxane), methylphenyl-based straight silicone resin (polydimethylsiloxane in which a part of methyl group is substituted with phenyl group), acrylic resin-modified silicone resin, polyester Examples thereof include a resin-modified silicone resin, an epoxy resin-modified silicone resin, an alkyd resin-modified silicone resin, and a rubber-based silicone resin. These may be used in combination. Among them, the silicone resin is preferably a methyl straight silicone resin, a methylphenyl straight silicone resin, or an acrylic resin-modified silicone resin.

  The silicone resin may be dissolved in an organic solvent or the like. Examples of the organic solvent include xylene and toluene.

  The number average molecular weight (Mn) of the silicone resin is not particularly limited. For example, the Mn of the silicone resin is preferably 10,000 or more, more preferably 20,000 or more. Further, Mn is preferably 5,000,000 or less, more preferably 3,000,000 or less. Note that Mn can be measured by GPC and can be obtained as a relative value in terms of polystyrene.

  Returning to the description of the entire binder resin, the content of the binder resin is not particularly limited. As an example, the binder resin is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more in the ink constituting the ink set in terms of solid content. Is more preferred. The content of the binder resin in the ink is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. When the content of the binder resin is less than 1% by mass, it is difficult to obtain desired performance as a binder, and the adhesiveness to a substrate tends to be reduced. On the other hand, when the content of the binder resin exceeds 40% by mass, the viscosity of the ink increases, and the ejection stability during inkjet printing tends to decrease.

(Dispersant)
The dispersant is included to disperse the pigment. The dispersant is not particularly limited. As an example, examples of the dispersant include an anionic surfactant, a nonionic surfactant, and a polymer dispersant. These may be used in combination.

  Anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, poly Examples thereof include oxyethylene alkyl sulfate salts and substituted derivatives thereof.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxy Examples thereof include propylene block polymers and substituted derivatives thereof.

  The polymer dispersant having both an acid value and a base value and having an acid value larger than the base value is preferable from the viewpoint of obtaining more stable dispersion characteristics. To give an example, the polymer dispersants include PB series manufactured by Ajinomoto Fine Techno Co., Ltd., Hinoact series manufactured by Kawaken Fine Chemical Co., Ltd., Solsperse series manufactured by Nippon Lubrizol Co., Ltd., and Kusumoto Kasei Co., Ltd. ) And Efka (registered trademark) series manufactured by BASF Japan K.K.

  The content of the dispersant is appropriately determined depending on the type and content of the pigment to be dispersed. For example, the content of the dispersant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the pigment. The content of the dispersant is preferably 150 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the pigment. When the content of the dispersant is less than 5 parts by mass, the pigment tends to be hardly dispersed. On the other hand, when the content of the dispersant exceeds 150 parts by mass, the raw material cost tends to increase and the dispersion of the pigment tends to be hindered.

(solvent)
The solvent is a liquid component for dissolving the binder resin in the ink constituting the ink set. The type of the solvent is not particularly limited. As an example, the solvent is water, a glycol ether solvent, an acetate solvent, an alcohol solvent, a ketone solvent, an ester solvent, a hydrocarbon solvent, a fatty acid ester solvent, an aromatic solvent, or the like. These may be used in combination. Among these, the solvent of the present embodiment preferably contains at least one of a glycol ether-based solvent and an acetate-based solvent. Both glycol ether solvents and acetate solvents have low viscosities and relatively high boiling points. Therefore, inks containing these as solvents have more improved drying properties and more excellent ejection stability during inkjet printing.

  Glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (iso) propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, and propylene glycol. Monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n -Butyl ether, triethylene glycol monomethyl ether Ter, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono- n-butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl methyl Chi glycol butyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether and the like.

  Acetate solvents are ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec-butyl ether acetate, Ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol Mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-ethoxybutyl Acetate, 3-methyl-3-propoxybutyl acetate, 3-methyl-3-isopropoxybutyl acetate, 3-methyl-3-n-butoxyethyl acetate, 3-methyl-3-isobutoxycibutyl acetate, 3-methyl Alkylene glycol monoalkyl ether acetates such as -3-sec-butoxy butyl acetate, 3-methyl-3-tert-butoxy butyl acetate, ethylene glycol Diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and the like.

  The solvent of the present embodiment preferably has a boiling point of 150 ° C. or higher, more preferably 180 ° C. or higher. The solvent preferably has a boiling point of 300 ° C. or lower, more preferably 280 ° C. or lower. When the boiling point is within the above range, the obtained ink has more improved drying properties and more excellent ejection stability during inkjet printing. Further, according to the ink, a clear printed matter with little bleeding is easily formed. When the boiling point of the solvent is less than 150 ° C., the ink tends to dry near the head nozzle, and the ejection stability tends to decrease. On the other hand, when the boiling point of the solvent exceeds 300 ° C., the ink is difficult to dry, and the drying step at the time of forming a printed matter tends to take time. In addition, the resulting printed matter tends to blur the image.

  The content of the solvent is not particularly limited. As an example, the solvent is preferably 50% by mass or more, and more preferably 60% by mass or more, of the ink constituting the ink set. Further, the content of the solvent in the ink is preferably 99% by mass or less, more preferably 80% by mass or less. When the content of the solvent is less than 50% by mass, the viscosity of the ink becomes high, and the ejection stability at the time of inkjet printing tends to decrease. On the other hand, when the content of the solvent exceeds 99% by mass, the ratio of the binder resin that can be added to the ink becomes low, and the desired performance tends to be hardly obtained.

(Optional component)
The inks constituting the ink set of the present embodiment may contain optional components as appropriate in addition to the components described above. Examples of the optional component include a heat stabilizer, an antioxidant, a preservative, an antifoaming agent, a penetrant, a reduction inhibitor, a leveling agent, a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, and a light stabilizer.

  Further, the type of the ink of the present embodiment may be a radical polymerization type ultraviolet curable ink or a cationic polymerization type ultraviolet curable ink. In these cases, the following components may be further contained in addition to the above components.

-Radical polymerization type ultraviolet curable inkjet ink In the case of a radical polymerization type ink, the ink mainly contains a reactive monomer, a reactive oligomer, and a photopolymerization initiator in addition to the above particles. Since the ink is of a radical polymerization type, the ink is inexpensive as compared with the cationic polymerization type, and there are many materials on the market, so that ink design is easy.

  The reactive monomer is not particularly limited. By way of example, the reactive monomers include various aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, allyl compounds, (meth) acrylamides, (meth) acrylates, and the like. More specifically, the reactive monomer is an aromatic vinyl monomer such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, etc .; vinyl acetate, vinyl butyrate, N-vinylformamide, N- Vinyl ester monomers such as vinyl acetamide, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; diallyl phthalate, trimethylolpropane diallyl ether, allyl glycidyl ether and the like Allyl compounds; acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide , Nt-butylacrylamide, acryloylmorpholine, methylenebisacrylamide, and other (meth) acrylamides; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Lauryl acid, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) -4-hydroxybutyl acrylate, glycidyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, (meth) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid Monofunctional (meth) acrylates such as isobornyl, acrylate = (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl, tetrahydrofurfuryl acrylate, phenyl (meth) acrylate; Ethylene glycol (meth) acrylate, di (meth) Diethylene glycol acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 5 to 14), propylene glycol di (meth) acrylate, di Dipropylene glycol (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 5 to 14), di (meth) acryl Acid-1,3-butylene glycol, 1,4-butanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate (n = 3 to 16), poly (1-meth) acrylate Methylbutylene glycol) (n = 5 to 20), di (meth) acyl Lylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, di (meth) acrylate Dicyclopentanediol (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanetrioxyethyl (meth) A) acrylate, trimethylolpropanetrioxypropyl (meth) acrylate, trimethylolpropanepolyoxyethyl (meth) acrylate, trimethylolpropanepolyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added virphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, Propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A Kishiji (meth) acrylate, a polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate. These reactive monomers may be used in combination. Among these, the reactive monomer is preferably 2- (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate or tetrahydrofurfuryl acrylate because of its relatively low viscosity.

  The content of the reactive monomer is not particularly limited. For example, the content of the reactive monomer is preferably 50% by mass or more, more preferably 70% by mass or more in the ink. Further, the content of the reactive monomer in the ink is preferably 95% by mass or less, more preferably 90% by mass or less. When the content of the reactive monomer is within the above range, the ink tends to exhibit appropriate curability. In addition, the ink is easily adjusted to an appropriate viscosity, and has excellent ejection stability during inkjet printing.

  The reactive oligomer is not particularly limited. For example, the reactive oligomer is urethane acrylate, polyester acrylate, epoxy acrylate, silicon acrylate, polybutadiene acrylate, or the like. Among these, the reactive oligomer is preferably a urethane acrylate from the viewpoint of excellent toughness, adhesion and flexibility, and more preferably an aliphatic urethane acrylate. These reactive oligomers may be used in combination.

  The content of the reactive oligomer is not particularly limited. For example, the content of the reactive oligomer in the ink is preferably 2% by mass or more, more preferably 5% by mass or more. Further, the content of the reactive oligomer in the ink is preferably 40% by mass or less, and more preferably 30% by mass or less. When the content of the reactive oligomer is within the above range, the toughness, adhesion, and flexibility of the obtained coating film are easily adjusted appropriately. In addition, the ink is easily adjusted to an appropriate viscosity, and has excellent ejection stability during inkjet printing.

  The photopolymerization initiator is not particularly limited. As an example, the photopolymerization initiator includes benzoins, benzyl ketals, aminoketones, titanocenes, bisimidazoles, hydroxyketones, acylphosphine oxides, and the like. The photopolymerization initiator may be used in combination. Among these, the photopolymerization initiator is preferably a hydroxyketone or an acylphosphine oxide in that it is highly reactive and hardly yellowed.

  The content of the photopolymerization initiator is not particularly limited. As an example, the content of the photopolymerization initiator in the ink is preferably 1% by mass or more, more preferably 2% by mass or more. Further, the content of the photopolymerization initiator in the ink is preferably 15% by mass or less, more preferably 12% by mass or less. When the content of the photopolymerization initiator is within the above range, the ink is easily cured at an appropriate curing rate and curing rate.

  Radical polymerization type ink, if necessary, dispersing aid, sensitizer, heat stabilizer, antioxidant, preservative, defoamer, resin binder, resin emulsion, reduction inhibitor, leveling agent, pH adjustment An agent, a pigment derivative, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer and the like may be blended. In particular, the ink of the present embodiment preferably contains (meth) acrylsilane as a dispersion aid.

  The (meth) acrylsilane is not particularly limited as long as it is a compound having a (meth) acryl group ((meth) acryloxy group or (meth) acryloyloxy group) and a hydrolyzable silyl group. The (meth) acryl group and the hydrolyzable silyl group can be bonded via an organic group. The (meth) acryl group can bond to an organic group via an oxygen atom. In this case, the (meth) acryl group becomes a (meth) acryloyl group. The organic group may be an aliphatic hydrocarbon group (the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination thereof), an aromatic hydrocarbon group, or a combination thereof. The organic group may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the hydrolyzable silyl group include a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group.

  (Meth) acrylsilanes include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxylan, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Methoxylan and the like.

  (Meth) acrylsilane can react with a hydroxyl group partially remaining in particles (for example, melamine-based beads) in the ink. The particles after the reaction have excellent compatibility with the reactive monomer. Therefore, since the ink of this embodiment contains (meth) acrylsilane, the re-aggregation of particles in the ink can be reduced, and the storage stability of the ink is more likely to be improved.

  The content of the (meth) acrylsilane is not particularly limited. For example, the content of (meth) acrylsilane is preferably 0.01% by mass or more, more preferably 0.02% by mass or more in the ink. Further, the content of (meth) acrylsilane in the ink is preferably 5% by mass or less, more preferably 1% by mass or less. When the content of the (meth) acrylsilane is within the above range, the ink easily improves the compatibility of the particles and the storage stability. (Meth) acrylsilane is particularly useful when melamine-based beads are included as particles. That is, the compatibility of the melamine beads with, for example, an acrylic monomer is improved by the (meth) acryl silane. As a result, the ink has better storage stability.

  The mixing ratio (mass ratio) of (meth) acrylsilane and melamine-based beads is preferably 1:10 to 1: 200, more preferably 1:20 to 1: 200, and 1:50. More preferably, it is １ ： 1: 200. When the compounding ratio is within the above range, the compatibility of the melamine-based beads with, for example, an acrylic monomer is further improved by the (meth) acrylsilane. As a result, the ink has more excellent storage stability.

-Cation polymerization type ultraviolet curable ink-jet ink In the case of a cation polymerization type ink, the ink mainly contains a dispersant, a cation polymerizable compound, and a photopolymerization initiator in addition to the above particles.

  The cationically polymerizable compound is not particularly limited. For example, the cationically polymerizable compound is an aromatic epoxide, an alicyclic epoxide, an aliphatic epoxide, or the like. Aromatic epoxides include di- or polyglycidyl ethers of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adduct, and novolak-type epoxy resins. The cycloaliphatic epoxide is a cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a compound having a cycloalkane ring such as at least one cyclohexene or cyclopentene ring with an oxidizing agent such as hydrogen peroxide or peracid. Contained compounds. Aliphatic epoxides include diglycidyl ethers of ethylene glycol, diglycidyl ether of propylene glycol and diglycidyl ether of 1,6-hexanediol such as diglycidyl ether of alkylene glycol, glycerin and di- or triglycidyl of alkylene oxide adduct thereof. Polyglycidyl ethers of polyhydric alcohols such as ethers, diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polyalkylene glycols such as polypropylene glycol or the diglycidyl ethers of its alkylene oxide adducts.

  The content of the cationically polymerizable compound is not particularly limited. As an example, the content of the cationically polymerizable compound in the ink is preferably 50% by mass or more, and more preferably 70% by mass or more. Further, the content of the cationically polymerizable compound in the ink is preferably 95% by mass or less, more preferably 90% by mass or less. When the content of the cationically polymerizable compound is within the above range, the ink has excellent curability of the obtained coating film.

  The photopolymerization initiator is not particularly limited. To give an example, the photopolymerization initiator is acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophene, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp′-dichlorobenzophene, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzyl dimethyl ketal, tetramethylthiuram monosulfide, Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, di tert-butyl peroxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one And methylbenzoyl formate.

  The content of the photopolymerization initiator is not particularly limited. As an example, the content of the photopolymerization initiator in the ink is preferably 1% by mass or more, more preferably 2% by mass or more. Further, the content of the photopolymerization initiator in the ink is preferably 15% by mass or less, more preferably 12% by mass or less. When the content of the photopolymerization initiator is within the above range, the ink has excellent curability of the obtained coating film.

  Returning to the description of the entire ink, the viscosity of the ink is not particularly limited. For example, the viscosity of the ink is preferably 2 mPa · s or more, more preferably 5 mPa · s or more. Further, the viscosity is preferably 50 mPa · s or less, and more preferably 30 mPa · s or less. When the viscosity is within the above range, the ink is less likely to cause ejection failure from the inkjet head, and has excellent ejection stability. In the present embodiment, the viscosity of the ink can be measured using a B-type viscometer (TVB-20LT, manufactured by Toki Sangyo Co., Ltd., rotor rotation speed 60 rpm).

  The method for adjusting the viscosity within the above range is not particularly limited. By way of example, the viscosity can be adjusted by the amount of each component added, the type and amount of solvent. As for the viscosity, a viscosity modifier such as a thickener may be used as needed.

  The surface tension of the ink is not particularly limited. The surface tension of the ink at 25 ° C. is preferably 20 dyne / cm or more, and more preferably 22 dyne / cm or more. Further, the surface tension of the ink at 25 ° C. is preferably 40 dyne / cm or less, more preferably 35 dyne / cm or less. When the surface tension is within the above range, the ink has excellent ejection stability. In the present embodiment, the surface tension can be measured using a static surface tensiometer (plate method) (CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd.).

  The ink of the present embodiment can form an ink image on the base material by discharging the ink to the base material using an ink jet device employing an ink jet system. The printed matter on which the ink image is formed can impart various degrees of matting properties to the base material by containing the particles, and can improve the design of the printed matter. Further, since the ink exhibits the matting property by containing the above-mentioned particles, it is not essential to form the unevenness independently as in the related art. As a result, according to the ink, the ink jet device that can be used at the time of ink jet printing is not easily limited, so that it is possible to increase the amount of discharge at one time or to apply the ink onto the base material in a short time, and to produce a printed matter. Performance can be improved.

<Production method of printed matter (other than ultraviolet curable inkjet ink)>
The method for producing a printed matter according to one embodiment of the present invention mainly includes a step of applying the above-described ink to a substrate by an ink-jet method and a step of drying the substrate. As a result of the drying, a printed matter on which an image is formed is produced.

(Applying step)
The method of applying the ink constituting the ink set to the base material by the ink jet recording method is not particularly limited. Such systems include continuous systems such as a charge modulation system, a microdot system, a charge ejection control system, and an ink mist system, piezo systems, pulse jet systems, bubble jet (registered trademark) systems, and electrostatic suction systems. A demand system and the like are exemplified.

  An ink jet device for applying ink supplies ink to a pressure chamber from an ink tank via an ink supply path, applies an electric signal corresponding to image data to the piezoelectric element, and drives the piezoelectric element to generate a pressure. This is a device that deforms a diaphragm constituting a part of the chamber, reduces the volume of the pressure chamber, and discharges ink in the pressure chamber as droplets from a discharge port of a nozzle (head).

  The head has a shuttle system (multi-pass system) and a line system (single-pass system). The multi-pass system uses a short serial head and performs recording while scanning the head in the width direction of the base material. On the other hand, the single-pass method uses a full line head that covers the entire area of the base material, and moves the full line head and the base material only once relatively to form an image on the entire surface of the base material. It is.

  The method for manufacturing a printed matter according to the present embodiment has a particularly excellent effect when a printed matter is manufactured using an inkjet apparatus employing a single pass method. That is, in the case where the unevenness is made independent and the matting property is exhibited as in the related art, it is difficult to adopt the single-pass method in which the unevenness easily overlaps. However, as described above, the ink used in the present embodiment exhibits matting properties by containing particles. Therefore, in the method of manufacturing a printed matter according to the present embodiment, it is not essential to form the unevenness independently as in the related art. As a result, the ink jet device that can be used during ink jet printing is hardly limited, and a single pass method can be adopted. As a result, the method for manufacturing a printed matter according to the present embodiment can increase the amount of discharge at one time, or can apply ink to the base material in a short time, and can improve the productivity of the printed matter.

  The substrate to which the ink is applied is not particularly limited. As an example, the substrate is a metal plate such as a steel plate, aluminum, stainless steel or the like, a plastic plate or film such as acrylic, polycarbonate, ABS, polypropylene, polyester, or vinyl chloride, a ceramic plate, concrete, wood, glass, or the like. These substrates are preferably treated with a pretreatment agent before printing. Examples of the pretreatment agent include a fluorine-based paint, a silicone-based paint, an acrylic silicone-based paint, an acrylic-based paint, an epoxy-based paint, and a urethane-based paint. Examples of a method for applying these pretreatment agents to a substrate include a spray method, a roll coater method, a curtain flow coater method, a brush coating method, a spatula coating method, a dipping method, and an ink jet method. The base material is made of cationic dyeable polyester (CDP) fiber, polyethylene terephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, polytrimethylene terephthalate (PTT) fiber, wholly aromatic polyester fiber, polylactic acid fiber, etc. A polyester fiber, an acetate fiber, a triacetate fiber, a polyurethane fiber, a nylon fiber, or the like, or a cloth made of a composite fiber thereof may be used. These can be appropriately selected depending on the application. When the substrate is a fabric, the fabric is preferably treated with a pretreatment agent before printing. Pretreatment agents include water-soluble polymers, water-insoluble inert organic compounds, flame retardants, ultraviolet absorbers, anti-reducing agents, antioxidants, pH adjusters, hydrotropic agents, defoamers, penetrants, and microporous formation. And the like. Examples of a method for applying these pretreatment agents to a fabric include a pad method, a spray method, a dipping method, a coating method, a laminating method, a gravure method, and an ink jet method.

(Drying process)
The substrate on which the ink has been applied is then dried. The drying conditions are not particularly limited. For example, the drying temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher. Further, the drying temperature is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, even more preferably 300 ° C. or lower. The drying time is preferably at least 1 minute, more preferably at least 2 minutes, even more preferably at least 3 minutes. Further, the drying time is preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 10 minutes or less. By such drying, the pigment in the ink hardly causes discoloration or the like, and the solvent can be removed. The drying is preferably performed at the same time or immediately after the ink is applied to the base material, in order to prevent bleeding of the ink.

  The obtained printed matter is a printed matter in which a base material and a print layer formed on the base material are formed. The printing layer contains the above-described particles and has a matte property. Therefore, in the method of manufacturing a printed matter according to the present embodiment, it is not essential to form the unevenness independently as in the related art. As a result, the ink jet device that can be used during ink jet printing is hardly limited, and a single pass method can be adopted. As a result, the method for manufacturing a printed matter according to the present embodiment can increase the amount of discharge at one time, or can apply ink to the base material in a short time, and can improve the productivity of the printed matter.

<Production method of printed matter (in the case of ultraviolet curable inkjet ink)>
In one embodiment of the present invention, a method for manufacturing an ink-jet print (hereinafter, also simply referred to as a method for manufacturing a print) is performed by an ink-jet method, particularly when an ink-jet print is manufactured using the above-described ultraviolet curable ink. A step of applying the ink on the base material and a step of irradiating the applied ink with ultraviolet rays to cure the ink. Hereinafter, each will be described.

(Applying step)
The applying step is a step of applying the above-described ink on a base material by an ink jet method. The substrate is not particularly limited. As the substrate, the same one as described above can be used.

  The base material may be formed with a chemical conversion coating, an undercoat, or the like on the surface. The chemical conversion coating is formed on the entire surface of the substrate, and can improve the coating film adhesion and corrosion resistance. The undercoating film is formed on the surface of the substrate or the chemical conversion treatment film, and can improve the coating film adhesion and corrosion resistance. The resin contained in the undercoat paint for forming the undercoat film is not particularly limited. For example, the resin is a polyester resin, an epoxy resin, an acrylic resin, or the like.

  As the ink jet device for applying ink, the same device as described above can be used. In addition, the method for manufacturing a printed matter according to the present embodiment has a particularly excellent effect when a printed matter is manufactured using an inkjet apparatus employing a single-pass method. That is, as described above, the ink used in the present embodiment exhibits matting properties by containing particles. Therefore, in the method for manufacturing a printed matter according to the present embodiment, the ink jet device that can be used during ink jet printing is hardly limited, and a single pass method can be adopted. As a result, the method for manufacturing a printed matter according to the present embodiment can increase the amount of discharge at one time, or can apply ink to the base material in a short time, and can improve the productivity of the printed matter.

(Curing process)
The curing step is a step of curing the applied ink by irradiating the applied ink with ultraviolet rays. The ink discharged onto the base material is cured by being irradiated with ultraviolet rays by an ultraviolet irradiation lamp attached to the ink jet device. Examples of the ultraviolet irradiation lamp include a mercury lamp and a gas / solid laser. Among these, the ultraviolet irradiation lamp is preferably a mercury lamp or a metal halide lamp. In addition, the ultraviolet irradiation lamp may be an ultraviolet light emitting diode (UV-LED) or an ultraviolet laser diode (UV-LD).

The integrated amount of ultraviolet light during curing is not particularly limited. Integrated light quantity is preferably at 40 mJ / cm ² or more, and more preferably 60 mJ / cm ² or more. Further, the integrated light quantity is preferably 500 mJ / cm ² or less, more preferably 400 mJ / cm ² or less. The integrated light quantity can be measured using, for example, an ultraviolet illuminometer / light meter (UV-351-25, manufactured by Oak Manufacturing Co., Ltd.) under the conditions of a measurement wavelength range of 240 to 275 nm and a measurement wavelength center of 254 nm.

  As described above, according to the method for producing a printed matter of the present embodiment, various degrees of matting properties are imparted by using the ink, and an inkjet printed matter having excellent design properties can be produced. In addition, according to such a method for manufacturing an ink-jet print, the ink-jet device to be used is not limited, and the discharge amount per discharge can be increased, or the ink can be applied onto the base material in a short time, The productivity of printed matter can be improved.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.

The raw materials used are shown below.
(particle)
Particle 1: silica beads, SS-50F, manufactured by Tosoh Silica Co., Ltd., average particle diameter 1.3 μm, refractive index 1.46, specific gravity 2.0
Particle 2: Acrylic beads, J-4PY, manufactured by Negami Industry Co., Ltd., average particle diameter 2.2 μm, refractive index 1.5, specific gravity 1.45
Particle 3: Melamine-based beads, Eposter S12, manufactured by Nippon Shokubai Co., Ltd., average particle diameter 1.2 μm, refractive index 1.65, specific gravity 1.5
Particle 4: Alumina beads, Aruna beads CB-P02, manufactured by Showa Denko KK, average particle diameter 2.0 μm, refractive index 1.7, specific gravity 3.78
Particle 5: Acrylic beads, J-4PY, manufactured by Negami Industry Co., Ltd., average particle diameter 3.3 μm, refractive index 1.5, specific gravity 1.45
Particle 6: titanium oxide, R-38L, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.4 μm, refractive index 2.72, specific gravity 4.0
(resin)
Resin 1: Fluorine resin, manufactured by Asahi Glass Co., Ltd., LF-200F, alternating ethylene trifluoride / vinyl monomer copolymer Resin 2: Acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd., BR-105, polymer of methacrylic acid ester Resin 3: Urethane acrylate, manufactured by Sartomer, CN991, aliphatic urethane acrylate Resin 4: acryloyl morpholine, manufactured by KJ Chemicals Co., Ltd., ACMO, acrylamide-based monomer Resin 5: acrylic monomer, manufactured by Osaka Organic Chemical Industry Co., Ltd. , MEDOL-10, monofunctional acrylic monomer (dispersant)
Dispersant 1: Polymer dispersant, BYK, DISPERBYK2008, modified acrylic block copolymer Dispersant 2: Polymer dispersant, BYK, BYKJET9151, block copolymer having tertiary amine (solvent)
Solvent: glycol ether solvent, manufactured by Japan Emulsifier Co., Ltd., diethylene glycol diethyl ether (DEDG), boiling point: 189 ° C.
(Acrylic silane)
Acrylic silane: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane (photopolymerization initiator)
Photopolymerization initiator: Irg184, α-hydroxyketone, manufactured by BASF Japan Ltd.

<Inkjet ink>
The inks of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared according to the formulation (unit is parts by mass) shown in Table 1 below. Specifically, ink was prepared by mixing each component with a resin and filtering the mixture. Using the obtained ink, a substrate (chromium-treated aluminum steel sheet was coated with a commercially available fluorine paint (Bonflon # 1000SR overcoat, manufactured by AGC Co., Ltd.) using an air spray at about 150 g / m 2 under the following inkjet conditions. ^{2 was} applied and dried in an environment of 200 ° C. for 3 minutes) to perform inkjet printing, thereby producing a printed matter.

<Inkjet conditions>
Single pass method dot size: 30pl
Nozzle diameter: 40 μm
Drive voltage: 80V
Pulse width: 10 μm
Frequency: 10kHz
Resolution: 400 × 400 dpi
Coating amount: 7.5 g / m ²
Substrate temperature: 50 ° C (heating)
Pattern: solid pattern

<Drying conditions>
Examples 1 and 2, which are solvent-based inkjet inks, were dried for 1 minute in a 200 ° C. environment after printing. In Examples 3 to 7 and Comparative Examples 1 to 3, which are UV-curable inkjet inks, drying was performed immediately after printing under the following conditions. UV irradiation lamp: metal halide lamp Irradiation intensity: 0.5 mW / cm ²
Integrated light quantity: 400 mJ / cm ²
Irradiation height: 40mm

  In producing the prints, the initial viscosity, matting property, ink stability, and ejection stability of each ink were evaluated according to the following evaluation criteria. Table 1 shows the results.

<Initial viscosity of ink>
The prepared ink was adjusted to 50 ° C., and the viscosity (mPa · s) was measured using a B-type viscometer (TVB-20LT, manufactured by Toki Sangyo Co., Ltd., rotor No. 1, rotor speed 60 rpm). .

<Matte property>
The obtained printed matter was measured at a measurement angle of 60 ° using a gloss checker (IG331, manufactured by HORIBA, Ltd.), and the mattability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The glossiness was 10 or less.
：: The glossiness exceeded 10 and was 20 or less.
Δ: The glossiness exceeded 20 and was 30 or less.
X: Over 30.

<Ink stability>
Using a B-type viscometer (product number: TVB-20LT, manufactured by Toki Sangyo Co., Ltd.), a temperature of 50 ° C. and a rotor No. 1. The ink viscosity (mPa · s) was measured under the condition of a rotor rotation speed of 60 rpm, and the ink viscosity immediately after production and the ink viscosity one month later were evaluated for ink stability according to the following evaluation criteria.
(Evaluation criteria)
A: The change in ink viscosity after one month from the ink viscosity immediately after preparation was less than 2%.
Good: The change in ink viscosity after one month from the ink viscosity immediately after preparation was 2% or more and less than 5%.
Δ: The change in ink viscosity after one month from the ink viscosity immediately after preparation was 5% or more and 10% or less.
X: The change in ink viscosity after one month from the ink viscosity immediately after production exceeded 10%.

<Discharge stability>
When the nozzle was continuously discharged for 60 minutes and after the nozzle was allowed to stand still after the discharge, clogging of the nozzles and scattering of the ink droplets (a phenomenon in which the ink droplets did not become one droplet of a desired size but were finely dispersed) were confirmed. Was evaluated according to the evaluation criteria described above.
(Evaluation criteria)
A: No clogging of nozzles and no dispersion of ink droplets.
：: No nozzle clogging.
Δ: The nozzle was partially clogged.
X: Many clogging was seen in the nozzle.

  As shown in Table 1, the inks of Examples 1 to 7 all had a small rate of change in ink viscosity and were excellent in storage stability. In addition, these inks were excellent in ejection stability and exhibited excellent matting properties. On the other hand, the ink of Comparative Example 1 using particles having a high specific gravity had insufficient storage stability, and also had poor matting properties and ejection stability. The ink of Comparative Example 2 using particles having a large average particle diameter was inferior in ejection stability. The ink of Comparative Example 3 using particles having a large refractive index and a large specific gravity was inferior in matting properties.

Claims (10)

  An inkjet ink containing particles having an average particle diameter of 0.4 to 2.5 μm, a refractive index of 1.4 to 1.7, and a specific gravity of 2.1 or less.   The inkjet ink according to claim 1, wherein the content of the particles is 0.5 to 15% by mass.   The ink-jet ink according to claim 1, wherein the particles include fine spherical crosslinkable polymer fine particles.   The inkjet ink according to claim 1, wherein the particles include melamine-based beads.   The inkjet ink according to claim 1, wherein the inkjet ink is a radical polymerization type ultraviolet curable ink.   The inkjet ink according to claim 5, comprising (meth) acrylsilane. The particles include melamine-based beads,
The inkjet ink according to claim 6, wherein a mixing ratio (mass ratio) of the (meth) acrylsilane and the melamine-based beads is 1:10 to 1: 200. A step of applying the inkjet ink according to any one of claims 1 to 4 onto a substrate by an inkjet method,
Drying the base material. A step of applying the inkjet ink according to any one of claims 5 to 7 on a substrate by an inkjet method,
Irradiating the applied ink-jet ink with ultraviolet rays to cure the ink-jet ink, the method comprising the steps of:   An inkjet print to which the inkjet ink according to any one of claims 1 to 7 has been applied.