JP2021017033A - Producing method of printed matter and producing apparatus of printed matter, and printed matter - Google Patents

Abstract

To provide a producing method of printed matters, which can suppress deterioration of dot image quality due to coalescence and color mixture of the dropped ink relative to base materials having different surface states, and can produce printed matters having high toughness.SOLUTION: A production method of printed matters comprises the steps of: forming an intermediate layer on a base material 412; forming an ink receiving layer by imparting an ink receiving layer forming liquid to the intermediate layer; and forming an image by imparting an ink to the ink receiving layer by an inkjet method, in which static surface tension γ1 of the ink receiving layer forming liquid and static surface tension γ2 of the ink satisfy the following formula γ1<γ2, and the viscosity of the ink receiving layer forming liquid at 25°C is 40 mPa s or larger and 20,000 mPa s or smaller.SELECTED DRAWING: Figure 4

Description

The present invention relates to a method for producing a printed matter, an apparatus for producing a printed matter, and a printed matter.

In recent years, digital printing by the inkjet method has come to be used for printing on resins, metals, glass, wood, and composite materials thereof in addition to paper.

In particular, attempts have been made to print on resin films, resin-impregnated papers, wood boards (MDF boards, particle boards, veneer boards), which are base materials used for floor materials, wall materials, packaging materials, and the like. In addition to solvent inks, water-based latex inks and UV inks are used for their printing from the viewpoint of VOC, and ink additives such as photopolymerization initiators are used because of their low drying energy and from the viewpoint of quality and safety. EB ink that does not require is also used.

For example, a method has been proposed in which an image is formed by applying a second active energy ray-curable liquid containing a coloring material on a first active energy ray-curable liquid by an inkjet method (). For example, see Patent Documents 1 and 2).
Further, as a method of always obtaining good image quality regardless of the surface condition of the base material, for example, adjusting the thickness of an uncured (liquid) ink receiving layer made of an active energy ray-curable material applied to the base material. Has proposed a method for adjusting the dot size of ink droplets (see, for example, Patent Document 3).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to suppress deterioration of dot image quality due to coalescence of dropped inks and color mixing on substrates having different surface conditions, and it is possible to produce a printed matter having high robustness. The purpose is to provide a method.

The method for producing a printed matter of the present invention includes an intermediate layer forming step of forming an intermediate layer on a substrate, and an ink receiving layer forming step of applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer. Including an image forming step of applying ink to the ink receiving layer by an inkjet method to form an image, the static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink are included. The following formula, γ ₁ <γ _2, is satisfied, and the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less.

According to the present invention, it is possible to suppress deterioration of dot image quality due to coalescence of dropped inks and color mixing on substrates having different surface states, and it is possible to produce a printed matter having high robustness. A manufacturing method can be provided.

FIG. 1A is a diagram showing an example of the method for producing a printed matter of the present invention. FIG. 1B is a diagram showing another example of the method for producing a printed matter of the present invention. FIG. 1C is a diagram showing another example of the method for producing a printed matter of the present invention. FIG. 2A is a diagram showing an example of an optical micrograph of a cross section of a printed matter printed by the method for producing a printed matter of the present invention. FIG. 2B is a diagram showing an example of an optical micrograph of a cross section of a printed matter printed by the method for producing a printed matter of the present invention. FIG. 2C is a diagram showing an example of an optical micrograph of a cross section of a printed matter printed by the method for producing a printed matter of the present invention. FIG. 3 is a diagram showing an example of an optical micrograph of a cross section of a printed matter when the viscosity of the ink receiving layer forming liquid does not meet the range of the present invention. FIG. 4 is a schematic view showing an example of the printed matter manufacturing apparatus of the present invention. FIG. 5 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention. FIG. 6 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention. FIG. 7 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention.

(Printed matter manufacturing method and printed matter manufacturing equipment)
The method for producing a printed matter of the present invention includes an intermediate layer forming step of forming an intermediate layer on a base material, and an ink receiving layer forming step of applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer. Including an image forming step of applying ink to the ink receiving layer by an inkjet method to form an image, the static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink are included. The following formula, γ ₁ <γ _2, is satisfied, and the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less, and if necessary, other steps. including.
The printed matter manufacturing apparatus of the present invention includes an intermediate layer forming means for forming an intermediate layer on a base material, and an ink receiving layer forming means for forming an ink receiving layer by applying an ink receiving layer forming liquid to the intermediate layer. , An image forming means for forming an image by applying ink to the ink receiving layer by an inkjet method, and the static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink. The following formula, γ ₁ <γ _2, is satisfied, and the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less, and if necessary, other means. Has.
The method for producing a printed matter of the present invention can be suitably carried out using the printed matter manufacturing apparatus of the present invention, and the intermediate layer forming step can be preferably carried out by the intermediate layer forming means, and the ink receiving. The layer forming step can be preferably carried out by the ink receiving layer forming means, the image forming step can be preferably carried out by the image forming means, and the other steps are preferably carried out by the other means. can do.

The present inventors have excellent wet spread of the dropped ink on substrates having different surface textures, and can suppress deterioration of image quality due to coalescence and color mixing of the dropped ink, and are robust. As a result of examining a method for producing a printed matter capable of obtaining a printed matter having a high quality, the following findings were obtained.
In the conventional technique, in the production of resin films, resin-impregnated papers, and printed matter for wood boards, the base material to be used (particularly, the surface state of the base material, the ink receiving layer previously applied to the surface of the base material, etc. There is a problem that the image quality changes depending on the surface condition of the image. In particular, the spread of the ink droplet dot gain and the coalescence and color mixing of adjacent ink droplets largely depend on the surface state of the base material (or the surface state of the ink receiving layer formed on the surface of the base material). The relationship between image quality and surface parameters such as unevenness characteristics, surface energy, penetrability, and non-penetration, which represent the characteristics of, has not been completely clarified. Ink droplet dot gain on the substrate and adjacent ink The coalescence of droplets and the suppression of color mixing were not compatible. Therefore, sufficient image quality has not been obtained. In addition, the adhesion between the base material and the image (ink) is weak, and the image is peeled off by rubbing or scratching, which causes a problem in robustness.
Further, in the conventional technique, since the active energy ray-curable liquid is applied to the base material by inkjet ejection, it is required to be a low-viscosity liquid. In this case, the dots formed in the ink receiving layer are likely to be displaced, and it is difficult to obtain a desired dot shape, so that it is difficult to obtain a good image. Moreover, since the dots are not contained in the ink receiving layer, the resistance to rubbing and scratching is low. Therefore, there is a problem that it is difficult to stably reproduce good image quality regardless of the base material and to simultaneously achieve the high robustness required in the industrial field.

Therefore, the present inventors provided an intermediate layer on the surface of the base material, and formed an ink receiving layer and an image on the intermediate layer by using an ink receiving layer forming liquid and an ink having specific properties on the base material. It has been found that stable image quality can be obtained regardless of the substrate by homogenizing the surface texture (surface roughness, wettability, etc.). Further, by providing the intermediate layer and forming the ink receiving layer and the image using the ink receiving layer forming liquid and the ink having specific properties, the ink is applied to the ink receiving layer having a uniform film thickness regardless of the base material. All of the dot-shaped droplets formed in (or at least a part of the shape thereof) are confined inside the ink receiving layer, which can provide a printed matter having strong resistance to rubbing and scratching, and also inside the ink receiving layer. It was found that it is possible to obtain a stable and high image quality (high definition, high resolution) image regardless of the base material because coalescence with adjacent dots and color mixing are less likely to occur.

<Intermediate layer forming step and intermediate layer forming means>
The intermediate layer forming step is a step of forming an intermediate layer on a base material.
The intermediate layer forming means is a means for forming an intermediate layer on a base material.
The intermediate layer forming step can be preferably carried out by the intermediate layer forming means.

-Base material-
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, resin film, resin-impregnated paper, synthetic paper made of synthetic fibers, natural paper, sheets such as non-woven fabric, cloth, leather, etc. Examples include wood, metal sheets, and glass plates.
Examples of the resin film include a polyester film; a polypropylene film; a polyethylene film; a plastic film such as nylon, vinylon, and acrylic, or a film obtained by laminating the films.
The resin film is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of strength, a uniaxially or biaxially stretched resin film is preferable.
Examples of the non-woven fabric include those obtained by spraying polyethylene fibers in a sheet shape and thermocompression bonding to form a sheet shape.
Examples of the wood include plywood such as MDF, HDF, particle board, and veneer, and a decorative board having a sheet bonded to the surface. The average thickness of these is preferably 2 mm or more and 30 mm or less.
Examples of the early glass plate include float glass, colored glass, tempered glass, wire-reinforced glass, frosted glass, frosted glass, and mirror glass. The average thickness of these is preferably 0.3 mm or more and 20 mm or less.

− Intermediate layer−
The intermediate layer is particularly limited as long as the surface texture (surface roughness, wettability, etc.) of the base material can be homogenized and the ink receiving layer described later can be formed on the surface of the intermediate layer. However, it can be appropriately selected according to the purpose.
The surface texture (for example, surface roughness, wettability, etc.) of the base material differs depending on the base material, and when the ink receiving layer forming liquid is directly applied to the base material, the outermost surface of the ink receiving layer May not be uniform. For example, when wood is used as the base material, the surface of the wood may not be smooth, and the liquid may not be properly wetted and spread due to its high absorbency. By providing the intermediate layer on the base material, a uniform ink receiving layer can be provided even on base materials having different surface textures. As a result, it is possible to prevent the printed matter from having changed in image quality and image due to the difference in the type of the base material used.
Further, for example, in a building, an image using a resin film as a base material of the printed matter and an image using wood as the base material may be arranged adjacent to each other. When images using different base materials are adjacent to each other, if there is a gap between the images, the images cannot be properly joined. According to the present invention, it is possible to suppress image deviation and image quality difference due to the base material, and it is possible to form a printed matter without a sense of discomfort.
Further, by providing the intermediate layer, the adhesion of the ink receiving layer to the base material can be improved.

The material of the intermediate layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, and acrylic polyol are mainly used. Examples thereof include urethane-based resins, vinyl chloride-vinyl acetate copolymers, polyester resins, butyral resins, chlorinated polypropylene, and chlorinated polyethylene as components. Further, examples thereof include those obtained by dissolving these materials in a solvent such as methyl ethyl ketone, dioxane, hexane, ethyl acetate and butyl acetate (solvent type resin). Examples of commercially available solvent-based resins include Fine Tack CT-3088, CT-3850, CT-5020, CT-5030, CT-6030, Quickmaster SPS-900-LV, SPS-945NT, SPS-1040NT-25 ( DIC Corporation) and the like.
Examples of the material of the intermediate layer include acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin, and epoxy resin. Examples thereof include a resin emulsion dispersed in an aqueous dispersion medium such as water. The volume average particle diameter of these resin components is not particularly limited as long as an emulsion is formed, and is preferably 150 nm or less, more preferably 5 nm or more and 100 nm or less. Examples of commercially available resin emulsions include Boncoat W-26 and W-386 (manufactured by DIC Corporation).

Further, as the material of the intermediate layer, it is preferable to contain an active energy ray-curable liquid and a resin powder.
Examples of the active energy ray-curable liquid include the same components as the ink receiving layer forming liquid described later.
Examples of the resin powder include crosslinked acrylic particles and crosslinked methacryl particles. Commercially available products include crosslinked acrylic monodisperse particles MX-100 (manufactured by Soken Kagaku Co., Ltd.) and crosslinked methacryl particles tough tick AR650 (manufactured by Nippon Exlan Industry Co., Ltd.). ) And so on. Further, examples of the sheet used as the lamination method include a hot melt film and the like, and examples thereof include a clamper (manufactured by Kurabo Industries Ltd., polyolefin-based, polyester-based, polyurethane-based) and the like.

The average thickness of the intermediate layer is, for example, preferably 0.1 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less.

The method for forming the intermediate layer on the base material is not particularly limited and may be appropriately selected depending on the intended purpose. The material may be used as it is or in a state of being dissolved or dispersed in a solvent. It can be carried out by applying by a known printing method, coating method or the like, drying and curing. For example, a method of applying a liquid which is a material of an intermediate layer, applying a liquid in which a resin is dissolved or dispersed to a base material, and then drying a solvent to form an intermediate layer, or applying a liquid which is a material of the intermediate layer. Later, there is a method of forming an intermediate layer by curing by irradiation with active energy rays. Other methods include a method of laminating an adhesive sheet as an intermediate layer, a method of applying resin powder and fixing by thermocompression bonding, and the like.
The method for applying the liquid, the melt, and the powder as the components of the intermediate layer on the base material (the intermediate layer forming means) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, knife coating method, nozzle coating method, die coating method, lip coating method, comma coating method, gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method. , Blade coating method, casting method, dip method, curtain coating method and other coating methods, spray, dispenser, inkjet method and the like.

In addition, when forming the intermediate layer, the base material is subjected to easy-adhesion treatment such as corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, etc., to bond the base material to the ink receiving layer. Adhesion can also be improved.

<Ink receiving layer forming step and ink receiving layer forming means>
The ink receiving layer forming step is a step of applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer.
The ink receiving layer forming means is a means for applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer.
The ink receiving layer forming step can be preferably carried out by the ink receiving layer forming means.

-Ink receiving layer forming liquid-
The ink receiving layer forming liquid is a liquid for forming an ink receiving layer for receiving ink, which will be described later, and contains a polymerizable compound, and contains a polymerization initiator, a polymerization accelerator, a surfactant, and a pigment. It is preferable to use the above, and if necessary, other components are contained.

In the present invention, the static surface tension γ ₁ of the ink receiving layer forming liquid at 25 ° C. and the static surface tension γ _{2 of the} ink described later satisfy the following equation, γ ₁ <γ ₂ . Dots formed with ink by satisfying the following equation, γ ₁ <γ _2, between the static surface tension γ ₁ of the ink receiving layer forming liquid at 25 ° C. and the static surface tension γ _{2 of the} ink described later. All (or at least a part of) of the above can be confined in the ink receiving layer to form a printed matter resistant to rubbing and scratching.
The static surface tension γ ₁ of the ink receiving layer forming liquid at 25 ° C. is preferably 60 mN / m or less, more preferably 40 mN / m or less.
Further, the difference (γ _2- γ ₁ ) between the static surface tension γ ₁ of the ink receiving layer forming liquid at 25 ° C. and the static surface tension γ _{2 of the} ink described later is 0 mN / m or more and 20 mN / m or less. Is preferable, and 6 mN / m or more and 8 mN / m or less is more preferable. The smaller the difference in static surface tension between the ink receiving layer forming liquid and the ink, the easier it is for the ink to wet and spread, so that a high dot gain can be obtained with a small amount of ink.
The static surface tension can be measured by, for example, a plate method or a ring method with an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science.

Further, in the present invention, the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less. When the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less, dots can be formed in the deep part, and a printed matter stronger against rubbing and scratching can be formed.
The viscosity can be measured, for example, with an Anton Pearl rheometer MCR301 using a cone plate CP25-1 at a shear rate of 10 / s at 25 ° C.

The polymerizable compound is a monomer or oligomer containing a functional group such as a vinyl group, an acryloyl group, or a methacryloyl group in the molecular structure, and is a monofunctional monomer having one functional group or a polyfunctional monomer having one or more functional groups. , Polyfunctional oligomers, urethane acrylate oligomers depending on the type of molecular structure, epoxy acrylate oligomers, polyester acrylate oligomers and the like.

Examples of the monofunctional monomer include γ-butyrolactone (meth) acrylate, isobornyl (meth) acrylate, formalized trimethylolpropane mono (meth) acrylate, trimethylrolpropane (meth) acrylic acid benzoic acid ester, and (meth) acryloyl. Morpholine, 2-hydroxypropyl (meth) acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether , Benzyl vinyl ether, ethyloxetane methyl vinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, ethoxy (4) nonylphenol (meth) acrylate, benzyl (meth) acrylate, caprolactone (meth) acrylate and the like. These may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, polytetramethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane di. (Meta) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol dimethacrylate [CH ₂ = CH-CO- (OC ₂ H ₄ ) n-OCOCH = CH ₂ (n≈9), same (n≈14) , Same (n≈23)], Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol dimethacrate [CH ₂ = C (CH ₃ ) -CO- (OC ₃ H ₆ ) _n- OCOC (CH ₃ ) = CH ₂ (n≈7)], 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) ) Acrylic, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane dimethanol di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, polyethylene glycol di ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, propylene oxide-modified tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, caprolactone-modified dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di ( Meta) acrylate, professional Pyreneoxide-modified glyceryl tri (meth) acrylate, polyester di (meth) acrylate, polyester tri (meth) acrylate, polyester tetra (meth) acrylate, polyester penta (meth) acrylate, polyester poly (meth) acrylate, polyurethane di (meth) Acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane penta (meth) acrylate, polyurethane poly (meth) acrylate, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol di Examples thereof include vinyl ether and ethoxylated (4) bisphenol di (meth) acrylate. These may be used alone or in combination of two or more.

Further, a mixed composition of each combination of the monofunctional monomer and the polyfunctional monomer and the monofunctional monomer and the polyfunctional oligomer may be used. In that case, from the viewpoint of robustness, the total amount of the ink receiving layer forming liquid may be increased. The polyfunctional monomer and the polyfunctional oligomer are preferably 50% by mass or more.

As the polymerization initiator, for example, if it is possible to generate active species such as radicals and cations by the energy of active energy rays or heat and initiate the polymerization of the ink receiving layer forming liquid. Good. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among these, a radical polymerization initiator is used. Is preferable. Further, the polymerization initiator is preferably contained in an amount of 1% by mass or more and 20% by mass or less based on the total amount of the ink receiving layer forming liquid in order to obtain a sufficient curing rate.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

The polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p. Examples thereof include amine compounds such as -2-ethylhexyl-dimethylaminobenzoate, N, N-dimethylbenzylamine, and 4,4'-bis (diethylamino) benzophenone. The content of the polymerization accelerator is not particularly limited and may be appropriately set according to the polymerization initiator used and the amount thereof.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, glyceryl monostearate, glyceryl monooleate, mono. Glycerin fatty acid esters such as diglyceryl stearate and diglyceryl monoisostearate, glycol fatty acid esters such as propylene glycol monostearate, sorbitan fatty acid esters such as sorbitan monostearate and sorbitan monooleate, sucrose stearic acid esters, POE ( 4.2) Lauryl ether, POE (40) hardened castor oil, POE (10) cetyl ether, POE (9) lauryl ether, POE (10) oleyl ether, monooleic acid POE (20) sorbitan, monolaurate POE (6) ) Sorbit, POE (15) cetyl ether, monopalmitate POE (20) sorbitan, POE (15) oleyl ether, POE (100) hardened castor oil, POE (20) POP (4) cetyl ether, POE (20) cetyl Ether, POE (20) oleyl ether, POE (20) stearyl ether, POE (50) oleyl ether, POE (25) cetyl ether, POE (25) lauryl ether, POE (30) cetyl ether, POE (40) cetyl ether And so on. These may be used alone or in combination of two or more.
The content of the surfactant is preferably 0.1% by mass or more and 2% by mass or less with respect to the total amount of the ink receiving layer forming liquid.

Examples of the pigment include white pigments, metal powder pigments, pearl luster pigments, fluorescent pigments and the like.
Examples of the white pigment include titanium dioxide, aluminum oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, silica sand, clay, talc, silica and the like.

The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic solvents, thickeners, dispersants, deodorants, ultraviolet blocking agents, antibacterial agents and rust preventives. Can be mentioned.

The method for preparing the ink receiving layer forming liquid can be prepared by mixing the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like are ball milled. , Kitty mill, disc mill, pin mill, dyno mill, etc., and disperse to prepare a pigment dispersion, and further add a polymerizable monomer, initiator, polymerization inhibitor, surfactant, etc. to the pigment dispersion. It can be prepared by mixing.

The method for applying the ink receiving layer forming liquid on the base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, knife coating method, nozzle coating method, die coating method, lip coating method, comma coating method, gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method. , Blade coating method, casting method, dip method, coating method such as curtain coating method, inkjet method and the like.

The average thickness of the ink receiving layer after curing is preferably 15 μm or more, more preferably 15 μm or more and 100 μm or less, further preferably 20 μm or more and 50 μm or less, and particularly preferably 20 μm or more and 30 μm or less. When the average thickness of the ink receiving layer after curing is 15 μm or less, the ink receiving layer is formed when all (or at least a part of) dots formed from the ink described later are formed inside the ink receiving layer. When the film thickness of is reduced, the thickness of dots (color ink) becomes smaller, and a high image density can be realized with a small amount of ink.
When the average thickness of the ink receiving layer after curing is 20 μm or more and 50 μm or less, the dot shape can be easily controlled, the ink can be appropriately spread, and the image density can be increased.
As a method of obtaining the average thickness of the ink receiving layer after curing, the ink receiving layer after curing is scraped off at five different locations, and the height from the base material to the surface of the ink receiving layer at that portion is determined by, for example, Keyence. Measure with a laser microscope VK-X100 and calculate the average value. It is obtained by dividing the average thickness of the intermediate layer from the calculated average value.

Further, before forming the ink receiving layer, it is preferable to apply a surface treatment such as a corona treatment to the intermediate layer to improve the uniformity of the coating film of the ink receiving layer.

<Image forming process and image forming means>
The image forming step is a step of applying ink to the ink receiving layer by an inkjet method to form an image.
The image forming means is a means for forming an image by applying ink to the ink receiving layer by an inkjet method.
The image forming step can be preferably carried out by the image forming means.
The "image" in the present invention includes all printed images (characters, figures, symbols, photographs, solid images, etc.) using the ink.
In the image forming step, the ink is applied to the surface of the ink receiving layer.

-Ink-
The ink preferably contains a polymerizable compound, a polymerization initiator and a coloring material, and further contains other components as necessary.

--Polymerizable compound ---
As the polymerizable compound, the same compound as the ink receiving layer forming liquid can be used.
It is preferable that the polymerizable compound in the ink contains a monofunctional monomer and a polyfunctional monomer.

--Polymerization initiator ---
As the polymerization initiator, the same one as the ink receiving layer forming liquid can be used.

--Color material ---
As the coloring material, various colors such as black, magenta, cyan, yellow, green, orange, purple, white, and glossy colors such as gold and silver are imparted according to the purpose and required characteristics of the ink in the present invention. Pigments can be used.
The content of the coloring material may be appropriately determined in consideration of a desired color density, dispersibility in the ink, etc., and is not particularly limited, but is 0.1% by mass or more and 20% by mass with respect to the total amount of the ink. The following is preferable.
Inorganic pigments and organic pigments can be used as the coloring material. These may be used alone or in combination of two or more.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments and isoindolinone pigments. Polycyclic pigments such as quinophthalone pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing rake (for example, basic dye type rake, acidic dye type rake, etc.), nitro pigment, nitroso pigment , Aniline black and the like.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained.
The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

As the ink, the ink containing the color material may be referred to as a color ink (sometimes simply referred to as ink), and the ink not containing the color material may be referred to as a clear ink. Further, the region where the ink (color ink) is ejected may be referred to as an image region, and the region where the clear ink is ejected may be referred to as a non-image region.
It is preferable that the clear ink is ejected or formed as dots other than the image region (non-image region) of the ink or at least around the boundary between the image region and the non-image region. By ejecting or forming dots of the clear ink other than the image region (non-image region) of the ink or at least around the boundary between the image region and the non-image region, the problem of dot spreading that tends to occur at the edge of the image region can be solved. , It is possible to provide a printed matter having less ink bleeding at the edge of an image.

--Other ingredients ---
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, an organic solvent, a surfactant, a polymerization inhibitor, a leveling agent, a defoaming agent, a fluorescent whitening agent, and a penetration promoting agent. Examples thereof include agents, wetting agents (moisturizers), fixing agents, viscosity stabilizers, rust inhibitors, preservatives, antioxidants, and ultraviolet absorbers.
It is preferable not to contain the organic solvent if possible. If the composition does not contain the organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. It becomes. The “organic solvent” means, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, and it is preferably less than 0.1% by mass.

The ink can be prepared by using the above-mentioned various components, and the preparation method and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like can be used in a ball mill, a kitty mill, or a disc. Prepared by putting it in a disperser such as a mill, pin mill, or dyno mill, and dispersing it to prepare a pigment dispersion, and further mixing the pigment dispersion with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. can do.

The static surface tension γ _{2 of the} ink at 25 ° C. is preferably 40 mN / m or less, more preferably 15 mN / m or less and 40 mN / m or less. However, it is necessary to adjust the tension so that it is equal to or less than the static surface tension of the ink receiving layer forming liquid. When the static surface tension of the ink at 25 ° C. is 40 mN / m or less, the wett spread of the dropped ink can be improved.

The viscosity of the ink used in the present invention is not particularly limited as long as it can be ejected from the nozzle of the inkjet head, and can be appropriately selected depending on the intended purpose. The viscosity at the ejection temperature is 3 mPa · s or more and 40 mPa. -S or less is preferable, 5 mPa · s or more and 15 mPa · s or less is more preferable, and 6 mPa · s or more and 12 mPa · s or less is further preferable.

As the inkjet method, for example, as the drive method of the discharge head, an on-demand type head using a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, an actuator using electrostatic force, or the like is used. Alternatively, a continuous injection type charge control type head or the like can be used.

The ink is three types, four types, or more types of ink depending on the color material (pigment) contained, and each is applied by an individual inkjet head. Further, one head may have a plurality of nozzle rows, and a head that ejects different types of ink from each nozzle row may be used. The head nozzle density required for each color varies depending on the desired image resolution and the number of scans. The head nozzle density includes, for example, 240 npi (nozzle per inch), 300 npi, 600 npi, 1,200 npi and the like.

The volume of the ink ejected from the inkjet head per droplet is preferably 1 pL or more and 50 pL or less, more preferably 2 pL or more and 50 pL or less, further preferably 10 pL or more and 50 pL or less, and most preferably 10 pL or more and 15 pL or less. When the volume of the ink ejected from the inkjet head per droplet is 1 pL or more and 50 pL or less, unnecessary coalescence, color mixing, and color gamut reduction can be suppressed.

The ejection speed of the ink droplets is preferably 5 m / s or more and 15 m / s or less, more preferably 7 m / s or more and 15 m / s or less, and further preferably 10 m / s or more and 15 m / s or less. When the ejection speed of the ink droplets is 5 m / s or more and 15 m / s or less, the ejection can be stably performed.

The dot density (image resolution) of the ejected droplets is preferably 240 dpi × 240 dpi (dot per inch) or more.

When the ejection times of a plurality of the inks, such as black ink, cyan ink, magenta ink, and yellow ink overlap (the time difference when each ink lands at the same position), the ink dots ejected earlier spread in the ink receiving layer. It is preferably short, preferably within 1 second, and more preferably within 0.5 seconds, because a blur-free image can be formed by ejecting subsequent ink dots before the ink dots can be formed.

The order of applying or ejecting the ink receiving layer forming liquid, the ink (here, color ink), and clear ink similar to the ink and containing no coloring material is either (A) or (B) below. Is.
(A) Ink receiving layer forming liquid, ink, clear ink in order (B) Ink receiving layer forming liquid, clear ink, ink in order It is preferable that the overlap of the ejection time of the ink and the clear ink is short, within 1 second. Is preferable.

The average thickness of the image formed by the ink after curing is not particularly limited and can be appropriately selected depending on the intended purpose, preferably 1 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less. The average thickness of the image formed by the clear ink is not particularly limited and can be appropriately selected depending on the intended purpose, and is preferably 1 μm or more and 20 μm or less.
Further, in the present invention, it is preferable that the average thickness of the image formed by the ink is thinner than the average thickness of the ink receiving layer formed by the ink receiving layer forming liquid. The ink can be embedded in the ink receiving layer forming liquid by making the average thickness of the image formed by the ink thinner than the average thickness of the ink receiving layer formed by the ink receiving layer forming liquid. As a result, a printed matter having high robustness can be obtained. The difference between the average thickness of the ink receiving layer formed by the ink receiving layer forming liquid and the average thickness of the image formed by the ink is preferably 100 μm or less.
Further, in the present invention, the sum of the average thickness of the ink receiving layer formed by the ink receiving layer forming liquid and the average thickness of the image formed by the ink is preferably 1 μm or more and 100 μm or less. When the sum of the average thickness of the ink receiving layer formed by the ink receiving layer forming liquid and the average thickness of the image formed by the ink is 1 μm or more and 100 μm or less, stable and high image quality regardless of the substrate. And a robust printed matter can be obtained.
As a method of obtaining the average thickness, the ink layer (image) and the ink receiving layer after curing at five different locations are scraped off, and the height from the base material to the surface of the image (ink layer) at that portion is, for example, a Keyence laser. It is obtained by measuring with a microscope VK-X100 and calculating an average value.

<Other processes and other means>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a curing step, a heating step, an embossing step, and a bending step.
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include curing means, heating means, embossing means, bending means and the like.
The other steps can be preferably carried out by the other means.

<< Curing process and curing means >>
The curing step is a step of curing the ink receiving layer and the image (ink layer) by an external stimulus.
The curing means is a means for curing the ink receiving layer and the image (ink layer) by an external stimulus.
By curing the ink receiving layer and the image (ink layer), an integrated cured product can be obtained.

The external stimulus is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include active energy rays and heat.

In addition to ultraviolet rays, the active energy rays can impart energy necessary for advancing the polymerization reaction of polymerizable components in the composition, such as electron beams, α rays, β rays, γ rays, and X-rays. It suffices, and is not particularly limited. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

The curing conditions are not particularly limited and may be appropriately selected depending on the intended purpose, but in the case of ultraviolet rays, it is preferable to use an irradiation device capable of irradiating with an intensity of 6 W / cm ² or more at an irradiation distance of 2 mm.
In the case of an electron beam, it is preferable that the acceleration voltage is 15 kGy or more at a location farthest from the electron beam irradiator to be cured.

The curing step is preferably performed within 10 seconds after the ink is ejected to the ink receiving layer. When the curing step is within 10 seconds, it is possible to suppress image distortion caused by the ink.
Further, when the clear ink is ejected, it means that it is within 10 seconds from the time when the ink (color ink) and the clear ink are ejected.

<< Heating process and heating means >>
The heating step is a step of heating and leveling the ink receiving layer and the image (ink layer) before curing.
The heating means is a means for heating and leveling the ink receiving layer and the image (ink layer) before curing.
When the heating step is performed, it is performed before the curing step.
The heating means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an infrared heater and a hot air heater.
The heating temperature is preferably, for example, 40 ° C. or higher and 100 ° C. or lower. When the heating temperature is 40 ° C. or higher and 100 ° C. or lower, distortion of the image of the ink can be suppressed.

<< Embossing process and embossing means >>
The embossing process is a process of forming an uneven pattern on a printed matter.
The embossing means is a means for forming an uneven pattern on a printed matter.
In the embossing process, methods such as embossing, chemical embossing, rotary screen processing, and raised printing, which are usually used for the purpose of imparting unevenness to wallpaper, decorative materials, etc., can be appropriately selected and used. it can.

Examples of the embossing means include a means for embossing with a cooling roller after heating, a means for embossing at once using a hot roller embossing, and the like.
The embossing depth by embossing is preferably 0.08 mm or more and 0.50 mm or less. When the embossing depth is 0.08 mm or more, a three-dimensional effect can be obtained, and when it is 0.50 mm or less, the wear strength of the surface can be improved.
Examples of the shape of the uneven pattern formed by the embossing include a wood grain conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a perforated groove.

The printed matter produced by the method for producing a printed matter of the present invention and the apparatus for producing a printed matter of the present invention has excellent wet spread of the dropped ink on a substrate having different surface textures, and the combined ink and the dropped ink are combined. Since deterioration of image quality due to color mixing can be suppressed and printed matter with high robustness can be produced, for example, construction of floor materials, wallpaper, interior materials, wall materials, width wood, ceiling materials, pillars, etc. Suitable for applications such as materials.

Here, the method for producing a printed matter of the present invention will be described in detail with reference to the drawings.
1A to 1C are conceptual diagrams showing an example of the principle of the method for producing a printed matter of the present invention. As shown in FIGS. 1A and 1B, the base material 10 forms an intermediate layer (not shown) and an ink receiving layer 11 on the base material 10, and the ink 12 ejected by the inkjet method is formed on the ink receiving layer 11. When applied, the static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ ₂ of the ink satisfy the following equation, γ ₁ <γ _2, and thus the ink receiving layer 13 Ink droplets are embedded inside to form dots 13. Further, as shown in FIG. 1B, the shape of the embedded dots can be changed by lowering the viscosity of the ink. Further, by adjusting the difference in static surface tension between the ink and the ink receiving layer, the embedded dots can be partially exposed on the surface layer of the ink receiving layer 13, and as a result, the image quality is improved. Can be done.

2A to 2C are optical micrographs showing an example of cutting in the thickness direction of the printed matter formed by the method for producing a printed matter of the present invention. As shown in FIG. 2A, the static surface tension γ1 of the ink-receiving layer-forming solution of the present invention, and the static surface tension γ2 of the ink, the following _equation, γ _{1 <γ 2,} was filled, the ink at 25 ° C. When the viscosity of the receiving layer forming liquid is 40 mPa · s or more and 20,000 mPa · s or less, the ink dots can be embedded inside the ink receiving layer. Further, by adjusting the viscosity of the ink receiving layer forming liquid at 25 ° C. to a low viscosity (2,000 mPa · s or less), the average thickness of the embedded ink dots can be reduced and the dot area can be increased. .. In this case, the image density can be increased. Further, as shown in FIG. 2C, by adjusting the relationship between the difference in static surface tension between the ink and the ink receiving layer, the embedded dots can be partially exposed on the surface layer of the ink receiving layer 13.
Further, when the viscosity of the ink receiving layer forming liquid at 25 ° C. is adjusted to 30 mPa · s or less, as shown in FIG. 3, the dots formed in the ink receiving layer are displaced, and the dot shape is formed inside the receiving layer. (In this case, voids are generated inside the dots), and the color development property is also lowered, so that a good image cannot be obtained.

FIG. 4 is a schematic view showing an example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus of FIG. 4 has a means for forming an intermediate layer on the base material 412 (not shown) and a coating roller 414 for applying an ink receiving layer forming liquid (ink receiving layer) 414 onto the intermediate layer. A discharge head unit composed of a black head 415, a magenta head 416, a cyan head 417, and a yellow head 418 as a head for applying a plurality of inks (color inks) downstream thereof by an inkjet method, and further. A downstream of it is an active energy ray irradiation device 419. In FIG. 4, 411 is a transport belt. The base material 412 is transported on the transport belt 20 in the direction of the arrow in FIG.
First, an intermediate layer is formed on the surface of the base material. Then, the ink receiving layer forming liquid (ink receiving layer) 414 is applied by the coating roller 413.
Next, the substrate on which the ink receiving layer is formed is scanned at a predetermined speed, and from a plurality of heads for ink (black head 415, magenta head 416, cyan head 417, and yellow head 418). Black, magenta, cyan, and yellow inks are ejected into the image region on the ink receiving layer according to the image pattern.
Next, the ink receiving layer and the ink are irradiated with the active energy rays under predetermined irradiation conditions by using the active energy ray irradiation device 419, and the ink is cured.
The printed matter manufacturing apparatus is configured as a single-pass printing apparatus in which the width that can be printed by the inkjet head is larger than the width of the substrate to be printed and the number of scans is one, but the width of the head is larger than the width of the substrate. It may be configured as a multi-pass printing apparatus provided with a drive mechanism (head unit or base material transfer) capable of a plurality of scanning times.

FIG. 5 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus of FIG. 5 has a means for forming an intermediate layer on the base material 512 (not shown) and a coating roller 513 for applying an ink receiving layer forming liquid (ink receiving layer) 514 onto the intermediate layer. And, as a head for applying a plurality of inks (color inks) downstream thereof by the inkjet method, a black head 515, a magenta head 516, a cyan head 517, a yellow head 518, and a clear color-free head. A discharge head unit composed of an ink head 519 and an active energy ray irradiation device 520 further downstream thereof are provided. In FIG. 5, 511 is a transport belt. The base material 512 is transported on the transport belt 511 in the direction of the arrow in FIG.
First, an intermediate layer is formed on the surface of the base material. Then, the ink receiving layer forming liquid (ink receiving layer) 514 is applied by the coating roller 513.
Next, the substrate on which the ink receiving layer is formed is scanned at a predetermined speed, and from a plurality of heads for ink (black head 515, magenta head 516, cyan head 517, and yellow head 518), Black, magenta, cyan, and yellow inks are ejected into the image region on the ink receiving layer according to the image pattern. After that, the clear ink head 519 ejects the clear ink to the non-image region on the ink receiving layer according to the image region and the inversion pattern.
Next, the ink receiving layer, the ink, and the clear ink are irradiated with the active energy rays under predetermined irradiation conditions by using the active energy ray irradiation device 520 and cured.
The printed matter manufacturing apparatus is configured as a single-pass printing apparatus in which the width that can be printed by the inkjet head is larger than the width of the substrate to be printed and the number of scans is one, but the width of the head is larger than the width of the substrate. It may be configured as a multi-pass printing apparatus provided with a drive mechanism (head unit or base material transfer) capable of a plurality of scanning times.

FIG. 6 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus of FIG. 6 has a means for forming an intermediate layer on the base material 612 (not shown) and a coating roller 613 for applying an ink receiving layer forming liquid (ink receiving layer) 614 onto the intermediate layer. And, as a head for applying clear ink by the inkjet method downstream thereof, a discharge head unit composed of a clear ink head 615 containing no coloring material, and a plurality of inks (color inks) for applying by the inkjet method. As the head, a black head 616, a magenta head 617, a cyan head 618, a yellow head 619, and an active energy ray irradiating device 620 further downstream thereof are provided. In FIG. 6, 611 is a transport belt. The base material 612 is transported on the transport belt 611 in the direction of the arrow in FIG.
First, an intermediate layer is formed on the surface of the base material. Then, the ink receiving layer forming liquid (ink receiving layer) 614 is applied by the coating roller 613.
Next, the base material on which the ink receiving layer is formed is scanned at a predetermined speed, and the clear ink is ejected from the clear ink head 615 to the non-image region on the ink receiving layer according to the image region and the inversion pattern. .. Then, from a plurality of heads for ink (black head 616, magenta head 617, cyan head 618, and yellow head 619), black, magenta, cyan, and image regions on the ink receiving layer are formed. The yellow ink is ejected according to the image pattern.
Next, the ink receiving layer, the clear ink, and the ink are irradiated with the active energy rays under predetermined irradiation conditions by using the active energy ray irradiation device 620 and cured.
The printed matter manufacturing apparatus is configured as a single-pass printing apparatus in which the width that can be printed by the inkjet head is larger than the width of the substrate to be printed and the number of scans is one, but the width of the head is larger than the width of the substrate. It may be configured as a multi-pass printing apparatus provided with a drive mechanism (head unit or base material transfer) capable of a plurality of scanning times.

FIG. 7 is a schematic view showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus of FIG. 7 has a means for forming an intermediate layer on the base material 712 (not shown) and a coating roller 713 for applying an ink receiving layer forming liquid (ink receiving layer) 714 onto the intermediate layer. A discharge head unit composed of a clear ink head 715 that does not contain a coloring material, and a plurality of inks (color inks) are applied by an inkjet method as a head for applying clear ink downstream thereof by an inkjet method. As the head, a black head 716, a magenta head 717, a cyan head 718, a yellow head 719, and further downstream thereof, a heating device 720 and an active energy ray irradiation device 721 are provided. In FIG. 7, 711 is a transport belt. The base material 712 is conveyed on the transfer belt 711 in the direction of the arrow in FIG.
First, an intermediate layer is formed on the surface of the base material. Then, the ink receiving layer forming liquid (ink receiving layer) 714 is applied by the coating roller 713.
Next, the base material on which the ink receiving layer is formed is scanned at a predetermined speed, and the clear ink is ejected from the clear ink head 715 to the non-image region on the ink receiving layer according to the image region and the inversion pattern. .. After that, from a plurality of heads for ink (black head 716, magenta head 717, cyan head 718, and yellow head 719), black, magenta, cyan, and the image region on the ink receiving layer are formed. The yellow ink is ejected according to the image pattern.
Next, after heating with the heating device 720 to level each liquid, the ink receiving layer, the clear ink, and the ink are irradiated with the active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 721. , Hardens.
The printed matter manufacturing apparatus is configured as a single-pass printing apparatus in which the width that can be printed by the inkjet head is larger than the width of the substrate to be printed and the number of scans is one, but the width of the head is larger than the width of the substrate. It may be configured as a multi-pass printing apparatus provided with a drive mechanism (head unit or base material transfer) capable of a plurality of scanning times.

(Printed matter)
The printed matter of the present invention is a printed matter produced by the method for producing a printed matter of the present invention, has the base material, the intermediate layer, and the ink receiving layer, and has an average thickness of the ink receiving layer after curing. , More than 15 μm, and further have other members as needed.
The printed matter of the present invention further has an image, and it is preferable that the image is present inside the ink receiving layer.
The base material, the intermediate layer, the ink receiving layer, and the image in the printed matter of the present invention are the same as those described in the method for producing a printed matter and the apparatus for producing a printed matter of the present invention.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation of ink receiving layer forming liquid A>
2-Acryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 94.9 parts by mass, Omnirad TPO (manufactured by IGM Resins) 5 parts by mass as an initiator, BYK-UV-3510 (manufactured by BYK) as a surfactant The ink receiving layer forming liquid A was prepared by stirring 0.1 parts by mass.
The static surface tension of the ink receiving layer forming liquid A at 25 ° C. was 29 mN / m, and the viscosity at 25 ° C. was 160 mPa · s.
The static surface tension at 25 ° C. was measured by the plate method with an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science. The viscosity at 25 ° C. was measured by an Anton Pearl rheometer MCR301 using a cone plate CP25-1 at a shear rate of 10 / s and 25 ° C. Hereinafter, the static surface tension and the viscosity were measured by the same method as the method for measuring the ink receiving layer forming liquid except that the temperature conditions were changed.

<Preparation of black ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 27 parts by mass of acryloylmorpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator 5.0 parts by mass of Omnirad TPO (manufactured by IGM Resins), 1 part by mass of Solspace 32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 7 parts by mass of SPECIAL BLACK 350 (black pigment, manufactured by BASF Japan) as a coloring material. Black ink was prepared by stirring the parts.
The static surface tension of the black ink at 25 ° C. was 35 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of magenta ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 27 parts by mass of acryloylmorpholin (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropaneethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.) Omnirad TPO (manufactured by IGM Resins) 5 parts by mass, Solspace 32000 (manufactured by Lubrizol) 1 part by mass as a surfactant / dispersant, CINQUASIA MAGENTA RT-355-D (magenta pigment, manufactured by BASF Japan) as a coloring material. Magenta ink was prepared by stirring 7 parts by mass.
The static surface tension of the magenta ink at 25 ° C. was 35 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of cyan ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 27 parts by mass of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylpropaneethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator 5 parts by mass of Omnirad TPO (manufactured by IGM Resins), 1 part by mass of Solspire 32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 40 parts by mass of IRGLITE BLUE GLVO (cyan pigment, manufactured by BASF Japan) as a coloring material. Cyan ink was prepared by stirring.
The static surface tension of the cyan ink at 25 ° C. was 35 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of yellow ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 27 parts by mass of acryloylmorpholin (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator Stir 5 parts by mass of Omnirad TPO (manufactured by IGM Resins), 1 part by mass of Solsperse32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 40 parts by mass of NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant) as a coloring material. The yellow ink was prepared by the above.
The static surface tension of the yellow ink at 25 ° C. was 35 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

Next, the prepared ink receiving layer forming liquid A, clear ink, black ink, magenta ink, cyan ink, and yellow ink as color inks were used in the printed matter manufacturing apparatus 100 shown in FIG. 4, and the printed matter 1 was as follows. Got
The inkjet image forming apparatus of FIG. 4 is a means (not shown) for forming an intermediate layer by coating the intermediate layer composition on the base material 412 so that the intermediate layer composition is 1.5 g / m ^2, and an ink on the intermediate layer. A coating roller 413 for applying the receiving layer forming liquid 414 and a head unit (black head 415, magenta head 416, cyan head 417, and yellow) for applying an ink containing a coloring material downstream thereof by a single-pass inkjet method. A discharge head unit including a magenta head 418), and an active energy ray irradiation device 419 further downstream thereof.
In FIG. 4, 411 represents a transfer roller, and the base material 412 is conveyed on the transfer roller from the left side to the right side in the figure at a constant speed.
First, the transport speed of the transport roller 411 was set to 15 m / min.
As the base material 412, a commercially available MDF panel was coated and dried so that the intermediate layer composition was 1.5 g / m ^2, and then the static surface tension was 29 mN / m and the viscosity at 25 ° C. was 160 mPa. The ink receiving layer forming liquid adjusted to s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays, which will be described later, was 20 μm.
Subsequently, black, magenta, cyan, and yellow inks were ejected from a plurality of ink heads into the ink receiving layer according to an image pattern.
As the discharge head unit, a GEN5 head (MH5420, 150 npi x 4 rows, 2 color compatible model) manufactured by Ricoh Printing Systems Co., Ltd. is used, and one GEN5 head (black and magenta 300 dpi each) is used as a black head and a magenta head. A total of two GEN5 heads (which can handle dot densities of cyan and yellow) and one GEN5 head (which can handle dot densities of 300 dpi each for cyan and yellow) were arranged in order with respect to the substrate transport direction.
At this time, the position adjusting mechanism of the discharge head unit was used to make adjustments so that the nozzle numbers of each GEN 5 would not deviate by 10 μm or more with respect to the substrate transport direction.
Further, the discharge head unit was heated to 40 ° C., and the discharge drive waveform was adjusted so that drawing could be performed with a droplet size of 7 pL and a discharge speed of 7 m / s. The color ink was ejected at an ejection frequency such that each of them was 300 dpi in the substrate conveying direction.
Finally, as the active energy ray irradiation device 419, a linear irradiation type UV-LED light source GJ-75 manufactured by Hamamatsu Photonics was used to irradiate the base material with ultraviolet rays from an irradiation distance of 10 mm within 3 seconds after forming the image pattern. , The coating film was cured to obtain a printed matter 1.

(Example 2)
An ink receiving layer forming liquid B having a static surface tension of 32 mN / m and a viscosity at 25 ° C. of 3,500 mPa · s was applied to a base material 412 provided with an intermediate layer similar to that of Example 1 with a roller coater. A printed matter 2 was obtained in the same manner as in Example 1 except that the ink receiving layer was formed so that the average thickness after irradiation with active energy rays was 20 μm.

<Preparation of ink receiving layer forming liquid B>
Stir 65.0 parts by mass of urethane acrylic oligomer CN929 (manufactured by Sartomer), 30.0 parts by mass of tripropylene glycol diacrylate SR306H (manufactured by Sartomer), and 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as an initiator. To prepare an ink receiving layer forming liquid B.
The static surface tension of the ink receiving layer forming liquid B at 25 ° C. was 32 mN / m, and the viscosity at 25 ° C. was 3,500 mPa · s.

(Example 3)
A roller coater is provided with an ink receiving layer forming liquid C having a static surface tension at 25 ° C. of 29 mN / m and a viscosity at 25 ° C. of 16,000 mPa · s on a base material 412 provided with an intermediate layer similar to that of Example 1. A printed matter 3 was obtained in the same manner as in Example 1 except that the ink receiving layer was formed so that the average thickness after irradiation with active energy rays was 30 μm.

<Preparation of ink receiving layer forming liquid C>
2-Acryloyloxypropylphthalic acid (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 94.9 parts by mass, Omnirad TPO (manufactured by IGM Resins) 5 parts by mass as an initiator, BYK-UV-3510 (manufactured by BYK) as a surfactant The ink receiving layer forming liquid C was prepared by stirring 0.1 parts by mass.
The static surface tension of the ink receiving layer forming liquid C at 25 ° C. was 29 mN / m, and the viscosity at 25 ° C. was 16,000 mPa · s.

(Example 4)
A commercially available glass plate is prepared as the base material 412, and the same intermediate layer composition as in Example 1 is coated so as to be 1.5 g / m ^2, and after forming the intermediate layer, the static surface tension at 25 ° C. is 34 mN. An ink receiving layer forming liquid D having a viscosity at / m and 25 ° C. adjusted to 10,700 mPa · s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm. , A printed matter of Example 4 was obtained in the same manner as in Example 1.

<Preparation of ink receiving layer forming liquid D>
The ink receiving layer forming liquid D was prepared by stirring 95.0 parts by mass of the urethane acrylic oligomer CN975 (manufactured by Sartomer) and 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as an initiator.
The static surface tension of the ink receiving layer forming liquid D at 25 ° C. was 34 mN / m, and the viscosity at 25 ° C. was 10,700 mPa · s.

(Example 5)
A commercially available MDF panel was prepared as the base material 412, and the same intermediate layer composition as in Example 1 was coated so as to be 1.5 g / m ^2, and after forming the intermediate layer, the static surface tension at 25 ° C. was 29 mN. An ink receiving layer forming liquid A having a viscosity adjusted to 160 mPa · s at / m and 25 ° C. was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm.
Subsequently, inside the liquid receiving layer, black, magenta, cyan, and yellow inks were added from a plurality of heads for ink heated to 40 ° C., and the droplet volume was changed to 7 pL and the ejection speed was changed to 15 m / s, respectively. A printed matter 5 was obtained in the same manner as in Example 1.

(Example 6)
A commercially available MDF panel was prepared as the base material 412, and the same intermediate layer composition as in Example 1 was coated so as to be 1.5 g / m ^2, and after forming the intermediate layer, the static surface tension at 25 ° C. was 29 mN. An ink receiving layer forming liquid A having a viscosity adjusted to 160 mPa · s at / m and 25 ° C. was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm.
Subsequently, black, magenta, cyan, and yellow inks were applied from a plurality of heads for color ink heated to 40 ° C. inside the liquid receiving layer to a droplet volume of 20 pL and an ejection speed of 7 m / s, respectively. A printed matter 6 was obtained in the same manner as in Example 1 except that the changes were made.

(Example 7)
An electron beam irradiation device (EC300 / 30/30 mA) manufactured by Iwasaki Electric Co., Ltd. is used as the active energy ray irradiation device 419 shown in FIG. 4, and an image pattern is formed inside the ink receiving layer from a plurality of heads for ink. After 8 seconds, the substrate was irradiated with an electron beam having an oxygen concentration of 500 ppm or less and an electron beam of a dose of 30 kGy accelerated at 90 kV from a distance of 10 mm.
In addition, a printed matter 7 was obtained in the same manner as in Example 1 except that the ink receiving layer was formed so that the average thickness of the ink receiving layer after irradiation with active energy rays was 30 μm.

(Example 8)
In Example 1, the printed matter manufacturing apparatus used was changed to the apparatus shown in FIG. 5, and the printed matter 8 was obtained as follows.
FIG. 5 is a schematic view showing a printed matter manufacturing apparatus used for producing Example 8. The printed matter manufacturing apparatus of FIG. 5 is a means (not shown) for forming an intermediate layer by coating a substrate 512 with an intermediate layer composition described later so as to have an intermediate layer composition of 1.5 g / m ^2, and on the intermediate layer. A coating roller 513 for applying the ink receiving layer forming liquid A514, and a head unit (black head 515, magenta head 516, cyan head 517, and head unit for applying ink containing a coloring material downstream thereof by a single-pass inkjet method. It has a discharge head unit made of a yellow head 518), a clear ink head 519 containing no coloring material, and an active energy ray irradiating device 520 similar to that shown in FIG. 4 further downstream thereof.
Similarly, first, the transport speed of the transport roller 511 was set to 15 m / min.
A commercially available MDF panel is prepared as the base material 512, coated and dried so that the intermediate layer composition is 1.5 g / m ^2, and then a static surface tension at 25 ° C. is applied using a roller coater. An ink receiving layer forming liquid A having a viscosity adjusted to 160 mPa · s at 29 mN / m at 25 ° C. was applied to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm.
Subsequently, black, magenta, cyan, and yellow inks are ejected from a plurality of ink heads into the ink receiving layer according to an image pattern, and then a coloring material is contained from the clear ink head 519. No clear ink was ejected into the ink receiving layer according to the inverted image pattern.
As the discharge head unit, a GEN5 head (MH5420, 150 npi x 4 rows, 2 color compatible model) manufactured by Ricoh Printing Systems Co., Ltd. is used, and one GEN5 head (black and magenta 300 dpi each) is used as a black head and a magenta head. One GEN5 head for cyan head and one yellow head (can handle 300 dpi dot density for each of cyan and yellow), and one GEN5 head for clear ink head (600 dpi dot density can be supported) ), A total of three are arranged in order with respect to the substrate transport direction, and the color ink has an ejection frequency of 300 dpi in each of the substrate transport directions, and the clear ink has an ejection frequency of 600 dpi. Discharged with.
Similarly, the position adjustment mechanism of the discharge head unit is adjusted so that the nozzle number of each GEN5 does not deviate by 10 μm or more with respect to the substrate transport direction, the discharge head unit is heated to 40 ° C., and the droplet size is 7 pL. The discharge drive waveform was adjusted so that drawing could be performed at a discharge speed of 7 m / s.
Finally, as the active energy ray irradiation device 520, a linear irradiation type UV-LED light source GJ-75 manufactured by Hamamatsu Photonics was used to irradiate the base material with ultraviolet rays from an irradiation distance of 10 mm within 3 seconds after forming the image pattern. The printed matter 8 was obtained by curing the coating film.

<Preparation of clear ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 27 parts by mass of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 42 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator A clear ink was prepared by stirring 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) and 1 part by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant / dispersant.
The static surface tension of the clear ink at 25 ° C. was 35 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

(Example 9)
In Example 8, the printed matter manufacturing apparatus used was changed to the apparatus shown in FIG. 6, and the printed matter 9 was obtained as follows.
FIG. 6 is a schematic view showing a printed matter manufacturing apparatus used for producing Example 9.
The printed matter manufacturing apparatus of FIG. 6 is a means (not shown) for forming an intermediate layer by coating the base material 612 so that the intermediate layer composition described later is 1.5 g / m ^2, and on the intermediate layer. A coating roller 613 for applying the ink receiving layer forming liquid A614, a clear ink head 615 downstream thereof that does not contain a coloring material, and a head unit for ejecting a plurality of inks containing a coloring material (black head 616, magenta). It has a head for 617, a head for cyan, and a head for yellow 619), and further downstream thereof has an active energy ray irradiation device 620 similar to that shown in FIG.
Similarly, first, the transport speed of the transport roller 511 was set to 15 m / min.
A commercially available MDF panel was prepared as the base material 612, coated and dried so that the intermediate layer composition was 1.5 g / m2, and then the static surface tension at 25 ° C. was 29 mN / m and 25 ° C. The ink receiving layer forming liquid A whose viscosity was adjusted to 160 mPa · s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm.
Subsequently, clear ink containing no coloring material is ejected from the clear ink head 615 into the ink receiving layer according to the inverted image pattern, and then from a plurality of ink heads, black, magenta, and cyan are used inside the ink receiving layer. Ink for and yellow was ejected according to the image pattern.
A printed matter 9 was obtained in the same manner as in Example 8 except for the above.

(Example 10)
In Example 5, the printed matter manufacturing apparatus used was changed to the apparatus shown in FIG. 7, and the printed matter 9 was obtained as follows.
FIG. 7 is a schematic view showing a printed matter manufacturing apparatus used for producing Example 10.
The printed matter manufacturing apparatus of FIG. 7 is a means (not shown) for forming an intermediate layer by coating the base material 712 so that the intermediate layer composition described later is 1.5 g / m ^2, and on the intermediate layer. A coating roller 713 for applying the ink receiving layer forming liquid A714, a clear ink head 715 that does not contain a coloring material downstream thereof, and a head unit for ejecting a plurality of inks containing a coloring material (black head 716, magenta). It has a head 717, a head 718 for cyan, and a head 719 for yellow), and further downstream thereof has a heating device 720 and an active energy ray irradiating device 620 similar to that shown in FIG.
Similarly, first, the transport speed of the transport roller 711 was set to 15 m / min.
A commercially available MDF panel was prepared as the base material 712, coated and dried so that the intermediate layer composition was 1.5 g / m ^2, and then the static surface tension at 25 ° C. was 29 mN / m, 25. The ink receiving layer forming liquid A whose viscosity at ° C. was adjusted to 160 mPa · s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm.
Subsequently, clear ink containing no coloring material is ejected from the clear ink head 715 into the ink receiving layer according to the inverted image pattern, and then from a plurality of ink heads, black, magenta, and cyan are used inside the ink receiving layer. Ink for and yellow was ejected according to the image pattern.
At this time, the color ink was ejected at an ejection frequency of 300 dpi in each of the substrate conveying directions, and the clear ink was ejected at an ejection frequency of 600 dpi.
Next, as a heating device, a combination of the Lutex blower G series manufactured by Hitachi Industrial Equipment Systems Co., Ltd., the electric heater XS-2 for generating high-temperature hot air manufactured by Kansai Electric Heat Co., Ltd., and the high blow nozzle 50AL manufactured by Kansai Electric Heat Co., Ltd. After leveling the coating film by applying warm air at a wind speed of 2 m / sec and 40 ° C. from the tip of the nozzle, the same activity as in Example 1 is applied to the curing of the ink receiving layer forming liquid, the ink and the clear ink. It was cured by irradiating it with energy rays.

(Example 11)
A commercially available glass plate was prepared as the base material 412, coated and dried so that the intermediate layer composition was 1.5 g / m ^2, and then the static surface tension at 25 ° C. was 29 mN / m, 25. Example 1 except that the following ink receiving layer forming liquid E whose viscosity at ° C. was adjusted to 300 mPa · s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 30 μm. In the same manner as above, a printed matter 11 was obtained.

<Preparation of ink receiving layer forming liquid E>
2-Acryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 90.9 parts by mass, Initiator: Omnirad TPO (manufactured by IGM Resins) by 5 parts by mass, UV-3510 (manufactured by BYK) The ink receiving layer forming solution E was prepared by stirring 0.1 part by mass and 4 parts by mass of the white pigment.
The static surface tension of the ink receiving layer forming liquid E at 25 ° C. was 29 mN / m, and the viscosity at 25 ° C. was 300 mPa · s.

(Example 12)
A commercially available glass plate was prepared as the base material 412, coated and dried so that the intermediate layer composition was 1.5 g / m ^2, and then the static surface tension was 29 mN / m and the viscosity at 25 ° C. The same as in Example 1 except that the following ink receiving layer forming liquid F adjusted to 41 mPa · s was applied with a roller coater to form an ink receiving layer so that the average thickness after irradiation with active energy rays was 15 μm. A printed matter 12 was obtained.

<Preparation of ink receiving layer forming liquid F>
2-Acryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 92.9 parts by mass, Omnirad TPO (manufactured by IGM Resins) 5 parts by mass as an initiator, BYK-UV-3510 (manufactured by BYK) as a surfactant The ink receiving layer forming liquid F was prepared by stirring 0.1 part by mass and 2 parts by mass of the white pigment.
The static surface tension of the ink receiving layer forming liquid F at 25 ° C. was 29 mN / m, and the viscosity at 25 ° C. was 41 mPa · s.

(Example 13)
In Example 1, the black, magenta, cyan, and yellow inks were adjusted so that the content of the surfactant was changed to 1.5 parts by mass and the static surface tension γ ₂ of the ink at 25 ° C. was 42 mN / m. A printed matter 13 was obtained in the same manner as in Example 1 except that the color ink was ejected into the ink receiving layer.

(Example 14)
A printed matter 14 was obtained in the same manner as in Example 1 except that the ejection speeds of black, magenta, cyan, and yellow inks were changed to 15 m / s in Example 1.

(Example 15)
A printed matter 15 was obtained in the same manner as in Example 1 except that the droplet volumes of the black, magenta, cyan, and yellow inks were changed to 20 pL in Example 1.

(Example 16)
In Example 1, a printed matter 15 was obtained in the same manner as in Example 1 except that the average thickness of the ink receiving layer forming liquid A after irradiation with the active energy rays was changed to 30 μm.

(Example 17)
A roller coater is provided with an ink receiving layer forming liquid G having a static surface tension at 25 ° C. of 27 mN / m and a viscosity at 25 ° C. of 1,800 mPa · s on a base material 412 provided with an intermediate layer similar to that of Example 1. The ink receiving layer was formed so that the average thickness after irradiation with active energy rays was 6 μm.
Subsequently, black, magenta, cyan, and yellow inks were placed inside the liquid receiving layer from a plurality of heads for ink heated to 40 ° C., respectively, with a droplet volume of 7 pL and a discharge rate of 7 m / s. The printed matter 17 was obtained in the same manner as in Example 1 under other conditions.

<Preparation of ink receiving layer forming liquid G>
Stir 62.0 parts by mass of urethane acrylic oligomer CN929 (manufactured by Sartomer), 33.0 parts by mass of tripropylene glycol diacrylate SR306H (manufactured by Sartomer), and 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as an initiator. To prepare an ink receiving layer forming liquid B.
The static surface tension of the ink receiving layer forming liquid B at 25 ° C. was 27 mN / m, and the viscosity at 25 ° C. was 1,800 mPa · s.

(Comparative Example 1)
In Example 9, the average thickness of the ink receiving layer forming liquid H after irradiation with active energy rays was adjusted so that the static surface tension of the ink receiving layer forming liquid at 25 ° C. was 22 mN / m and the viscosity at 25 ° C. was 22 mPa · s. A printed matter 18 was obtained in the same manner as in Example 9 except that the ink receiving layer was formed so as to have a thickness of 20 μm.

<Preparation of ink receiving layer forming liquid H>
(2-Methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 70.0 parts by mass, dendritic acrylate 30.0 parts by mass, Omnirad TPO (Omnirad TPO) as an initiator The ink receiving layer forming liquid G was prepared by stirring 5 parts by mass of IGM Resins) and 1 part by mass of BYK-UV-3510 (manufactured by BYK) as a surfactant.
The static surface tension of the ink receiving layer forming liquid G at 25 ° C. was 22 mN / m, and the viscosity at 25 ° C. was 22 mPa · s.

(Comparative Example 2)
A printed matter 19 was obtained in the same manner as in Example 3 except that the static surface tension γ _{2 of the} ink containing the coloring material was adjusted to 24 mN / m in Example 3.

<Preparation of black ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 28 parts by mass of acryloylmorpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator 5.0 parts by mass of Omnirad TPO (manufactured by IGM Resins), 2 parts by mass of Solspace 32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 7 parts by mass of SPECIAL BLACK 350 (black pigment, manufactured by BASF Japan) as a coloring material. Black ink was prepared by stirring the parts.
The static surface tension of the black ink at 25 ° C. was 24 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of magenta ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 28 parts by mass of acryloylmorpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropaneethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.) Omnirad TPO (manufactured by IGM Resins) 5 parts by mass, Solsperse 32000 (manufactured by Lubrizol) 2 parts by mass as a surfactant / dispersant, CINQUASIA MAGENTA RT-355-D (magenta pigment, manufactured by BASF Japan) as a coloring material. Magenta ink was prepared by stirring 7 parts by mass.
The static surface tension of the magenta ink at 25 ° C. was 24 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of cyan ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 28 parts by mass of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator 5 parts by mass of Omnirad TPO (manufactured by IGM Resins), 2 parts by mass of Solspace 32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 40 parts by mass of IRGLITE BLUE GLVO (cyan pigment, manufactured by BASF Japan) as a coloring material Cyan ink was prepared by stirring.
The static surface tension of the cyan ink at 25 ° C. was 24 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

<Preparation of yellow ink>
25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 28 parts by mass of acryloylmorpholin (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex Co., Ltd.), initiator Stir 5 parts by mass of Omnirad TPO (manufactured by IGM Resins), 2 parts by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant / dispersant, and 40 parts by mass of NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant) as a coloring material. By doing so, a yellow ink was prepared.
The static surface tension of the yellow ink at 25 ° C. was 24 mN / m, and the viscosity at 40 ° C. was 10 mPa · s.

(Comparative Example 3)
A printed matter 20 was obtained in the same manner as in Example 1 except that the ink receiving layer was formed by the ink receiving layer forming liquid A without providing the intermediate layer on the base material in Example 1.

In addition, "surface roughness" and "wetting property" were measured as the surface properties of the base material. "Surface roughness" is the arithmetic mean roughness Ra (μm) measured with a laser microscope VK-X100 manufactured by KEYENCE CORPORATION, and "wetting property" is water with a contact angle meter DMs-401 manufactured by Kyowa Interface Science Co., Ltd. The contact angle (°) with the base material is shown.

Next, with respect to the obtained printed matter 1 to 20 of Examples 1 to 17 and Comparative Examples 1 to 3, "bleeding between ink droplets", "misalignment", and "color development (color development density)" were performed as follows. ) ”,“ Color density unevenness ”,“ Glossiness ”, and“ Robustness ”were evaluated. The evaluation results are shown in Table 6.

<Blur and misalignment between ink droplets>
The dot shape of the obtained printed matter was visually observed with an optical microscope and evaluated based on the following evaluation criteria. If the evaluation is "○" or higher, there is no problem in actual use.

[Evaluation criteria]
◎: Sufficiently superior to the conventional inkjet print image using active energy curable ink 〇: Equivalent to the inkjet print image using conventional active energy curable ink ×: Inkjet printing using conventional active energy curable ink Inferior to the image

<Color development (color development density)>
Five 10 mm square solid images (printed matter 1 to 20) are made with four-color process black (black obtained by superimposing four colors of CMYK), and five solid image samples are made by eXact (manufactured by X-rite). The locations were measured, and the average color density was determined according to the following criteria. If the evaluation is "Δ" or higher, there is no problem in actual use.

[Evaluation Criteria-Color Density-]
⊚: Average color density is more than 1.5 〇: Average color density is more than 1.3 and 1.5 or less Δ: Average color density is more than 1.1 and 1.3 or less ×: Average color density Value is 1.1 or less

<Uneven color density>
Each of the five solid image samples prepared by measuring the color development density was measured at five locations, the maximum value and the minimum value of the color development density of the solid image were extracted, and the average value of the differences was determined according to the following criteria. If the evaluation is "Δ" or higher, there is no problem in actual use.

[Criteria-Color density unevenness-]
⊚: Difference between maximum and minimum color density is less than 0.02 〇: Difference between maximum and minimum color density is 0.02 or more and less than 0.04 Δ: Difference between maximum and minimum color density Is 0.04 or more and less than 0.06 ×: The difference between the maximum value and the minimum value of the color development density is 0.06 or more

<Glossiness>
The 60 ° gloss (gloss) was measured at 5 locations of each of the 5 solid image samples prepared by measuring the color development density using a micro-gloss gloss meter (manufactured by BYK-Gardner), and the average value was calculated. As a target test, in Example 1, 5 solid images were prepared without providing an ink receiving layer, and 60 ° gloss (gloss) was measured at 5 locations of each of the 5 samples by a micro-gloss gloss meter (BYK-Gardner). ), And the average value was calculated. The following standard is the value expressed as a percentage by dividing each average value of the 60 ° gloss (gloss) of the solid image prepared by measuring the color development density by the average value of the 60 ° gloss (gloss) of the solid image of the target test. Judged by. In addition, it was judged that the evaluation of "Δ" (less than 5%) was equivalent to or no improvement was observed.

[Criteria-Glossiness-]
⊚: Value (glossiness) is 20% or more 〇: Value (glossiness) is 10% or more and less than 20% Δ: Value (glossiness) is 5% or more and less than 10% ×: Value (glossiness) is less than 5%

<Robustness>
The obtained printed matter 1-27 was carried out by the Taber wear method according to JIS K 7204, and evaluated according to the following evaluation criteria. A CS-5 wear wheel was used as the wear wheel, and the surface of the obtained printed matter was subjected to a load of 1 kg and 3000 rotations.

[Evaluation criteria]
◎: Sufficiently superior to the conventional inkjet print image using active energy curable ink 〇: Equivalent to the inkjet print image using conventional active energy curable ink ×: Inkjet printing using conventional active energy curable ink Inferior to the image

From the results in Table 6, it was found that the printed matter 1 to 17 of Examples 1 to 17 was a printed matter excellent in image quality and robustness characteristics as compared with the printed matter 18 to 20 of Comparative Examples 1 to 3.

Aspects of the present invention are, for example, as follows.
<1> An intermediate layer forming step of forming an intermediate layer on a base material, and
An ink receiving layer forming step of applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer,
An image forming step of applying ink to the ink receiving layer by an inkjet method to form an image is included.
The static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink satisfy the following equation, γ ₁ <γ ₂ .
This is a method for producing a printed matter, characterized in that the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less.
<2> The method for producing a printed matter according to <1>, wherein the static surface tension γ _{2 of the} ink at 25 ° C. is 40 mN / m or less.
<3> The method for producing a printed matter according to any one of <1> to <2>, wherein the ink is applied to the inside of the ink receiving layer.
<4> The method for producing a printed matter according to any one of <1> to <3>, wherein the ejection speed of ejecting the ink is 10 m / s or more.
<5> The method for producing a printed matter according to any one of <1> to <4>, wherein the volume of the ejected ink per droplet is 10 pL or more.
<6> The method for producing a printed matter according to any one of <1> to <5>, wherein the average thickness of the ink receiving layer is 20 μm or more.
<7> The method for producing a printed matter according to any one of <1> to <6>, wherein the dot density for ejecting the ink is 240 dpi × 240 dpi or more.
<8> The method for producing a printed matter according to any one of <1> to <7>, further comprising a curing step, wherein the curing step is performed by at least one of ultraviolet rays and an electron beam.
<9> The ink is a plurality of inks.
The method for producing a printed matter according to any one of <1> to <8>, wherein the overlap of the ejection times of the plurality of inks is 1 second or less.
<10> The method for producing a printed matter according to any one of <1> to <9>, wherein the ink is ejected to the ink receiving layer and then irradiated with active energy rays within 10 seconds.
<11> The method for producing a printed matter according to any one of <1> to <10>, wherein the clear ink containing no coloring material is discharged to a region other than the region where the image is formed.
<12> The method for producing a printed matter according to any one of <1> to <11>, wherein the ink contains a coloring material.
<13> The method for producing a printed matter according to any one of <1> to <12>, wherein the ink receiving layer forming liquid and the ink are applied or ejected in the following order (A) or (B). Is.
(A) Ink receiving layer forming liquid, ink, clear ink in order (B) Ink receiving layer forming liquid, clear ink, inking order <14> The time difference between the ink and the clear ink is within 1 second. The method for producing a printed matter according to any one of <11> to <13>.
<15> The method for producing a printed matter according to any one of <11> to <14>, wherein the ink and the clear ink are ejected and then irradiated with active energy rays within 10 seconds.
<16> The method for producing a printed matter according to any one of <10> to <15>, wherein the ink receiving layer and the ink are heated before irradiating the active energy rays.
<17> The method for producing a printed matter according to any one of <11> to <16>, wherein the average thickness of the clear ink layer formed by the clear ink is 1 μm or more and 10 μm or less.
<18> The method for producing a printed matter according to any one of <1> to <17>, wherein the ink receiving layer forming liquid contains a pigment.
<19> A printed matter produced by the method for producing a printed matter according to any one of <1> to <18>.
It has the base material, the intermediate layer, and the ink receiving layer.
The printed matter is characterized in that the average thickness of the ink receiving layer after curing is more than 15 μm.
<20> An intermediate layer forming means for forming an intermediate layer on a base material, and
An ink receiving layer forming means for forming an ink receiving layer by applying an ink receiving layer forming liquid to the intermediate layer,
It has an image forming means for forming an image by applying ink to the ink receiving layer by an inkjet method.
The static surface tension γ ₁ of the ink receiving layer forming liquid at 25 ° C. and the static surface tension γ _{2 of the} ink satisfy the following equation, γ ₁ <γ ₂ .
It is a printed matter manufacturing apparatus characterized in that the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less.

According to the method for producing printed matter according to <1> to <18>, the printed matter according to <19>, and the printed matter manufacturing apparatus according to <20>, the conventional problems are solved and the present invention is used. The object of the invention can be achieved.

413 Coating Roller 519, 615, 715 Clear Ink Head 415, 515, 616, 716 Black Head 416, 516, 617, 717 Magenta Head 417, 517, 618, 718 Cyan Head 418, 518, 618, 719 Yellow Head for 419, 520, 620, 721 Active energy ray irradiation device 412, 512, 612, 712 Base material 411, 511, 611, 711 Conveyance belt 720 Heating device

Japanese Unexamined Patent Publication No. 2011-230501 JP-A-2017-13506 US Publication 2006/0092254

Claims (20)

An intermediate layer forming step of forming an intermediate layer on a base material,
An ink receiving layer forming step of applying an ink receiving layer forming liquid to the intermediate layer to form an ink receiving layer,
An image forming step of applying ink to the ink receiving layer by an inkjet method to form an image is included.
The static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink satisfy the following equation, γ ₁ <γ ₂ .
A method for producing a printed matter, wherein the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less. The method for producing a printed matter according to claim 1, wherein the static surface tension γ _{2 of the} ink at 25 ° C. is 40 mN / m or less. The method for producing a printed matter according to any one of claims 1 to 2, wherein the ink is applied to the inside of the ink receiving layer. The method for producing a printed matter according to any one of claims 1 to 3, wherein the ejection speed for ejecting the ink is 10 m / s or more. The method for producing a printed matter according to any one of claims 1 to 4, wherein the volume of the ejected ink per droplet is 10 pL or more. The method for producing a printed matter according to any one of claims 1 to 5, wherein the average thickness of the ink receiving layer is 20 μm or more. The method for producing a printed matter according to any one of claims 1 to 6, wherein the dot density for ejecting the ink is 240 dpi × 240 dpi or more. The method for producing a printed matter according to any one of claims 1 to 7, further comprising a curing step, wherein the curing step is performed by at least one of ultraviolet rays and an electron beam. The ink is a plurality of inks,
The method for producing a printed matter according to any one of claims 1 to 8, wherein the overlap of the ejection times of the plurality of inks is 1 second or less. The method for producing a printed matter according to any one of claims 1 to 9, wherein the ink receiving layer is irradiated with active energy rays within 10 seconds after the ink is ejected. The method for producing a printed matter according to any one of claims 1 to 10, wherein a clear ink containing no coloring material is discharged to a region other than the region where the image is formed. The method for producing a printed matter according to any one of claims 1 to 11, wherein the ink contains a coloring material. The method for producing a printed matter according to any one of claims 1 to 12, wherein the ink receiving layer forming liquid and the ink are applied or ejected in the following order (A) or (B).
(A) Ink receiving layer forming liquid, ink, clear ink in order (B) Ink receiving layer forming liquid, clear ink, ink in order The method for producing a printed matter according to any one of claims 11 to 13, wherein the time difference between the ink and the clear ink is within 1 second. The method for producing a printed matter according to any one of claims 11 to 14, wherein the active energy rays are irradiated within 10 seconds after the ink and the clear ink are discharged. The method for producing a printed matter according to any one of claims 10 to 15, wherein the ink receiving layer and the ink are heated before being irradiated with the active energy rays. The method for producing a printed matter according to any one of claims 11 to 16, wherein the average thickness of the clear ink layer formed by the clear ink is 1 μm or more and 10 μm or less. The method for producing a printed matter according to any one of claims 1 to 17, wherein the ink receiving layer forming liquid contains a pigment. A printed matter produced by the method for producing a printed matter according to any one of claims 1 to 18.
It has the base material, the intermediate layer, and the ink receiving layer.
A printed matter characterized in that the average thickness of the ink receiving layer after curing is more than 15 μm. An intermediate layer forming means for forming an intermediate layer on a base material,
An ink receiving layer forming means for forming an ink receiving layer by applying an ink receiving layer forming liquid to the intermediate layer,
An image forming means for forming an image by applying ink to the ink receiving layer by an inkjet method is included.
The static surface tension γ ₁ of the ink receiving layer forming liquid and the static surface tension γ _{2 of the} ink satisfy the following equation, γ ₁ <γ ₂ .
An apparatus for producing a printed matter, wherein the viscosity of the ink receiving layer forming liquid at 25 ° C. is 40 mPa · s or more and 20,000 mPa · s or less.