Method of producing record having stereoscopic image

Abstract

To provide a method of producing a record having a stereoscopic image capable of easily forming a stereoscopic image excellent in convexoconcave evenness though small in a number of processes.SOLUTION: A method of producing a record having a stereoscopic image includes: a process of applying a first liquid composition containing a foam-accelerating / suppressing constituent to a recording medium having a foamed layer; a process of applying an ink to the recording medium; a process of applying a second liquid composition containing no foam-accelerating / suppressing constituent, and no coloring agent; and a process of heating the recording medium to form a stereoscopic image. A region of the recording medium applied with the ink includes a first region and a second region having each different ink application amount one another, and the summation of the first liquid composition applied to the first region, the ink, and a volatile solvent contained in the second liquid composition is 95 mass% or more and 105 mass% or less based on a summation of the first liquid composition applied to the second region, the ink, and a volatile solvent contained in the second liquid composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a recorded matter having a three-dimensional image. [Background technology]

[0002] Conventionally, three-dimensional images such as wallpaper and Braille have been created by printing methods using UV ink overlays, physical extrusion methods such as embossing, 3D printers, and thermally expandable plastic foams. Thermally expandable plastic foams, among others, are known to exhibit functions such as heat insulation, heat insulation, sound insulation, sound absorption, vibration damping, and weight reduction, depending on the foam material and the state of the bubbles formed.

[0003] In the field of wallpaper, a technique is known in which an azo compound such as azodicarbonamide (ADCA) is used as a foaming agent, and a foam layer containing such a foaming agent and a resin such as polyvinyl chloride is foamed to form a textured structure. The textured structure must be easy to form and must be able to adjust the texture height to a sufficient level for not only monochrome images but also color images.

[0004] For example, a method has been proposed in which a planar image is recorded on the surface of a foamable sheet, and a grayscale image (light-absorbing pattern) based on distance image data representing a three-dimensional shape is formed on the surface of the base layer of the foamable sheet, and then light is irradiated from the base layer side to generate heat corresponding to the grayscale of the image, causing the foamable sheet to expand in accordance with the distance image data (Patent Document 1).

[0005] Furthermore, a method for forming a three-dimensional image using a recording medium having a foamed resin layer has been proposed (Patent Document 2). In this three-dimensional image forming method, a release film and a heat-absorbing ink layer are first provided on the surface of the foamed resin layer of the recording medium, and then the heat-absorbing ink is applied to the area to be expanded. Next, the desired area is thermally expanded and raised by radiating radiant heat, and then the release film and the heat-absorbing ink layer are simultaneously peeled off, thereby forming the desired three-dimensional image. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-150812 [Patent Document 2] Patent No. 6447546 Summary of the Invention [Problem to be solved by the invention]

[0007] However, in the method proposed in Patent Document 1, since the light-absorbing pattern is not formed directly on the foam layer, it is difficult to achieve sufficient foaming. Furthermore, after recording an image on the foam layer, it is necessary to record a light-absorbing pattern of a grayscale image based on distance image data representing a three-dimensional shape on the back side. While this method makes it easy to make the unevenness heights uniform, it increases the number of image recording steps and requires erasing the light-absorbing pattern remaining on the back side.

[0008] Furthermore, the three-dimensional image forming method proposed in Patent Document 2 requires the time and effort of peeling off the release film and heat absorbing ink layer after thermally expanding the desired area. Furthermore, the peeled release film and heat absorbing ink layer become waste, which poses the problem of wasteful disposal.

[0009] Therefore, an object of the present invention is to provide a method for producing a recorded matter having a three-dimensional image, which can easily form a three-dimensional image having excellent unevenness while reducing the number of steps. [Means for solving the problem]

[0010] That is, according to the present invention, a method for producing a three-dimensional image includes the steps of: applying a first liquid composition containing an expansion-promoting / inhibiting component that promotes or inhibits the expansion of the expanded beads to a recording medium having a substrate and a foam layer provided on the substrate, the foam layer containing expanded beads that expand when heated and a binder resin; applying an ink containing a coloring material to the recording medium; applying a second liquid composition that does not contain an expansion-promoting / inhibiting component that promotes or inhibits the expansion of the expanded beads and a coloring material to the recording medium; and heating the recording medium to which the first liquid composition, the ink, and the second liquid composition have been applied to form a three-dimensional image. the area of ​​the recording medium to which the ink has been applied includes a first area and a second area to which the amount of ink applied is different, the amount of ink applied to the first area is greater than the amount of ink applied to the second area, and the total amount of volatile solvent contained in the first liquid composition, the ink, and the second liquid composition applied to the first area is 95% by mass or more and 105% by mass or less based on the total amount of volatile solvent contained in the first liquid composition, the ink, and the second liquid composition applied to the second area. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a method for producing a recorded matter having a three-dimensional image, which can easily form a three-dimensional image having excellent unevenness while reducing the number of steps. DETAILED DESCRIPTION OF THE INVENTION

[0012] <Method of manufacturing a recorded material having a stereoscopic image> The present invention will be described in further detail below with reference to preferred embodiments. Physical property values ​​are values ​​at room temperature (25°C) unless otherwise specified. The "volatile solvent" contained in the first liquid composition, ink, and second liquid composition refers to a solvent with a boiling point of 150°C or less under normal pressure (1 atmosphere).

[0013] The method for producing a recorded material having a three-dimensional image of the present invention (hereinafter also referred to simply as "the method for producing a recorded material") comprises the steps of applying a first liquid composition to a recording medium, applying an ink containing a colorant to the recording medium, and applying a second liquid composition to the recording medium. The method for producing a recorded material of the present invention further comprises the step of heating the recording medium to which the first liquid composition, ink, and second liquid composition have been applied to form a three-dimensional image. The recording medium has a substrate and a foam layer formed on the substrate, the foam layer containing expandable particles that expand upon heating and a binder resin. The first liquid composition contains an expansion-promoting / inhibiting component that promotes or inhibits the expansion of the expandable particles. The second liquid composition does not contain an expansion-promoting / inhibiting component that promotes or inhibits the expansion of the expandable particles and a colorant. The area of ​​the recording medium to which the ink has been applied includes a first area and a second area in which different amounts of ink have been applied, and the amount of ink applied to the first area is greater than the amount of ink applied to the second area. The total amount of volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the first region is 95% by mass or more based on the total amount of volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the second region. Also, the total amount of volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the first region is 105% by mass or less based on the total amount of volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the second region.

[0014] Assume that the first liquid composition is applied in equal amounts to the first region and the second region, and the second liquid composition is not applied to either region. In this case, if the amount of ink applied to the first region is different from the amount of ink applied to the second region, the total amount of the volatile solvent in the first liquid composition and ink applied to the first region will be different from the total amount of the volatile solvent in the first liquid composition and ink applied to the second region. As a result, the drying efficiency by heating in each region will be different, and the drying efficiency will be higher in the region where the amount of volatile solvent applied is low, and the expansion of the expanded beads will be more efficiently promoted or suppressed. On the other hand, in the region where the amount of volatile solvent applied is high, the endothermic reaction due to the evaporation of the volatile solvent contributes more significantly, and therefore the expansion of the expanded beads will be less efficiently promoted or suppressed than in the region where the amount of volatile solvent applied is low. This results in different degrees of expansion of the expanded beads between the region where the amount of volatile solvent applied is low and the region where the amount of volatile solvent applied is high, resulting in differences in the height of the irregularities formed.

[0015] As a result of further investigation, the inventors discovered that applying the second liquid composition to regions where less ink is applied can eliminate differences in the amount of volatile solvent caused by differences in the amount of ink applied. They further discovered that this can suppress differences in the height of unevenness caused by differences in the degree of foaming of the foamed particles, leading to the present invention. Specifically, the sum of the volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the first region is defined as "V1," and the sum of the volatile solvents contained in the first liquid composition, ink, and second liquid composition applied to the second region is defined as "V2." In this case, in the method for producing a recorded matter of the present invention, V1 is set to 95% to 105% by mass of V2, i.e., "(V1 / V2) × 100" is set to 95% to 105% by mass. This reduces the difference in the amount of volatile solvent applied between regions, and the difference in the endothermic reaction due to the evaporation of the volatile solvent between regions does not become very large, making it possible to form a three-dimensional image in which the difference in unevenness height caused by differences in the degree of foaming of the foamed beads is suppressed.

[0016] If V1 is less than 95% by mass or more than 105% by mass of V2, the difference in endothermic reaction due to vaporization of the volatile solvent between regions with a low and high amount of volatile solvent applied becomes excessively large. This results in large differences in the degree of foaming of the expanded beads, making it impossible to suppress the difference in the height of the unevenness formed and forming a three-dimensional image with excellent unevenness uniformity. The total amount of volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the first region is preferably 98% by mass or more based on the total amount of volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the second region. The total amount of volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the first region is preferably 102% by mass or less based on the total amount of volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the second region.

[0017] The order of the step of applying the first liquid composition to the recording medium, the step of applying the ink containing a colorant to the recording medium, and the step of applying the second liquid composition containing no foam-promoting / suppressing component and no colorant to the recording medium is not particularly limited, and they may be performed in any order. For example, by using a printer equipped with tanks each filled with the first liquid composition, the ink containing a colorant, and the second liquid composition, the above three steps can be carried out almost simultaneously.

[0018] (Recording medium) The method for producing a recorded matter of the present invention uses a recording medium having a substrate and a foam layer provided on the substrate, the foam layer containing foam particles that expand when heated and a binder resin.

[0019] [Base material] Examples of the substrate include paper made from ordinary natural pulp; kenaf paper; plastic film sheets such as polypropylene, polyethylene, and polyester; and so-called synthetic paper and nonwoven fabrics made from synthetic fibers, synthetic pulp, and synthetic resin films.

[0020] [Foam particles] The foam particles may be made of a chemical foaming agent or a thermally expandable foaming agent.

[0021] Chemical blowing agents include azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), p,p-oxybisbenzenesulfonhydrazide (OBSH), and dinitrosopentamethylenetetramine (DPT).

[0022] The thermally expandable foaming agent is a foam particle such as a microcapsule foaming agent having a core-shell structure, which has a shell layer containing a resin and a volatile material encapsulated within the shell layer. When heat is applied to the thermally expandable foaming agent, the resin constituting the shell layer softens and the volatile material in the core vaporizes, expanding in volume and inflating like a balloon.

[0023] The shell layer is formed from a resin, such as polystyrene, a styrene-acrylic acid ester copolymer, a polyamide resin, a polyacrylic acid ester, polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, vinylidene chloride-acrylonitrile, a methacrylic acid ester-acrylic acid copolymer, vinylidene chloride-acrylic acid copolymer, or vinylidene chloride-acrylic acid ester copolymer.

[0024] Examples of volatile materials include low molecular weight hydrocarbons such as ethane, ethylene, propane, propene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, heptane, and petroleum ether; chlorofluorocarbons such as CClF, CClF, CClF, and CClF-CClF; and tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, and trimethyl-n-propylsilane. Among these, it is preferable to use low molecular weight hydrocarbons with a molecular weight of 120 or less.

[0025] The foam layer contains a binder resin that functions as a binder to enhance adhesion between the substrate and the foam layer. Examples of binder resins that can be used include water-soluble polymers and polymers soluble in organic solvents. Examples of binder resins include polyvinyl alcohol, modified polyvinyl alcohol, polyacrylamide, and vinyl acetate; cellulose derivatives such as oxidized starch, etherified starch, carboxymethyl cellulose, and hydroxyethyl cellulose; casein; gelatin; soy protein; maleic anhydride resin; conjugated diene copolymer latexes such as styrene-butadiene copolymer and methyl methacrylate-butadiene copolymer; (meth)acrylic polymer latexes such as (meth)acrylic acid ester polymers and copolymers; vinyl polymer latexes such as ethylene-vinyl acetate copolymer; functionally modified polymer latexes of these various polymers; thermosetting synthetic resins such as melamine resin and urea resin; and synthetic resins such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and alkyd resin.

[0026] The mass ratio of expanded beads to binder resin is preferably 5:95 to 90:10. By setting the mass ratio of expanded beads to binder resin within the above range, it is possible to improve both the expandability of the expanded beads and the binding ability of the binder resin to the substrate. The foam layer can further contain components such as pigments, antioxidants, dyes, and surfactants, as long as the expandability is not impaired.

[0027] To produce a recording medium, a coating liquid for a foam layer containing expanded particles is first applied to the surface of a substrate to form a coating layer. The formed coating layer is then dried to form a foam layer, thereby obtaining a recording medium. Conventional tools such as an air knife coater, die coater, blade coater, gate roll coater, bar coater, rod coater, roll coater, gravure coater, and curtain coater can be used to apply the coating liquid for a foam layer to the surface of the substrate. Examples of methods for drying the coating layer include blowing hot air. Drying conditions (temperature, air volume, time, etc.) can be appropriately set depending on the type of substrate and the composition of the coating liquid. However, the drying temperature must be lower than the foaming initiation temperature of the expanded particles used.

[0028] 2g / m per side of substrate 2 It is preferable to provide a foam layer of 2 g / m or more. 2 By providing the foamed layer, it is possible to further improve the foaming property. Note that a recording medium (product) on which a foamed layer containing foamed particles is previously provided may also be used.

[0029] A backcoat layer may be provided on the surface of the substrate opposite to the surface on which the foam layer is provided. The backcoat layer may be the same layer as the foam layer containing the foam particles, or may be a layer other than the foam layer. Furthermore, an adhesive layer containing an adhesive resin such as an acrylic resin, or an ink-receiving layer for fixing a coloring material may be formed.

[0030] (First liquid composition) The first liquid composition contains an expansion promoting / suppressing component (also called an expansion controlling component) that promotes or suppresses the expansion of the expanded particles contained in the foam layer of the recording medium.

[0031] The foam-promoting / inhibiting component can be appropriately selected and used depending on the type of thermoplastic resin, etc. Examples of foam-promoting / inhibiting components include 2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone. The content (mass %) of the foam-promoting / inhibiting component in the first liquid composition is preferably 10 mass % or more and 70 mass % or less, based on the total mass of the first liquid composition.

[0032] The absolute value of the difference (|SP1-SP2|) between the solubility parameter (SP1) of the resin contained in the shell layer of the expanded beads (thermally expandable foaming agent) and the solubility parameter (SP2) of the foaming-promoting / suppressing component is preferably 3.5 or less. When the absolute value of the difference in solubility parameters is within the above numerical range, the resin constituting the shell layer can be more efficiently softened, and expanded beads having a shell layer with a softened resin can be efficiently expanded. This allows for the formation of three-dimensional images with excellent unevenness.

[0033] Furthermore, the absolute value of the difference (|HSP1-HSP2|) between the Hansen solubility parameter (HSP1) of the resin contained in the shell layer of the expanded beads (thermally expandable blowing agent) and the solubility parameter (HSP2) of the foaming-promoting / suppressing component is preferably 20.0 or less. When the absolute value of the difference in Hansen solubility parameters is within the above-mentioned range, the expandability of the expanded beads in the region to which the first liquid composition is applied can be further improved.

[0034] The solubility parameter (SP value) is a value calculated by calculation, and the Hansen solubility parameter (HSP value) is an actual value measured and calculated by dynamic light scattering.

[0035] As components other than the liquid component, water-soluble organic compounds that are solid at a temperature of 25° C., such as urea or its derivatives, trimethylolpropane, and trimethylolethane, can be used. Furthermore, the first liquid composition may contain various additives, such as a pH adjuster, an antifoaming agent, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, an antireducing agent, and a chelating agent, as needed.

[0036] (Ink containing coloring material) Dyes and pigments can be used as colorants. The dye is preferably an anionic dye, and more preferably a dye having an azo skeleton, a dye having a phthalocyanine skeleton, a dye having an anthrapyridone skeleton, or a dye having a xanthene skeleton. From the viewpoint of ink reliability, a dye that can be dissolved in ink is preferred. Furthermore, from the viewpoint of image color development, a dye that easily aggregates on a recording medium is preferred. By appropriately selecting the type of skeleton, the number of anionic groups, and the like, the balance between solubility in ink and aggregation on a recording medium can be adjusted.

[0037] The content (mass %) of the dye in the ink is preferably 1.0 mass % or more and 10.0 mass % or less, and more preferably 2.0 mass % or more and 8.0 mass % or less, based on the total mass of the ink.

[0038] Specific examples of pigments include inorganic pigments such as carbon black and titanium oxide; and organic pigments such as azo, phthalocyanine, quinacridone, isoindolinone, imidazolone, diketopyrrolopyrrole, and dioxazine. Pigment dispersion methods include resin-dispersed pigments, which use a resin as a dispersant, and self-dispersed pigments, in which hydrophilic groups are bonded to the pigment particle surface. Resin-bonded pigments, in which organic groups containing a resin are chemically bonded to the pigment particle surface, and microencapsulated pigments, in which the pigment particle surface is coated with a resin, can also be used. Pigments dispersed by different methods can also be used in combination. The pigment content (mass %) in the ink is preferably 1.0% to 10.0% by mass, and more preferably 2.0% to 8.0% by mass, based on the total mass of the ink.

[0039] The ink containing the colorant is preferably an aqueous ink containing water as the aqueous medium. The aqueous medium may further contain a water-soluble organic solvent. Deionized water (ion-exchanged water) is preferably used as the water. Any water-soluble organic solvent that can be used in inkjet inks, such as alcohols, glycols, alkylene glycols, polyethylene glycols, nitrogen-containing compounds, and sulfur-containing compounds, can be used as the water-soluble organic solvent. The water content (mass %) in the ink is preferably 50.0% to 95.0% by mass based on the total mass of the ink. Furthermore, the water-soluble organic solvent content (mass %) in the ink is preferably 3.0% to 50.0% by mass based on the total mass of the ink. If the water-soluble organic solvent content is less than 3.0% by mass, reliability such as sticking resistance may be insufficient when the ink is used in an inkjet recording device. On the other hand, if the water-soluble organic solvent content exceeds 50.0% by mass, ink supply problems may occur.

[0040] The ink may further contain water-soluble organic compounds that are solid at room temperature (25° C.), such as urea or its derivatives, trimethylolpropane, and trimethylolethane. Furthermore, the ink may contain various additives, such as surfactants, resins, pH adjusters, antifoaming agents, rust inhibitors, preservatives, antifungal agents, antioxidants, antireducing agents, and chelating agents, as needed.

[0041] (Second liquid composition) The second liquid composition does not contain a foaming promoting / suppressing component that promotes or suppresses the foaming of the foam particles contained in the foam layer of the recording medium, and does not contain a coloring material. The second liquid composition is preferably at least one of a clear ink and a reaction liquid, and more preferably a clear ink. The clear ink can suitably contain components other than the coloring material that are used in the above-mentioned inks that contain a coloring material.

[0042] The reaction liquid contains a reactant that reacts with the ink. This reactant is a component that, upon contact with the ink, aggregates components in the ink that have anionic groups (such as resins and self-dispersing pigments). Examples of the reactant include polyvalent metal ions, cationic components such as cationic resins, and organic acids.

[0043] Polyvalent metal ions include Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Sr 2+ , Ba 2+ and Zn 2+ Divalent metal ions such as Fe 3+ , Cr 3+ , Y 3+ and Al 3+ In order to incorporate polyvalent metal ions into the reaction solution, polyvalent metal salts (which may be hydrates) formed by combining polyvalent metal ions with anions can be used. Examples of anions include Cl. - , Br - , I - , ClO - , ClO2 - , ClO3 - , ClO4 - , NO2 - , NO3 - , SO4 2- , CO3 2- , HCO3 - , PO4 3- , HPO4 2- , and H2PO4 - Inorganic anions such as HCOO - , (COO - )2, COOH(COO - ), CH3COO - , C2H4(COO - )2, C6H5COO - , C6H4(COO - )2 and CH3SO3 -When a polyvalent metal ion is used as the reactant, the content (mass %) of the reactant in the reaction solution calculated as a polyvalent metal salt is preferably 1.0 mass % or more and 10.0 mass % or less based on the total mass of the reaction solution.

[0044] The organic acid-containing reaction solution has buffering properties in the acidic range (less than pH 7.0, preferably pH 2.0 to 5.0), converting anionic groups in the ink components into the acid form and causing them to aggregate. Examples of organic acids include monocarboxylic acids and their salts, such as formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, glycolic acid, lactic acid, salicylic acid, pyrrolecarboxylic acid, furancarboxylic acid, picolinic acid, nicotinic acid, thiophenecarboxylic acid, levulinic acid, and coumaric acid; dicarboxylic acids and their salts and hydrogen salts, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, sebacic acid, phthalic acid, malic acid, and tartaric acid; tricarboxylic acids and their salts and hydrogen salts, such as citric acid and trimellitic acid; and tetracarboxylic acids and their salts and hydrogen salts, such as pyromellitic acid.

[0045] Examples of cationic resins include resins having a primary to tertiary amine structure and resins having a quaternary ammonium salt structure. Examples of cationic resins include resins having structures such as vinylamine, allylamine, vinylimidazole, vinylpyridine, dimethylaminoethyl methacrylate, ethyleneimine, and guanidine. To enhance solubility in the reaction solution, a cationic resin can be used in combination with an acidic compound or the cationic resin can be subjected to a quaternization treatment. When a cationic resin is used as a reactant, the content (mass %) of the cationic resin in the reaction solution is preferably 1.0 mass % or more and 10.0 mass % or less based on the total mass of the reaction solution. The reaction solution can contain, in addition to the reactant, the same components as those that can be contained in the ink, such as water, water-soluble organic solvents, and other additives.

[0046] Both the clear ink, which is the second liquid composition, and the reaction liquid may be applied to the recording medium. When both the clear ink and the reaction liquid are applied to the recording medium, the process of applying the second liquid composition to the recording medium includes a process of applying the clear ink to the recording medium and a process of applying the reaction liquid to the recording medium. The total amount of volatile solvent is calculated as the total amount of volatile solvent contained in the first liquid composition, ink, clear ink, and reaction liquid. Note that the reactant in the reaction liquid may react not only with the ink but also with the clear ink.

[0047] (Heating of recording medium) The method for producing a recorded matter of the present invention includes a step of heating a recording medium to which a first liquid composition, ink, and second liquid composition have been applied to form a three-dimensional image. Heating the recording medium to which the first liquid composition, ink, and second liquid composition have been applied causes the foamed particles contained in the foam layer of the recording medium to foam, forming a three-dimensional image and obtaining the desired recorded matter. The heating temperature of the recording medium is preferably equal to or higher than the foaming initiation temperature of the foamed particles, and more preferably equal to or higher than the foaming initiation temperature of the foamed particles and equal to or lower than the foaming initiation temperature of the foamed particles + 15°C. Examples of devices that can be used to heat the recording medium include a dryer, oven, heater, and iron. [Example]

[0048] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. "Parts" and "%" used to describe the amounts of components are based on mass unless otherwise specified.

[0049] <Preparation of expanded particles> Expanded beads were prepared according to Example 1 of JP 2013-71075 A, which consisted of a core made of isopentane and isooctane and a shell layer made of acrylonitrile-methacrylic acid copolymer encapsulating the core. The expansion initiation temperature of the expanded beads was measured using a thermomechanical analyzer (TMA) (product name "TMA2940" manufactured by TA Instruments) and was found to be 90°C.

[0050] <Preparation of recording media> (Recording medium A) Polypropylene synthetic paper (trade name "New Yupo FGS110", manufactured by Yupo Corporation) was prepared as a substrate. Acrylic emulsion (trade name "Movinyl 7820", manufactured by Japan Coating Resin) and foamed particles were added to ion-exchanged water at a mass ratio of resin:foamed particles = 100:50, and the mixture was thoroughly stirred to prepare Coating Solution A. The coating amount was 40 g / m. 2 The coating liquid A was applied to the substrate prepared so as to have the following thickness, and then dried in an oven at 60° C. for 5 minutes to obtain recording medium A.

[0051] (Recording medium B) Alumina hydrate (trade name "DISPERSAL HP14", manufactured by Sasol) was added to ion-exchanged water in an amount to give a 30% content. Furthermore, 1.6 parts of methanesulfonic acid was added to 100 parts of alumina hydrate, and the mixture was stirred to obtain a colloidal sol. The obtained colloidal sol was diluted with ion-exchanged water to obtain inorganic particle dispersion 1, which had a 27% content of inorganic particles, i.e., alumina hydrate.

[0052] Polyvinyl alcohol (trade name "PVA235", manufactured by Kuraray, polymerization degree: 3,500, saponification degree: 88%) was dissolved in ion-exchanged water to obtain a polyvinyl alcohol aqueous solution with a solid content of 8.0%. The obtained polyvinyl alcohol aqueous solution was added to and mixed with inorganic particle dispersion liquid 1 so that the amount of polyvinyl alcohol was 11 parts per 100 parts of inorganic particles. Meanwhile, orthoboric acid, a crosslinking agent, was dissolved in ion-exchanged water to obtain a boric acid aqueous solution with an orthoboric acid content of 3.0%. The obtained boric acid aqueous solution was added to and mixed with inorganic particle dispersion liquid 1 so that the amount of boric acid was 2 parts per 100 parts of inorganic particles, to obtain ink-receiving layer coating solution 1. A coating amount of 10 g / m was applied to the surface of the above-mentioned recording medium A. 2 After that, the ink receiving layer coating liquid 1 was applied so that the ink receiving layer had a thickness of 1000 nm, and then dried in an oven at 60° C. for 20 minutes to obtain a recording medium B.

[0053] <Preparation of First Liquid Composition> Three liquids, X, Y, and Z, with different solubility parameters and Hansen solubility parameters were prepared. Liquid X was dimethyl sulfoxide (DMSO), liquid Y was N-methyl-2-pyrrolidone (NMP), and liquid Z was acetic acid.

[0054] 30 parts of Liquid X, 20 parts of ethylene glycol, 0.2 parts of a nonionic surfactant (trade name "Acetylenol E100", manufactured by Kawaken Fine Chemicals), and 49.8 parts of ion-exchanged water were mixed. After thorough stirring, the mixture was filtered under pressure using a filter with a pore size of 1.2 μm to obtain Liquid Composition X. Furthermore, first Liquid Compositions Y and Z were obtained in the same manner as the above-described first Liquid Composition X, except that Liquid Y and Z were used, respectively, instead of Liquid X. The volatile solvent in the obtained first Liquid Compositions X, Y, and Z was all ion-exchanged water.

[0055] <Preparation of pigment dispersion> (Pigment dispersion 1) A mixture was obtained by mixing 10.0 parts of a pigment (CI Pigment Red 122), 9.4 parts of a liquid containing a styrene-acrylic acid copolymer (Resin A) with an acid value of 120 mg KOH / g and a weight-average molecular weight of 8,000, and 80.6 parts of ion-exchange water. The resulting mixture and 200 parts of 0.3 mm diameter zirconia beads were placed in a batch-type vertical sand mill (Imex) and dispersed for 5 hours while cooling with water. After centrifuging to remove coarse particles, the mixture was pressure-filtered through a 3.0 μm pore-size cellulose acetate filter (Advantec) to prepare Pigment Dispersion 1, which contained 10.0% pigment and 3.0% resin dispersant (Resin A).

[0056] (Pigment dispersion 2) Pigment Dispersion Liquid 2 was prepared in the same manner as in the case of Pigment Dispersion Liquid 1 described above, except that CI Pigment Blue 15:3 was used as the pigment.

[0057] (Pigment dispersion 3) Pigment Dispersion Liquid 3 was prepared in the same manner as in the case of Pigment Dispersion Liquid 1 described above, except that CI Pigment Yellow 74 was used as the pigment.

[0058] <Preparation of ink and second liquid composition> The components (unit: parts) shown in Table 1 were mixed, thoroughly stirred, and then pressure filtered through a filter with a pore size of 1.2 μm to obtain inks 1 to 3 and a second liquid composition (clear ink, reaction liquid). In Table 1, "Acetylenol E100" is the trade name of a nonionic surfactant manufactured by Kawaken Fine Chemicals. The volatile solvent in the obtained inks 1 to 3, clear ink, and reaction liquid was all ion-exchanged water.

[0059] TIFF2023085222000001.tif84170

[0060] <Production of Recorded Materials> The first liquid compositions X, Y, and Z, inks 1 to 3, clear ink, and reaction liquid were each filled into a cartridge, and the cartridge was set in an inkjet recording device (trade name "PIXUS PRO-10S", manufactured by Canon). In this example, an image recorded under the condition that eight ink droplets of approximately 3.8 ng were applied to a unit area of ​​1 / 600 inch x 1 / 600 inch was defined as having a recording duty of 100.0%.

[0061] Example 1 Using the inkjet recording device described above, first liquid composition X and ink 1 were applied to a first region of recording medium A at a recording duty of 60.0%, respectively. Furthermore, first liquid composition X, ink 1, and clear ink (second liquid composition) were applied to a second region of recording medium A at recording duties of 60.0%, 30.0%, and 27.5%, respectively. The recording medium was then heated at 95°C for 30 seconds using a hot air dryer to form a three-dimensional image, resulting in recorded matter 1. The total amount of volatile solvents V1 contained in the first liquid composition, ink, and clear ink applied to the first region was 21.5 ng. Furthermore, the total amount of volatile solvents V2 contained in the first liquid composition, ink, and clear ink applied to the second region was 21.5 ng, and "(V1 / V2) x 100" was 100%.

[0062] (Examples 2 to 15, Comparative Examples 1 to 3) Three-dimensional images were formed in the same manner as in Example 1 described above, except that the conditions shown in Tables 2-1 and 2-2 were used, and records 2 to 18 were obtained. The total amount V1 (ng) of the volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the first region is shown in Table 2-1. The total amount V2 (ng) of the volatile solvent contained in the first liquid composition, ink, and second liquid composition applied to the second region, as well as "(V1 / V2) x 100" (%), are shown in Table 2-2.

[0063] TIFF2023085222000002.tif173170

[0064] TIFF2023085222000003.tif165170

[0065] <Evaluation> (Unevenness of unevenness) The surface of the obtained recorded material was visually observed and evaluated for unevenness according to the following evaluation criteria. The results are shown in Table 3. AA: There was almost no difference in the height of the irregularities between the regions, and the irregularities were sufficiently high. A: There was almost no difference in unevenness height between the regions, but the unevenness height was slightly lower. B: There was a slight difference in unevenness height between the regions, but it was barely noticeable. C: There was a slight difference in unevenness height between the regions, but it was not a problematic level. D: There was a clear difference in unevenness height between the regions.

[0066] TIFF2023085222000004.tif137170

[0067] The disclosure of this embodiment includes the following method. (Method 1) A step of applying a first liquid composition containing an expansion-promoting / expansion-suppressing component that promotes or suppresses the expansion of the expanded beads to a recording medium having a substrate and a foam layer formed on the substrate, the foam layer containing expanded beads that expand when heated and a binder resin; applying an ink containing a coloring material to the recording medium; applying a second liquid composition to the recording medium, the second liquid composition not containing a foaming promoting / suppressing component that promotes or suppresses the foaming of the expanded beads and a coloring material; and heating the recording medium onto which the first liquid composition, the ink, and the second liquid composition have been applied to form a three-dimensional image, the area of ​​the recording medium to which the ink has been applied includes a first area and a second area to which the amount of ink applied is different, and the amount of ink applied to the first area is greater than the amount of ink applied to the second area; A method for producing a recorded matter having a three-dimensional image, wherein the total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the first region is 95% by mass or more and 105% by mass or less, based on the total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the second region. (Method 2) A method for producing a recorded matter having a three-dimensional image according to Method 1, wherein the total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the first region is 98% by mass or more and 102% by mass or less, based on the total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the second region. (Method 3) The foamed particles are a thermally expandable foaming agent having a shell layer containing a resin and a volatile material encapsulated in the shell layer, 3. The method for producing a recorded matter having a three-dimensional image according to Method 1 or 2, wherein the volatile material is a low-molecular-weight hydrocarbon having a molecular weight of 120 or less. (Method 4) The method for producing a recorded matter having a three-dimensional image according to any one of Methods 1 to 3, wherein the second liquid composition is a clear ink.

Claims

1. a step of applying a first liquid composition containing an expansion-promoting / expansion-suppressing component that promotes or suppresses expansion of the expanded beads to a recording medium having a substrate and a foam layer formed on the substrate, the foam layer containing expanded beads that expand when heated and a binder resin; applying an ink containing a coloring material to the recording medium; applying a second liquid composition to the recording medium, the second liquid composition not containing a foaming promoting / suppressing component that promotes or suppresses the foaming of the expanded beads and a coloring material; and heating the recording medium onto which the first liquid composition, the ink, and the second liquid composition have been applied to form a three-dimensional image, the area of ​​the recording medium to which the ink has been applied includes a first area and a second area to which the amount of ink applied is different, and the amount of ink applied to the first area is greater than the amount of ink applied to the second area; a total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the first region is 95% by mass or more and 105% by mass or less, based on the total amount of volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the second region.

2. 2. The method for producing a recorded material having a three-dimensional image according to claim 1, wherein the sum of the volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the first region is 98% by mass or more and 102% by mass or less, based on the sum of the volatile solvents contained in the first liquid composition, the ink, and the second liquid composition applied to the second region.

3. the foamed beads are a thermally expandable foaming agent having a shell layer containing a resin and a volatile material encapsulated in the shell layer, 3. The method for producing a recorded matter having a three-dimensional image according to claim 1, wherein the volatile material is a low-molecular-weight hydrocarbon having a molecular weight of 120 or less.

4. 3. The method for producing a recorded matter having a three-dimensional image according to claim 1, wherein the second liquid composition is a clear ink.

5. A method for producing a recorded matter as described in claim 1 or 2, wherein the volatile solvent is a solvent having a boiling point of 150°C or less at 1 atmosphere.

6. A method for producing a recorded matter described in claim 1 or 2, wherein the foaming promoting / inhibiting component is at least one selected from the group consisting of 2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

7. A method for producing a recorded matter described in claim 1 or 2, wherein the content (mass %) of the foam-promoting / inhibiting component in the first liquid composition is 10 mass % or more and 70 mass % or less, based on the total mass of the first liquid composition.

8. The foamed particles are a thermally expandable foaming agent having a shell layer containing a resin and a volatile material encapsulated within the shell layer, The method for producing a recorded matter according to claim 1 or 2, wherein the absolute value of the difference (|SP 1 -SP 2 |) between the solubility parameter (SP 1 ) of the resin contained in the shell layer and the solubility parameter (SP 2 ) of the foaming promoting / inhibiting component is 3.5 or less.

9. The foamed particles are a thermally expandable foaming agent having a shell layer containing a resin and a volatile material encapsulated within the shell layer, 3. The method for producing a recorded matter according to claim 1, wherein the absolute value (|HSP 1 -HSP 2 |) of the difference between the Hansen solubility parameter (HSP 1 ) of the resin contained in the shell layer and the Hansen solubility parameter (HSP 2 ) of the foaming promoting / inhibiting component is 20.0 or less.

10. The ink is an aqueous ink containing water, The method for producing a recorded matter according to claim 1 or 2, wherein the content (% by mass) of the water in the ink is 50.0% by mass or more and 95.0% by mass or less based on the total mass of the ink.

11. A method for producing a recorded matter as described in claim 1 or 2, wherein the second liquid composition is at least one of a clear ink and a reaction liquid.

12. In the process of forming a three-dimensional image by heating the recording medium to which the first liquid composition, the ink, and the second liquid composition have been applied, 3. The method for producing a recorded matter according to claim 1, wherein the heating temperature of the recording medium is equal to or higher than the foaming initiation temperature of the foamed particles and equal to or lower than the foaming initiation temperature + 15[deg.]C.

13. A method for producing a recorded matter described in claim 1 or 2, in which the first liquid composition, the ink, and the second liquid composition are each applied to the recording medium using an inkjet recording device.