Method for manufacturing recording material having three-dimensional image, manufacturing apparatus for recording material having three-dimensional image, and foaming promoting liquid

Abstract

This invention relates to a method for manufacturing a recordable object with a three-dimensional image, an apparatus for manufacturing a recordable object with a three-dimensional image, and a foaming accelerator liquid. The method for manufacturing a recordable object with a three-dimensional image includes the steps of: applying a foaming accelerator liquid containing water and a foaming accelerator component to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing foaming particles and a binder resin; and foaming the foamed particles by heating the foamed layer to form a three-dimensional image. The foamed particles have a shell containing a thermoplastic resin and a volatile material encapsulated within the shell. The foaming accelerator component contains a compound without hydroxyl groups. The heating temperature of the foamed layer of the recording medium to which the foaming accelerator liquid has been applied is above and below the foaming start temperature of the foamed particles that react with the foaming accelerator component. A method for manufacturing a recordable object with a three-dimensional image is provided, wherein the method can easily form a three-dimensional image with a clear sense of depth and can suppress the peeling of the foamed layer from the substrate.

Description

[0001] This application is a divisional application of patent application No. 202180077534.2 (International Application No.: PCT / JP2021 / 042301), filed on November 17, 2021, entitled "Method for manufacturing a record having a three-dimensional image, apparatus for manufacturing a record having a three-dimensional image, and foaming accelerator". Technical Field

[0002] The present invention relates to a method for manufacturing a record having a three-dimensional image, an apparatus for manufacturing a record having a three-dimensional image, and a foaming accelerator. Background Technology

[0003] Three-dimensional images, such as wallpaper and Braille, are typically formed using methods such as UV ink coating, physical extrusion methods such as embossing, and printing methods using 3D printers and thermally expanded plastic foam. Thermally expanded plastic foam is known to exhibit properties such as thermal insulation, sound insulation, sound absorption, vibration damping, and lightweighting, depending on the foam material and the state of the formed bubbles.

[0004] In the wallpaper industry, it is known to use azo compounds such as azodicarbonamide (ADCA) as foaming agents and to form a textured structure by foaming a foam layer containing such a foaming agent and a resin such as polyvinyl chloride. For example, a method has been proposed that includes: recording an image with ink containing a coloring material with light absorption properties, then irradiating the image with light to generate heating differences according to light absorption properties, and selectively raising the foam layer to form a three-dimensional image (Patent Document 1).

[0005] In addition, the following method has been proposed (Patent Document 2). A planar image is recorded on the surface of a foamable sheet, and a shadow image (light-absorbing pattern) based on distance image data exhibiting a three-dimensional shape is formed on the surface of a substrate layer of the foamable sheet. Then, light is applied from the substrate layer side according to the gray level of the image to generate heat, thereby causing the foamable sheet to expand according to the distance image data. In addition, a method has been proposed that includes: attaching a liquid for inhibiting, preventing, or promoting expansion to a thermally expanding layer containing polyvinyl chloride or acrylic resin and a chemical foaming agent; and then heating to form an uneven structure (Patent Document 3). In addition, a method has been proposed that includes: applying or printing a plasticizer for the shell wall resin of the foamable capsule onto a three-dimensional image forming layer made of a recording material used to form a three-dimensional image in which a three-dimensional image forming layer containing a foamable capsule is disposed; and heating and foaming the foamable capsule to form a three-dimensional image (Patent Document 4).

[0006] [List of Citations]

[0007] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Publication No. H09-207428

[0009] [Patent Document 2] Japanese Patent Application Publication No. 2001-150812

[0010] [Patent Document 3] Japanese Patent Application Publication No. 2014-514187

[0011] [Patent Document 4] Japanese Patent Application Publication No. H10-129116 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] However, in the method proposed in Patent Document 1, it is necessary to apply ink containing a coloring material with high light absorption, such as black ink, to the part where thermal foaming is desired. Therefore, the part where ink containing a coloring material with low light absorption is applied is difficult to foam. Furthermore, in the case of the method proposed in Patent Document 2, since a light absorption pattern is not directly formed in the foaming layer, it is difficult to achieve sufficient foaming of the foaming layer. Moreover, in the method proposed in Patent Document 3, since a chemical foaming agent is used, variations are likely to occur in the foamed area, making it difficult to exhibit a clear texture. Additionally, in the method proposed in Patent Document 4, since the three-dimensional image forming layer peels off from the support when the foamable capsule foams, further improvements are needed.

[0014] Therefore, an object of the present invention is to provide a method for manufacturing a recorder having a three-dimensional image, which can easily form a three-dimensional image exhibiting a clear texture and suppress the peeling of the foam layer from the substrate. Furthermore, an object of the present invention is to provide an apparatus for manufacturing a recorder having a three-dimensional image, which can easily form a three-dimensional image exhibiting a clear texture and suppress the peeling of the foam layer from the substrate. Additionally, an object of the present invention is to provide a foaming accelerator liquid for use in the above-described method for manufacturing a recorder having a three-dimensional image.

[0015] Solution for solving the problem

[0016] Specifically, the present invention provides a method for manufacturing a record with a three-dimensional image, comprising the following steps: applying a foaming promoting liquid containing water and a foaming promoting component that lowers the foaming start temperature of the foaming particles to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating; and causing the foamed particles to foam to form a three-dimensional image by heating the foamed layer of the recording medium to which the foaming promoting liquid has been applied, wherein the foamed particles comprise: a shell containing a thermoplastic resin; and a volatile material encapsulated within the shell, the binder resin comprising a water-insoluble resin, the foaming promoting component comprising a compound without hydroxyl groups, and the temperature at which the foamed layer of the recording medium to which the foaming promoting liquid has been applied is above the foaming start temperature of the foamed particles that interact with the foaming promoting component and below the maximum foaming temperature of the foamed particles.

[0017] Furthermore, the present invention provides an apparatus for manufacturing a record with a three-dimensional image, comprising: a foaming accelerator liquid application unit that applies a foaming accelerator liquid containing water and a foaming accelerator component that lowers the foaming start temperature of the foaming particles to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating; and a heating unit that causes the foamed particles to foam to form a three-dimensional image by heating the foamed layer of the recording medium to which the foaming accelerator liquid has been applied, wherein the foamed particles comprise: a shell containing a thermoplastic resin; and a volatile material encapsulated within the shell, the binder resin comprising a water-insoluble resin, the foaming accelerator component comprising a compound without hydroxyl groups, and the temperature at which the foamed layer of the recording medium to which the foaming accelerator liquid has been applied is above the foaming start temperature of the foamed particles that interact with the foaming accelerator component and below the maximum foaming temperature of the foamed particles.

[0018] Furthermore, the present invention provides a foaming accelerator liquid for use in a method for manufacturing a recorder having a three-dimensional image. The method includes the following steps: applying a foaming accelerator liquid containing water and a foaming accelerator component that lowers the foaming start temperature of the foaming particles to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating; and causing the foamed particles to foam to form a three-dimensional image by heating the foamed layer of the recording medium to which the foaming accelerator liquid has been applied, wherein the foamed particles comprise: a shell containing a thermoplastic resin; and a volatile material encapsulated within the shell, the binder resin comprising a water-insoluble resin, the foaming accelerator component comprising a compound without hydroxyl groups, and the temperature at which the foamed layer of the recording medium to which the foaming accelerator liquid has been applied is above the foaming start temperature of the foamed particles that interact with the foaming accelerator component and below the maximum foaming temperature of the foamed particles.

[0019] The effects of the invention

[0020] This invention provides a method for manufacturing a recorder with a three-dimensional image, which can easily form a three-dimensional image exhibiting a clear texture and suppress the peeling of the foam layer from the substrate. Furthermore, this invention provides an apparatus for manufacturing a recorder with a three-dimensional image, which can easily form a three-dimensional image exhibiting a clear texture and suppress the peeling of the foam layer from the substrate. Additionally, this invention provides a foaming accelerator liquid used in the above-described method for manufacturing a recorder with a three-dimensional image. Attached Figure Description

[0021] [ Figure 1 [A cross-sectional view illustrating an example of a recording medium used in the method for manufacturing a record with a three-dimensional image according to the present invention.]

[0022] [ Figure 2 This is a schematic diagram illustrating the structure of a manufacturing apparatus for a recorder having a three-dimensional image according to the present invention. Detailed Implementation

[0023] The invention will be described in more detail below by presenting preferred embodiments. Hereinafter, water-based inkjet ink will be referred to simply as "ink" in certain circumstances. Unless otherwise stated, physical property values ​​are values ​​at room temperature (25°C).

[0024] (Method for manufacturing a record with three-dimensional images)

[0025] The method for manufacturing a recordable with a three-dimensional image according to the present invention (hereinafter also simply referred to as the "method for manufacturing a recordable") includes the following steps: applying a foaming accelerator liquid to a recording medium; and foaming foam particles to form a three-dimensional image. As a recording medium, the recording medium includes: a substrate; and a foamed layer disposed on the substrate and containing a binder resin and foamed foam particles that foam upon heating. In the step of applying the foaming accelerator liquid to the recording medium, a foaming accelerator liquid containing a foaming accelerator component that lowers the foaming start temperature of the foamed foam particles is applied to the recording medium. In the step of foaming foam particles to form a three-dimensional image, the foamed layer of the recording medium to which the foaming accelerator liquid has been applied is heated to cause the foamed foam particles to foam, thereby forming a three-dimensional image. Furthermore, each foamed particle includes: a shell containing a thermoplastic resin; and a volatile material encapsulated within the shell. Then, the temperature at which the foamed layer of the recording medium to which the foaming accelerator liquid has been applied is heated is above the foaming start temperature of the foamed foam particles that interact with the foaming accelerator component and below the maximum foaming temperature of the foamed foam particles. Here, the highest foaming temperature of the foaming particles is the highest foaming temperature of the foaming particles without interaction with the foaming promoting ingredients.

[0026] In the method for manufacturing a recording medium according to the present invention, a foaming promoting liquid containing a foaming promoting component is applied to a recording medium having a foamed layer containing foamed particles. The foaming promoting component is a component capable of lowering the foaming start temperature of the foamed particles. That is, the foaming start temperature of the foamed particles in the foamed layer of the recording medium to which the foaming promoting liquid has been applied has been lowered. Therefore, after applying the foaming promoting liquid, when the foamed layer of the recording medium is heated to a temperature above but below the maximum foaming temperature of the foamed particles that react with the foaming promoting component, the foamed particles in the foamed layer to which the foaming promoting liquid has been applied can be effectively foamed. In this way, a three-dimensional image exhibiting a clear uneven structure is formed, thereby obtaining a target recording medium. Furthermore, a compound without hydroxyl groups is used as the foaming promoting component. The reason why this foaming promoting component promotes foaming when the foamed particles are heated is not necessarily clear. However, the inventors have deduced that the foaming promoting component promotes the softening of the binder resin in the shell or foam layer of the foamed particles, thereby improving the foaming properties of the foamed particles. Furthermore, the temperature at which the foaming layer to which the foaming promoting liquid has been applied is preferably above and below the foaming start temperature of the foamed particles reacting with the foaming promoting component. This allows for effective foaming of the foamed particles reacting with the foaming promoting component through heating, enabling the formation of a three-dimensional image exhibiting a clearer uneven structure. Furthermore, the temperature at which the foaming layer to which the foaming promoting liquid has been applied is preferably above and below the foaming start temperature of the foamed particles reacting with the foaming promoting component, and below the foaming start temperature of the foamed particles not reacting with the foaming promoting component. This allows for foaming of the foamed particles reacting with the foaming promoting component through heating, while suppressing the foaming of the foamed particles not reacting with the foaming promoting component through heating, enabling the formation of a three-dimensional image exhibiting a clearer uneven structure.

[0027] The foaming accelerator contains water and foaming-promoting components. To address this, by using a water-insoluble resin as the binder resin contained in the foamed layer of the recording medium, the dissolution of the binder resin in the foaming accelerator can be suppressed. As a result, the reduction in adhesion between the substrate and the foamed layer can be suppressed, and conversely, the peeling of the foamed layer from the substrate when the foam particles are foamed can be suppressed.

[0028] The foaming initiation temperature and maximum foaming temperature of foamed particles reacting with foaming promoters can be measured using the method described below. First, the foamed particles are immersed in a foaming accelerator containing the foaming promoter for 10 seconds to allow them to react with the promoter. As a sample, 25 μg of the foamed particles immersed in the foaming accelerator is placed in an aluminum container with a diameter of 7 mm and a depth of 1 mm. The aluminum container is mounted on a thermomechanical analyzer, and under a load of 0.1 N applied from above, the temperature is increased from 60 °C to 200 °C at a heating rate of 5 °C / min. The displacement in the vertical direction at the measurement end (the displacement of the height of the portion occupied by the sample) is measured. The temperature at which the displacement begins is then used as the foaming initiation temperature of the foamed particles reacting with the foaming promoter. Furthermore, the temperature at which the displacement reaches its maximum is used as the maximum foaming temperature of the foamed particles reacting with the foaming promoter. Additionally, the foaming initiation temperature and maximum foaming temperature of foamed particles not reacting with the foaming promoter are defined as follows. That is, these temperatures refer to the temperature at which displacement begins and the temperature at which displacement reaches its maximum, respectively. They are measured using the same method as in the case of foam particles interacting with foaming promotion components, except that foam particles not interacting with foaming promotion components are used as samples.

[0029] A method for heating a foamed layer to which a foaming accelerator has been applied can be a method using a heating device capable of heating the foamed particles in the foamed layer to a desired temperature.

[0030] Any image can be recorded (printed) by applying ink containing dyes or pigments as coloring materials to a recording medium before or after applying a foaming accelerator to a foaming layer, or before or after heating a foaming layer to which a foaming accelerator has been applied. For example, printing can be performed not only by inkjet recording methods that apply ink using an inkjet system, but also by printing methods such as electrophotographic systems using toners, latex, UV, and sublimation transfer. From the viewpoint of being able to record finer images, recording images by inkjet recording methods is preferred.

[0031] (Recording medium)

[0032] Figure 1 This is a cross-sectional view schematically illustrating an example of a recording medium used in the method for manufacturing a record with a three-dimensional image according to the present invention. Figure 1 As shown, the recording medium 10 includes: a substrate 11; and a foamed layer 12 disposed on the substrate 11 and containing foamed particles 13 that are foamed by heating. Details of the recording medium used in the method of manufacturing the recording article of the present invention will be described below.

[0033] [Substrate]

[0034] Substrate 11 serves as a support for the foamed layer 12. Figure 1 There are no particular restrictions on the type of substrate. Substrates include, for example, ordinary paper made from natural pulp; kraft paper; plastic films made of polypropylene, polyethylene, polyester, etc.; so-called synthetic paper and nonwoven fabrics obtained by making pseudo-paper from synthetic fibers, synthetic pulp and synthetic resin films; and so on.

[0035] [Foaming Layer]

[0036] like Figure 1 As shown, the foam layer 12 is a layer disposed on at least one surface of the substrate 11 and containing foam particles 13 and binder resin 14. Each foam particle 13 is a heat-expandable microcapsule comprising: a capsule-shaped shell 15 containing a thermoplastic resin; and a volatile material 16 encapsulated inside the shell 15. When the foam particle 13 is heated, the thermoplastic resin contained in the shell 15 softens, and the volatile material 16 encapsulated inside the shell 15 evaporates, thereby expanding in volume. Thus, the foam particle 13 expands like a balloon.

[0037] The thermoplastic resin contained in the shell includes, for example, polystyrene, styrene-acrylate copolymer, polyamide resin, polyacrylate, polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, vinylidene chloride-acrylonitrile, methacrylate-acrylic copolymer, vinylidene chloride-acrylic copolymer, vinylidene chloride-acrylate copolymer, etc.

[0038] Volatile materials include, for example, low molecular weight hydrocarbons such as ethane, ethylene, propane, propylene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, heptane, and petroleum ether; chlorofluorocarbons such as CCl3F, CCl2F2, CClF3, and CClF2-CClF2; tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, and trimethyln-propylsilane; and so on. Preferably, the volatile materials are hydrocarbons with a molecular weight of 120 or less. Furthermore, there is no particular limitation on the lower limit of the molecular weight of the volatile materials (hydrocarbons), but, for example, 50 or more is preferred. Based on the total mass of the foam layer, the content of foamed particles in the foam layer is preferably 5% by mass or more and 95% by mass or less.

[0039] The foam layer 12 contains an adhesive resin 14 to enhance adhesion to the substrate 11. Figure 1When the foaming particles in the foamed layer foam upon heating, the binder resin plays a crucial role in preventing the foamed layer from peeling off from the substrate. A water-insoluble resin is used as the binder resin. When the binder resin contains a water-insoluble resin, the binder resin becomes less likely to dissolve in the water of the foaming accelerator, thus suppressing the reduction in adhesion between the substrate and the foamed layer caused by the foaming accelerator. Furthermore, even when an aqueous ink containing water is applied to the recording medium, the reduction in adhesion between the foamed layer and the substrate can be suppressed. Here, a water-insoluble resin refers to a resin that retains 95% or more by mass after immersion in warm water at 80°C for 2 hours. The water-insoluble resin is preferably at least one selected from the group consisting of acrylic resins and polyurethane resins. Furthermore, the water-insoluble resin is more preferably at least one selected from the group consisting of acrylic resins without ester groups and polyurethane resins without ester groups. Finally, the water-insoluble resin is preferably a non-water-absorbent resin. Based on the total mass of the foamed layer, the content of water-insoluble resin in the foamed layer is preferably 10% by mass or more and 95% by mass or less. Furthermore, the foamed layer may contain both water-soluble and water-insoluble resins, as long as the advantageous effects of the present invention are achieved. Additionally, the glass transition temperature of the binder resin is preferably -10°C or more and 30°C or less. When the glass transition temperature of the binder resin is within the above range, it can prevent the binder resin from inhibiting the foaming of the foamed particles.

[0040] The preferred mass ratio between the foamed particles and the binder resin is 5:95 to 90:10. By setting the mass ratio between the foamed particles and the binder resin within this range, both the foaming properties of the foamed particles and the bonding performance between the binder resin and the substrate can be improved. The foamed layer may further contain components such as pigments, antioxidants, dyes, and surfactants, as long as the foaming properties are not compromised.

[0041] (Methods for manufacturing recording media)

[0042] To manufacture recording media, a foamed layer containing foamed particles is first coated onto the surface of a substrate using a coating liquid to form a coating layer. This coating layer is then dried to form a foamed layer, thus obtaining the recording media. Conventionally known equipment such as air knife coaters, die coaters, doctor blade coaters, roller coaters, bar coaters, rod coaters, roll coaters, gravure coaters, and curtain coaters can be used to coat the foamed layer onto the substrate surface. Drying methods for the coating layer include, for example, blowing hot air. Drying conditions (temperature, airflow rate, time, etc.) can be appropriately set according to the type of substrate and the composition of the coating liquid. However, the drying temperature needs to be lower than the foaming initiation temperature of the foamed particles used.

[0043] Preferably, 2 g / m is applied to one surface of the substrate. 2 The above foaming layer. By setting 2g / m 2 The above foaming layer further improves foamability. Note that recording media (articles) with a pre-set foaming layer containing foam particles can be used.

[0044] A back coating may be formed on the surface of the substrate, on the surface opposite to the surface where the foam layer is formed. The back coating may be the same layer as the foam layer containing the foamed particles, or it may be a different layer from the foam layer. Additionally, an adhesive layer containing an adhesive resin such as an acrylic resin and an ink receiving layer for fixing the coloring material may be formed.

[0045] (Foaming promoter)

[0046] The foaming accelerator of the present invention is a foaming accelerator used in the manufacturing method of the above-described record. Details of the foaming accelerator will be described below.

[0047] [Foaming Promoter Ingredients]

[0048] The foaming accelerator contains foaming-promoting components that lower the foaming initiation temperature of the foamed particles. By applying the foaming accelerator containing the foaming-promoting components to the foamed layer of the recording medium using methods such as jetting or coating with an inkjet system, the thermoplastic resin contained in the shell of the foamed particles can be softened. It is speculated that, as a result, the foaming initiation temperature and the maximum foaming temperature of the foamed particles can be shifted to the lower temperature side.

[0049] The foaming accelerator can be a component that softens the thermoplastic resin contained in the shell of the foamed particles and does not contain hydroxyl groups, and can be appropriately selected and used depending on the type of thermoplastic resin, etc. Foaming accelerators include, for example, 2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc. Preferably, the boiling point of the non-hydroxyl-containing compound used as the foaming accelerator is higher than the temperature at which the foaming layer is heated. When the boiling point of this compound is higher than the temperature at which the foaming layer is heated, the compound is unlikely to evaporate even when the foaming layer is heated, thereby helping to soften the thermoplastic resin in the shell of the foamed particles. Based on the total mass of the foaming accelerator liquid, the content of the non-hydroxyl-containing compound used as the foaming accelerator is preferably 10% by mass or more and 70% by mass or less.

[0050] The absolute value (|SP1-SP2|) of the difference between the solubility parameter (SP1) of the thermoplastic resin forming the shell layer of the foamed particles (microcapsules) and the solubility parameter (SP2) of the foaming promoting component is preferably 3.5 or less. When the absolute value of the difference in solubility parameters is within the above-mentioned range, the foaming properties of the region in the foaming layer where the foaming promoting liquid containing the foaming promoting component is applied can be further improved.

[0051] Furthermore, it is preferable that the absolute value (|HSP1-HSP2|) of the difference between the solubility parameter (HSP2) of the foaming promoting component and the Hansen solubility parameter (HSP1) of the thermoplastic resin forming the shell layer of the foamed particles (microcapsules) is 20 or less. When the absolute value of the difference in Hansen solubility parameters is within the above-mentioned range, the foaming properties of the region in the foaming layer where the foaming promoting liquid containing the foaming promoting component is applied can be further improved.

[0052] The solubility parameters (SP values) of the thermoplastic resin and foaming promoting components forming the shell are calculable values. Additionally, the Hansen solubility parameters (HSP values) of the thermoplastic resin and foaming promoting components forming the shell are actual measured values ​​calculated based on dynamic light scattering measurements.

[0053] [Other ingredients]

[0054] When the foaming accelerator is a liquid at room temperature (25°C), the foaming accelerator itself can be used as a foaming accelerator. Furthermore, the foaming accelerator may contain components other than the foaming accelerator (other components). For example, to improve the spray stability of the foaming accelerator, it is preferable that the foaming accelerator further contains liquid components such as solvents. As a solvent, a water-soluble organic solvent such as water can be used. As water, deionized water (ion-exchanged water) is preferred. Water-soluble organic solvents include alcohols, glycols, glycol ethers, and nitrogen-containing compounds.

[0055] As a component other than the liquid component, water-soluble organic compounds that are solid at 25°C can be used, such as urea and its derivatives, trimethylolpropane, and trimethylolethane. Furthermore, the foaming accelerator can contain various additives as needed, such as pH adjusters, defoamers, rust inhibitors, preservatives, fungicides, antioxidants, reduction inhibitors, and chelating agents.

[0056]

[0057] The apparatus for manufacturing a recorder with a three-dimensional image (hereinafter also simply referred to as the "recorder manufacturing apparatus") of the present invention includes: a foaming accelerator liquid application unit that applies a foaming accelerator liquid to a recording medium; and a heating unit that heats a foamed layer of the recording medium to which the foaming accelerator liquid has been applied. The recording medium includes: a substrate; and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating. The foaming accelerator liquid contains water and a foaming accelerator component that lowers the foaming initiation temperature of the foamed particles. The heating unit is a unit that heats the foamed layer of the recording medium to cause the foamed particles to foam, thereby forming a three-dimensional image. Each foamed particle includes: a shell containing a thermoplastic resin; and a volatile material encapsulated within the shell. The binder resin in the foamed layer comprises a water-insoluble resin, and the foaming accelerator component comprises a compound without hydroxyl groups. Then, the temperature of the foamed layer of the recording medium, to which the foaming accelerator has been applied, is heated to a temperature above but below the foaming start temperature of the foaming particles that react with the foaming accelerator component. The ink, foaming accelerator, and recording medium used in this recording device are the same as those used in the above-described recording method. The recording device of the present invention can be advantageously used in the above-described recording method.

[0058] The apparatus for manufacturing recordings may further include an ink container for holding ink, and an ink application unit for ejecting ink from an inkjet head to record an image on a recording medium. Additionally, the apparatus may include a foaming agent container for holding a foaming agent. Furthermore, the apparatus may include a transport unit for transporting the recording medium.

[0059] The arrangement of the foaming accelerator application unit, the ink application unit, and the heating unit can be appropriately adjusted. The arrangement of the foaming accelerator application unit, the ink application unit, and the heating unit in the recording device will be described below with reference to the accompanying drawings.

[0060] Figure 2 This is a schematic diagram illustrating the structure of a manufacturing apparatus for a record of a three-dimensional image according to the present invention.

[0061] exist Figure 2 In the manufacturing apparatus shown, the recording medium 21 is conveyed in the direction of arrow A via a conveying unit for conveying the recording medium. The ink application unit 24 can be arranged upstream or downstream of the foaming accelerator liquid application unit 22, and can be arranged upstream or downstream of the heating unit 23 along the conveying direction A of the recording medium 21. Figure 2 (a) shows the configuration in which the ink application device 24 is arranged downstream of the foaming accelerator application unit 22 and downstream of the heating unit 23 along the conveying direction A of the recording medium 21. Figure 2(b) shows the configuration in which the ink application device 24 is arranged downstream of the foaming liquid application unit 22 and upstream of the heating unit 23 along the conveying direction A of the recording medium 21. Figure 2 (c) shows the configuration in which the ink application device 24 is arranged upstream of the foaming accelerator application unit 22 and upstream of the heating unit 23 along the conveying direction A of the recording medium 21.

[0062] By the transmission direction arranged on the recording medium 21 ( Figure 2 The foaming agent application unit 22, which includes an inkjet system recording head that sprays foaming agent at a predetermined position (in the direction of the middle arrow A), can apply the foaming agent to the foaming layer of the recording medium 21.

[0063] Heating unit 23 is a unit that heats the foamed layer of the recording medium 21 to which a foaming accelerator has been applied. Heating unit 23 may be a heating device capable of heating the foamed particles in the foamed layer to a desired temperature. Heating unit includes, for example, a dryer, an oven, a heater, and an iron.

[0064] [Example]

[0065] The invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples described below without departing from its spirit. Unless otherwise stated, the amounts of ingredients described in “parts” and “%” are by mass.

[0066] <Preparation of Foamed Granules>

[0067] Foamed particles X, Y, and Z were prepared. Foamed particle X was manufactured under the trade name "Advancell EMH204" (manufactured by SEKISUICHEMICAL CO., LTD., volatile material: isopentane (molecular weight 72.2)). Foamed particle Y was manufactured under the trade name "Expancel 007-40" (manufactured by Japan Fillite Co., Ltd., volatile material: isobutane (molecular weight 58.1)). Foamed particle Z was manufactured under the trade name "Matsumoto Microsphere F-30" (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., volatile material: isopentane (molecular weight 72.1)). The shell of foamed particles X, Y, and Z was thermoplastic resin. The foaming initiation temperature and maximum foaming temperature of foamed particles X, Y, and Z were measured using a thermomechanical analyzer (TMA) (trade name "TMA2940", manufactured by TA Instruments) as follows. A 25 μg sample was placed in an aluminum container with a diameter of 7 mm and a depth of 1 mm, and a load of 0.1 N was applied from above. Under these conditions, the sample was heated from 60 °C to 200 °C at a heating rate of 5 °C / min, and the displacement in the vertical direction at the measurement end was measured. The temperature at which the displacement began was then measured as the "foaming start temperature," and the temperature at which the displacement reached its maximum value was measured as the "maximum foaming temperature." The results are shown in Table 1.

[0068] [Table 1]

[0069] Table 1

[0070]

[0071] <Measurement of foaming initiation temperature and maximum foaming temperature based on the interaction between foaming particles and foaming promoting ingredients>

[0072] (Preparation of foaming accelerator liquid for reacting foaming particles with foaming accelerator components)

[0073] Prepare components A to I as shown in Table 2. Mix 10g of each component A to I with 90g of water to form a liquid containing 10g of each component and 90g of water (component E is 100% water) as a foaming accelerator. React these foaming accelerators A' to I' with 20g of foaming particles (foaming particles X, Y, and Z) as shown in Table 2. Subsequently, the foaming initiation temperature and maximum foaming temperature of each group of foaming particles reacting with the foaming accelerator were measured using the same method as in the case where the foaming particles were not reacted with the foaming accelerator. The measurement results are shown in Table 2. Note that the abbreviations in Table 2 have the following meanings.

[0074] • DMSO: Dimethyl sulfoxide

[0075] • DMF: N,N-Dimethylformamide

[0076] •NMP: N-methyl-2-pyrrolidone

[0077] • iPrOH: Isopropanol

[0078] • PGME: Propylene Glycol Monomethyl Ether

[0079] [Table 2]

[0080]

[0081] <Preparation of Recording Media>

[0082] (Recording medium X)

[0083] As the substrate, polypropylene synthetic paper (trade name "New Yupo FGS110", manufactured by Yupo Corporation) was prepared. 100 parts of an acrylic resin with a glass transition temperature of 0°C and 50 parts of foaming particles X were added to ion-exchanged water, and then stirred thoroughly to obtain coating solution X. The obtained coating solution X was applied to the substrate, resulting in an application rate of 40 g / m². 2 Then, it is dried in an oven at 80°C for 5 minutes to form a foamed layer, thereby obtaining recording medium X. Note that the acrylic resin used to prepare this recording medium X is a water-insoluble and non-water-absorbent resin and does not contain ester groups.

[0084] (Recording medium Y)

[0085] The recording medium Y is obtained in the same manner as the recording medium X described above, except that foaming particles Y are used instead of foaming particles X, and coating liquid Y is used instead of coating liquid X.

[0086] (Recording medium Z)

[0087] Coating liquid Z was obtained by replacing foaming particle X with foaming particle Z and by using polyvinylpyrrolidone as a water-absorbing resin instead of acrylic resin. Then, coating liquid Z was applied to a substrate instead of coating liquid X and dried in an oven at 60°C for 5 minutes. Otherwise, recording medium Z was obtained in the same manner as the recording medium X described above.

[0088] (Recording medium W)

[0089] Except for obtaining coating liquid Z by using acrylate with ester groups instead of polyvinylpyrrolidone, recording medium W is obtained in the same manner as the recording medium Z described above.

[0090] <Preparation of foaming accelerator applied to recording medium>

[0091] Foaming accelerator A was obtained by mixing 30 parts of component A, 0.5 parts of a nonionic surfactant (trade name "Acetylenol E100", manufactured by Kawaken Fine Chemicals Co., Ltd.), and 69.5 parts of deionized water, followed by thorough stirring and pressure filtration through a 1.2 μm filter. Foaming accelerators B to I were then obtained in the same manner as foaming accelerator A, except that components B to I were used instead of component A.

[0092] <Production of Records>

[0093] The ink cartridges are filled with foaming accelerators A through I respectively and connected to an inkjet recording device (trade name "PIXUSMG3630", manufactured by Canon Inc.). In this embodiment, the recording duty of an image recorded under conditions where two ink droplets, each approximately 11.2 ng, are applied to a unit area of ​​1 / 600 inch × 1 / 600 inch is defined as 100%.

[0094] (Example 1)

[0095] Using the aforementioned inkjet recording apparatus, foaming accelerator A is applied to the foamed layer of the recording medium X, bringing the recording task to 100%. Subsequently, the foamed layer to which foaming accelerator A has been applied is heated to 150°C using a hot air gun (trade name "HL2010E1", manufactured by SAKAGUCHI EH VOCCORP.). In this manner, a three-dimensional image is formed by foaming the foam particles X in the foamed layer to which foaming accelerator A has been applied, thus obtaining the recorded object 1.

[0096] (Examples 2-8 and Comparative Examples 1-19)

[0097] Except for the conditions shown in Table 3, records 2 to 8 and 10 to 28 were obtained in the same manner as in Example 1 above.

[0098] (Example 9)

[0099] Foaming accelerator B was applied to the foamed layer of the recording medium Y using Polyspoit. The foamed layer with applied foaming accelerator B was then heated to 80°C using a hot air gun (trade name "HL2010E1", manufactured by SAKAGUCHI EH VOC CORP.). In this way, a three-dimensional image was formed by foaming the foam particles Y in the foamed layer with applied foaming accelerator B, thus obtaining the recorded object 9.

[0100] <Evaluation>

[0101] (textured texture)

[0102] The surface texture of each record produced was visually observed according to the evaluation criteria given below to evaluate its tactile quality. The results are shown in Table 3.

[0103] A: The unevenness can be observed.

[0104] C: It is impossible to observe concavity and convexity.

[0105] (The heated foam layer peels off from the substrate)

[0106] The surfaces of each record produced were visually inspected according to the evaluation criteria given below to check whether the foam layer peeled off from the substrate after heating. The results are shown in Table 3.

[0107] A: No peeling of the foam layer from the substrate was observed.

[0108] C: The foam layer was observed to peel off from the substrate.

[0109] [Table 3]

[0110] Table 3

[0111]

[0112] This invention is not limited to the embodiments described above, and various changes and modifications are possible without departing from the spirit and scope of the invention. Therefore, the claims are appended to disclose the scope of the invention.

[0113] This application claims priority based on Japanese Patent Application No. 2020-191592, filed on November 18, 2020, the entire contents of which are incorporated herein by reference.

[0114] Explanation of reference numerals in the attached figures

[0115] 10: Recording medium

[0116] 11: Substrate

[0117] 12: Foaming layer

[0118] 13: Foaming granules

[0119] 14: Adhesive resin

[0120] 15: Shell

[0121] 16: Volatile materials

[0122] 21: Recording medium

[0123] 22. Foaming promoter application unit

[0124] 23: Heating Unit

[0125] 24: Ink application unit

Claims

1. A method for manufacturing a record with a three-dimensional image, characterized in that, Includes the following steps: A foaming accelerator liquid containing water and a foaming accelerator component that lowers the foaming initiation temperature of the foaming particles is applied to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating. and By heating the foaming layer of the recording medium to which the foaming accelerator liquid has been applied, the foaming particles are foamed to form a three-dimensional image, wherein... The foamed particles comprise: a shell containing thermoplastic resin; and a volatile material encapsulated within the shell. The adhesive resin contains a water-insoluble resin. The foaming-promoting ingredient contains a compound that does not have hydroxyl groups, and The temperature at which the foaming layer of the recording medium, to which the foaming accelerator has been applied, is heated is above the foaming start temperature of the foaming particles that interact with the foaming accelerator and below the maximum foaming temperature of the foaming particles.

2. The method for manufacturing a record with a three-dimensional image according to claim 1, wherein the volatile material is a hydrocarbon with a molecular weight of less than 120.

3. The method for manufacturing a record of a three-dimensional image according to claim 1 or 2, wherein the content of the foamed particles in the foamed layer is 5% by mass or more and 95% by mass or less, based on the total mass of the foamed layer.

4. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 3, wherein the water-insoluble resin is a non-absorbent resin.

5. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 4, wherein the water-insoluble resin is at least one selected from the group consisting of acrylic resins without ester groups and polyurethane resins without ester groups.

6. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 5, wherein the content of water-insoluble resin in the foam layer is 10% by mass or more and 95% by mass or less, based on the total mass of the foam layer.

7. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 6, wherein the boiling point of the compound is higher than the temperature at which the foaming layer of the recording medium to which the foaming accelerator has been applied is heated.

8. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 7, wherein the compound is at least one selected from the group consisting of 2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide and N-methyl-2-pyrrolidone.

9. A method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 8, wherein the content of the compound in the foaming promoting liquid is 10% by mass or more and 70% by mass or less, based on the total mass of the foaming promoting liquid.

10. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 9, wherein the absolute value (|SP1-SP2|) of the difference between the solubility parameter (SP1) of the thermoplastic resin and the solubility parameter (SP2) of the foaming promoting component is 3.5 or less.

11. The method for manufacturing a record having a three-dimensional image according to any one of claims 1 to 10, wherein the absolute value of the difference (|HSP1 - HSP2|) between the Hansen solubility parameter (HSP1) of the thermoplastic resin and the Hansen solubility parameter (HSP2) of the foaming promoting component is 20 or less.

12. An apparatus for manufacturing a recording with a three-dimensional image, characterized in that, include: A foaming accelerator application unit applies a foaming accelerator containing water and a foaming accelerator component that lowers the foaming start temperature of the foaming particles to a recording medium comprising a substrate and a foaming layer disposed on the substrate and containing a binder resin and foaming particles that foam upon heating. and A heating unit heats the foaming layer of a recording medium to which the foaming agent has been applied, causing the foamed particles to foam and form a three-dimensional image. The foamed particles comprise: a shell containing thermoplastic resin; and a volatile material encapsulated within the shell. The adhesive resin contains a water-insoluble resin. The foaming-promoting ingredient contains a compound that does not have hydroxyl groups, and The temperature at which the foaming layer of the recording medium, to which the foaming accelerator has been applied, is heated is above the foaming start temperature of the foaming particles that interact with the foaming accelerator and below the maximum foaming temperature of the foaming particles.

13. A foaming accelerator used in a method for manufacturing a record having a three-dimensional image, the method comprising the steps of: A foaming accelerator liquid containing water and a foaming accelerator component that lowers the foaming initiation temperature of the foaming particles is applied to a recording medium comprising a substrate and a foamed layer disposed on the substrate and containing a binder resin and foamed particles that foam upon heating. and By heating the foaming layer of the recording medium to which the foaming accelerator liquid has been applied, the foaming particles are foamed to form a three-dimensional image, wherein... The foamed particles comprise: a shell containing thermoplastic resin; and a volatile material encapsulated within the shell. The adhesive resin contains a water-insoluble resin. The foaming-promoting ingredient contains a compound that does not have hydroxyl groups, and The temperature at which the foaming layer of the recording medium, to which the foaming accelerator has been applied, is heated is above the foaming start temperature of the foaming particles that interact with the foaming accelerator and below the maximum foaming temperature of the foaming particles.

Images