Foaming promotion liquid, method for manufacturing recorded article having three-dimensional image, and apparatus for manufacturing recorded article having three-dimensional image

Abstract

To provide a method for manufacturing a recorded article having a three-dimensional image, that is capable of forming a three-dimensional image having a sufficient foaming height even if the heating temperature applied to a recording medium having a foaming layer is low.SOLUTION: A method for manufacturing a recorded article having a three-dimensional image includes the steps of: applying a foaming promotion liquid to a recording medium having a base material and a foaming layer provided on the base material and containing foaming particles having shell layers including polyacrylonitrile copolymers; and heating the recording medium to which the foaming promotion liquid has been applied. The foaming promotion liquid includes a good solvent for the polyacrylonitrile copolymers and a poor solvent for the polyacrylonitrile copolymers.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a foaming promoting liquid, a method for manufacturing a recording material having a stereoscopic image, and a manufacturing apparatus for a recording material having a stereoscopic image.

Background Art

[0002] In recent years, in the printing industry, as digitization progresses, not only flat images but also digitization of three-dimensional images with concavo-convex expressions have been demanded.

[0003] A method has been proposed in which a photothermal conversion material such as black ink is applied onto a recording medium having a foaming layer containing foaming particles, and by irradiating with light, the portion to which black ink is applied is selectively foamed and expanded more than the portion to which no black ink is applied to form a three-dimensional image having concavo-convexities (Patent Document 1). However, since the black ink applied to form the convex portion may affect the appearance of the image, particularly when printing a color image, it is necessary to process the portion to which black ink is applied, which causes laboriousness.

[0004] On the other hand, in Patent Documents 2 and 3, after applying a plasticizer for the shell wall resin of the foaming capsules onto the stereoscopic image forming layer of a recording material for stereoscopic image formation provided with a stereoscopic image forming layer containing foaming capsules and heating, a method has been proposed in which the portion to which the plasticizer is applied is selectively promoted in foaming property more than the portion to which no plasticizer is applied to form a stereoscopic image.

[0005] Further, in Patent Document 4, a liquid containing a material that swells or dissolves the microcapsules is applied onto a medium provided with a foaming layer containing microcapsule-type foaming particles, and by heating, a method has been proposed in which the portion to which the liquid is applied is selectively suppressed in foaming property more than the portion to which no liquid is applied to form a stereoscopic image.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] From the standpoint of energy conservation and safety, there is a need to lower the heating temperature in the foaming process.

[0008] However, in the above-mentioned Patent Documents 2 and 3, if the heating temperature for foaming is lowered, foaming becomes insufficient, making it difficult to achieve sufficient height for the raised parts of the 3D image. In addition, the liquid containing a plasticizer may reduce the binding strength of the binder resin contained in the 3D image forming layer of the material being recorded, which may cause the foamed layer to peel off the substrate.

[0009] Furthermore, in the above-mentioned Patent Document 4, in order to cause foaming in the portion to which the foam-suppressing liquid is not applied, it is necessary to heat the material at a temperature higher than the temperature at which foaming of the foam particles begins.

[0010] Therefore, the object of the present invention is to provide a foaming accelerator capable of forming a three-dimensional image with sufficient foaming height even when the heating temperature is low when heating a recording medium having a foamed layer, a method for manufacturing a recording material having a three-dimensional image, and an apparatus for manufacturing a recording material having a three-dimensional image. [Means for solving the problem]

[0011] The above objectives are achieved by the present invention as described below.

[0012] According to the present invention, the foaming accelerator for stereoscopic image formation comprises a good solvent for polyacrylonitrile copolymers and a poor solvent for polyacrylonitrile copolymers. The mass ratio of the content of the good solvent to the content of the poor solvent in the foaming accelerator (content of good solvent: content of poor solvent) is 20:80 to 90:10. The foaming accelerator is provided, characterized in that both the good solvent and the poor solvent have boiling points higher than the heating temperature when heating the recording medium for the formation of a three-dimensional image.

[0013] Furthermore, according to the present invention, the present invention includes a step of applying a foaming accelerator to a recording medium having a substrate and a foamed layer provided on the substrate, which contains foamed particles having a shell layer containing a polyacrylonitrile copolymer, A step of heating the recording medium to which the foaming accelerator has been applied to form a three-dimensional image, A method for manufacturing a recording having a three-dimensional image having, The foaming accelerator comprises a good solvent for the polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer. The mass ratio of the content of the good solvent to the content of the poor solvent in the foaming accelerator (content of good solvent: content of poor solvent) is 20:80 to 90:10. Both the good solvent and the poor solvent have boiling points higher than the heating temperature when the recording medium is heated. A method for manufacturing a recording material having a three-dimensional image is provided, characterized in that the ratio of the amount of the good solvent applied to the recording medium to the content of the foam particles per unit area contained in the foam layer is 80% by mass or less.

[0014] Furthermore, according to the present invention, a foaming accelerator dispenser is provided for dispenseing a foaming accelerator to a recording medium having a substrate and a foamed layer provided on the substrate, which contains foamed particles having a shell layer containing a polyacrylonitrile copolymer. A heating device that heats the recording medium to which the foam-promoting liquid has been applied to form a three-dimensional image, A manufacturing apparatus for a recording medium having a three-dimensional image, where the foaming accelerator liquid contains a good solvent for the polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer, where the mass ratio of the content of the good solvent to the content of the poor solvent in the foaming accelerator liquid (content of good solvent: content of poor solvent) is 20:80 to 90:10, where both the good solvent and the poor solvent have a boiling point higher than the heating temperature when heating the recording medium, A manufacturing apparatus for a recording medium having a three-dimensional image is provided, wherein the ratio of the amount of the good solvent applied to the recording medium to the content of the foaming particles per unit area contained in the foaming layer is 80% by mass or less.

Effects of the Invention

[0015] According to the present invention, it is possible to provide a foaming accelerator liquid, a manufacturing method for a recording medium having a three-dimensional image, and a manufacturing apparatus for a recording medium having a three-dimensional image, which can form a three-dimensional image having a sufficient foaming height even when the heating temperature when heating the recording medium having a foaming layer is low.

Brief Description of the Drawings

[0016] [Figure 1] It is a cross-sectional view schematically showing an example of a recording medium used in a manufacturing method for a recording medium having a three-dimensional image. [Figure 2] It is a schematic diagram showing a schematic configuration of a manufacturing apparatus for a recording medium having a three-dimensional image. [Figure 3] It is a diagram showing a specific example of the order of arrangement of a foaming accelerator liquid application device, a heating device, and an ink application device in a manufacturing apparatus for a recording medium having a three-dimensional image.

Embodiments for Carrying Out the Invention

[0017] The present invention will be described in more detail below with reference to preferred embodiments. Hereafter, water-based ink for inkjet printing may be simply referred to as "ink." Foaming accelerators for forming three-dimensional images may be simply referred to as "foaming accelerators." Methods for manufacturing recordings having three-dimensional images may be simply referred to as "methods for manufacturing recordings," and apparatus for manufacturing recordings having three-dimensional images may be simply referred to as "apparatus for manufacturing recordings." Good solvents for polyacrylonitrile copolymers may be simply referred to as "good solvents," and poor solvents for polyacrylonitrile copolymers may be simply referred to as "poor solvents." Unless otherwise specified, physical property values ​​are given at room temperature (25°C).

[0018] <Method for manufacturing a recording material containing a three-dimensional image> The present invention provides a method for manufacturing a recording medium comprising the steps of: applying a foaming accelerator to a substrate and a recording medium having a foamed layer on the substrate containing foamed particles having a shell layer containing polyacrylonitrile copolymer; and heating the recording medium to which the foaming accelerator has been applied to form a three-dimensional image.

[0019] Furthermore, the foaming accelerator of the present invention contains a good solvent for the polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer. The mass ratio of the content of the good solvent to the content of the poor solvent in the foaming accelerator (content of good solvent: content of poor solvent) is 20:80 to 90:10.

[0020] A good solvent for polyacrylonitrile copolymers is a solvent that can dissolve polyacrylonitrile copolymers (the first solvent). On the other hand, a poor solvent for polyacrylonitrile copolymers is a solvent that cannot dissolve polyacrylonitrile (the second solvent). In this specification, a solvent in which the amount of polyacrylonitrile copolymer dissolved per 1 L of solvent is 1 g or more is considered a good solvent for polyacrylonitrile copolymers, and a solvent in which the amount of polyacrylonitrile copolymer dissolved per 1 L of solvent is less than 1 g is considered a poor solvent. The polyacrylonitrile copolymer used to determine whether a solvent is a good or poor solvent is prepared by mixing a good solvent and a poor solvent for polyacrylonitrile used in the shell layer of foamed particles, and applying this foaming accelerator to a recording medium having a foamed layer containing foamed particles having a shell layer containing polyacrylonitrile copolymer. The good solvent has the effect of softening the polyacrylonitrile copolymer contained in the shell layer of the foamed particles. However, if a foaming accelerator with a high concentration of a good solvent is applied to the foamed layer of the recording medium, the shell layer of the foamed particles is excessively softened, making it easier for holes to form in the shell layer of the foamed particles when the recording medium is heated. Therefore, a poor solvent that does not contribute to the softening of the polyacrylonitrile copolymer is included in the foaming accelerator along with the good solvent. This makes it possible to soften the shell layer of the foamed particles to which the foaming accelerator has been applied while making it difficult for holes to form. As a result of the softening of the shell layer, the foaming start temperature of the foamed particles is lowered, and as a result, a three-dimensional image with sufficient foam height can be formed even if the heating temperature when forming the three-dimensional image is lowered.

[0021] Furthermore, both the good solvent and the poor solvent for polyacrylonitrile copolymer have boiling points higher than the heating temperature when the recording medium is heated for the formation of a three-dimensional image. If the boiling points of the good solvent and the poor solvent are lower than the heating temperature when the recording medium is heated, heating will cause vigorous vaporization of the good solvent and the poor solvent by boiling. As a result, the amount of good solvent and poor solvent contained in the foamed layer of the recording medium to which the foaming accelerator has been applied will decrease, making it difficult to control the softening of the shell layer of the foamed particles. In other words, if the boiling point of the good solvent is below the heating temperature, heating will cause the good solvent to boil, making it difficult to soften the shell layer of the foamed particles. Also, if the boiling point of the poor solvent is below the heating temperature and the boiling point of the good solvent is higher than the heating temperature, heating will cause the poor solvent to boil, increasing the concentration of the good solvent contained in the foaming accelerator, making it difficult to suppress the formation of holes in the shell layer of the foamed particles.

[0022] Furthermore, in order to accommodate high-speed printing systems, the static surface tension of the foaming accelerator is preferably 24 mN / m or more and 40 mN / m or less, more preferably 24 mN / m or more and 36 mN / m or less, and even more preferably 25 mN / m or more and 33 mN / m or less. By controlling the static surface tension of the foaming accelerator within this range, the foaming accelerator can be quickly and generally uniformly penetrated into the foam layer. As a result, subsequent heating makes it possible to foam the entire foam layer in the area to which the foaming accelerator has been applied, and a sufficient foam height can be obtained. If the static surface tension is less than 24 mN / m, the penetration of the foaming accelerator is too fast, so the foaming accelerator cannot be sufficiently contributed to the foam particles in the upper part of the foam layer, and it becomes difficult to obtain a sufficient foam height even with subsequent heating. If the static surface tension is greater than 40 mN / m, the foaming accelerator does not penetrate sufficiently, so the foaming accelerator cannot be sufficiently contributed to the foam particles in the lower part of the foam layer, and it becomes difficult to obtain a sufficient foam height even with subsequent heating. Furthermore, in order to allow the foaming accelerator to contribute more effectively to the overall foaming measurement between the time of application and heating, the dynamic surface tension of the foaming accelerator at 1000 ms is preferably 34 mN / m or less, and more preferably 32 mN / m or less. The static surface tension of the foaming accelerator can be measured at a temperature of 25°C using an automatic surface tensimeter (e.g., product name "DY-300", manufactured by Kyowa Interface Science). The dynamic surface tension h of the foaming accelerator can be measured at a temperature of 25°C using a dynamic surface tensimeter using the maximum bubble pressure method (e.g., product name "BUBBLE PRESSURE TENSIOMETER BP-2100", manufactured by KRUSS). The maximum bubble pressure method is a method of determining the surface tension of a liquid by measuring the maximum pressure required to release bubbles generated at the tip of a probe (a thin tube) immersed in the liquid to be measured, and then measuring the surface tension of the liquid from the measured maximum pressure. Specifically, the maximum pressure is measured while continuously generating bubbles at the tip of the probe. The time from the moment a new bubble surface forms at the tip of the probe until the maximum bubble pressure (the point at which the radius of curvature of the bubble equals the radius of the probe tip) is reached is called the "lifetime." In other words, the maximum bubble pressure method is a method for measuring the surface tension of a liquid in motion. In this invention, the surface tension at a lifetime of 1000 ms was measured.The static and dynamic surface tension of the foaming accelerator can be adjusted by the type and content of components such as good solvents, poor solvents, and surfactants in the foaming accelerator.

[0023] Furthermore, from the viewpoint of improving the permeability of the foaming accelerator to the foamed layer of the recording medium, the viscosity of the foaming accelerator is preferably 1.5 mPa·s to 5.0 mPa·s, and more preferably 1.5 mPa·s to 2.7 mPa·s. By controlling the viscosity within this range, it is possible to effectively permeate a sufficient amount of foaming accelerator into the foamed layer and to make the foaming accelerator function generally uniformly throughout the foamed layer. Subsequent heating allows the entire foamed layer to foam, thus achieving a sufficient foaming height. The viscosity of the foaming accelerator can be measured under conditions of 25°C using an E-type viscometer (product name "RE-80L", manufactured by TOKI), etc. The viscosity of the foaming accelerator can be adjusted by the type and content of components such as good solvents, poor solvents, and surfactants in the foaming accelerator.

[0024] Furthermore, the ratio of the amount of good solvent added to the foaming accelerator to the amount of foaming particles per unit area contained in the foamed layer is 80% by mass or less. If this ratio is greater than 80% by mass, holes are more likely to form in the shell layer of the foaming particles. There is no particular lower limit to the ratio of the amount of good solvent added to the foaming accelerator to the amount of foaming particles per unit area contained in the foamed layer, but it is preferably 5% by mass or more.

[0025] When the thickness of the foam layer is dμm, in the process of forming a three-dimensional image, it is preferable that the recording medium to which the foam-accelerating solution has been applied is heated at least (d / 10) seconds after the foam-accelerating solution has been applied to the recording medium. This allows the foam-accelerating solution to penetrate uniformly into the foam layer. There is no particular upper limit on the time from the application of the foam-accelerating solution to heating, but in the case of high-speed printing, it is preferable that it be within (2d) seconds.

[0026] In this invention, the foaming start temperature of foamed particles to which the foaming accelerator has been applied can be lowered. When forming a three-dimensional image, the foaming accelerator is applied to the area to be foamed, and then heated at a heating temperature lower than the foaming start temperature of the foamed particles. As a result, only the area to which the foaming accelerator has been applied will foam, while the area to which the foaming accelerator has not been applied will not foam because it is heated below the foaming start temperature. If the heating temperature when forming the three-dimensional image is higher than the foaming start temperature of the foamed particles, the area to which the foaming accelerator has not been applied may also expand.

[0027] The foaming start temperature of foaming particles treated with foaming accelerator can be measured by the following method. First, to treat the foaming particles with foaming accelerator, immerse them in the foaming accelerator for 10 seconds. 25 μg of the foaming particles immersed in the foaming accelerator are placed as a sample in an aluminum container with a diameter of 7 mm and a depth of 1 mm. The aluminum container is attached to a thermomechanical analyzer, and with a load of 0.1 N applied from above to the foaming particles, the container is heated from 60°C to 200°C at a heating rate of 5°C / min, and the vertical displacement of the measurement terminal (the displacement of the height of the portion occupied by the sample) is measured.

[0028] The temperature at which displacement begins is defined as the foaming onset temperature for foamed particles treated with the foaming accelerator. The foaming onset temperature for foamed particles not treated with the foaming accelerator is defined as follows: that is, the temperature at which displacement begins, measured in the same manner as for foamed particles treated with the foaming accelerator, except that foamed particles not treated with the foaming accelerator are used as the sample.

[0029] The method for heating a foamed layer to which a foaming accelerator has been applied is any method that uses a heating device capable of heating the foam particles in the foamed layer to a desired temperature.

[0030] Before or after applying the foaming accelerator to the foamed layer, or before or after heating the foamed layer to which the foaming accelerator has been applied, an ink containing dyes or pigments as colorants may be applied to the recording medium to record (print) any image. Furthermore, it is preferable to use water-based ink as the ink. The printing is not limited to an inkjet recording method in which ink is applied using an inkjet method, but may also be an electrophotographic method using toner, latex, UV, or sublimation transfer printing method. Among these, it is preferable to record the image using an inkjet recording method because it is possible to record a more detailed image.

[0031] (Recording medium) Figure 1 is a schematic cross-sectional view showing an example of a recording medium used in the method for manufacturing a recording material having a three-dimensional image according to the present invention. As shown in Figure 1, the recording medium 10 has a base material 11 and a foamed layer 12 provided on the base material 11 that contains foamed particles 13 that foam when heated. The details of the recording medium used in the method for forming a three-dimensional image and manufacturing a recording material according to the present invention will be described below.

[0032] [Base material] The base material 11 functions as a support for the foamed layer 12. The type of base material is not particularly limited. Examples of base materials include paper made from ordinary natural pulp; kenaf paper; plastic film sheets such as polypropylene, polyethylene, and polyester; and so-called synthetic paper or nonwoven fabrics made from synthetic fibers, synthetic pulp, or synthetic resin films.

[0033] [Foam layer] As shown in Figure 1, the foamed layer 12 is a layer provided on at least one surface of the substrate 11, containing foamed particles 13 and a binder resin 14. The foamed particles 13 are thermally expandable microcapsules having a capsule-shaped shell layer 15 containing a thermoplastic resin and a volatile material 16 enclosed within the shell layer 15. When heat is applied to the foamed particles 13, the thermoplastic resin constituting the shell layer 15 softens, and the volatile material 16 enclosed within the shell layer 15 vaporizes and expands in volume. As a result, the foamed particles 13 expand like a balloon.

[0034] The shell layer may contain thermoplastic resins other than polyacrylonitrile copolymers. Examples of thermoplastic resins other than polyacrylonitrile copolymers that can be contained in the shell layer include polystyrene, styrene-acrylic acid ester copolymers, polyamide resins, polyacrylic acid esters, polyvinylidene chloride, polymethyl methacrylate, vinylidene chloride-acrylonitrile, methacrylic acid ester-acrylic acid copolymers, vinylidene chloride-acrylic acid copolymers, and vinylidene chloride-acrylic acid ester copolymers.

[0035] 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 CCl3F, CCl2F2, CClF3, and CClF2-CClF2; and tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, and trimethyl-n-propylsilane. Among these, the volatile material is preferably a hydrocarbon with a molecular weight of 120 or less. There is no particular lower limit to the molecular weight of the volatile material (hydrocarbon), but it is preferably 50 or more. The content of foamed particles in the foamed layer is preferably 5% by mass or more and 95% by mass or less, based on the total mass of the foamed layer.

[0036] The foamed layer 12 contains a binder resin 14 to improve adhesion to the substrate 11. The binder resin plays an important role in suppressing the peeling of the foamed layer from the substrate when the foamed particles in the foamed layer foam due to heat. There are no particular restrictions on the binder resin, but it is preferable that it contains a water-insoluble resin. The water-insoluble resin is preferably at least one selected from the group consisting of acrylic resins and urethane resins. Furthermore, it is even more preferable that the water-insoluble resin is at least one selected from the group consisting of acrylic resins without ester groups and urethane resins without ester groups. The content of the water-insoluble resin in the foamed layer is preferably 10% by mass or more and 95% by mass or less based on the total mass of the foamed layer. The foamed layer may also contain a water-soluble resin together with the water-insoluble resin, as long as the effects of the present invention are obtained. Furthermore, the glass transition temperature of the binder resin is preferably -10°C or more and 30°C or less. By setting the glass transition temperature of the binder resin within the above range, it is possible to suppress the binder resin from hindering the foaming of the foamed particles.

[0037] The mass ratio of foamed particles to binder resin is preferably 5:95 to 90:10. By keeping the mass ratio of foamed particles to binder resin within the above range, both the foaming properties of the foamed particles and the binding properties of the binder resin to the substrate can be improved. The foamed layer may also contain components such as pigments, antioxidants, dyes, and surfactants, as long as they do not impair the foaming properties.

[0038] To obtain sufficient foaming height, the thickness dμm of the foam layer is preferably 10μm or more, more preferably 20μm or more, and even more preferably 25μm or more. There is no particular upper limit to the thickness dμm of the foam layer, but for example, it can be 100μm or less.

[0039] Furthermore, the recording medium may have an ink-receiving layer.

[0040] (Method of manufacturing recording medium) To manufacture a recording medium, first, a coating liquid for a foamed layer containing foamed particles is applied to the surface of a substrate to form a coating layer. Then, the formed coating layer is dried to form a foamed layer, thereby obtaining a recording medium. Conventional known air knife coaters, die coaters, blade coaters, gate roll coaters, bar coaters, rod coaters, roll coaters, gravure coaters, curtain coaters, etc., can be used to apply the coating liquid for the foamed layer to the surface of the substrate. Methods for drying the coating layer include, for example, blowing hot air onto it. Drying conditions (temperature, airflow, time, etc.) should be set appropriately depending on the type of substrate and the composition of the coating liquid. However, the drying temperature must be lower than the foaming start temperature of the foamed particles used.

[0041] Alternatively, a recording medium having a pre-formed foamed layer containing foamed particles may be used.

[0042] A back coat layer may be provided on the surface of the substrate opposite to the surface on which the foam layer is provided. The back coat layer may be the same layer as the foam layer containing foam particles, or it may be a layer other than the foam layer. In addition, an adhesive layer containing an adhesive resin such as acrylic resin or an ink-receiving layer for fixing colorants may be formed.

[0043] <Foaming accelerator> The following is a detailed explanation of the foaming accelerator.

[0044] The foaming accelerator contains a good solvent for the polyacrylonitrile copolymer, which is the shell layer of the foaming particles, and a poor solvent for the polyacrylonitrile copolymer. Both the good solvent and the poor solvent have boiling points higher than the heating temperature. The good solvent for the polyacrylonitrile copolymer can promote the foaming of the foaming particles and can therefore be called a foaming accelerator component.

[0045] The good solvent for the polyacrylonitrile copolymer is preferably at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0046] The poor solvent for the polyacrylonitrile copolymer is preferably at least one selected from the group consisting of water, toluene, and isobutyl alcohol, and more preferably water.

[0047] The boiling points of the good solvent and the poor solvent are preferably 100°C or higher, and more preferably 110°C or higher.

[0048] The foaming accelerator may contain other components in addition to the solvents described above, such as good and poor solvents. For example, it is preferable to include additional liquid components such as solvents to improve the discharge stability of the foaming accelerator. As solvents, water and various water-soluble organic solvents can be used. As water, deionized water (ion-exchanged water) is preferred. Examples of water-soluble organic solvents include alcohols, glycols, glycol ethers, and nitrogen-containing compounds.

[0049] Furthermore, if necessary, various additives such as pH adjusters, defoamers, rust inhibitors, preservatives, fungicides, antioxidants, reduction inhibitors, and chelating agents may be included in the foaming accelerator.

[0050] The content of a good solvent for polyacrylonitrile copolymer in the foaming accelerator is preferably 20% by mass or more and 90% by mass or less, based on the total mass of the foaming accelerator. By setting the content of the good solvent to 20% by mass or more, the shell layer of the foamed particles can be sufficiently softened, making it easier to lower the foaming initiation temperature of the foamed particles. On the other hand, by setting the content of the good solvent to 90% by mass or less, it becomes easier to suppress the formation of holes in the shell layer of the foamed particles.

[0051] The content of the good solvent relative to the polyacrylonitrile is preferably 31% by mass or more and 70% by mass or less, based on the total mass of the foaming accelerator.

[0052] <Manufacturing apparatus for recording materials containing three-dimensional images> The present invention relates to a recording apparatus for producing a three-dimensional image, comprising: a foaming accelerator application device for applying a foaming accelerator to a substrate and a recording medium having a foam layer on the substrate containing foam particles having a shell layer containing polyacrylonitrile copolymer; and a heating device for heating the recording medium to which the foaming accelerator has been applied to form a three-dimensional image. The ink, foaming accelerator, and recording medium used in this recording apparatus are the same as those used in the recording method described above. The recording apparatus can be suitably used in the recording method described above.

[0053] The recording device may also include an ink storage section for storing ink, and an ink application means for ejecting ink from an inkjet recording head to record an image on a recording medium. Furthermore, the recording device may also include a foaming accelerator storage section for storing foaming accelerator liquid. Additionally, the recording device may include a transport means for transporting the recording medium.

[0054] The details of the recording apparatus of this embodiment will be described below with reference to the drawings. The recording apparatus described below is an example of this embodiment, and the recording apparatus of the present invention is not limited to the following description.

[0055] Figure 2 is a schematic diagram showing the general configuration of the manufacturing apparatus for recording materials having a three-dimensional image according to this embodiment.

[0056] The recording apparatus 20 includes a foaming accelerator dispenser 22, a heating device 23, an ink dispenser 24, and a conveying device 25.

[0057] The recording medium 21 is transported in the direction of arrow A in Figure 2 by a transport device 25, which serves as a transport means for transporting the recording medium. The transport device 25 has a transport belt 26, which is an endless belt, and two rollers 27 and 28 that hold the transport belt 26. The recording medium 21 is transported in the direction of arrow A by the rotational drive of the rollers 27 and 28. The transport device 25 may also have a platen 29 that restricts the vertical displacement of the transport belt 26.

[0058] The foaming accelerator device 22, which is a means for providing foaming accelerators, has an inkjet recording head that ejects foaming accelerator liquid, and ejects the foaming accelerator liquid from the inkjet recording head onto the recording medium 21 that has been transported by the transport device 25.

[0059] The heating device 23, which is a heating means, heats the foamed layer of the recording medium 21 to which the foaming accelerator liquid has been applied. The heating device 23 can be any heating device capable of heating the foamed particles in the foamed layer to a desired temperature. Examples of heating devices 23 include a hair dryer, oven, heating element, and iron.

[0060] When the thickness of the foamed layer is dμm, the heating device 23 preferably heats the recording medium to which the foaming accelerator has been applied starting (d / 10) seconds after the foaming accelerator has been applied to the recording medium.

[0061] The ink application device 24, which is an ink application means, has an inkjet recording head that ejects ink and applies ink from the inkjet recording head to the recording medium 21 that has been foamed by the heating device 23. The ink application device 24 may be located either upstream or downstream of the foaming accelerator application device 22 with respect to direction A, which is the transport direction of the recording medium 21, and may also be located either upstream or downstream of the heating device 23. Figure 2 shows the configuration when the ink application device 24 is located downstream of the foaming accelerator application device 22 and downstream of the heating device 23 with respect to the transport direction (direction A) of the recording medium 21.

[0062] Figure 3 shows the arrangement of the foaming accelerator dispenser 22, the heating device 23, and the ink dispenser 24 with respect to the transport direction of the recording medium 21.

[0063] Figure 3(a) shows the configuration when the ink application device 24 is located downstream of the foaming accelerator application device 22 and downstream of the heating device 23 with respect to the transport direction A of the recording medium 21. Figure 3(b) shows the configuration when the ink application device 24 is located downstream of the foaming accelerator application device 22 and upstream of the heating device 23 with respect to the transport direction A of the recording medium 21. Figure 3(c) shows the configuration when the ink application device 24 is located upstream of the foaming accelerator application device 22 and upstream of the heating device 23 with respect to the transport direction A of the recording medium 21. [Examples]

[0064] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way by the following examples unless it exceeds the gist of the invention. Regarding the amount of components, "parts" and "%" refer to mass unless otherwise specified.

[0065] <Preparing the foaming particles> As shown in Table 1, foamed particles H1 to H3, each having a shell layer containing a polyacrylonitrile copolymer, were prepared. The foaming initiation temperature of the foamed particles was measured according to the measurement method described above.

[0066] [Table 1]

[0067] <Creation of recording media> (Recording medium M1) Polypropylene synthetic paper (product name "New Yupo FGS110", manufactured by Yupo Corporation) was prepared as the base material. 100 parts of the acrylic resin "Mowinyl6950" (acrylic resin manufactured by Japan Coating Resin), which has a glass transition temperature of 0°C, and 50 parts of foamed particles H1 were added to deionized water and thoroughly stirred to obtain coating solution 1 with a solid content concentration of 43%. The obtained coating solution 1 was applied at a coating rate of 40 g / m². 2 After coating the substrate in this manner, the foam layer was formed by drying in an 80°C oven for 5 minutes, and recording medium M1 was obtained. The foam particle content per unit area was 13.3 g / m². 2 The thickness d of the foamed layer was 40 μm.

[0068] (Recording media M2 and M3) Recording media M2 and M3 were obtained by the same method as recording media M1, except that foamed particle H1 was replaced with foamed particle H2 and H3, respectively. The foamed particle content per unit area was 13.3 g / m². 2 The thickness d of the foamed layer was 40 μm.

[0069] <Preparation of foaming accelerator> (Foaming accelerator L1) 35 parts of dimethyl sulfoxide (boiling point: 189°C), a good solvent for polyacrylonitrile copolymers, 64.5 parts of ion-exchanged water (boiling point: 100°C), a poor solvent for polyacrylonitrile copolymers, and 0.5 parts of a nonionic surfactant (trade name "Acetylenel E60", manufactured by Kawaken Fine Chemicals) were mixed. After thorough stirring, the mixture was pressure-filtered through a pore-size 1.2 μm filter to obtain foaming accelerator L1.

[0070] (Foaming accelerator L2) Foaming accelerator L2 was prepared in the same manner as foaming accelerator L1, except that 60 parts of dimethyl sulfoxide were used and 39.5 parts of toluene (boiling point: 111°C) were used instead of deionized water.

[0071] (Foaming accelerator L3) Foaming accelerator L3 was prepared using the same method as foaming accelerator L1, except that isobutyl alcohol (boiling point: 108°C) was used instead of deionized water.

[0072] (Foaming accelerator L4) Foaming accelerator L4 was prepared in the same manner as foaming accelerator L1, except that N,N-dimethylformamide (boiling point: 153°C) was used instead of dimethyl sulfoxide.

[0073] (Foaming accelerator L5) Foaming accelerator L5 was prepared in the same manner as foaming accelerator L1, except that dimethylacetamide (boiling point: 165°C) was used instead of dimethyl sulfoxide.

[0074] (Foaming accelerator L6) Foaming accelerator L6 was prepared using the same method as foaming accelerator L1, except that N-methylpyrrolidone (boiling point: 202°C) was used instead of dimethyl sulfoxide.

[0075] (Foaming accelerator L7) Foaming accelerator L7 was prepared in the same manner as foaming accelerator L1, except that 20 parts of dimethyl sulfoxide and 79.5 parts of deionized water were used.

[0076] (Foaming accelerator L8) Foaming accelerator L8 was prepared in the same manner as foaming accelerator L2, except that 90 parts of dimethyl sulfoxide and 9.5 parts of toluene were used.

[0077] (Foaming accelerator L9) Foaming accelerator L9 was prepared using the same method as foaming accelerator L1, except that isopropyl alcohol (boiling point: 82°C) was used instead of deionized water.

[0078] (Foaming accelerator L10) Foaming accelerator L10 was prepared in the same manner as foaming accelerator L1, except that 18 parts of dimethyl sulfoxide and 81.5 parts of deionized water were used.

[0079] (Foaming accelerator L11) Foaming accelerator L11 was prepared in the same manner as foaming accelerator L2, except that 92 parts of dimethyl sulfoxide and 7.5 parts of toluene were used.

[0080] (Foaming accelerator L12) Foaming accelerator L12 was prepared in the same manner as foaming accelerator L1, except that "Acetylenel E100" (manufactured by Kawaken Fine Chemicals) was used instead of "Acetylenel E60".

[0081] (Foaming accelerator L13) Foaming accelerator L13 was prepared in the same manner as foaming accelerator L2, except that 88 parts of dimethyl sulfoxide and 11.5 parts of toluene were used.

[0082] (Foaming accelerator L14) Foaming accelerator L14 was prepared in the same manner as foaming accelerator L1, except that 64.65 parts of deionized water were used and 0.35 parts of "BYK-349" (manufactured by Bic Chemie Japan) were used instead of "Acetyleneol E60".

[0083] (Foaming accelerator L15) Foaming accelerator L15 was prepared in the same manner as foaming accelerator L1, except that 60 parts of dimethyl sulfoxide and 39.5 parts of deionized water were used.

[0084] The viscosity of the foaming accelerator was measured using an E-type viscometer (product name "RE-80L", manufactured by TOKI). The static surface tension of the foaming accelerator was measured using an automatic surface tensimeter (product name "DY-300", manufactured by Kyowa Interface Science). The dynamic surface tension of the foaming accelerator at 1000 ms was measured using a dynamic surface tensimeter (product name "BUBBLE PRESSURE TENSIOMETER BP-2100", manufactured by KRUSS) using the maximum bubble pressure method.

[0085] The static surface tension of the foaming accelerator was measured at a temperature of 25°C using an automatic surface tensimeter (product name "DY-300", manufactured by Kyowa Interface Science Co., Ltd.).

[0086] The dynamic surface tension of the foaming accelerator was measured at a temperature of 25°C using a dynamic surface tensimeter (product name "BUBBLE PRESSURE TENSIOMETER BP-2100", manufactured by KRUSS) based on the maximum bubble pressure method. In this example, the dynamic surface tension was measured at a lifetime of 1000 ms.

[0087] Table 2 shows the viscosity, static surface tension, and dynamic surface tension of foaming accelerators L1 to L15.

[0088] [Table 2]

[0089] <Examples 1-14, Comparative Examples 1-4> <Formation of three-dimensional images (manufacturing of recordings)> Using the recording apparatus shown in Figure 2, 12 g / m² of foaming accelerator L1 is added to the foamed layer of the recording medium M1, which has been preheated to a paper surface temperature of 30°C. 2 The foaming accelerator was applied, and 5 seconds after application, the recording was heated with 90°C hot air for 10 seconds to obtain recording material 1. The amount of good solvent applied in the foaming accelerator L1 was 32% by mass, relative to the amount of foaming particles per unit area contained in the foamed layer of the recording medium M1.

[0090] In Examples 2 to 14 and Comparative Examples 1 to 4, recordings 2 to 18 were obtained in the same manner as in Example 1, except that the type of foaming accelerator and recording medium shown in Table 3, the amount of foaming accelerator applied to the recording medium, the ratio of the amount of good solvent applied to the foaming particle content, the time from application of the foaming accelerator to heating, and the heating temperature were used.

[0091] Note that the "Ratio of good solvent amount to foam particle content (mass%)" listed in Table 3 means "the ratio of good solvent amount applied to the recording medium to the foam particle content per unit area contained in the foam layer."

[0092] <Rating> Using a digital micrometer (product name "M-30", manufactured by Sony), the height of the foamed portion (foam height) of each of the obtained recordings 1 to 18 was measured, relative to the height of the unfoamed portion on the surface. The measurement results are shown in Table 3. A: The difference in surface area is 200 μm or more. B: The difference in surface area is between 100 μm and less than 200 μm. C: The difference in surface area is less than 100 μm.

[0093] [Table 3] [Explanation of symbols]

[0094] 10 Recording media 11 Base material 12 Foam layer 13 Foaming particles 14 Binder resin 15 Shell Layers 16. Volatile materials 21 Recording media 22 Foam-promoting liquid dispensing device 23 Heating device 24 Ink Dispenser

Claims

1. A foaming-promoting liquid for forming a three-dimensional image, the foaming-promoting liquid containing a good solvent for a polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer, a mass ratio of the content of the good solvent to the content of the poor solvent in the foaming-promoting liquid (content of the good solvent:content of the poor solvent) is 20:80 to 90:10; The foaming-promoting liquid is characterized in that the good solvent and the poor solvent both have boiling points higher than the heating temperature when the recording medium is heated for forming a three-dimensional image.

2. 2. The foam-promoting liquid according to claim 1, wherein the good solvent is at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

3. The foam-promoting liquid according to claim 1, wherein the poor solvent is at least one selected from the group consisting of water, toluene, and isobutyl alcohol.

4. The foam-promoting liquid according to claim 1 , wherein the poor solvent is water.

5. 2. The foam-promoting liquid according to claim 1, wherein the foam-promoting liquid has a static surface tension of 24 mN / m or more and 40 mN / m or less.

6. 2. The foam-promoting liquid according to claim 1, wherein the foam-promoting liquid has a static surface tension of 25 mN / m or more and 33 mN / m or less.

7. 2. The foam-promoting liquid according to claim 1, wherein the foam-promoting liquid has a dynamic surface tension of 34 mN / m or less after 1000 ms.

8. 2. The foam-promoting liquid according to claim 1, wherein the viscosity of the foam-promoting liquid is 1.5 mPa·s or more and 2.7 mPa·s or less.

9. 2. The foaming-promoting liquid according to claim 1, wherein the content of the good solvent in the foaming-promoting liquid is 20% by mass or more and 90% by mass or less, based on the total mass of the foaming-promoting liquid.

10. The foam-promoting liquid described in claim 1, further containing a surfactant.

11. The foam-promoting liquid according to claim 1, wherein the good solvent is a solvent in which the amount of the polyacrylonitrile copolymer dissolved per 1 L of the solvent is 1 g or more.

12. The foam-promoting liquid according to claim 1, wherein the poor solvent is a solvent in which the amount of the polyacrylonitrile copolymer dissolved per 1 L of the solvent is less than 1 g.

13. applying a foaming-promoting liquid to a recording medium having a substrate and a foam layer provided on the substrate, the foam layer containing foamed particles having a shell layer containing a polyacrylonitrile copolymer; a step of heating the recording medium to which the foaming-promoting liquid has been applied to form a three-dimensional image; A method for producing a recorded product having a three-dimensional image comprising: the foaming-promoting liquid contains a good solvent for the polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer, a mass ratio of the content of the good solvent to the content of the poor solvent in the foaming-promoting liquid (content of the good solvent:content of the poor solvent) is 20:80 to 90:10; the good solvent and the poor solvent both have boiling points higher than the heating temperature when the recording medium is heated, A method for producing a recorded matter having a three-dimensional image, characterized in that the ratio of the amount of the good solvent applied to the recording medium to the content of the foamed particles per unit area contained in the foamed layer is 80 mass % or less.

14. The method for producing a recorded matter having a three-dimensional image according to claim 13, wherein the heating temperature is lower than a foaming initiation temperature of the foamed particles.

15. 14. The method for manufacturing a recorded matter having a three-dimensional image according to claim 13, wherein, in the step of forming the three-dimensional image, when the thickness of the foam layer is d μm, the recording medium to which the foam-promoting liquid has been applied is heated at least (d / 10) seconds after the foam-promoting liquid has been applied to the recording medium.

16. a foaming-promoting liquid applying device that applies a foaming-promoting liquid to a recording medium having a substrate and a foam layer provided on the substrate, the foaming layer containing foamed particles having a shell layer containing a polyacrylonitrile copolymer; a heating device that heats the recording medium to which the foaming-accelerating liquid has been applied, thereby forming a three-dimensional image; A manufacturing apparatus for a recorded product having a three-dimensional image, the foaming-promoting liquid contains a good solvent for the polyacrylonitrile copolymer and a poor solvent for the polyacrylonitrile copolymer, a mass ratio of the content of the good solvent to the content of the poor solvent in the foaming-promoting liquid (content of the good solvent:content of the poor solvent) is 20:80 to 90:10; the good solvent and the poor solvent both have boiling points higher than the heating temperature when the recording medium is heated, An apparatus for producing a recorded matter having a three-dimensional image, characterized in that the ratio of the amount of the good solvent applied to the recording medium to the content of the foamed particles per unit area contained in the foamed layer is 80 mass % or less.

17. The apparatus for producing a recorded matter having a three-dimensional image according to claim 16, wherein the heating device controls the heating temperature to a temperature lower than the foaming start temperature of the foamed particles.

18. 17. The apparatus for manufacturing a recorded product having a three-dimensional image according to claim 16, wherein the heating device heats the recording medium to which the foaming-promoting liquid has been applied at least (d / 10) seconds after the foaming-promoting liquid has been applied to the recording medium when the thickness of the foamed layer is d μm.

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