Thermal transfer image receiving sheet, print and method for producing print

Abstract

To provide a thermal transfer image receiving sheet capable of manufacturing a printed matter having high brilliance.SOLUTION: A thermal transfer image receiving sheet includes a substrate, a resin layer and a reception layer. The resin layer includes a bright pigment and a resin material.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a thermal transfer image receiving sheet, a print, and a method for producing a print. [Background technology]

[0002] Various image forming methods are known in the art. Among them, the dye-sublimation thermal transfer method is capable of freely adjusting the density gradation, and therefore is capable of forming high-quality images comparable to silver halide photography.

[0003] The dye-sublimation thermal transfer method involves overlapping a thermal transfer sheet having a colorant layer containing a sublimation dye with a thermal transfer image receiving sheet having a receiving layer, and then heating the thermal transfer sheet with a thermal head provided on the thermal transfer printer, thereby transferring the sublimation dye in the colorant layer to the receiving layer of the thermal transfer image receiving sheet, thereby forming an image and obtaining a printed matter.

[0004] In recent years, a wide variety of designs are required for printed matter. For example, prints are being imparted with a glossy appearance having a high overall shine, or a lustrous appearance having a high partial shine (such as regular or irregular dots). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide a thermal transfer image receiving sheet capable of producing a printed matter having high glitter.An object of the present disclosure is to provide a printed matter produced using the thermal transfer image receiving sheet.An object of the present disclosure is to provide a method for producing a printed matter using the thermal transfer image receiving sheet. [Means for solving the problem]

[0006] The thermal transfer image receiving sheet of the present disclosure includes a substrate, a resin layer, and a receiving layer, The resin layer includes a glittering pigment and a resin material.

[0007] The print of the present disclosure is a print produced using the thermal transfer image receiving sheet, An image is formed on the receiving layer.

[0008] The method for producing a print according to the present disclosure includes: preparing the thermal transfer image receiving sheet; forming an image on a receptor layer of a thermal transfer image receptor sheet; forming a protective layer on the receiving layer; Includes. Effect of the Invention

[0009] According to the present disclosure, a thermal transfer image receiving sheet capable of producing a printed matter having high glitteriness can be provided. According to the present disclosure, a printed matter produced using the thermal transfer image receiving sheet can be provided. According to the present disclosure, a method for producing a printed matter using the thermal transfer image receiving sheet can be provided. [Brief description of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view of a thermal transfer image receiving sheet according to an embodiment. [Diagram 2] 1 is a schematic cross-sectional view of a thermal transfer image receiving sheet according to an embodiment. [Diagram 3] FIG. 4 is a diagram for explaining the light-accepting angle in measuring the average spectral reflectance. [Figure 4] FIG. 2 is a schematic cross-sectional view of a print according to one embodiment. [Diagram 5] 1 is a photographed image of the thermal transfer image-receiving sheet of Example 4 taken from the receiving layer side at a magnification of 500 times. [Figure 6] This is a binarized image of the photographed image in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] (Thermal transfer image receiving sheet) As shown in FIG. 1, a thermal transfer image receiving sheet 10 of the present disclosure includes a substrate 11, a resin layer 12, and a receiving layer 13 in this order in the thickness direction. In one embodiment, the thermal transfer image receiving sheet 10 includes an intermediate layer 14 between the substrate 11 and the resin layer 12, as shown in FIG. In one embodiment, the thermal transfer image receiving sheet 10 includes a primer layer (not shown) between the resin layer 12 and the receiving layer 13 .

[0012] In the hue measured from the receiving layer side of the thermal transfer image receiving sheet of the present disclosure, the L value is preferably from 55 to 95, more preferably from 70 to 90, and particularly preferably from 71 to 83. This can improve the contrast with the glittering pigment and further improve the glittering properties.

[0013] The L value is measured using a spectrophotometer (X-Rite, i1Pro2) or an equivalent device under the following conditions. (Measurement conditions) ·Light source: D65 Measurement field of view: 2° Measurement lighting conditions: M0 (ISO 13655-2009)

[0014] When light is incident on the surface of the receiving layer at an incident angle of 45°, the average spectral reflectance R (see FIG. 3) in the wavelength region of 400 nm to 700 nm (at 20 nm intervals) at the regular reflection receiving angle is preferably 250 or more, more preferably 300 or more. This can improve the contrast with the bright pigment and further improve the brilliance.

[0015] In addition, the average of R is preferably 800 or less. In the present disclosure, the spectral reflectance R is measured in accordance with JIS Z 8722:2000.

[0016] As a measuring device, for example, a spectroscopic variable angle colorimeter GC2000 manufactured by Nippon Denshoku Industries Co., Ltd. or a device having equivalent functions can be used. As a light source, a halogen lamp or the like can be used.

[0017] When light is incident on the surface of the receiving layer at an incident angle of 45°, the minimum spectral reflectance in the wavelength region of 400 nm to 700 nm at the regular reflection receiving angle is R1 and the maximum spectral reflectance is R2, and R1 / R2 is preferably 0.9 or less, and more preferably 0.85 or less, thereby further improving the brilliance.

[0018] R1 / R2 is preferably 0.3 or more, and more preferably 0.5 or more, whereby the brilliance can be further improved.

[0019] In the thermal transfer image receiving sheet of the present disclosure, the ratio of the total area of ​​the black parts to the total area of ​​the white parts described below is preferably 0.10 or more and 0.52 or less. By making the ratio 0.10 or more, the brilliance of the printed matter can be improved. By making the above ratio 0.52 or less, the durability and image visibility of the printed matter can be improved. The above ratio is more preferably 0.12 or more and 0.51 or less, and even more preferably 0.13 or more and 0.40 or less.

[0020] Here, an optical microscope is used to photograph the thermal transfer image receiving sheet from the receiving layer side at 500x magnification to obtain an 8-bit grayscale image, the photographed image is analyzed using image analysis software, the light and dark of the obtained analysis image are inverted, and automatic threshold processing is performed using the ISODATA method to determine the threshold of the brightness distribution in the analysis image, and the image is binarized as black for values ​​below the threshold and white for values ​​above the threshold, and the number and total area of ​​black areas, as well as the total area of ​​white areas, are obtained.

[0021] In addition, the number of black parts is counted as 1 completely independent part. Therefore, for example, a black part consisting of two connected circular black parts forming an aggregate is counted as 1 black part.

[0022] In the thermal transfer image receiving sheet of the present disclosure, the average area of ​​the black portion is 55 μm 2 More than 300μm 2 The average area of ​​the black portion is preferably 55 μm 2 By making the average area of ​​the black portion 300 μm or more, the brilliance of the printed matter can be improved. 2By making the average area of ​​the black portion 60 μm or less, the durability of the printed matter and the image visibility can be improved. 2 More than 250μm 2 Less than 70μm is more preferable. 2 More than 220μm 2 The following is even more preferable: The average area of ​​the black parts is a value obtained by dividing the total area of ​​the black parts by the number of the black parts.

[0023] The black part when the photographed image is binarized may be derived from the glittering pigment described below. The white part when the photographed image is binarized may be derived from the resin material described below.

[0024] In the present disclosure, the optical microscope is, for example, "Digital Microscope VHX-500" manufactured by Keyence Corporation. In the present disclosure, the image analysis software is, for example, "Image J." In the present disclosure, the ISODATA method is a method for automatically determining a threshold value by utilizing the luminance distribution of an analysis image. Automatic threshold processing by the ISODATA method can be performed by a conventionally known method.

[0025] In the thermal transfer image receiving sheet of the present disclosure, the ratio is set to 0.10 or more and 0.52 or less, and the average area of ​​the black portion is set to 55 μm 2 More than 300μm 2 By making the following, it is possible to obtain a printed matter having excellent glitter, durability, and improved image visibility.

[0026] Since the resin layer of the thermal transfer image receiving sheet of the present disclosure contains a glittering pigment, in the binarized image, the black parts are generally derived from the glittering pigment, and the white parts are generally derived from the resin material.

[0027] By making the ratio 0.10 or more, the content of the glittering pigment in the printed matter can be maintained, so that a printed matter with excellent glitteriness can be obtained. Also, by making the ratio 0.52 or less, the content of the resin material in the resin layer in the printed matter can be maintained, so that a printed matter with excellent durability can be obtained. Also, by making the ratio 0.52 or less, a printed matter with excellent image visibility can be obtained.

[0028] The average area of ​​the black part is 55μm 2 By setting the average area of ​​the black portion to 300 μm or more, the size of the glittering pigment can be maintained, and the glittering pigment can contribute favorably to glittering, so that a print product with excellent glittering properties can be obtained. 2 By making the average area of ​​the black portions 300 μm or less, it is possible to suppress the occurrence of sparse portions of the resin material in the printed matter. In other words, the resin material of the resin layer in the printed matter can be uniformly dispersed, so that a printed matter having excellent durability can be obtained. 2 By setting the following, a printed matter having excellent image visibility can be obtained. Hereinafter, each layer included in the thermal transfer image receiving sheet of the present disclosure will be described.

[0029] (base material) As the substrate, for example, a paper substrate or a film made of a resin material (hereinafter simply referred to as a "resin film") can be used.

[0030] Examples of paper substrates include fine paper, art paper, coated paper, resin coated paper, cast coated paper, paperboard, synthetic paper, and impregnated paper.

[0031] Examples of resin materials constituting the resin film include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), 1,4-polycyclohexylene dimethylene terephthalate, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymers; polyamides such as nylon 6 and nylon 6,6; polyolefins such as polyethylene (PE), polypropylene (PP), and polymethylpentene; vinyl resins such as polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, and polyvinylpyrrolidone (PVP); (meth)acrylic resins such as polyacrylate and polymethacrylate; imide resins such as polyimide and polyetherimide; cellulose resins such as cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB); styrene resins such as polystyrene (PS); polycarbonate; and ionomer resins. The resin film may be a stretched film or an unstretched film.

[0032] In the present disclosure, "(meth)acrylic" is meant to encompass both "acrylic" and "methacrylic", and "(meth)acrylate" is meant to encompass both "acrylate" and "methacrylate".

[0033] Furthermore, a laminate made of two or more types of paper base materials, a laminate made of two or more types of resin films, or a laminate of a paper base material and a resin film can be used as the base material.

[0034] These laminates can be produced by utilizing a dry lamination method, a wet lamination method, an extrusion method, or the like.

[0035] The thickness of the substrate is preferably from 100 μm to 200 μm, and more preferably from 120 μm to 170 μm, which can further improve curl suppression of the printed matter.

[0036] (Resin layer) The resin layer includes a glittering pigment and a resin material. The ratio of the content of the bright pigment to the content of the resin material (PV ratio = content of bright pigment / content of resin material; by mass) is preferably from 0.5 to 4, and more preferably from 1 to 3. This can further improve the brightness of the thermal transfer image receiving sheet.

[0037] Examples of the luster pigment include metal pigments, pearl pigments, and coated pigments, and the like, with the coated pigments being preferred. In the present disclosure, the term "coated pigment" refers to particles in which a core material is coated with a coating material such as a metal or metal oxide. The resin layer may contain two or more types of luster pigments.

[0038] Examples of the metal pigment include particles composed of aluminum, iron, titanium, zirconium, silicon, cerium, nickel, chromium, brass, tin, brass, bronze, zinc, silver, platinum, gold, and oxides thereof.

[0039] Examples of pearl pigments include pigments in which a base material such as mica, which is a natural mineral, is coated with titanium oxide, fish scale powder, shell fragments, and pearl fragments.

[0040] The material constituting the core of the coated pigment may be an inorganic material or an organic material. Examples of inorganic materials include glass, aluminum, and alumina. Examples of the organic material include resin materials such as polyester, polyamide, polyolefin, vinyl resin, and (meth)acrylic resin. Among these, the material constituting the core is preferably an inorganic material, and particularly preferably glass, since it has little effect on the color of the metal to be coated and can further improve the brilliance of the thermal transfer image-receiving sheet.

[0041] The shape of the core material is not particularly limited, and may be spherical, needle-like, or scaly. Among these, the scaly shape is preferred from the viewpoint that the flatter the surface, the less diffuse reflection there is, and the stronger the brilliance can be obtained. The scaly shape is a flake-like shape. The aspect ratio (major axis / thickness) of the scaly core material is preferably 2 or more, more preferably 5 or more and 100 or less, and even more preferably 10 or more and 50 or less.

[0042] Examples of the coating material include aluminum, iron, titanium, zirconium, silicon, cerium, nickel, chromium, brass, tin, brass, bronze, zinc, silver, platinum, gold, and oxides thereof. Among these, silver is particularly preferred. By changing the coating material, it is possible to obtain various color tones. As the coating material, resin materials such as (meth)acrylic resin, polyolefin, vinyl resin, polyester, and polyamide may be used.

[0043] By using a coated pigment in which glass is coated with a coating material such as a metal or a metal oxide, the brilliance can be further improved, and by using a coated pigment in which glass is coated with silver, the brilliance can be further improved.

[0044] The shape of the glittering pigment is not particularly limited, and may be spherical, needle-like, or scaly. Among these, from the viewpoint of glittering, scaly is preferred. The scaly shape refers to a flake-like shape. The aspect ratio (major axis / thickness) of the scaly glittering pigment is preferably 2 or more, more preferably 5 or more and 100 or less, and even more preferably 10 or more and 50 or less.

[0045] The use of a coated pigment in which scaly glass is coated with a coating material such as a metal or metal oxide can improve the brilliance, and the use of a coated pigment in which scaly glass is coated with silver can improve the brilliance even further. For example, a coated pigment in which scaly glass is coated with a coating material can improve the brilliance even more than a coated pigment in which a scaly core material made of another inorganic material is coated with a coating material.

[0046] By using a first coated pigment in which natural mica or synthetic mica is coated with titanium oxide or the like in combination with a second coated pigment in which the first coated pigment is further coated with iron oxide, the resin layer can be made into a gold-toned layer.

[0047] The average particle size of the glittering pigment is preferably from 1 μm to 100 μm, more preferably from 7 μm to 40 μm, and even more preferably from 15 μm to 40 μm, which can further improve glittering while suppressing the occurrence of printing unevenness during image formation.

[0048] The average particle size of the luster pigment can be measured by the laser diffraction / scattering method. The particle size of the scaly particles is the light scattering equivalent diameter when the scaly particles are measured by the laser diffraction / scattering method. The light scattering equivalent diameter is defined as the diameter of a sphere that shows the closest light scattering pattern to the measured light scattering pattern of the particles and has the same refractive index as the particles.

[0049] The particle thickness of the glittering pigment is preferably 0.5 μm or more and 10 μm or less, which can further improve glittering while suppressing the occurrence of printing unevenness during image formation.

[0050] The particle thickness of the glittering pigment can be measured by extracting a predetermined number (preferably 100 or more) of scaly particles from the particle group to be measured and measuring their thickness using an electron microscope. The above-mentioned aspect ratio can also be measured by extracting a predetermined number (preferably 100 or more) of scaly particles from the particle group to be measured and measuring the major axis and thickness of each particle using an electron microscope.

[0051] The content of the bright pigment in the resin layer is preferably from 25% to 80% by mass, more preferably from 40% to 70% by mass, which can further improve the brightness while suppressing the occurrence of printing unevenness during image formation.

[0052] The coating of the core material can be formed, for example, by vapor deposition. Alternatively, commercially available coated pigments may be used.

[0053] Examples of the resin material include polyester, urethane resin, polyolefin, (meth)acrylic resin, polyamide, vinyl resin, cellulose resin, imide resin, and ionomer resin.

[0054] Among these, from the viewpoint of ensuring the expression of the luster of the bright pigment and the adhesion between layers, polyester or urethane resins are preferred, and urethane resins are more preferred. The resin layer may contain two or more types of resin materials.

[0055] The glass transition temperature (Tg) of the resin material is preferably from 40° C. to 100° C., and more preferably from 50° C. to 90° C. This can further improve the brilliance. In the present disclosure, Tg is a value determined by DSC (differential scanning calorimetry) in accordance with JIS K 7121.

[0056] The content of the resin material in the resin layer is preferably from 20% by mass to 75% by mass, and more preferably from 30% by mass to 60% by mass, which can improve the retention of the bright pigment.

[0057] The resin layer may contain additives, such as coloring materials, ultraviolet absorbing materials, plasticizers, coloring inhibitors, surfactants, matting materials, deodorants, flame retardants, weather resistant materials, thread friction reducing materials, slip materials, antioxidants, ion exchange materials, and dispersants.

[0058] In one embodiment, the resin layer contains a coloring material other than the glittering pigment. This allows the color of the thermal transfer image receiving sheet to be adjusted, the contrast with the glittering pigment to be improved, and glittering properties to be further improved. From the viewpoint of glittering properties, the coloring material is preferably a black pigment. Examples of black pigments include carbon black, acetylene black, lamp black, black smoke, iron black, and aniline black. Among them, carbon black is preferable.

[0059] The content of the coloring material other than the glittering pigment in the resin layer is preferably from 0.01% by mass to 0.3% by mass, more preferably from 0.02% by mass to 0.2% by mass, which can improve the glittering properties.

[0060] The thickness of the resin layer is preferably from 1 μm to 10 μm, and more preferably from 1.5 μm to 4 μm, which can further improve the brilliance.

[0061] The ratio of the thickness of the resin layer to the particle thickness of the glittering pigment (resin layer thickness / glittering pigment particle thickness) is preferably 1 to 10, more preferably 1.5 to 5. This can further improve glittering properties. Also, the ease of forming the resin layer can be improved.

[0062] The resin layer can be formed by dispersing or dissolving the above-mentioned materials in a suitable solvent to prepare a coating solution, applying the solution to a substrate to form a coating film, and drying the coating film. Known coating methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, and rod coating can be used. From the viewpoint of brilliance, it is preferable to disperse the bright pigment for 30 minutes to 1 hour using a paint shaker. If the bright pigment is dispersed for more than 1 hour, the particle size may become small, resulting in reduced brilliance.

[0063] The resin layer can also be formed on the substrate by melt-extruding a resin composition containing a bright pigment, a resin material, and the like.

[0064] (Receptive layer) The receiving layer includes at least one resin material, such as polyolefin, vinyl resin, (meth)acrylic resin, cellulose resin, polyester, polyamide, polycarbonate, polystyrene, urethane resin, and ionomer resin.

[0065] The content of the resin material in the receiving layer is preferably from 80% by mass to 98% by mass, and more preferably from 90% by mass to 98% by mass.

[0066] In one embodiment, the receptor layer contains at least one release agent, which can improve releasability from the thermal transfer sheet during image formation.

[0067] Examples of the release agent include solid waxes, surfactants, silicone oils, and silicone resins.

[0068] Examples of solid waxes include polyethylene wax, amide wax, and Teflon (registered trademark) powder.

[0069] Examples of the surfactant include fluorine-based surfactants and phosphate-based surfactants.

[0070] Examples of silicone oils include amino-modified silicone, epoxy-modified silicone, aralkyl-modified silicone, epoxy-aralkyl-modified silicone, alcohol-modified silicone, vinyl-modified silicone, and urethane-modified silicone.

[0071] The receiving layer may contain the additive described above.

[0072] The thickness of the receiving layer is preferably from 0.5 μm to 20 μm, more preferably from 1.0 μm to 10 μm, which can improve the density of the image formed on the receiving layer.

[0073] The receiving layer can be formed by dispersing or dissolving the above-mentioned materials in an appropriate solvent to prepare a coating liquid, applying this onto the resin layer or primer layer by the above-mentioned coating means to form a coating film, and drying this.

[0074] (Middle class) In one embodiment, the thermal transfer image receiving sheet includes an intermediate layer containing a colorant and a resin material between the substrate and the resin layer, which allows the color of the thermal transfer image receiving sheet to be adjusted, the contrast with the glittering pigment to be improved, and the glittering properties to be further improved.

[0075] Examples of coloring materials include carbon black, acetylene black, lamp black, black smoke, iron black, aniline black, silica, calcium carbonate, titanium oxide, cadmium red, cadmium phosphate red, chrome red, vermilion, red iron oxide, azo pigments, alizarin lake, quinacridone, cochineal lake perylene, yellow ocher, aureolin, cadmium yellow, cadmium orange, chrome yellow, zinc yellow, Naples yellow, nickel yellow, azo pigments, greenish yellow, ultramarine, rock ultramarine, cobalt, phthalocyanine, anthraquinone, indicoid, cinnabar green, cadmium green, chrome green, phthalocyanine, azomethine, perylene, and aluminum pigments. The intermediate layer may contain two or more types of coloring materials.

[0076] The content of the coloring material in the intermediate layer is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 0.2% by mass or less, and even more preferably 0.015% by mass or more and 0.1% by mass or less. This can improve the brilliance. In one embodiment, the content of the coloring material in the intermediate layer may be 0.01% by mass or more and 70% by mass or less.

[0077] Examples of the resin material include polyolefin, vinyl resin, (meth)acrylic resin, cellulose resin, polyester, polyamide, polycarbonate, polystyrene, urethane resin, and ionomer resin.

[0078] Among these, urethane resins and polyesters are preferred from the viewpoint of ensuring the expression of the luster of the luster pigment and the adhesion between layers.

[0079] The content of the resin material in the intermediate layer is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less. This allows the glittering property of the bright pigment to be expressed while ensuring adhesion between the layers. In one embodiment, the content of the resin material in the intermediate layer may be 10% by mass or more and 99.9% by mass or less.

[0080] The intermediate layer may include the additive described above.

[0081] The thickness of the intermediate layer is preferably from 0.1 μm to 5 μm, and more preferably from 0.3 μm to 1.5 μm, which can further improve the brilliance.

[0082] The intermediate layer can be formed by dispersing or dissolving the above-mentioned materials in an appropriate solvent to prepare a coating liquid, applying this onto the substrate by the above-mentioned coating means to form a coating film, and drying this.

[0083] (Primer layer) In one embodiment, the thermal transfer image receiving sheet includes a primer layer between the resin layer and the receiving layer, which can improve adhesion between the layers.

[0084] The primer layer contains at least one resin material, such as polyester, urethane resin, polycarbonate, (meth)acrylic resin, styrene resin, vinyl resin, and cellulose resin. The primer layer may also contain the above-mentioned additive.

[0085] The thickness of the primer layer is, for example, not less than 0.1 μm and not more than 3 μm.

[0086] The primer layer can be formed by dispersing or dissolving the above-mentioned materials in an appropriate solvent to prepare a coating liquid, applying this to the resin layer by the above-mentioned coating means to form a coating film, and drying this.

[0087] (Printed matter) The printed matter 20 of the present disclosure is produced using the thermal transfer image receiving sheet 10, and as shown in FIG. 4, comprises a substrate 11, a resin layer 12, and a receiving layer 13 on which an image is formed.

[0088] In one embodiment, the print 20 includes a protective layer 21 on the receiving layer 13 as shown in FIG.

[0089] (image) In the print of the present disclosure, an image is formed on the receiving layer. Examples of the image forming method include a dye-sublimation type thermal transfer recording method and a melting type thermal transfer recording method. The image is not particularly limited and may be a photograph, a character, a pattern, a symbol, or a combination thereof.

[0090] (protective layer) In one embodiment, the print includes a protective layer on the receiving layer, which can significantly improve the scratch resistance and storage stability of the image formed on the receiving layer.

[0091] The protective layer contains at least one resin material, such as (meth)acrylic resin, styrene resin, vinyl resin, polyolefin, polyester, polyamide, imide resin, cellulose resin, thermosetting resin, and actinic radiation curing resin.

[0092] In the present disclosure, the term "actinic radiation curable resin" refers to a resin in a cured state obtained by irradiating an actinic radiation curable resin with actinic radiation.

[0093] In addition, in the present disclosure, "actinic rays" refers to radiation that chemically acts on an actinic ray-curable resin to promote polymerization, and specifically refers to visible light, ultraviolet light, X-rays, electron beams, α-rays, β-rays, γ-rays, etc.

[0094] The content of the resin material in the protective layer is not particularly limited, but from the viewpoint of the scratch resistance and storage stability of the image, it is preferably from 50% by mass to 95% by mass.

[0095] The protective layer may contain the additive described above.

[0096] The thickness of the protective layer is preferably from 3 μm to 10 μm, and more preferably from 5 μm to 10 μm, which can further improve the scratch resistance and storage stability of the image.

[0097] (Manufacturing method of prints) The method for producing a print according to the present disclosure includes: preparing the thermal transfer image receiving sheet; forming an image on a receptor layer of a thermal transfer image receptor sheet; and forming a protective layer on the receiving layer.

[0098] Each step included in the method for producing a print product will be described below. Note that the step of preparing the thermal transfer image receiving sheet has been described above, so a description thereof will be omitted here.

[0099] (image forming process) The image can be formed by, for example, a conventionally known dye-sublimation type thermal transfer recording method or a melting type thermal transfer recording method.

[0100] (Protective layer formation process) The protective layer can be formed, for example, by transferring the protective layer from a thermal transfer sheet.

[0101] The thermal transfer sheet may be heated uniformly or non-uniformly during the transfer of the protective layer. By heating the thermal transfer sheet uniformly, the glossiness of the printed matter can be improved. By heating the thermal transfer sheet non-uniformly, the matteness of the printed matter can be improved.

[0102] An embodiment of the thermal transfer image receiving sheet, the print, and the method for producing the print of the present disclosure will be described below. Note that the thermal transfer image receiving sheet, the print, and the method for producing the print of the present disclosure are not limited to these embodiments.

[0103] The thermal transfer image receiving sheet of the present disclosure includes a substrate, a resin layer, and a receiving layer, The resin layer includes a glittering pigment and a resin material.

[0104] In one embodiment, the glitter pigment is a coated pigment comprising a core material and a coating material coating the core material.

[0105] In one embodiment, the core material is glass and the cladding material is silver.

[0106] In one embodiment, the average particle size of the glitter pigment is 1 μm or more and 100 μm or less.

[0107] In one embodiment, the particle thickness of the glitter pigment is from 0.5 μm to 10 μm.

[0108] In one embodiment, the ratio of the thickness of the resin layer to the particle thickness of the glittering pigment (thickness of the resin layer / thickness of the glittering pigment particle) is 1 or more and 10 or less.

[0109] In one embodiment, the resin material contained in the resin layer is at least one of a polyester resin and a urethane resin.

[0110] In one embodiment, the thermal transfer image receiving sheet includes an intermediate layer containing a colorant and a resin material between the substrate and the resin layer.

[0111] In one embodiment, the L value measured from the surface side of the receptor layer of the thermal transfer image-receiving sheet is 55 or more and 95 or less.

[0112] In one embodiment, an optical microscope is used to photograph the thermal transfer image receiving sheet from the receiving layer side at a magnification of 500 times to obtain an 8-bit grayscale photographed image, the photographed image is analyzed using image analysis software, the light and dark of the obtained analysis image are inverted, and automatic threshold processing is performed by the ISODATA method to determine a threshold value for the luminance distribution in the analysis image, and binarization is performed to binarize the area below the threshold into black and the area above the threshold into white. The number and total area of ​​the black parts, and the total area of ​​the white parts are obtained, and the ratio of the total area of ​​the black parts to the total area of ​​the white parts is 0.10 or more and 0.52 or less, and the average area of ​​the black parts is 55 μm 2 More than 300μm2 The following is the result.

[0113] The print of the present disclosure is a print produced using the thermal transfer image receiving sheet, An image is formed on the receiving layer.

[0114] The method for producing a print product according to the present disclosure includes the steps of: preparing the thermal transfer image receiving sheet; forming an image on a receptor layer of a thermal transfer image receptor sheet; and forming a protective layer on the receiving layer. EXAMPLES

[0115] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples. In addition, unless otherwise specified, the contents, mixing ratios, etc. are based on mass.

[0116] Example 1 As a substrate, a 36 μm thick porous PP film (Mitsui Chemicals Tohcello Co., Ltd., SP-U) was coated with a coating liquid for adhesive layer having the following composition and dried, and non-coated paper (Kitakami High-Tech Paper Co., Ltd., Non-coated K-156, thickness 156 μm) was laminated through the adhesive layer to prepare a substrate. A coating liquid 1 for resin layer having the following composition was coated on the surface of this porous PP film and dried to form a resin layer having a thickness of 2 μm.

[0117] (Coating liquid for adhesive layer) Polyol resin 30 parts by weight (Takelac (registered trademark) A-969V, manufactured by Mitsui Chemicals, Inc.) Isocyanate compound 10 parts by weight (Takenate (registered trademark) A-5, manufactured by Mitsui Chemicals, Inc.) Ethyl acetate 60 parts by weight

[0118] (Resin layer coating liquid 1) Silver-coated glass flake A 26.4 parts by weight (Nippon Sheet Glass Co., Ltd., Metashine (registered trademark) ST1018PSR1, average particle size 18 μm, particle thickness 1 μm) Urethane resin A 44.1 parts by weight (Tosoh Corporation, Nipporan (registered trademark) 5253, solid content 30%) Methyl ethyl ketone (MEK) 6.5 parts by weight Normal propyl acetate (NPAC) 21.3 parts by weight

[0119] A coating solution for the receiving layer having the following composition was applied onto the resin layer, and dried to form a receiving layer having a thickness of 4 μm, thereby obtaining a thermal transfer image receiving sheet. The L value of the thermal transfer image receiving sheet was measured using a spectrophotometer (X-Rite, i1Pro2) and found to be 83.09. The same measurement was performed in the following examples, and the results are shown in Table 2.

[0120] (Coating solution for receiving layer) Vinyl chloride-vinyl acetate copolymer 12 parts by weight (Nissin Chemical Industry Co., Ltd., Solvine (registered trademark) C) Epoxy modified silicone 0.8 parts by weight (Shin-Etsu Chemical Co., Ltd., X-22-3000T) Amino-modified silicone 0.24 parts by weight (Shin-Etsu Chemical Co., Ltd., X-22-1660B-3) Toluene 30 parts by weight ·MEK 30 parts by mass

[0121] Test Example 2, Examples 3 to 6 A thermal transfer image-receiving sheet was produced in the same manner as in Example 1, except that the structure of the resin layer was changed as shown in Table 1.

[0122] The details of the materials used are as follows: Titanium oxide coated glass flakes: Nippon Sheet Glass Co., Ltd., Metashine (registered trademark) GT1030RSR1, average particle diameter 30 μm, particle thickness 1 μm Silver-coated glass flake B: Metashine (registered trademark) ST1018RSR1, manufactured by Nippon Sheet Glass Co., Ltd., average particle diameter 30 μm, particle thickness 1 μm Polyester: Toyobo Co., Ltd., Vylonal (registered trademark) MD1480, solid content ratio 25%

[0123] Example 7 An intermediate layer coating solution 1 having the following composition was applied to one surface of the substrate and dried to form an intermediate layer having a thickness of 2 μm. On this intermediate layer, a resin layer and a receptor layer were formed in the same manner as in Example 1 to obtain a thermal transfer image-receiving sheet.

[0124] (Intermediate layer coating solution 1) Urethane resin A 20 parts by weight · Bright pigment 10 parts by mass (Aluminum pigment (acrylic coating), average particle size 10μm) Toluene 75 parts by weight ·MEK 75 parts by mass

[0125] Examples 8 to 10 A thermal transfer image-receiving sheet was produced in the same manner as in Example 7, except that the constitution of the resin layer was changed as shown in Table 1.

[0126] Example 11 A thermal transfer image receiving sheet was produced in the same manner as in Example 7, except that the composition of the resin layer was changed as shown in Table 1 and intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 2 having the following composition.

[0127] (Intermediate layer coating fluid 2) Urethane resin A 31.9 parts by weight Carbon black (CB) 0.02 parts by weight ·MEK 59.4 parts by mass ·NPAC 8.1 parts by mass Isopropyl alcohol (IPA) 0.01 parts by weight

[0128] Example 12 A thermal transfer image receiving sheet was produced in the same manner as in Example 7, except that the composition of the resin layer was changed as shown in Table 1 and intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 3 having the following composition.

[0129] (Intermediate layer coating fluid 3) Urethane resin A 31.9 parts by weight Carbon black (CB) 1 part by weight ·MEK 59.4 parts by mass ·NPAC 8.1 parts by mass ·IPA 0.01 parts by mass

[0130] Test Example 13 A thermal transfer image-receiving sheet was produced in the same manner as in Example 7, except that the composition of Coating Solution 1 for Resin Layer was changed to Coating Solution 2 for Resin Layer below.

[0131] (Resin layer coating liquid 2) Silver-coated glass flake A 12 parts by weight Urethane resin A 20 parts by weight Carbon black (CB) 0.02 parts by weight ·MEK 59.4 parts by mass ·NPAC 8.1 parts by mass ·IPA 0.01 parts by mass

[0132] Test Example 14 A thermal transfer image-receiving sheet was produced in the same manner as in Example 1, except that the composition of Coating Fluid 1 for Resin Layer was changed to Coating Fluid 2 for Resin Layer.

[0133] Test Example 15 test A white solid image was formed on the receiving layer of the thermal transfer image receiving sheet of Example 14 using a dye-sublimation thermal transfer printer (DS620, manufactured by Dai Nippon Printing Co., Ltd.) and a genuine ribbon for the printer, to obtain a printout of 152.4 mm length x 203.2 mm width. The transfer of the protective layer was performed by setting the printer to gloss mode, and the image gradation of the white solid image was 0 / 255 gradation.

[0134] Test Example 16 Other than changing the transfer of the protective layer to matte mode, test A print was obtained in the same manner as in Example 15.

[0135] Test Example 17 A thermal transfer image receiving sheet was produced in the same manner as in Example 1, except that Resin Layer Coating Solution 3 having the following composition was applied instead of Resin Layer Coating Solution 1 and dried to form a resin layer having a thickness of 1.5 μm.

[0136] (Resin layer coating liquid 3) Acrylic resin coated aluminum pigment 19.8 parts by weight (Average particle size 10μm) Urethane resin A 44.1 parts by weight (Tosoh Corporation, Nipporan (registered trademark) 5253, solid content 30%) ·MEK 6.5 parts by mass ·NPAC 21.3 parts by mass

[0137] Test Example 18 A thermal transfer image receiving sheet was produced in the same manner as in Example 1, except that Resin Layer Coating Solution 4 having the following composition was applied instead of Resin Layer Coating Solution 1, and then dried to form a resin layer having a thickness of 2 μm.

[0138] (Resin layer coating liquid 4) Titanium oxide-coated silver pearl mica pigment: 26.4 parts by weight (Merck Co., Ltd., Iriodin (registered trademark) 123, Bright Luster Satin Average particle size 13μm) Urethane resin A 44.1 parts by weight (Tosoh Corporation, Nipporan (registered trademark) 5253, solid content 30%) ·MEK 6.5 parts by mass ·NPAC 21.3 parts by mass

[0139] Test Example 19 A thermal transfer image receiving sheet was produced in the same manner as in Example 1, except that Resin Layer Coating Solution 5 having the following composition was applied instead of Resin Layer Coating Solution 1 and dried to form a resin layer having a thickness of 2 μm.

[0140] (Resin layer coating liquid 5) Titanium oxide-coated silver pearl mica pigment: 26.4 parts by weight (TWINCLEPEARL (registered trademark) 200, manufactured by Nihon Koken Kogyo Co., Ltd., average particle size 13 μm, particle thickness 0.5 μm) Urethane resin A 44.1 parts by weight (Tosoh Corporation, Nipporan (registered trademark) 5253, solid content 30%) ·MEK 6.5 parts by mass ·NPAC 21.3 parts by mass

[0141] Reference example 1 A thermal transfer image-receiving sheet was produced in the same manner as in Example 1, except that the composition of the resin layer coating liquid was changed to the following resin layer coating liquid 6.

[0142] (Resin layer coating liquid 6) Urethane resin A 40 parts by weight Titanium oxide 24 parts by weight (TCA888, manufactured by Tochem Products Co., Ltd.) ·MEK 76 parts by mass Toluene 76 parts by weight

[0143] <<Spectral reflectance measurement>> Working Example , Test Example and reference The spectral reflectance R of the thermal transfer image receiving sheet and the print of the example was measured in accordance with JIS Z 8722:2000.

[0144] Specifically, a spectroscopic variable angle colorimeter (GC2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the , Test Example and referenceThe spectral reflectance R of the wavelength region of 400 nm to 700 nm (at 20 nm intervals) at the regular reflection receiving angle when light was incident at an incident angle of 45° on the receiving layer of the example thermal transfer image receiving sheet and the protective layer of the print was measured and averaged. The results are shown in Table 2.

[0145] As above, Example , Test Example and reference The minimum spectral reflectance R1 and maximum spectral reflectance R2 in the wavelength range of 400 nm to 700 nm at the regular reflection receiving angle when light was incident at an incident angle of 45° on the receiving layer of the example thermal transfer image receiving sheet and the protective layer of the print were measured, and R1 / R2 was calculated. The results are shown in Table 2.

[0146] <<Image acquisition and image analysis>> The thermal transfer image receiving sheet obtained in Example 4 was photographed from the receiving layer side at a magnification of 500 times using an optical microscope to obtain an 8-bit grayscale photographed image (FIG. 5). The optical microscope used was a digital microscope VHX-500 manufactured by Keyence Corporation.

[0147] Next, the captured images were analyzed using image analysis software, the brightness of the resulting analysis image was inverted, and the threshold of the brightness distribution in the analysis image was determined by automatic threshold processing using the ISODATA method, and the image was binarized as black for areas below the threshold and white for areas above the threshold (Figure 6), and the number and total area of ​​black areas, as well as the total area of ​​white areas, were obtained. ImageJ was used as the image analysis software.

[0148] From these data, the ratio of the total area of ​​the black areas to the total area of ​​the white areas and the average area of ​​the black areas were calculated. The calculation results are shown in Table 2. test Example 2 , Examples 3 to 16, Test Example 17 ~19 and reference Similarly, the ratio of the total area of ​​the black parts to the total area of ​​the white parts and the average area of ​​the black parts were calculated for Example 1. The calculation results are shown in Table 2.

[0149] <<Brilliance evaluation>> Working Example , Test Example and referenceThe receiving layer surface of the thermal transfer image receiving sheet of the example and the protective layer surface of the print were visually observed and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2. The glittering shine refers to a shine such as a sparkle or glint that is caused by the particle size and distribution of the glittering material, the reflection characteristics, and the orientation conditions.

[0150] (Evaluation Criteria) A: Has a very good sparkling shine B: Has a good sparkling shine C: Has a somewhat good sparkling shine D: Has a sparkling shine E: Does not have a sparkling shine

[0151] [Table 1]

[0152] [Table 2] [Explanation of symbols]

[0153] 10: thermal transfer image receiving sheet, 11: substrate, 12: resin layer, 13: receiving layer, 14: intermediate layer, 20: print, 21: protective layer

Claims

1. The present invention includes a substrate, a resin layer, and a receiving layer, the resin layer contains a glittering pigment, a resin material, and carbon black, The bright pigment is a coated pigment having a core material and a coating material that coats the core material, A thermal transfer image-receiving sheet, wherein the core material is glass and the covering material is silver.

2. 2. The thermal transfer image receiving sheet according to claim 1, wherein the average particle size of the glittering pigment is from 1 [mu]m to 100 [mu]m.

3. 3. The thermal transfer image receiving sheet according to claim 1, wherein the particle thickness of the glittering pigment is from 0.5 to 10 [mu]m.

4. The thermal transfer image receiving sheet according to any one of claims 1 to 3, wherein the ratio of the thickness of the resin layer to the particle thickness of the glittering pigment (resin layer thickness / glittering pigment particle thickness) is 1 or more and 10 or less.

5. 5. The thermal transfer image receiving sheet according to claim 1, wherein the resin material contained in the resin layer is at least one of a polyester and a urethane resin.

6. 6. The thermal transfer image receiving sheet according to claim 1, further comprising an intermediate layer between the substrate and the resin layer, the intermediate layer containing a coloring material and a resin material.

7. 7. The thermal transfer image receiving sheet according to claim 1, wherein an L value measured from the surface side of the receiving layer is 55 or more and 95 or less.

8. The thermal transfer image receiving sheet is photographed from the receiving layer side at a magnification of 500 times using an optical microscope to obtain an 8-bit grayscale photographed image, the photographed image is analyzed using image analysis software, the brightness of the obtained analysis image is inverted, and an automatic threshold processing is performed by the ISODATA method to determine a threshold value for the brightness distribution in the analysis image, and the image is binarized to black for values ​​below the threshold and white for values ​​equal to or above the threshold. The number and total area of ​​the black parts, and the total area of ​​the white parts are obtained. a ratio of a total area of ​​the black portions to a total area of ​​the white portions is 0.10 or more and 0.52 or less; The average area of ​​the black portion is 55 μm ２ 300 μm or more ２ Below is the The thermal transfer image receiving sheet according to any one of claims 1 to 7.

9. A print produced by using the thermal transfer image receiving sheet according to any one of claims 1 to 8, A print having an image formed on the receptor layer.

10. A step of preparing a thermal transfer image receiving sheet according to any one of claims 1 to 8; forming an image on a receptor layer of the thermal transfer image receptor sheet; forming a protective layer on the receiving layer; A method for producing a printed matter comprising the steps of:

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