JP2020199686A - Laminate, combination of laminate and thermal transfer sheet, combination of laminate, thermal transfer sheet, and intermediate transfer medium, and printed matter - Google Patents

Abstract

To provide a laminate that allows a printed matter with an image having stereoscopic and floating feels formed thereon to be created on demand.SOLUTION: A laminate has a first base material, a mirror layer, and a transparent resin layer and has a mirror reflectivity of 60% or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate, a combination of a laminate and a thermal transfer sheet, a combination of a laminate, a thermal transfer sheet and an intermediate transfer medium, and a printed matter.

Conventionally, a sublimation thermal transfer method and a thermal melt transfer method are known as methods for producing a printed matter.
In the sublimation type thermal transfer method, a thermal transfer sheet having a colored layer containing a sublimation dye and a transfer target are superposed, and heat is applied to the thermal transfer sheet to transfer the sublimation dye to the transfer target (sublimation transfer). ), Form an image, and obtain a print.
Further, in the heat melt transfer method, a heat transfer sheet having a colored layer containing a coloring material and a resin material and a transferred body are superposed, and heat is applied to the heat transfer sheet to make the colored layer into the transferred body. It is a method of transferring, forming an image, and obtaining a printed matter.

Further, as another method for producing a printed matter, a substrate, a receiving layer of an intermediate transfer medium having a receiving layer, and a colored layer of a thermal transfer sheet having a colored layer containing a sublimation dye are superposed on the thermal transfer sheet. Heat is applied to sublimate and transfer the sublimation dye to the receiving layer to form an image, and then the receiving layer of the intermediate transfer medium and the transferee are superposed and heat is applied to the intermediate transfer medium. A method is known in which a receiving layer on which an image is formed is transferred to a transfer target to obtain a printed matter.

In recent years, a wide variety of design properties are required for the printed matter thus obtained. For example, in Patent Document 1, a plurality of metallic luster images are laminated to give a three-dimensional effect to the image, and the printed image is printed. The design of things is being improved.

However, the photographic paper proposed in Patent Document 1 needs to have a metallic luster layer provided in a plurality of layers in advance, and is not suitable for on-demand production of a photographic paper in which an image having a three-dimensional effect is formed. There wasn't.

Japanese Unexamined Patent Publication No. 2018-34326

The present invention has been made in view of the above problems, and an object to be solved is to provide a laminated body capable of producing a printed matter on which an image having a three-dimensional effect is formed on demand. ..
Another object to be solved by the present invention is to provide a combination of the laminate and the thermal transfer sheet, and a combination of the laminate, the thermal transfer sheet and the intermediate transfer medium.
Further, an object to be solved by the present invention is to provide a printed matter having a high design property by forming an image having a three-dimensional effect produced by using this laminated body.

The laminate of the present invention includes a first base material, a mirror layer, and a transparent resin layer.
It is characterized by having a specular reflectance of 60% or more.

In one embodiment, the thickness of the transparent resin layer is 50 μm or more and 3000 μm or less.

In one embodiment, the transparent resin layer has a visible light transmittance of 50% or more.

The combination of the laminate and the thermal transfer sheet of the present invention is a combination of the laminate and the thermal transfer sheet, and the thermal transfer sheet includes a second base material and an ink layer.

In one embodiment, the lightness L ^* of the ink layer is 50 or less.

In one embodiment, the thermal transfer sheet has a colored layer so that it is surface-sequential with the ink layer.
An underlayer is further provided between the ink layer and the colored layer in a surface-sequential manner, or between the second base material and the ink layer.

In one embodiment, the visible light transmittance of the ink layer is less than 50%.

In one embodiment, the concealment rate of the underlying layer is 50% or more.

The combination of the laminate of the present invention, the thermal transfer sheet, and the intermediate transfer medium is
A combination of the above laminate, a thermal transfer sheet, and an intermediate transfer medium.
The thermal transfer sheet is the second base material and
The intermediate transfer medium is characterized by including a third base material and a transfer layer.

The printed matter of the present invention includes a first base material, a mirror layer, a transparent resin layer, an ink layer, a receiving layer on which an image is formed, or a colored layer on which an image is formed.
The laminate composed of the base material, the mirror layer and the transparent resin layer has a specular reflectance of 60% or more.

In one embodiment, the position where the ink layer is formed and the position of the image are shifted in the horizontal direction.

In one embodiment, the ink layer has the same or similar shape to the image.

According to the present invention, it is possible to provide a laminated body capable of producing a printed matter on which an image having a three-dimensional effect is formed on demand.
Further, the problem to be solved by the present invention can provide a combination of the laminate and the thermal transfer sheet, and a combination of the laminate, the thermal transfer sheet and the intermediate transfer medium.
Further, according to the present invention, it is possible to provide an image having a three-dimensional effect and a printed matter having a high degree of design.

It is a schematic cross-sectional view which shows one Embodiment of the laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the thermal transfer sheet which constitutes the combination of the laminated body of this invention and a thermal transfer sheet. It is a schematic cross-sectional view which shows one Embodiment of the thermal transfer sheet which constitutes the combination of the laminated body of this invention and a thermal transfer sheet. It is a schematic cross-sectional view which shows one Embodiment of the thermal transfer sheet which constitutes the combination of the laminated body of this invention, a thermal transfer sheet, and an intermediate transfer medium. It is a schematic cross-sectional view which shows one Embodiment of the intermediate transfer medium which constitutes the combination of the laminated body of this invention, a thermal transfer sheet, and an intermediate transfer medium. It is a schematic cross-sectional view which shows one Embodiment of the intermediate transfer medium which constitutes the combination of the laminated body of this invention, a thermal transfer sheet, and an intermediate transfer medium. It is a schematic cross-sectional view which shows one Embodiment of the intermediate transfer medium which constitutes the combination of the laminated body of this invention, a thermal transfer sheet, and an intermediate transfer medium. It is a front view which shows one Embodiment of the printed matter of this invention. FIG. 5 is a schematic cross-sectional view taken along the line AA of the printed matter of FIG. It is a schematic cross-sectional view which shows one Embodiment of the printed matter of this invention. It is a schematic cross-sectional view which shows one Embodiment of the printed matter of this invention.

(Laminate)
As shown in FIG. 1, the laminate 10 of the present invention includes a first base material 11, a mirror layer 12 on the first base material, and a transparent resin layer 13 on the mirror layer 12.

The laminate of the present invention is characterized in that its specular reflectance is 60% or more.
As a result, an image of the ink layer formed on the transparent resin layer is formed in the mirror layer by using the thermal transfer sheet or the intermediate transfer medium described later. Therefore, when an image is formed on the ink layer, this image can be seen behind the image, giving a three-dimensional effect to the image and improving the design of the printed matter. Further, as will be described later, by adjusting the brightness L ^* or the like of the ink layer, it is possible to give a floating feeling to the formed image in addition to the stereoscopic effect.
In the present invention, the specular reflectance of the laminated body is determined by irradiating light from the transparent resin layer side at an incident angle of 45 ° using a color change colorimeter (GC-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.). Especially to measure.

Hereinafter, each layer included in the laminate of the present invention will be described.

(1st base material)
As the first base material, paper base materials such as high-quality paper, art paper, coated paper, resin coated paper, cast coated paper, paperboard, synthetic paper and impregnated paper, polyethylene terephthalate (PET), polyvinyl terephthalate (PBT), etc. Polyvinyl naphthalate (PEN), 1,4-polycyclohexylene methylene terephthalate, ethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer and other polyesters, nylon 6 and nylon 6,6 Polyamide, polyethylene (PE), polypropylene (PP), polyolefins such as polymethylpentene, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. , Acetalized PVA (vinylone), vinyl chloride-vinyl acetate copolymer and vinyl resin such as polyvinylpyrrolidone (PVP), polyvinyl acetal such as polyvinylacetacetal and polyvinylbutyral, poly (meth) acrylate, poly (meth) acrylate, (Meta) acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate and polybutyl (meth) acrylate, imide resins such as polyimide and polyetherimide, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP) ), Cellulose triacetate, and cellulose resin such as cellulose acetate butyrate (CAB), styrene resin such as polystyrene (PS), polyarylate, polycarbonate, biodegradable aliphatic polyester, biodegradable polycarbonate, biodegradable polylactic acid. , A film composed of a biodegradable resin such as biodegradable polyvinyl alcohol, biodegradable cellulose acetate, biodegradable polycaprolactone, and a resin material such as ionomer resin (hereinafter, simply referred to as "resin film") can be used. ..

The first base material is preferably a resin film because it has high smoothness and can further improve the stereoscopic effect and floating feeling of the formed image.
The resin film may be a stretched film, an unstretched film, a uniaxially stretched film, or a biaxially stretched film. Further, as the base material, a laminate of the above-mentioned materials can also be used.
In the present invention, "(meth) acrylic" includes both "acrylic" and "methacryl".
Further, in the present invention, "(meth) acrylate" includes both "acrylate" and "methacrylate".

In one embodiment, the first base material can be a laminate of the above resin films. The resin film can be laminated by using, for example, conventionally known methods such as a dry laminating method, a wet laminating method, and a hot laminating method.
Further, for the purpose of improving the adhesion between the adjacent layers and the laminated resin films, it is preferable that the resin films are subjected to surface treatment such as primer treatment and corona discharge treatment.

The thickness of the first base material is not particularly limited and is preferably changed as appropriate depending on the intended use, but may be, for example, 1 μm or more and 3000 μm or less. Preferably, it is 500 μm or more and 1500 μm or less.
Further, it is preferable that the amount of deflection measured according to the bending strength test specified in JIS X 6305-1 of the first base material is 50 mm or less. As a result, the first base material can satisfactorily hold the mirror layer and prevent the occurrence of deflection in the mirror layer, so that a printed matter in which an image having a high three-dimensional effect is formed can be obtained.

(Mirror layer)
The laminate of the present invention is provided with a mirror layer on the first base material, and the mirror layer may be provided on the entire surface of the first base material, and the first base material may be provided according to the shape of the image to be formed or the like. It may be provided in a part. Further, when it is provided on a part of the first base material, it may be shaped according to the shape of the formed image.

The configuration of the mirror layer is not particularly limited as long as the specular reflectance can be achieved. In one embodiment, the mirror layer comprises metals such as aluminum, indium, magnesium, tin, sodium, titanium, zirconium, lead, yttrium, gold and chromium, as well as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide. It can be a vapor-deposited film composed of inorganic oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide.
Examples of the method for forming the vapor deposition layer include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, and a thermochemical vapor deposition method. Examples include a chemical vapor deposition method (CVD method, CVD method) such as a phase growth method and a photochemical vapor deposition method.

In one embodiment, the mirror layer is formed by a coating liquid containing a metal pigment. Examples of the metal pigment include aluminum, nickel, chromium, brass, tin, brass, bronze, zinc, silver, platinum, gold and oxides thereof, and particles such as glass subjected to metal deposition. Further, in such a form, the mirror layer may contain the above-mentioned resin material and additive.
Such a mirror layer is known as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method, a rod coating method, or the like by dispersing or dissolving the above material in water or an appropriate solvent. It can be formed by applying it on the first base material to form a coating film and drying it.

The thickness of the mirror layer is preferably changed as appropriate according to its configuration, but can be, for example, 0.01 μm or more and 100 μm or less.

(Transparent resin layer)
The laminate of the present invention preferably has a transparent resin layer on the mirror layer, and the visible light transmittance of the transparent resin layer is 50% or more.
In the present invention, the visible light transmittance of the transparent resin layer is measured at 520 to 670 nm using an ultraviolet visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation).
The visible light transmittance of the transparent resin layer may be measured on the transparent resin layer before lamination or on the transparent resin layer peeled from the laminate of the present invention.

The structure of the transparent resin layer is not particularly limited as long as the visible light transmittance can be achieved, and a structure including the resin material, for example, the resin film described above can be used.

Further, the transparent resin layer may contain additives such as filler, plastic material, antistatic material, ultraviolet absorber, inorganic particles, organic particles, mold release material and dispersant as long as the characteristics of the present invention are not impaired. it can.
Further, the transparent resin layer can contain a coloring material such as a pigment or a dye as long as the visible light transmittance can be achieved.

The thickness of the transparent resin layer is preferably 50 μm or more and 3000 μm or less, more preferably 90 μm or more and 1000 μm or less, and further preferably 130 μm or more and 800 μm or less. As a result, the stereoscopic effect and the floating feeling of the formed image can be further enhanced, and the design of the printed matter can be further improved.

The transparent resin layer can be formed by laminating a resin film on the mirror layer via a conventionally known adhesive. Further, the transparent resin layer is obtained by dispersing or dissolving the above resin material in water or an appropriate solvent, and using a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method, a rod coating method, or the like. It can also be formed by applying it on a mirror layer to form a coating film by a known means and drying the coating film.

(Combination of laminate and thermal transfer sheet)
The combination of the laminate of the present invention and the thermal transfer sheet is composed of the laminate and a thermal transfer sheet including a second base material and an ink layer having a visible light transmittance of less than 50%.
Since the laminates constituting the combination of the present invention have been described above, the description thereof will be omitted here.

(Thermal transfer sheet)
As shown in FIG. 2, the thermal transfer sheet 20 constituting the combination of the present invention includes at least a second base material 21 and an ink layer 22.
In one embodiment, the thermal transfer sheet 20 may include a plurality of ink layers 22 (not shown). In this case, the plurality of ink layers may be provided in a surface-sequential manner, or may be provided in a laminated state.
In one embodiment, the thermal transfer sheet 20 includes a colored layer 23 so as to be surface-sequential with the ink layer 22, as shown in FIG. As shown in FIG. 3, a plurality of colored layers 23 may be provided.
Further, in one embodiment, as shown in FIG. 4, the thermal transfer sheet 20 may include a base layer 24 so as to be surface-sequential with the ink layer 22 and the colored layer 23. Further, as shown in FIG. 5, the base layer 24 may be provided between the second base material 21 and the ink layer 22.
Further, in one embodiment, as shown in FIG. 4, the thermal transfer sheet 20 may include a receiving layer 25 so as to be surface-sequential with the ink layer 22 and the colored layer 23. Further, as shown in FIG. 4, the receiving layer 25 may be provided between the second base material 21 and the ink layer 22. As shown in FIG. 5, when the base layer 24 is provided, the receiving layer 25 is provided between the second base material 21 and the base layer 24.
Further, in one embodiment, the thermal transfer sheet 20 may have a metallic luster layer between the ink layer 22 and the receiving layer 25 (not shown). When the thermal transfer sheet 20 includes the base layer 24, it is provided between the base layer 24 and the receiving layer 25.
Further, in one embodiment, the thermal transfer sheet 20 may be provided with a protective layer so as to be surface-sequential with the ink layer 22 and the like (not shown).
Further, the thermal transfer sheet 20 may have a back surface layer on the surface of the second base material 21 opposite to the surface on which the ink layer 22 is provided (not shown).

Hereinafter, each layer included in the thermal transfer sheet will be described.

(Second base material)
As the second base material, a material that can be used as the first base material can be appropriately selected and used.

(Ink layer)
The thermal transfer sheet includes an ink layer containing a coloring material on the second base material. The thermal transfer sheet may be provided with a plurality of ink layers, and these may be provided so as to be surface-sequential, or may be provided in a laminated manner. This ink layer is transferred onto the transparent resin layer of the laminate, and an image is formed in the mirror layer included in the laminate.

The coloring material is not particularly limited, and is, for example, a black coloring material such as carbon black, acetylene black, lamp black, black smoke, iron black and aniline black, and a white coloring material such as silica, calcium carbonate and titanium oxide. , Cadmium red, cadmium red, chrome red, vermilion, red iron oxide, azo pigments, alizarin lake, quinacridone, cochineal lake perylene and other red colorants, yellow ocher, aureolin, cadmium yellow, cadmium orange, chrome yellow, zink yellow, Yellow colorants such as Naples Yellow, Nickel Yellow, Azo Pigments, Greenish Yellow, Ultramarine, Rocks Blue, Cobalt, Phthalocyanin, Anthracinone, Indicoids and other blue colorants, Green pigments include, for example, Sinavar Examples thereof include green coloring materials such as green, cadmium green, chrome green, phthalocyanine, azomethine and perylene, and metal coloring materials such as aluminum pigments.
Among these, when transferred onto the transparent resin layer, the image of the ink layer formed in the mirror layer can be made to appear as if it is a shadow of the formed image, and in addition to the three-dimensional effect, a floating feeling can be obtained. A black colorant is particularly preferable because it can be imparted.

Further, in one embodiment, the ink layer may contain the above resin material. Further, the ink layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The L ^* a ^* b ^* color-based lightness L ^* of the ink layer is preferably 50 or less, and more preferably 30 or less. As a result, a higher floating feeling can be given to the image formed on the ink layer.
"L ^* a ^* b ^* color system" means a color system standardized by the CIE (International Commission on Illumination) and adopted in JIS Z 8781-4: 2013. In the L ^* a ^* b ^* color system, L ^* represents lightness, and a ^* and b ^* represent chromaticity.
In the present invention, the brightness L ^* is measured as follows.
First, a transparent glass plate (GB300 manufactured by AS ONE Corporation) having a thickness of 5 mm is prepared. Next, the ink layer is transferred from the thermal transfer sheet onto the transparent glass plate. This was installed on the sample luminous flux side of an ultraviolet visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation), and a transparent glass plate was installed as a blank on the control luminous flux side, and L ^* a at 520 to 670 nm. ^* B ^* Measure the brightness L ^{* of the} color system.

The visible light transmittance of the ink layer is preferably less than 50%. As a result, a higher floating feeling can be given to the image formed on the ink layer.
In the present invention, the visible light transmittance of the ink layer is measured as follows.
First, a transparent glass plate (GB300 manufactured by AS ONE Corporation) having a thickness of 5 mm is prepared. Next, the ink layer is transferred from the thermal transfer sheet onto the transparent glass plate. This was installed on the sample luminous flux side of an ultraviolet visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation), and a transparent glass plate was installed as a blank on the control luminous flux side to determine the transmittance at 520 to 670 nm. Measure.

The ink layer is formed by dispersing or dissolving the above material in water or an appropriate solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , It can be formed by applying it on a second base material or a receiving layer to form a coating film, and drying the coating film.

(Colored layer)
In one embodiment, the thermal transfer sheet comprises a colored layer so that it is surface-sequential with the ink layer. The thermal transfer sheet may be provided with a plurality of colored layers containing different coloring materials so as to be surface-sequential. This colored layer is transferred onto the ink layer transferred to the laminate to form an image.

The colored layer contains at least one colorant, which may be a pigment or a dye. Moreover, the dye may be a sublimation dye.

In one embodiment, the colored layer can include the above resin material. Further, the colored layer can contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

In one embodiment, the colored layer is prepared by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and rolling-coating method, reverse roll-coating method, gravure-coating method, reverse gravure-coating method, bar-coating method, rod-coating method, etc. It can be formed by applying it on a second base material to form a coating film by a known means of the above, and drying the coating film.

(Underground layer)
In one embodiment, the thermal transfer sheet includes a base layer so as to be surface-sequential with the ink layer or between the second base material and the ink layer. By transferring the ink layer onto the transparent resin layer of the laminate provided in the laminate and transferring the base layer onto the ink layer, the ink layer is shielded, so that the image formed on the ink layer is formed. The sharpness can be improved.

The concealment rate of the underlying layer is preferably 50% or more, and more preferably 70% or more. Thereby, the image sharpness can be further improved.
The concealment rate is measured as follows.
First, a transparent glass plate (GB300 manufactured by AS ONE Corporation) having a thickness of 5 mm is prepared. Next, the base layer is transferred from the thermal transfer sheet onto the transparent glass plate, and the transmittance α is measured by an ultraviolet visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). The concealment rate can be obtained by substituting the measured transmittance α into the following equation.
Concealment rate = (100-α)%

In one embodiment, the underlying layer comprises the white pigment. The content of the white pigment in the base layer is preferably 70% by mass or more and 90% by mass or less, and more preferably 75% by mass or more and 85% by mass or less. Thereby, the image sharpness can be further improved.

Further, in one embodiment, the base layer may contain the above resin material. Further, the base layer can contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

From the viewpoint of image clarity, the thickness of the base layer is preferably 0.3 μm or more and 10 μm or less, and more preferably 1 μm or more and 5 μm or less.

In one embodiment, the base layer is prepared by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and rolling-coating method, reverse roll-coating method, gravure-coating method, reverse gravure-coating method, bar-coating method, rod-coating method, etc. It can also be formed by applying it to an arbitrary layer on the second base material or the second base material to form a coating film by a known means of the above, and drying the coating film.

(Receptive layer)
In one embodiment, the thermal transfer sheet comprises a receiving layer so that it is surface-sequential with the ink layer.
Further, in another embodiment, the thermal transfer sheet includes a receiving layer between the second base material and the ink layer.
Furthermore, in other embodiments, the thermal transfer sheet comprises a receiving layer between the second substrate and the underlying layer.

The visible light transmittance of the receiving layer is preferably 50% or more. Thereby, even when the receiving layer is transferred to the entire range of the first base material, it is possible to prevent the image of the ink layer formed on the mirror layer from being concealed.

The receiving layer can contain resin materials such as polyolefin, vinyl resin, (meth) acrylic resin, cellulose resin, polyester, polyamide, polycarbonate, styrene resin, epoxy resin, polyurethane and ionomer resin.

The content of the resin material in the receiving layer is not particularly limited, and can be, for example, 80% by mass or more and 98% by mass or less.

In one embodiment, the receiving layer comprises a mold release material. This makes it possible to improve the releasability from the thermal transfer sheet.
Examples of the release material include solid waxes such as polyethylene wax, polyamide wax and Teflon (registered trademark) powder, fluorine-based or phosphoric acid ester-based surfactants, silicone oil, reactive silicone oil, and curable silicone oil. Examples thereof include various modified silicone oils and silicone resins.
As the silicone oil, an oily one can be used, but a modified silicone oil is preferable. As the modified silicone oil, amino-modified silicone, epoxy-modified silicone, aralkyl-modified silicone, epoxy-aralkyl-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone and the like can be preferably used, but epoxy-modified silicone and aralkyl-modified silicone can be preferably used. , Epoxy-aralkyl modified silicones are particularly preferred.

The content of the release material in the receiving layer is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. As a result, the releasability from the thermal transfer sheet can be further improved.

In one embodiment, the receiving layer comprises white pigments such as titanium dioxide, zirconia dioxide, zinc oxide, calcium carbonate, calcium sulfate, barium sulfate, barium carbonate, silica and alumina. As a result, the ink layer can be concealed, and the sharpness of the image formed on the receiving layer can be improved.
In this case, the hiding rate of the ink layer by the receiving layer is preferably 50% or more, and more preferably 70% or more. Thereby, the image sharpness can be further improved.

The content of the white pigment in the receiving layer is preferably 70% by mass or more and 90% by mass or less, and more preferably 75% by mass or more and 85% by mass or less. Thereby, the image sharpness can be further improved.

In addition, the receiving layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the receiving layer is preferably 0.5 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less. Thereby, the density of the image formed on the receiving layer can be improved.

In one embodiment, the receiving layer disperses or dissolves the above-mentioned material in water or a suitable solvent, and roll coat method, reverse roll coat method, gravure coat method, reverse gravure coat method, bar coat method, rod coat method, etc. It can also be formed by applying it on a second base material or an arbitrary layer on the second base material to form a coating film by a known means of the above, and drying the coating film.

(Metallic luster layer)
In one embodiment, the thermal transfer sheet comprises a metallic luster layer between the ink layer and the receiving layer. When the thermal transfer sheet includes a base layer, a metallic luster layer is provided between the base layer and the receiving layer. When the thermal transfer sheet is provided with a metallic luster layer, the design of the printed matter produced by using the combination of the present invention can be further improved.
The metallic luster layer may be provided only on the portion where the ink layer is provided or a part thereof, or may be provided beyond the range in which the ink layer is provided.

In one embodiment, the metallic luster layer contains the aluminum paste or metal powder. Further, in one embodiment, the metallic luster layer contains the above resin material. Further, the metallic luster layer may contain the above-mentioned additive.

The thickness of the metallic luster layer is not particularly limited, but can be, for example, 0.5 μm or more and 10 μm or less.

In one embodiment, the metallic glossy layer is prepared by dispersing or dissolving the above-mentioned material in water or a suitable solvent, and rolling-coating method, reverse roll-coating method, gravure-coating method, reverse gravure-coating method, bar-coating method and rod-coating method. It can also be formed by applying it on a second base material or an arbitrary layer on the second base material to form a coating film by a known means such as, and drying the coating film.

(Protective layer)
In one embodiment, the thermal transfer sheet is provided with a protective layer so as to be surface-sequential with the ink layer and the like. By transferring this protective layer to the laminated body after image formation, the durability of the produced printed matter can be improved.

The protective layer contains a resin material, and examples thereof include polyester, (meth) acrylic resin, epoxy resin, styrene resin, acrylic polyol resin, polyurethane, ionizing radiation curable resin, and ultraviolet absorbing resin.

In one embodiment, the protective layer comprises an isocyanate compound. Examples of the isocyanate compound include xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.

The protective layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the protective layer is preferably 0.5 μm or more and 7 μm or less, and more preferably 1 μm or more and 5 μm or less. As a result, the durability of the produced print can be further improved.

The protective layer is prepared by dispersing or dissolving the above material in water or a suitable solvent to obtain a coating liquid, which is used as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod. It can be formed by applying it on a second base material or an arbitrary layer on the second base material to form a coating film by a known means such as a coating method, and drying the coating film.

(Back layer)
In one embodiment, the thermal transfer sheet includes a back surface layer on a surface opposite to the surface on which the ink layer of the second base material is provided. As a result, the blocking resistance of the thermal transfer sheet can be improved.

In one embodiment, the back layer comprises one or more resin materials, such as cellulose resin, styrene resin, vinyl resin, polyester, polyurethane, silicone modified polyurethane, fluorine modified polyurethane and (meth) acrylic resin. Can be mentioned.

In one embodiment, the back layer comprises inorganic or organic particles. This makes it possible to further prevent sticking and wrinkles due to heating during thermal transfer.
Examples of the inorganic particles include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, and oxides such as silica. , Graphite, sulphate, and inorganic particles such as boron hydroxide. As the organic particles, organic resin particles made of (meth) acrylic resin, Teflon (registered trademark) resin, silicone resin, lauroyl resin, phenol resin, acetal resin, styrene resin, polyamide and the like, or these are reacted with a cross-linking material. Examples thereof include crosslinked resin particles that have been formed.

The thickness of the back layer is not particularly limited, and can be, for example, 0.1 μm or more and 2 μm or less.

The back layer is formed by dispersing or dissolving the above material in water or a suitable solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , It can be formed by applying it on a second base material to form a coating film and drying it.

(Combination of laminate, thermal transfer sheet, and intermediate transfer medium)
The combination of the laminate of the present invention, the thermal transfer sheet, and the intermediate transfer medium is composed of the laminate, the thermal transfer sheet, and an intermediate transfer medium including a third base material and a transfer layer.
Since the laminates constituting the combination of the present invention have been described above, the description thereof will be omitted here.

(Thermal transfer sheet)
As described above, the thermal transfer sheet 20 constituting the combination of the present invention includes a second base material 21 and at least one ink layer 22. When the thermal transfer sheet 20 includes a plurality of ink layers 22, the ink layers 22 may be provided in a surface-sequential manner or may be provided in a laminated state.
Further, the thermal transfer sheet 20 can be provided with a colored layer 23 so as to be surface-sequential with the ink layer 22.
Further, in one embodiment, the thermal transfer sheet 20 may be provided with a base layer 24 so as to be surface-sequential with the ink layer 22 and the colored layer 23. As shown in FIG. 6, the base layer 24 may be provided on the ink layer 22.
Further, in one embodiment, the thermal transfer sheet 20 may have a metallic luster layer on the ink layer 22 (not shown).
Further, in one embodiment, the thermal transfer sheet 20 may be provided with a protective layer so as to be surface-sequential with the ink layer 22 and the like (not shown).
Further, the thermal transfer sheet 20 may have a back surface layer on the surface of the second base material 21 opposite to the surface on which the ink layer 22 is provided (not shown).
Since the materials constituting each layer and their thicknesses have been described above, the description thereof is omitted here.

(Intermediate transfer medium)
As shown in FIG. 7, the intermediate transfer medium 30 constituting the combination of the present invention includes a third base material 31 and a transfer layer 32.
In one embodiment, the transfer layer 32 comprises a receiving layer 33, as shown in FIG.
Further, in one embodiment, the transfer layer 32 includes a release layer 34 between the third base material 31 and the receiving layer 33, as shown in FIG.
In one embodiment, the transfer layer 32 included in the intermediate transfer medium 30 may include a protective layer between the receiving layer 33 and the release layer 34 (not shown). The intermediate transfer medium 30 may not have the release layer 34 and may have a protective layer under the receiving layer 33.

(Third base material)
As the third base material, a material that can be used as the first base material can be appropriately selected and used.

(Receptive layer)
The material and thickness constituting the receiving layer can be the same as that of the receiving layer that the above-mentioned thermal transfer sheet can have.

(Peeling layer)
The transfer layer included in the intermediate transfer medium may include a release layer under the receiving layer. This makes it possible to improve the transferability of the transfer layer after image formation.

In one embodiment, the release layer contains one or more of the above resin materials.

The content of the resin material in the release layer is preferably 50% by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 85% by mass or less. Thereby, the transferability of the second transfer layer after image formation can be further improved.

In one embodiment, the release layer comprises a resin material such as (meth) acrylic resin, cellulose resin, vinyl resin, polyurethane, silicone resin and fluororesin.
Further, in one embodiment, the peeling layer is a natural wax such as beeswax, whale wax, wood wax, rice bran wax, carnauba wax, candelilla wax and montan wax, paraffin wax, microcrystallin wax, oxide wax, ozokelite, ceresin and ester. Synthetic waxes such as waxes and polyethylene waxes, higher saturated fatty acids such as margaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, floic acid and behenic acid, higher saturated monovalent alcohols such as stearyl alcohol and behenyl alcohol, and sorbitan fatty acids. It contains waxes such as higher esters such as esters, stearic acid amides and higher fatty acid amides such as oleic acid amides.
The release layer may contain both the above-mentioned resin material and wax, and may contain two or more of these.

The release layer may contain the above additives as long as the characteristics of the present invention are not impaired.

The thickness of the release layer is preferably 0.5 μm or more and 3 μm or less, and more preferably 0.7 μm or more and 2 μm or less. Thereby, the transferability of the transfer layer after image formation can be further improved.

For the formation of the release layer, the above materials are dispersed or dissolved in water or an appropriate solvent, and known methods such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method are known. By means, it can be formed by applying it on a third base material to form a coating film and drying it.

(Protective layer)
The material and thickness of the protective layer can be the same as that of the protective layer that the above-mentioned thermal transfer sheet can have.

(Printed paper)
As shown in FIGS. 10 and 11, the printed matter 40 of the present invention includes a first base material 41, a mirror layer 42, a transparent resin layer 43, an ink layer 44, and a receiving layer 46 on which an image 45 is formed. At least prepare. When the image is formed by the heat-melt transfer method (transfer of the colored layer), the receiving layer may not be provided (not shown).
When the receiving layer has high transparency, as shown in FIGS. 11 and 12, the receiving layer is received over the entire range of the first base material 41, for example, beyond the range in which the ink layer 44 and the base layer 47 are formed. Layers may be formed. Further, it may be formed only in the range where the base layer is formed.
Further, although the printed matter produced by using the combination of the laminate and the thermal transfer sheet is shown here, the printed matter may be produced by using the combination of the laminate, the thermal transfer sheet and the intermediate transfer medium. In this case, in FIG. 11, the image 45 is formed on the ink layer 44 side of the receiving layer 46.
According to the photographic paper having such a configuration, as shown in FIGS. 10 and 11, an image of an ink layer is formed inside, and it seems that this image exists behind the image, and the photographic paper has a three-dimensional effect. Can be given, and its design can be remarkably improved.
Further, in one embodiment, as shown in FIG. 12, the printed matter 40 of the present invention includes a base layer 47 between the ink layer 44 and the image 45 or the receiving layer 46.
Further, in one embodiment, the printed matter 40 includes a metallic luster layer between the ink layer 44 and the receiving layer 46 (not shown).
Further, in one embodiment, the printed matter 40 includes a protective layer on the receiving layer 46 (not shown).
Further, when a printed matter is produced using a combination of a laminate, a thermal transfer sheet, and an intermediate transfer medium, the printed matter 40 is provided with a protective layer and a release layer on the receiving layer 46 (not shown).

Hereinafter, each layer included in the printed matter will be described. Since the configurations of the first base material, the mirror layer, the transparent resin layer, the metallic luster layer, the peeling layer, etc. have been described above, the description thereof will be omitted here.

(Ink layer)
In the printed matter of the present invention, the ink layer is transferred to the mirror layer, and it can be made to appear that an image is formed at the position of the mirror layer. As a result, it seems that the image is formed deeper than the image formed on the ink layer, so that a three-dimensional effect can be given to the printed matter.
The shape and size of the ink layer included in the printed matter are not particularly limited, but the shape of the ink layer is the same as at least a part of the image to be formed from the viewpoint of imparting a floating feeling to the printed matter. Alternatively, it preferably has a similar shape.
Note that "at least a part" does not have to have the same shape as the entire image formed on the printed matter. For example, when a pattern and characters are formed as an image, only the pattern has the same shape. Yes, it means that it may give a feeling of floating only to this.
From the same viewpoint, the size of the ink layer is preferably larger than the size of the formed image.
Since the configurations of other ink layers have been described above, the description thereof will be omitted here.

(Receptive layer)
In one embodiment, the print of the invention comprises a receiving layer. The formation position of the receiving layer is not particularly limited as long as the receiving layer has transparency. For example, it may be provided only in the range where the base layer is formed, or may be provided in the entire range of the first base material.

(image)
The image is not particularly limited, and characters, figures, patterns, and the like can be appropriately selected. From the viewpoint of imparting a floating feeling to the printed matter, as shown in FIGS. 11 and 12, it is preferable that the position where the image 45 is formed and the position where the ink layer 44 is formed are displaced in the horizontal direction. .. The position is not limited to this, and as shown in FIG. 13, the position where the image 45 is formed and the position where the ink layer is formed may be the same position.
Further, the image 45 formation position is preferably the same as the base layer 47 formation position. Thereby, the sharpness of the formed image can be improved.
In the printed matter of the present invention, both an image with a floating feeling and an image without a floating feeling may be formed.

(Underground layer)
In one embodiment, the printed matter of the present invention includes a base layer between the ink layer and the image or receiving layer. It is preferable that the base layer is provided in the entire position corresponding to the image forming position. As a result, the ink layer is shielded, and the sharpness of the formed image can be improved.

The printed matter of the present invention can be produced by using the combination of the above-mentioned laminate and the thermal transfer sheet.
(1) In one embodiment, an ink layer is transferred from a thermal transfer sheet onto a transparent resin layer included in a laminate, and then a colored layer included in the thermal transfer sheet or another thermal transfer sheet is transferred to form an image. Can produce a printed matter. Further, before the transfer of the colored layer, the base layer provided by the thermal transfer sheet or another thermal transfer sheet may be transferred onto the ink layer.
(2) In one embodiment, the ink layer is transferred from the thermal transfer sheet onto the transparent resin layer included in the laminate, the receiving layer included in the thermal transfer sheet or another thermal transfer sheet is transferred, and then the thermal transfer sheet or another. A printed matter can be produced by sublimating and transferring a sublimation dye from the colored layer provided on the thermal transfer sheet onto the receiving layer. Further, after the ink layer is transferred and before the colored layer is transferred, the base layer provided by the thermal transfer sheet or another thermal transfer sheet may be transferred onto the ink layer.
The above-mentioned production method is merely an example, and is not limited thereto.

The printed matter of the present invention can be produced by using the combination of the above-mentioned laminate, the thermal transfer sheet, and the intermediate transfer medium.
(1) In one embodiment, a colored layer is transferred from a thermal transfer sheet onto a transfer layer provided in an intermediate transfer medium to form an image, and an ink layer is transferred from the thermal transfer sheet onto this image. Next, the transfer layer, the coloring layer, and the ink layer are transferred from the intermediate transfer medium onto the transparent resin layer of the laminated body to prepare a printed matter. Further, after the ink layer is transferred onto the image, the base layer may be transferred from the thermal transfer sheet.
(2) In one embodiment, an image is formed by sublimating and transferring a sublimation dye from the colored layer provided on the thermal transfer sheet onto the receiving layer on the receiving layer provided by the intermediate transfer medium, and the thermal transfer sheet is formed on the image. Transfer the ink layer from. Next, a print can be produced by transferring the transfer layer and the ink layer provided with the receiving layer from the intermediate transfer medium onto the transparent resin layer of the laminate. Further, after the ink layer is transferred onto the image, the base layer may be transferred from the thermal transfer sheet.
The above-mentioned production method is merely an example, and is not limited thereto.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, the content, compounding ratio, etc. are based on mass, unless otherwise described below.

Example 1
As the first base material, a vinyl chloride card having a thickness of 0.7 mm was prepared. An aluminum vapor deposition film having a thickness of 100 nm was formed on the entire first base material by the PVD method to form a mirror layer.

A polyethylene terephthalate (PET) film having a thickness of 100 μm was laminated as a transparent resin layer on the mirror layer formed as described above via an adhesive to obtain the laminate of the present invention.
The specular reflectance of the obtained laminate is measured by irradiating light from the transparent resin layer side at an incident angle of 45 ° using a color change colorimeter (GC-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.). As a result, it was 90%.
The visible light transmittance of the PET film was 90% when measured at a wavelength of 520 to 670 nm using an ultraviolet visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation).

Examples 2 and 3
A laminate was produced in the same manner as in Example 1 except that the thickness of the PET film was changed to the numerical value shown in Table 1. In addition, the specular reflectance of the laminated body and the visible light transmittance of the PET film used were measured in the same manner as above, and are summarized in Table 1.

Example 4
The same as in Example 1 except that a coating liquid for forming a mirror layer having the following composition was applied to a vinyl chloride card having a thickness of 0.7 mm instead of the aluminum vapor deposition film and dried to form a mirror layer having a thickness of 1 μm. To prepare a laminated body. Moreover, the specular reflectance of the laminated body was measured in the same manner as described above, and is summarized in Table 1.
<Coating liquid for forming a mirror layer>
50 parts by mass of metal pigment (manufactured by BASF Japan, Metascheen (registered trademark) 41-0010)
50 parts by mass of methyl ethyl ketone (MEK)

Example 5
Instead of the aluminum vapor deposition film, an indium vapor deposition film having a thickness of 100 nm was formed on a vinyl chloride card having a thickness of 0.7 mm by the PVD method to form a mirror layer, and the laminate was formed in the same manner as in Example 1. Made. Moreover, the specular reflectance of the laminated body was measured in the same manner as described above, and is summarized in Table 1.

Example 6
Example 1 and Example 1 except that the PET film used as the transparent resin layer was changed to a yellow transparent PET film having a thickness of 100 μm (manufactured by Toray Industries, Inc., Lumirror (registered trademark) colored with Ye dye). A laminate was produced in the same manner. The visible light transmittance of this PET film was measured in the same manner as in Example 1 and found to be 60%. In addition, the specular reflectance of the laminated body and the visible light transmittance of the PET film used were measured in the same manner as above, and are summarized in Table 1.

Example 7
A laminate was produced in the same manner as in Example 1 except that the first base material was changed to coated paper having a thickness of 1 mm.

Comparative Example 1
In place of the aluminum vapor deposition film, a coating liquid for forming a mirror layer having the following composition was applied onto a vinyl chloride card having a thickness of 0.7 mm and dried to form a mirror layer having a thickness of 1 μm. A laminate was produced in the same manner. Moreover, the specular reflectance of the laminated body was measured in the same manner as described above, and is summarized in Table 1. (Coating liquid for forming a mirror layer)
20 parts by mass of polyurethane (manufactured by Tosoh Corporation, NIPPORAN (registered trademark) 5253)
・ Metal pigment 10 parts by mass (aluminum powder)
・ 75 parts by mass of toluene ・ 75 parts by mass of MEK

Comparative Example 2
Example 1 and Example 1 except that the PET film used as the transparent resin layer was changed to a yellow transparent PET film having a thickness of 100 μm (manufactured by Toray Industries, Inc., colored with carbon black on Lumirror (registered trademark)). A laminate was produced in the same manner. In addition, the specular reflectance of the laminated body and the visible light transmittance of the PET film used were measured in the same manner as above, and are summarized in Table 1.

<< Evaluation of design >>
Using the laminate obtained in the above example, a printed matter was produced by the following two methods. The design of the printed matter was sensory evaluated by a monitor test of 10 people. Specifically, scoring was performed according to the following criteria, and the design of the printed matter was evaluated according to the following criteria based on the average score. The evaluation results are summarized in Table 1.
(Score)
5: The formed image appeared to have an extremely high stereoscopic effect and a floating feeling.
4: The formed image appeared to have a high stereoscopic effect and a floating feeling.
3: The formed image appeared to have a stereoscopic effect and a floating feeling.
2: The formed image seemed to have a little stereoscopic effect and a floating feeling.
1: The formed image did not appear to have a stereoscopic effect and a floating feeling.
(Evaluation criteria)
A: 4.5 points or more B: 3.5 points or more and less than 4.5 points C: 1.5 points or more and less than 3.5 points NG: less than 1.5 points

(Preparation of photographic paper using thermal transfer sheet: Design evaluation-1)
As a second base material, a 4.5 μm-thick PET film (manufactured by Toray Industries, Inc., Lumirror (registered trademark)) was prepared. An ink layer forming coating solution having the following composition was applied to one surface of the PET film and dried to form an ink layer having a thickness of 1 μm.
<Coating liquid for forming an ink layer>
・ Carbon black 5 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 5 parts by mass ・ MEK 90 parts by mass

The ink layer formed as described above and the coating liquid for forming a base layer having the following composition were applied and dried so as to be surface-sequential to form a base layer having a thickness of 1 μm.
<Coating liquid for forming the base layer>
・ (Meta) acrylic resin 3 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 1 part by mass ・ Titanium oxide 16 parts by mass ・ Toluene 40 parts by mass ・ MEK 40 parts by mass

A coating liquid for forming a receiving layer having the following composition was applied and dried so as to be surface-sequential with the base layer formed as described above to form a receiving layer having a thickness of 1 μm.
<Coating liquid for forming a receiving layer>
-95 parts by mass of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., Solveine (registered trademark) CNL)
・ Epoxy modified silicone oil 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., KP-1800U)
・ 200 parts by mass of toluene ・ 200 parts by mass of MEK

The coating liquids A, B and C for forming a colored layer containing the sublimation dye having the following composition and the coating liquid for forming a protective layer are sequentially surface-ordered so as to be surface-sequential to the ink layer, the base layer and the receiving layer. It was applied and dried to form dye layers A to C having a thickness of 0.7 μm and a protective layer having a thickness of 1 μm, respectively.
<Coating liquid A for forming a colored layer>
・ Cyan sublimation dye 5 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 5 parts by mass
90 parts by mass of MEK <Coating liquid B for forming a colored layer>
・ Magenta sublimation dye 5 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 5 parts by mass ・ MEK 90 parts by mass <Coating liquid C for forming colored layer>
・ Yellow sublimation dye 5 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 5 parts by mass
-MEK 90 parts by mass <coating liquid for forming a protective layer>
-(Meta) acrylic resin 9.5 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
-0.5 parts by mass of polyester (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200)
・ 20 parts by mass of toluene ・ 20 parts by mass of MEK

A coating liquid for forming a back layer having the following composition was applied to the other surface of the second base material and dried to form a back layer having a thickness of 0.1 μm to obtain a thermal transfer sheet.
<Coating liquid for forming the back layer>
-Polyvinyl butyral 2 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) BX-1)
-Polyisocyanate 9.2 parts by mass (manufactured by DIC Corporation, Burnock (registered trademark) D750)
-Phosphate ester-based surfactant 1.3 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd., Prysurf (registered trademark) A208N)
・ 0.3 parts by mass of talc (Nippon Talc Industry Co., Ltd., Micro Ace (registered trademark) P-3)
・ Toluene 43.6 parts by mass ・ MEK 43.6 parts by mass

The brightness L ^{* of the} ink layer included in the thermal transfer sheet was measured by the method described in the above specification and found to be 40.
Further, the visible light transmittance of the transferred ink layer was measured by the method described in the above specification and found to be 40%.

Using the following printer, the ink layer included in the thermal transfer sheet was transferred onto the transparent resin layer included in the laminates produced in the above Examples and Comparative Examples under the condition of energy gradation 255/255.

The base layer 24 was transferred onto the ink layer under the condition of energy gradation 255/255. The transfer of the base layer was performed so as to be displaced by 0.3 mm in the horizontal direction from the transfer position of the ink layer.

Next, the receiving layer 25 is transferred to the entire range of the first base material 11 under the condition of energy gradation 255/255, and the sublimation dye is energized from the colored layers A to C provided in the thermal transfer sheet on the receiving layer. A gray image was formed by sublimation transfer under the condition of gradation 128/255. The image formation position was set to coincide with the formation position of the base layer.
After the image formation, the protective layer was transferred from the thermal transfer sheet to the entire surface of the receiving layer under the condition of energy gradation 255/255 to obtain a printed matter.

(Printer)
Thermal head: KEE-57-12GAN2-STA (manufactured by Kyocera Corporation)
Average resistance of heating element: 3303 (Ω)
Main scanning direction Print density: 300 dpi
Sub-scanning direction print density: 300 dpi
1-line period: 2.0 (msec.)
Printing start temperature: 35 (° C)
Pulse duty ratio: 85%
Printing voltage: 21 (V)

Further, in the laminated body of Example 4, the base layer and the image formation position are shifted by 0.3 mm in the horizontal direction from the formation position of the ink layer (described in the table as Example 4), and the base layer and the image. A printed matter (listed in the table as Example 4') was prepared in which the formation position was the same as the formation position of the ink layer.

(Preparation of photographic paper using thermal transfer sheet and intermediate transfer medium: Design evaluation-2)
As a third base material, a PET film having a thickness of 12 μm (manufactured by Toray Industries, Inc., Lumirer®) was prepared. A coating liquid for forming a release layer having the following composition was applied to one surface of the PET film and dried to form a release layer having a thickness of 1 μm.
<Coating liquid for forming a release layer>
-(Meta) acrylic resin 9.5 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
-0.5 parts by mass of polyester (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200)
・ 20 parts by mass of toluene ・ 20 parts by mass of MEK

On the release layer formed as described above, a coating liquid for forming a protective layer having the following composition was applied and dried to form a protective layer having a thickness of 2 μm.
<Coating liquid for forming a protective layer>
100 parts by mass of (meth) acrylic polyol resin (manufactured by Taisei Fine Chemicals Co., Ltd., 6KW-700, solid content 36.5%, Tg 102 ° C., Mw55000, hydroxyl value 30.1)
-Isocyanate compound 3.6 parts by mass (manufactured by Mitsui Chemicals, Inc., Takenate (registered trademark) D110N, solid content 75%)
・ MEK 92 parts by mass

A coating liquid for forming a receiving layer having the following composition was applied onto the protective layer formed as described above and dried to form a receiving layer having a thickness of 2 μm to obtain an intermediate transfer medium.
<Coating liquid for forming a receiving layer>
-95 parts by mass of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., Solveine (registered trademark) CNL)
・ Epoxy modified silicone oil 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., KP-1800U)
・ 200 parts by mass of toluene ・ 200 parts by mass of MEK

As a second base material, a 4.5 μm-thick PET film (manufactured by Toray Industries, Inc., Lumirror (registered trademark)) was prepared. The above-mentioned coating liquids A, B and C for forming a colored layer, the coating liquid for forming a base layer having the following composition, and the above-mentioned coating liquid for forming an ink layer are sequentially applied to one surface of a PET film. After drying, colored layers A to C, base layers and ink layers having a thickness of 0.7 μm were formed.
The visible light transmittance of the ink layer was measured and found to be 10%.
<Coating liquid for forming the base layer>
・ Titanium oxide 5 parts by mass ・ Vinyl chloride-vinyl acetate copolymer 5 parts by mass ・ MEK 90 parts by mass

A coating liquid for forming a back layer having the following composition was applied to the other surface of the second base material and dried to form a back layer having a thickness of 0.1 μm to obtain a thermal transfer sheet.
<Coating liquid for forming the back layer>
-Polyvinyl acetal 86.8 parts by mass (manufactured by Sekisui Chemical Co., Ltd., Eslek (registered trademark) BM-2, hydroxyl value 19% by mass)
-Isocyanate compound 9.7 parts by mass-Zinc stearyl phosphate 1 part by mass (manufactured by Sakai Chemical Industry Co., Ltd., purified by LBT-1830)
・ 1 part by mass of zinc stearate (SZ-PF manufactured by Sakai Chemical Industry Co., Ltd.)
-0.5 parts by mass of talc (manufactured by Nippon Talc Industry Co., Ltd., Micro Ace (registered trademark) P-3)
・ Polyethylene wax 1 part by mass (manufactured by Toyo Adre Co., Ltd., polywax 3000)
・ MEK 200 parts by mass ・ Toluene 100 parts by mass

The brightness L ^{* of the} ink layer included in the thermal transfer sheet was measured by the method described in the above specification and found to be 40.
Further, the visible light transmittance of the transferred ink layer was measured by the method described in the above specification and found to be 40%.

Using the above card printer, the colored layers A to C provided in the thermal transfer sheet were transferred onto the receiving layer provided in the intermediate transfer medium under the condition of energy gradation 128/255 to form a gray image.

The base layer included in the thermal transfer sheet was transferred to the image forming position on the receiving layer under the condition of energy gradation 255/255.

Next, the ink layer was transferred under the condition of the energy gradation of 255/255 by shifting the image and the base layer formation position by 0.3 mm in the horizontal direction.

Next, using the card printer, the release layer, the protective layer, the receiving layer on which the image is formed, the base layer, and the ink layer provided in the intermediate transfer medium produced as described above are provided in the above Examples and Comparative Examples. A printed matter was obtained by transferring onto the transparent resin layer provided in the produced laminate.
In the laminate of Example 4, the ink layer was formed by shifting the image and the base layer formation position by 0.3 mm (described in the table as Example 4), and the ink layer was used as the image and the base layer. A printed matter (listed in the table as Example 4') formed at the same position as the forming position was prepared.

10: Laminate, 11: 1st base material, 12: Mirror layer, 13: Transparent resin layer, 20: Thermal transfer sheet, 21: 2nd base material, 22: Ink layer, 23; Colored layer, 24: Base layer, 25: Receptive layer, 30: Intermediate transfer medium, 31: Third substrate, 32: Transfer layer, 33: Receptive layer, 34: Peeling layer, 40: Printed paper, 41: Image

Claims (12)

A first base material, a mirror layer, and a transparent resin layer are provided.
A laminated body having a specular reflectance of 60% or more. The laminate according to claim 1, wherein the thickness of the transparent resin layer is 50 μm or more and 3000 μm or less. The laminate according to claim 1 or 2, wherein the transparent resin layer has a visible light transmittance of 50% or more. A combination of the laminate according to any one of claims 1 to 3 and a thermal transfer sheet.
A combination of a laminate and a thermal transfer sheet, wherein the thermal transfer sheet includes a second base material and an ink layer. The combination of the laminate according to claim 4 and the thermal transfer sheet, wherein the lightness L ^{* of the} ink layer is 50 or less. A colored layer is provided so that the thermal transfer sheet is surface-sequential to the ink layer.
The combination of the laminate and the thermal transfer sheet according to claim 4 or 5, further comprising a base layer between the ink layer and the colored layer in a surface-sequential manner, or between the second base material and the ink layer. The combination of the laminate according to any one of claims 4 to 6 and a thermal transfer sheet, wherein the visible light transmittance of the ink layer is less than 50%. The laminate according to any one of claims 4 to 7, wherein the concealment rate of the base layer is 50% or more. A combination of the laminate according to any one of claims 1 to 3, a thermal transfer sheet, and an intermediate transfer medium.
The thermal transfer sheet includes a second base material and an ink layer.
A combination of a laminate, a transfer sheet, and an intermediate transfer medium, wherein the intermediate transfer medium includes a third base material and a transfer layer. A first base material, a mirror layer, a transparent resin layer, an ink layer, and a receiving layer on which an image is formed or a colored layer on which an image is formed are provided.
A printed matter having a mirror surface reflectance of 60% or more of a laminate having the first base material, the mirror layer, and the transparent resin layer. The printed matter according to claim 10, wherein the position where the ink layer is formed and the position of the image are displaced in the horizontal direction. The printed matter according to claim 10 or 11, wherein the ink layer has the same shape or a similar shape as at least a part of the image.