JP2006182012A - Printing object and method for forming printing object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing object by sublimation transfer capable of realizing a desired matte pattern with various surface forms such as a matte pattern having a deep unevenness, and a method for producing the printing object. <P>SOLUTION: In order to obtain the printing object 1, a thermal transfer receiving sheet provided with a receiving layer 3 on a base material 2 and a thermal transfer sheet having a sublimation dye-containing dye layer on a base material are laminated and heated to form a thermal transfer image 5 by a sublimation dye on the receiving layer 3. Afterwards, using a thermal transfer sheet provided with a thermal transfer protective layer on a base material, on at least a part of the thermal transfer image 5, a protective layer 4 is provided by thermal transfer, and on at least a part of the protective layer 4, the printing object 1 has a matte-like form formed on the surface by die-pressing an emboss plate having the unevenness on its surface under a certain heating condition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a printed material for sublimation transfer capable of realizing a desired mat pattern having various surface shapes such as a mat pattern having deep unevenness, and a method for producing the printed material.

  Conventionally, as a variety of printing methods for forming an image, the dye in the color material layer is sublimed and diffused by heat and the dye is transferred to the image receiving sheet, and the color material layer is melted and softened by heating. Are widely used for thermal transfer, ink jet, and electrophotography. Among them, thermal sublimation transfer can be dyed with a sublimation dye and a thermal transfer sheet in which a dye layer in which a sublimation transfer dye used as a recording material is melted or dispersed in a binder resin is supported on a base material sheet such as a polyester film. There has been proposed a method of forming various full-color images by superimposing an image receiving sheet on which a receiving layer is formed on a material to be transferred, such as paper or plastic film, and thermally transferring a sublimation dye. In this case, a thermal head of the printer is used as the heating means, and the color dots in which a large number of heating amounts of three colors or four colors are adjusted are transferred to the image receiving sheet by heating for a very short time. The color dots reproduce the full color of the document.

  The image formed in this manner is very clear and excellent in transparency because the color material used is a dye, and thus the resulting image is excellent in reproducibility and gradation of intermediate colors, It is possible to form a high-quality image similar to a conventional image by offset printing or gravure printing and comparable to a full-color photographic image. At present, a thermal transfer recording method is widely used as a simple printing method. Since the thermal transfer recording method can easily form various images, the thermal transfer recording method is used in printed materials that require a relatively small number of printed sheets, such as ID card creation, business photographs, or personal computer printers and video printers. .

  The above heat-sensitive sublimation transfer method can control the amount of dye transferred in dot units according to the amount of energy applied to the thermal transfer sheet, so it is excellent in forming a gradation image, but the formed image is a normal printing ink. Unlike the above, the coloring material is not a pigment, is a dye having a relatively low molecular weight, and has no vehicle, so that it has a disadvantage of poor durability such as light resistance, weather resistance, and abrasion resistance. On the other hand, a protective layer thermal transfer sheet having a thermal transfer resin layer is superimposed on an image obtained by thermal transfer of a sublimation dye, and the thermal transfer resin layer is transferred using a thermal head, a heating roll, etc. A method for forming a protective layer is known.

  Further, there is a demand for such a printed material having a protective layer on the surface, in which the surface does not have high glossiness and a mat-like printed material having fine irregularities on the surface. In contrast, there are the following three methods. (1) As a specification of media, there is a method of creating a protective layer having surface irregularities. For example, as described in Patent Document 1, in a protective layer thermal transfer sheet in which a release layer and a protective layer are laminated on a base material, the release layer contains filler (particles), and the surface of the release layer is The surface of the protective layer is roughened, and the protective layer is thermally transferred onto the image (the release layer remains on the substrate side) to make the surface of the protective layer uneven. In addition, there is a protective layer thermal transfer sheet in which a release layer and a protective layer are laminated on a base material, in which foamable particles are contained in the release layer, and the release layer and the protective layer are transferred onto the image. Furthermore, in the protective layer thermal transfer sheet provided with a protective layer on the substrate, when the protective layer itself was provided on the substrate, a printing plate cylinder having irregularities on the surface was used to have this uneven shape. The protective layer is printed on the base material, and the protective layer is unevenly transferred on the image by thermally transferring the protective layer. The above method for producing a protective layer having surface irregularities is technically difficult as a method for obtaining a desired mat pattern having various surface shapes. In particular, it is very difficult to provide unevenness having a depth of 5 μm or more.

  In addition, as a method of obtaining a mat-like printed matter on the surface, (2) using a protective layer thermal transfer sheet, the strength of the thermal energy at the time of thermal transfer of the protective layer on the image is increased and the surface gloss of the protective layer is increased. There are ways to change. In this method, for example, as disclosed in Patent Document 2, in a protective layer transfer sheet in which a heat transferable protective layer and an adhesive layer are sequentially laminated on a substrate, the protective layer is composed of a thermoplastic resin and an inorganic layered compound. In the method of forming a protective layer by thermal transfer using the protective layer transfer sheet on the image on the body, the amount of surface gloss of the protective layer can be varied by variably controlling the amount of heating during thermal transfer. Has been. In the method (2) for producing a protective layer having surface irregularities, a desired mat pattern having deep irregularities cannot be obtained.

Further, as a method of obtaining a mat-like print on the surface, (3) a method of matting the surface of the print by pressing a roller or a plate having irregularities on the surface after the print is formed is assumed. . However, even in this method, the present situation is that a desired mat pattern having various surface shapes cannot be realized.
JP 2004-122756 A JP 2004-106260 A

  Therefore, in order to solve the above-described problems, the present invention provides a printed material for sublimation transfer capable of realizing a desired mat pattern having various surface shapes such as a mat pattern having deep unevenness. And a method for creating the printed matter.

  According to the first aspect of the present invention, a thermal transfer image-receiving sheet provided with a receiving layer on a base material and a thermal transfer sheet having a dye layer containing a sublimation dye on the base material are stacked and heated to form a printed matter. In this method, a thermal transfer image with a sublimation dye is formed on the receiving layer, and a protective layer is then formed on at least a part of the thermal transfer image using a thermal transfer sheet provided with a thermal transferable protective layer on a substrate. A printed matter characterized in that a mat shape is formed on the surface by embossing an embossed plate having a concavo-convex shape on the surface under heating conditions on at least a part of the protective layer after the thermal transfer. It is a creation method.

The invention described in claim 2 is characterized in that a release treatment is performed on the surface of the concavo-convex shape of the embossed plate. The invention according to claim 3 is characterized in that the uneven shape of the embossed plate has a Ra value of 0.5 to 20 μm measured by a three-dimensional surface roughness shape measuring machine and the number of uneven portions of 0.5 to 20 μm. Is characterized by having 10 to 200 per 1 mm ² . In the invention according to claim 4, the ratio of the reflection density in the region of the reflection density of 1.5 or more of the thermal transfer image of the printed material before and after the embossing process of the embossed plate is [reflection density value after processing / Reflection density value before processing] × 100, which is 80 to 120%, and no change in density is recognized.

  The invention according to claim 5 is a sublimation dye which is provided with a receiving layer on a substrate, and the receiving layer is thermally transferred from a thermal transfer sheet having a dye layer containing a sublimation dye on the substrate by heating. In a printed matter in which a thermal transfer image is formed and a protective layer is provided on at least a part of the thermal transfer image by thermal transfer, at least a part of the protective layer has an uneven shape on the surface under heating conditions. The printed matter is characterized in that a mat shape is formed on the surface by embossing. The invention according to claim 6 is characterized in that the protective layer is made of a thermoplastic resin having transparency and a glass transition temperature of 80 to 120 ° C.

The invention according to claim 7 is characterized in that the unevenness shape of the surface of the printed material has an Ra value of 0.5 to 10 μm measured by a three-dimensional surface roughness shape measuring machine and 0.5 to 10 μm unevenness. The number is 10 to 200 per 1 mm ² . The invention described in claim 8 is characterized in that a glossiness measured at an incident angle of 45 ° on the surface of the printed material is 30 to 70%.

  The printed product of the present invention includes a thermal transfer image-receiving sheet provided with a receiving layer on a base material and a thermal transfer sheet having a dye layer containing a sublimable dye on the base material. A thermal transfer image is formed by a photosensitive dye, and then a protective layer is thermally transferred onto at least a part of the thermal transfer image using a thermal transfer sheet on which a thermal transferable protective layer is provided on a substrate, and then the protection is performed. It is obtained by a method of forming a mat shape on the surface of a layer by embossing an embossed plate having a concavo-convex shape on at least a part of the layer under heating conditions. Thereby, a printed matter having a mat shape on the surface can be easily produced.

Further, the uneven shape of the embossed plate to be used has a Ra value measured by a three-dimensional surface roughness shape measuring machine of 0.5 to 20 μm, and the number of unevenness of 0.5 to 20 μm is 10 to 200 per 1 mm ^2. The surface roughness of the printed material is 0.5 to 10 μm and the Ra value measured with a three-dimensional surface roughness measuring machine is 0.5 to 10 μm. The number of irregularities of 20 μm is 10 to 200 per 1 mm ² , and a desired mat pattern having various surface shapes such as a mat pattern having deep irregularities can be realized. Moreover, the said protective layer has transparency, and shall consist of a thermoplastic resin with a glass transition temperature of 80-120 degreeC, In the embossing process by an embossing plate, it is in the shape of the surface unevenness | corrugation of an embossing plate. An approximate print of excellent quality having a mat shape on the surface is obtained. Further, before and after the embossing plate embossing process, the ratio of the reflection density in the region having a reflection density of 1.5 or more of the thermal transfer image of the printed product is [reflection density value after processing / reflection density value before processing] × 100. 80% to 120%, and an excellent quality with no change in the density of the printed matter is obtained.

  FIG. 1 is a schematic view showing an embodiment of a printed product 1 of the present invention, in which a receiving layer 3 and a protective layer 4 are laminated on a substrate 2, and the receiving layer 3 includes a substrate. From the thermal transfer sheet having a dye layer containing a sublimable dye thereon, a thermal transfer image 5 is formed by the sublimation dye thermally transferred by heating, and the protective layer 4 is formed on the entire surface of the receiving layer 3 so as to cover the thermal transfer image 5. Is provided by thermal transfer. In the printed matter 1, a mat shape is formed on the entire surface of the protective layer 4. FIG. 2 is a schematic view showing another embodiment of the printed product 1 of the present invention. The receiving layer 3, the adhesive layer 6, and the protective layer 4 are laminated on the substrate 2. 3, a thermal transfer image 5 by a sublimation dye thermally transferred by heating is formed from a thermal transfer sheet having a dye layer containing a sublimation dye on a substrate, and the receptor layer 3 is formed so as to cover the thermal transfer image 5. Are provided with an adhesive layer 6 and a protective layer 4 by thermal transfer. In the printed matter 1, a mat shape is formed on the entire surface of the protective layer 4. It is not limited to that shown in the figure, and the formation position of the thermal transfer image, the formation position of the protective layer, and the formation position of the concavo-convex shape can be appropriately changed.

Hereinafter, each layer constituting the printed matter of the present invention will be described in detail.
(Base material)
It is desirable that the base material 2 of the printed material has a role of holding the receiving layer, and has mechanical characteristics that can withstand heat applied during image formation and that does not hinder handling. The material of such a substrate is not particularly limited. For example, polyester, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polystyrene, acrylic, poly Vinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / Various plastic films or sheets such as hexafluoropropylene, polychlorotrifluoroethylene, and polyvinylidene fluoride Can be used is not particularly limited.

  White film formed by adding a white pigment or filler to these plastic films or sheets, or sheets having microvoids inside the base sheet, as well as condenser paper, glassine paper, sulfuric acid paper, synthetic paper (Polyolefin-based, polystyrene-based), fine paper, art paper, coated paper, cast coated paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin-added paper, cellulose fiber paper, and the like can be used. Moreover, the laminated body by arbitrary combinations of said base material can also be used. Typical examples include a laminate of cellulose fiber paper and synthetic paper, and cellulose fiber paper and a plastic film. Moreover, the base material which carried out the easy adhesion process on the surface and / or the back surface of said base material can also be used. The thickness of these base materials is usually about 3 to 300 μm. In the present invention, it is preferable to use a base material of 75 to 175 μm in consideration of mechanical suitability and the like. Moreover, when the adhesiveness of a base material and the layer provided on it is scarce, it is preferable to perform an easily bonding process or a corona discharge process on the surface.

(Receptive layer)
The receiving layer 3 used in the printed product of the present invention is generally composed mainly of a thermoplastic resin. Examples of the material for forming the receiving layer include polyolefin resins such as polypropylene, vinyl chloride / vinyl acetate copolymer resins, ethylene / vinyl acetate copolymer resins, halogenated polymers such as polyvinylidene chloride resins, and polyvinyl acetate. Resins, polyester resins such as polyacrylic ester resins, polystyrene resins, polyamide resins, copolymer resins of olefin resins such as ethylene and propylene and other vinyl monomers, cellulose resins such as ionomers and cellulose diacetate, Polycarbonate resins, polyvinyl acetal resins, polyvinyl butyral resins and the like can be mentioned, among which polyester resins, vinyl chloride / vinyl acetate copolymers, and mixtures thereof are particularly preferable. Among them, for example, a resin having good adhesiveness during heating such as a polyamide resin, a vinyl chloride / vinyl acetate copolymer resin, and a polyester resin is preferable.

  In the sublimation transfer recording, a release agent can be mixed in the receiving layer for the purpose of preventing fusion with the receiving layer or a decrease in printing sensitivity during image formation. Preferable release agents used in combination include silicone oil, phosphate ester surfactants, fluorine surfactants, and the like, among which silicone oil is desirable. As the silicone oil, modified silicone oils such as epoxy modification, vinyl modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are desirable.

  One or more release agents are used. Moreover, the addition amount of the release agent is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the receiving layer forming resin. When the range of the addition amount is not satisfied, problems such as fusion between the sublimation type thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet or a decrease in printing sensitivity may occur. By adding such a releasing agent to the receiving layer, the releasing agent bleeds out on the surface of the receiving layer after the transfer to form a releasing layer. Further, these release agents may not be added to the receiving layer but may be separately applied on the receiving layer. The receiving layer is prepared by dissolving a resin as described above with a necessary additive such as a mold release agent in a suitable organic solvent or by dispersing a dispersion in an organic solvent or water. It is formed by coating and drying by a coating method. In forming the receiving layer, a white pigment, a fluorescent brightening agent, or the like can be added for the purpose of improving the whiteness of the receiving layer and further enhancing the sharpness of the transferred image. The receiving layer formed as described above may have any thickness, but generally has a thickness of 1 to 50 μm in a dry state.

  FIG. 3 is a schematic view showing one embodiment of a protective layer thermal transfer sheet used in forming the printed product of the present invention. The protective layer thermal transfer sheet 10 has a configuration in which a release layer 12, a protective layer 13, and an adhesive layer 14 are sequentially laminated on a substrate 11. In the case of this protective layer thermal transfer sheet, the protective layer and the adhesive layer are transferred onto the thermal transfer image of the receiving layer of the printed matter by heating to a necessary place with an appropriate area. The protective layer thermal transfer sheet is not limited to the illustrated one, and only the protective layer may be provided on the substrate, the adhesive layer may be removed, or the protective layer thermal transfer sheet may be appropriately changed.

The layers constituting the protective layer thermal transfer sheet used in the present invention will be described below.
(Base material)
As the base material 11 used in the protective layer thermal transfer sheet of the present invention, the same base material as that used in the conventional thermal transfer sheet can be used as it is, and the surface of the sheet is subjected to an easy adhesion treatment. Some and others can be used and are not particularly limited.

  Specific examples of preferable base materials include, for example, polyester films such as polyethylene terephthalate, polycarbonate, polyamide, polyimide, cellulose acetate, polyvinylidene chloride, polyvinyl chloride, polystyrene, fluororesin, polypropylene, polyethylene, and ionomer. Cellophane and the like, and composite films in which two or more of these are laminated can also be used. Although the thickness of these base materials is suitably changed according to the material so that the strength and heat resistance are appropriate, it is usually preferably about 2.5 to 10 μm.

(Release layer)
On the substrate, a release layer 12 that makes the transferability of the protective layer formed thereon suitable can be provided. As the resin for forming the release layer, any conventionally known resin having excellent release properties can be used. For example, waxes, silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol , Acrylic resins, acrylic-styrene resins, thermally crosslinkable epoxy-amino resins, and thermally crosslinkable alkyd-amino resins. These release resins can be used alone or as a mixture.

  In the release layer, various fillers can be added to the release resin material as described above. Examples of the filler used include known pigments such as silica, alumina, clay, and talc, and plastic pigments made of thermosetting resins, thermoplastic resins, waxes, and the like. To form a release layer, add a resin as described above and, if necessary, a filler, a crosslinking agent or a catalyst, and prepare a coating solution dissolved or dispersed in a general-purpose solvent such as methyl ethyl ketone, toluene, or isopropyl alcohol. Then, the coating solution is applied and dried on the base material by a conventionally known method such as gravure coating or gravure reverse coating so as to have a thickness (dry basis) of about 0.5 to 5 μm.

(Protective layer)
As the resin for forming the protective layers 4 and 13, any conventionally known various resins having excellent durability and transparency can be used. For example, acrylic resin, cellulose resin, polyvinyl acetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, polyamide resin, polyimide resin, polyamideimide resin, and the like can be given. As these thermoplastic resins, those having a glass transition temperature of 80 to 120 ° C. are preferably used. Moreover, said thermoplastic resin can be used individually or in mixture. If the glass transition temperature is less than 80 ° C, the protective layer is likely to be fused to the embossed plate during the embossing process, and bleeding of the thermal transfer image occurs when the printed material is stored at a high temperature. It becomes easy.

  In addition, when a thermoplastic resin having a glass transition temperature exceeding 120 ° C. is used, curling is likely to occur in a printed product after the embossing process using an embossing plate. This is because it is necessary to increase the processing temperature. Also, during the embossing process with the embossing plate, it is necessary to increase the heating temperature under the condition that at least one of the embossing plate itself and the printed material is heated. In some cases, blistering, i.e., blister-like deformation, tends to occur on a portion of the substrate surface. In order to form a protective layer from the resin as described above, the resin as described above is dissolved or dispersed in a general-purpose solvent such as methyl ethyl ketone, toluene or isopropyl alcohol, and if necessary, an ultraviolet absorber or a fluorescent whitening agent. Agent, inorganic or organic filler component, surfactant, mold release agent, etc. are added to prepare a coating solution, and the coating solution is made thick (dry basis) by a conventionally known method such as gravure coating or gravure reverse coating. It is formed by coating and drying so as to have a thickness of 0.5 to 10 μm, more preferably 1.0 to 5.0 μm. The protective layer is not limited to a single layer, and may be composed of multiple layers. The thickness of the protective layer combined with a single layer or multiple layers is preferably within the above range, and when it is too thin, the performance as the protective layer cannot be sufficiently exhibited. If the thickness is too thick, transfer defects such as tailing tend to occur during thermal transfer of the protective layer.

(Adhesive layer)
In the present invention, when the protective layer has sufficient adhesiveness, it is not necessary to form an adhesive layer. However, the adhesive layer 14 is formed on the surface of the protective layer to transfer the protective layer and protect it after the transfer. It is preferable to improve the adhesion of the layer to the printed matter. As the adhesive layer, any conventionally known heat-sensitive adhesive can be used, but it is more preferably formed from a thermoplastic resin having a glass transition temperature of 50 to 100 ° C., for example, an ultraviolet absorbing resin, an acrylic resin, or vinyl chloride. -Select a resin having an appropriate glass transition temperature from a resin having a good adhesive property when heated, such as a vinyl acetate copolymer resin, an epoxy resin, a polyester resin, a polycarbonate resin, a butyral resin, a polyamide resin, or a vinyl chloride resin. It is preferable.

(Heat resistant slipping layer)
The protective layer thermal transfer sheet is preferably provided with a heat-resistant slipping layer on the back surface of the base material, that is, the surface opposite to the surface on which the protective layer is provided, in order to prevent adverse effects such as sticking and wrinkles due to the heat of the thermal head. . The thickness of the heat resistant slipping layer is about 0.1 to 2 μm in terms of solid content.

  Moreover, in this invention, when forming the thermal transfer image by a sublimation dye in a receiving layer, the thermal transfer sheet which has the dye layer containing a sublimation dye on a base material is used. As this substrate, the same substrate as that used in the protective layer thermal transfer sheet can be used. In addition, when the dye layer is bonded with a sublimable dye having a hue of yellow, magenta, cyan, black, or the like with a binder resin and heated, the sublimable dye moves to the receiving layer described above and is fixed. In the printed matter of the present invention, it is an essential condition that a thermal transfer image is formed with a sublimation dye, but thermal transfer of a heat-meltable ink layer may be used in combination. The heat-meltable ink layer can be composed of a colorant such as a colored pigment or dye, a wax or a resin binder, and melts when heated, and is transferred and fixed to the receiving layer for each ink layer. In the present invention, the above protective layer thermal transfer sheet and the thermal transfer sheet having the dye layer are separately prepared and used, or the dye layer and the protective layer are provided in the same order on the same substrate. Each of them can be used by thermal transfer with a thermal head.

(Method for forming printed matter)
In the method for forming a printed matter of the present invention, a thermal transfer image-receiving sheet provided with a receiving layer on a base material and a thermal transfer sheet having a dye layer containing a sublimation dye on the base material are superposed on each other and heated. Forming a thermal transfer image with a sublimable dye on the layer, and then providing a thermal transfer sheet on at least a portion of the thermal transfer image using a thermal transfer sheet provided with a thermal transferable protective layer on the substrate; A printed matter in which a mat shape is formed on the surface by embossing an embossed plate having a concavo-convex shape on at least one of the embossed plate and the printed material on at least a part of the protective layer. It is a creation method. Further, it is desirable that a release treatment is applied to the uneven surface of the embossed plate. Furthermore, the uneven shape of the embossed plate has a Ra value measured by a three-dimensional surface roughness shape measuring machine of 0.5 to 20 μm, and the number of uneven portions of 0.5 to 20 μm is 10 to 200 per 1 mm ^2. It is preferable to have one.

(Embossed version)
The embossed plate used for forming the mat shape on the surface of the printed material is not limited with respect to the uneven shape of the surface, and the embossed plate can be copied onto the protective layer of the printed material. It ’s fine. For example, as shown in FIG. 4, the printed product 1 is not shown, but is conveyed in the direction of an arrow by a pair of conveying rolls sandwiching the printed material, and a roll-shaped emboss having a concavo-convex surface. The printed material 1 passes between the plate 20 and the pressure-bonding roll 21 opposite thereto, and the embossing plate 20 and the pressure-bonding roller 21 rotate in the rotation direction shown in the figure, while applying pressure to the long-sized printed material 1. As a result, a mat shape having irregularities on the surface of the protective layer of the printed material can be continuously formed. In this case, in order to make the surface of the embossing plate 20 heated, or to make the protective layer surface of the printed material heated, the printed material before the embossing plate embossing treatment is irradiated with infrared rays or the like. Heating can be used, or these conditions can be used in combination.

  Further, as shown in FIG. 5, as the embossing plate embossing process, the print 1 is conveyed by a pair of conveying rolls 33 and 34, and a roll 31, a roll 37, and a roll 38 are arranged inside the endless belt 30. The endless belt is stretched and moves in the direction of the arrow indicated by A to circulate. The surface of the endless belt 30 (on the side not in contact with the rolls 31, 37, 38) has an uneven shape, and since the roll 31 is heated, the uneven portion of the belt is It is in a heated state. The printed product 1 is pressed between the roll 31 and the roll 32 while the protective layer surface of the printed product is in contact with the uneven portion of the belt. By rotating the roll 31 and the roll 32 in the directions shown, the endless belt 30 smoothly circulates in the direction A. As a result, a mat shape is continuously formed on the surface of the elongated printed material, and the printed material 1 is conveyed in the direction indicated by B by the rotation of the conveying rollers 35 and 36.

  The embossing process using the embossing plate is not limited to the example shown in the figure, and a flat embossing plate is used. A printed material is placed between the embossing plate and the flat plate, and either the embossing plate or the printed material is heated. The embossed plate is pressed against a flat table and pressed, and then the adjacent portion of the pressed print portion is similarly pressed. This is a so-called hot stamp method. By repeating this processing operation in the same manner, a mat shape can be formed on the surface of the printed matter. However, a method using the above-mentioned roll-shaped embossed plate that can continuously form a mat shape on the surface of a long print or a method using an embossed plate of an endless belt are preferably employed.

  In the embossing process using the embossing plate as described above, even if the embossing plate is in the form of a roll, endless belt, or flat plate, the material of the uneven surface is particularly limited as long as the releasability from the printed material can be secured. Not. For example, a thermosetting resin, a UV (ultraviolet ray) curable resin, or a metal or the like that can ensure the releasability of the protective layer on the surface of the printed material from the thermoplastic resin is desirable. Further, as a method of processing the uneven shape on the surface of this embossed plate, any method may be used as long as a desired mold is provided, and a sandblasting method, engraving method, etching method, electric perforation method, which are the same methods as those for normal plate making A plating method or the like can be employed. These methods can also be performed in combination. The group of uneven shapes formed on the surface of the embossed plate is not necessarily a regular repeating pattern (pattern) but preferably a random (random) array of unevenness having the same or different sizes. As a suitable pattern in the practice of the present invention, a quadrangular pyramid having four side surfaces, a shape left after cutting the four-sided quadrangular pyramid, a triangular pyramid having three side surfaces, a cone, a partial sphere, a parabola, and a parabola Examples include a rounded outer shape having a shape at the tip.

  In addition, a fluororesin, a silicone resin, or a long-chain alkyl resin compound is applied as a release agent to the uneven surface of the embossed plate, and if necessary, heat curing, curing by ionizing radiation irradiation Thus, a release treatment in which a release agent layer is formed can be performed. Also, when the embossed plate is made of metal, metal coating treatment such as electroplating, diffusion plating, vapor deposition plating, electroless plating, thermal spraying; ceramic coating by CVD, PVD, ion plating, sputtering, vacuum deposition, etc. It is also preferable to perform a mold release treatment by performing a non-metal coating treatment or a composite coating treatment thereof. Specific examples include electrolytic plating and electroless plating of hard chromium and the like; ceramic coating treatment of titanium nitride (TiN), chromium nitride (CrN), titanium nitride aluminum (TiAlN), and the like.

  If the releasability between the protective layer surface of the printed material and the uneven surface of the embossed plate is insufficient, the protective layer having transparency on the surface of the printed material will be fogged, and the appearance of the printed material may be impaired. In the stamping process using a plate, in the case of continuous processing, jamming occurs and a problem arises. Therefore, it is preferable to perform the mold release treatment of the uneven portion of the embossed plate as described above.

三次元表面粗さ形状測定機で測定したＲａ値が０．５〜２０μｍである凹凸形状のエンボス版を使用して、印画物に型押しを行い、印画物の表面には１ｍｍ²の単位面積当たりで、エンボス版の凹凸の個数と同じである１０〜２００個の凹凸を有し、三次元表面粗さ形状測定機で測定したＲａ値が、エンボス版のＲａ値よりは少な目である０．５〜１０μｍのＲａ値の印画物が得られる。エンボス版の凹凸は、図６でｍで示す単位が１つであり、この凹凸数やそれらの間隔、ならびに個々の凹凸の性質、例えば、凹凸の深さ、反射エッジの角度、および形状は、０．５〜２０μｍの凹凸の個数が１ｍｍ²当たり１０〜２００個を有する条件下で、所望に変化させることができる。 In the present invention, the uneven shape of the embossed plate to be used is an unevenness having an Ra value of 0.5 to 20 μm measured by a three-dimensional surface roughness shape measuring machine, and the number of unevenness of 0.5 to 20 μm is 1 mm ^2. What has 10-200 per is preferable. The embossed plate is embossed so that the unevenness of the surface of the printed material has an Ra value of 0.5 to 10 μm measured by a three-dimensional surface roughness shape measuring machine and 0.5 to 10 μm. number of can be made to have a 10 to 200 per 1 mm ^2, a desired mat pattern can be realized having various surface shapes of the mat pattern or the like having a suitable uneven. Regarding the Ra value measured by the three-dimensional surface roughness shape measuring instrument in the uneven shape of the embossed plate and the uneven surface of the printed material in the present invention, both are measured according to the standard of JIS B0601 (-1994). It is obtained. That is, as shown in FIG. 7, a portion of the measurement length l is extracted from the roughness curve in the direction of the center line (m), the center line (m) of the extracted portion is the X axis, and the direction of the vertical magnification is Y. When the roughness curve is expressed as y = f (x), the value obtained by the following formula is expressed in micrometers (μm), which is the arithmetic average roughness Ra.

Using a concavo-convex embossed plate with a Ra value of 0.5 to 20 μm measured with a three-dimensional surface roughness profile measuring machine, the printed material is embossed, and a unit area of 1 mm ² is formed on the surface of the printed material. The Ra value of 10 to 200, which is the same as the number of unevenness of the embossed plate, is less than the Ra value of the embossed plate. A print with an Ra value of 5-10 μm is obtained. The unevenness of the embossed plate has one unit indicated by m in FIG. 6, and the number of the unevenness and the interval between them and the properties of the individual unevenness, for example, the depth of the unevenness, the angle of the reflection edge, and the shape are as follows: It can be changed as desired under the condition that the number of irregularities of 0.5 to 20 μm is 10 to 200 per 1 mm ² .

The number of concavo-convex of 0.5 to 20 μm in the concavo-convex shape of the embossed plate in the present invention means all calculated by the method described below. Further, the number of irregularities of 0.5 to 10 μm in the irregular shape on the surface of the printed material in the present invention is the same as the number of irregularities of 0.5 to 20 μm of the embossed plate used in the embossing process for the printed material.
(Measurement condition)
Measuring machine name: 3D surface roughness shape measuring machine Surfcom 1400-3DF (manufactured by Tokyo Seimitsu Co., Ltd.)
Parameter calculation standard: JIS-B0601; '82, B0031; Measurement type according to '82 standard: Roughness measurement (analysis condition)
Cut-off type: Phase compensation cut-off wavelength: 0.8μm
Short wavelength cut-off filter: None Measurement speed: 0.600 mm / s
Tilt correction data: Entire range Tilt correction: Plane correction Measurement range: 2 mm x 4 mm
Measurement pitch: 20 μm
Number of measurement points: 101 × 201 points Peak count level: Upper limit value → 0.5 μm, Lower limit value → −0.5 μm
(Concavity and convexity calculation method)
Let P be the number of peaks obtained by the above analysis. Since the measurement range is 2 mm × 4 mm, if the peak number of 1 mm × 1 mm width is A,
A = (P / 4) ² ... (1)
Can be calculated.
(When there is a protrusion of 20 μm or more)
If the absolute values of the maximum peak height and the maximum valley depth obtained by the above measurement exceed 20 μm, the upper limit value and the lower limit value of the peak count are reanalyzed as 20 μm, and the obtained values are similarly expressed in Equation (1). Substitute and calculate. By subtracting the obtained value from the calculated value when the upper limit value and the lower limit value of the previous peak count are 0.5 μm, a preferable number of irregularities can be obtained.
The uneven shape of the surface of the printed material is an unevenness having an Ra value of 0.5 to 10 μm measured by a three-dimensional surface roughness shape measuring machine, and the number of unevenness of 0.5 to 10 μm is 10 to 200 per 1 mm ^2. If the Ra value is too small, that is, if the depth of the unevenness is shallow, the mat pattern is difficult to reproduce and is not visually attractive. If the Ra value is too large, that is, if the depth of the irregularities is too deep, the function as a protective layer on the thermal transfer image becomes insufficient. On the other hand, if the number of irregularities is less than the above range, the feeling of pattern disappears and it is not beautiful. On the other hand, if the number of irregularities is too large, the number of convex portions on the surface of the printed material is reduced as a whole, and the appearance is not beautiful. In the present invention, the printed matter obtained by the embossing process using an embossed plate preferably has a glossiness of 30 to 70% measured at an incident angle of 45 ° on the surface. The above glossiness is obtained by measuring the specular glossiness at an incident angle of 45 ° based on JIS Z 8741. When the glossiness exceeds 70%, the glossiness is too high and the matte feeling is small, while when the glossiness is less than 30%, the matte feeling is too strong and the thermal transfer image becomes invisible.

  Further, in the printed matter obtained by the embossing process using the embossing plate of the present invention, the ratio of the reflection density in the region having a reflection density of 1.5 or more of the thermal transfer image of the printed product before and after the embossing process of the embossing plate is [ Reflected density value after processing / reflected density value before processing] × 100, and preferably 80 to 120%. In other words, before and after the embossing plate embossing process, the reflection density change is within a range of ± 20% in the area where the reflection density of the thermal transfer image of the printed product is 1.5 or more. Concentration change is not recognized.

(Experimental example)
The present invention will be described in more detail by experimental examples. In the text, “part” or “%” is based on mass unless otherwise specified.
(Thermal transfer image receiving sheet and thermal transfer sheet used)
Canon sublimation transfer printer (compact photo printer) CP-200 dedicated image receiving paper and ink ribbon (thermal transfer sheet) were used. However, a film coated with a protective layer made of a resin having a specified Tg (glass transition temperature) shown in Table 1 with a thickness of 4 μm is attached to the overcoat portion of the ink ribbon. Changed.

(Printing conditions)
Using Canon's sublimation transfer printer CP-200, a printed matter having a solid black image of three colors of yellow, magenta, and cyan was formed using the thermal transfer image receiving sheet and the thermal transfer sheet. .

(Embossing with embossed plate)
Using the embossed plate (Each Ra value and the number of irregularities is an average value) in which the Ra value of the irregular shape on the surface of the embossed plate shown in Table 1 and the number of irregularities per 1 mm ² are defined, each print With the heat roller laminator (FUJI LAMIPACKER LPD23-5PRO), the lamination temperature shown in Table 1 (the surface temperature of the embossed plate) was formed so as to overlap the surface (protective layer surface) and form an uneven shape on the surface of the printed material. The mold pressing process was performed.

(Glossiness measurement method)
The glossiness of each printed material having a concavo-convex shape obtained by the above-described thermal transfer image and embossing with an embossed plate was measured under the following conditions. Glossiness was measured at an incident angle of 45 ° with a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Reflection density measurement method)
The maximum value was measured by the reflection density of the solid black portion of each printed matter on which the uneven shape was formed by the heat transfer image and the embossing process using the embossed plate. The measuring instrument was a reflection densitometer Macbeth RD-914 manufactured by Gretag-Macbeth, and was measured using a Bk filter. However, the reflection density of both the embossed plate before and after the stamping treatment was measured. Further, in the obtained reflection density, the ratio of the reflection density was calculated by [reflection density value after processing / reflection density value before processing] × 100 (%).

(Measurement method of uneven shape of printed matter)
The Ra values of the concavo-convex portions of each printed matter on which the concavo-convex shape was formed by the stamping process using the thermal transfer image and the embossed plate were measured, and the average values are shown in Table 1. As described above, the Ra value of the concavo-convex portion is the arithmetic average roughness Ra measured according to the standard of JIS B0601. The number of irregularities of 0.5 to 20 μm per mm ² in the irregular shape on the surface of the embossed plate is calculated from the data measured with a three-dimensional surface roughness meter according to the standard of JIS B0601 under the following conditions. And the same number as the number of the unevenness is the number of the unevenness of the printed matter. The results are shown in Table 1. Detailed measurement conditions, analysis conditions, calculation method of the number of irregularities, etc. are shown below.
(Measurement condition)
Measuring machine name: 3D surface roughness shape measuring machine Surfcom 1400-3DF (manufactured by Tokyo Seimitsu Co., Ltd.)
Parameter calculation standard: JIS-B0601; '82, B0031; Measurement type according to '82 standard: Roughness measurement (analysis condition)
Cut-off type: Phase compensation cut-off wavelength: 0.8μm
Short wavelength cut-off filter: None Measurement speed: 0.600 mm / s
Tilt correction data: Entire range Tilt correction: Plane correction Measurement range: 2 mm x 4 mm
Measurement pitch: 20 μm
Number of measurement points: 101 × 201 points Peak count level: Upper limit value → 0.5 μm, Lower limit value → −0.5 μm
(Concavity and convexity calculation method)
Let P be the number of peaks obtained by the above analysis. Since the measurement range is 2 mm × 4 mm, if the peak number of 1 mm × 1 mm width is A,
A = (P / 4) ² ... (1)
Can be calculated.
(When there is a protrusion of 20 μm or more)
If the absolute values of the maximum peak height and the maximum valley depth obtained by the above measurement exceed 20 μm, the upper limit value and the lower limit value of the peak count are reanalyzed as 20 μm, and the obtained values are similarly expressed in Equation (1). Substitute and calculate. By subtracting the obtained value from the calculated value when the upper limit value and the lower limit value of the previous peak count are 0.5 μm, a preferable number of irregularities can be obtained.

(appearance)
The surface appearance of each printed material on which the concavo-convex shape was formed by the above-described thermal transfer image and embossing with an embossed plate was visually examined and evaluated according to the following criteria.
A: Appearance is embossed and non-glossy and has a desired mat pattern and is beautiful.
Δ: Appearance is not recognized as a desired mat pattern in terms of embossed state and non-glossiness.
X: The appearance of the embossed state and non-glossiness are not recognized as desired mat patterns.

＊１；エンボス形状、非光沢性には問題ないが、印画物の基本性能（高温保存時の滲み等）で問題が発生した。 Table 1 shows the results of the measurements and evaluations described above for each printed matter having a concavo-convex shape formed by the stamping process using the thermal transfer image and the embossed plate.

* 1: There was no problem with the embossed shape and non-glossiness, but there were problems with the basic performance of the printed matter (bleeding during high-temperature storage).

  As described above, in the printed materials of Experimental Examples 1 to 8, the glossiness measured at an incident angle of 45 ° on the surface of the printed material is all in the range of 30 to 70%. The maximum density after embossing with the embossed plate is slightly lower, but there is no problem. In addition, the printed materials of Experimental Examples 1 to 8 are beautiful in appearance and have a desired mat pattern with respect to the embossed state and non-glossiness. On the other hand, in Experimental Example 9, the surface was not subjected to any embossing process with an embossed plate, and no mat pattern was observed. The printed matter of Experimental Example 10 has an uneven shape on the surface of the printed matter, has an Ra value of less than 0.5 μm and is too shallow, and is not satisfactory in appearance. In addition, the printed materials of Experimental Examples 11, 16, and 17 are uneven shapes on the surface of the printed material, the Ra value is larger than 10 μm, and the surface is too rough. There are also problems such as bleeding when the printed matter is stored at high temperature.

The printed materials of Experimental Examples 12 and 16 are uneven in shape on the surface of the printed material, and the number of unevenness is less than 10 per 1 mm ² . The prints of Experimental Examples 13 and 17 have a concavo-convex shape on the surface of the print product, the number of concavo-convexs exceeding 200 per 1 mm ² , and there are generally few convex portions on the surface of the print product, which is not beautiful in appearance. The printed matter of Experimental Example 14 has no problem in appearance, but the glass transition temperature of the resin constituting the protective layer is 50 ° C. and has a low Tg, and the basic performance of the printed matter (bleeding during high-temperature storage, etc.) Will cause problems. The printed matter of Experimental Example 15 has an uneven shape on the surface of the printed matter and has an Ra value of less than 0.5 μm and is too shallow, and is not satisfactory in appearance.

  Further, before and after the embossing plate embossing process, the ratio of the reflection density in the region having a reflection density of 1.5 or more of the thermal transfer image of the printed material [reflection density value after processing / reflection density value before processing] × 100 The ratio of the reflection density of all the printed materials in Experimental Examples 1 to 8 was 80 to 120%, and no change in density was visually observed. On the other hand, the printed matter in Experimental Examples 13 and 17 had a ratio of the reflection density smaller than 80%, and the density change was visually observed before and after the embossing stamping process. .

It is the schematic which shows one embodiment of the printed matter of this invention. It is the schematic which shows other embodiment of the printed matter of this invention. It is the schematic which shows one Embodiment of the protective layer thermal transfer sheet used when forming the printed matter of this invention. It is the schematic which shows one embodiment of the embossing plate used when forming the printed matter of this invention. It is the schematic which shows other embodiment of the embossing plate used when forming the printed matter of this invention. It is the schematic explaining the number of the unevenness | corrugations on the surface of an embossing plate. It is the schematic explaining the Ra value measured with the three-dimensional surface roughness shape measuring machine.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Printed object 2 Base material 3 Receiving layer 4 Protective layer 5 Thermal transfer image 6 Adhesive layer 10 Protective layer thermal transfer sheet 11 Base material 12 Release layer 13 Protective layer 14 Adhesive layer 20 Embossing plate 21 Crimp roll 30 Endless belt 31, 32, 37 , 38 rolls 33, 34, 35, 36 transport rolls

Claims (8)

  In a method in which a thermal transfer image-receiving sheet provided with a receiving layer on a substrate and a thermal transfer sheet having a dye layer containing a sublimable dye are heated on the substrate and heated to form a printed matter, the receiving layer is sublimated. A thermal transfer image is formed by a photosensitive dye, and then a protective layer is thermally transferred onto at least a part of the thermal transfer image using a thermal transfer sheet on which a thermal transferable protective layer is provided on a substrate, and then the protection is performed. A method for producing a printed material, wherein a mat shape is formed on a surface of a layer by embossing an embossed plate having an uneven surface on a surface under heating conditions.   The method for forming a printed matter according to claim 1, wherein a release treatment is performed on the uneven surface of the embossed plate. As for the uneven shape of the embossed plate, the Ra value measured by a three-dimensional surface roughness shape measuring machine is 0.5 to 20 μm, and the number of uneven portions of 0.5 to 20 μm is 10 to 200 per 1 mm ^2. The method for forming a printed matter according to claim 1, comprising:   Before and after the embossing plate embossing process, the ratio of the reflection density in the region having a reflection density of 1.5 or more of the thermal transfer image of the printed product is [reflection density value after processing / reflection density value before processing] × 100. The method for forming a printed matter according to claim 1, wherein a change in density is not recognized.   A receiving layer is provided on a substrate, and a thermal transfer image is formed on the receiving layer by a sublimation dye thermally transferred by heating from a thermal transfer sheet having a dye layer containing a sublimation dye on the substrate. In a printed matter in which a protective layer is provided by thermal transfer on at least a part of an image, an embossed plate having a concavo-convex shape is embossed on at least a part of the protective layer on a surface under heating conditions. Printed matter characterized by having a mat shape.   The printed matter according to claim 5, wherein the protective layer is made of a thermoplastic resin having transparency and a glass transition temperature of 80 to 120 ° C.
As for the uneven shape on the surface of the printed material, the Ra value measured by a three-dimensional surface roughness shape measuring machine is 0.5 to 10 μm, and the number of uneven portions of 0.5 to 10 μm is 10 to 200 per 1 mm ^2. The printed matter according to claim 5, wherein The printed matter according to claim 5, wherein the glossiness measured at an incident angle of 45 ° on the surface of the printed matter is 30 to 70%.

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