JP2002002108A - Protective layer transfer sheet - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a protective layer thermal transfer sheet having excellent writing properties and a sealability corresponding to various writing instruments. SOLUTION: In a protective layer transfer sheet in which a heat transferable protective layer is provided releasably on at least a part of an opposite surface of a substrate sheet having a heat-resistant lubricating layer on one surface, The outermost surface layer is composed of an acrylic resin and at least one of hydroxymethylcellulose and carboxymethylcellulose, and the outermost surface layer of the protective layer after the transfer has a crack shape or a shape having micropores. The printing ink and the inks of various writing tools penetrate into the voids, and are easy to dry and fix, and a protective layer excellent in writing properties and printing properties corresponding to various writing tools can be obtained. Further, as a protective layer transfer sheet, the protective layer is excellent in film-cutting property from the base sheet, and in the resulting print after transfer of the protective layer, the gloss and transparency of the protective layer are good.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective layer transfer sheet provided with a protective layer so that it can be peeled off.
The present invention relates to a protective layer transfer sheet capable of providing an image formed by a thermal transfer recording method with a printing property, a water-based pen, a fountain pen and the like.

[0002]

2. Description of the Related Art At present, a thermal transfer recording method is widely used as a simple printing method. In the thermal transfer recording method, since various images can be easily formed, the number of prints may be relatively small, for example, a printed matter such as creation of an ID card such as an identification card, a business photograph, a printer of a personal computer, a video printer, etc. Used in When a full-color gradation image such as a face photograph is preferable as a thermal transfer sheet to be used, an ink layer such as yellow, magenta, and cyan (and further, if necessary) is formed on a continuous base sheet. And black) are repeatedly provided face-to-face.
Such a thermal transfer sheet is roughly classified into a so-called fusion transfer type thermal transfer sheet, in which a color material layer is melted and softened by heating, and the color material layer itself is transferred to an object to be transferred, that is, an image receiving sheet. Thus, the dye in the color material layer is sublimated, and the dye is transferred to the image receiving sheet.

When an identification card or the like is manufactured using the above-described heat transfer sheet, a monotonous image such as a character or a number can be easily formed by using a heat-fusion type heat transfer sheet. Has the drawback that it is inferior in durability, especially abrasion resistance. On the other hand, when a thermal sublimation transfer type thermal transfer sheet is used, a gradation image such as a face photograph can be precisely formed, but the formed image is different from that using ordinary printing ink. There is no vehicle, and it is formed of a dye, but has a drawback that it is inferior in durability such as weather resistance, friction resistance and chemical resistance.

In order to cope with the above, an image obtained by thermal transfer of a hot-melt colorant layer or a thermo-sublimable dye is printed on the image.
A method is known in which a protective layer thermal transfer sheet having a thermal transfer resin layer is overlaid, the thermal transfer resin layer is transferred using a thermal head, a heating roll, or the like, and a protective layer is formed on an image. By providing this protective layer, the rub resistance, chemical resistance, solvent resistance and the like of the image can be improved to some extent, and the light resistance is further improved by adding an ultraviolet absorber and the like in the protective layer. It becomes possible.

[0005]

Problems to be Solved by the Invention
No. 0 and the like have a protective layer transfer sheet having a surface layer of a porous structure in which fine particles such as colloidal silica are dispersed in a binder resin, and those having a printing property and a writing property of an aqueous ink are described. Have been. However, in this example, although the water-based ink has good water absorption, the writing property of an oil-based ink or a water-resistant pen causes bleeding and the like, and the writing property does not have a writing property corresponding to various writing tools. There is. Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a protective layer heat transfer sheet having excellent writing properties and imprintability corresponding to various writing instruments.

[0006]

According to the present invention, in order to solve the above-mentioned problems, a heat transferable protective layer is provided on at least a part of an opposite side of a base sheet having a heat-resistant lubricating layer on one side. In the protective layer transfer sheet provided with, the thermal transferable protective layer, has a printing performance / writing performance, the outermost surface layer after transfer is composed of an acrylic resin, hydroxymethylcellulose, at least one of carboxymethylcellulose. Things.

It is preferable that the outermost surface layer of the protective layer after the transfer has a crack shape or a shape having micropores. Further, it is desirable that the ratio of at least one of the above-mentioned hydroxymethylcellulose and carboxymethylcellulose to the acrylic resin is 0.1% to 50%. The thickness of the protective layer outermost layer after the transfer,
Desirably, it is 0.5 μm to 5 μm.

[0008]

Next, the present invention will be described in more detail with reference to embodiments. FIG. 1 is a cross-sectional view showing one embodiment of a protective layer transfer sheet 7 of the present invention, which has a heat-resistant lubricating layer 3 on one surface of a base sheet 1 and the other side of the base sheet 1. A heat transferable protective layer 2 is provided on the surface, and the heat transferable protective layer 2 has a configuration in which a stamping / writing protection layer 4 and an adhesive layer 5 are formed in this order from the base sheet 1 side. The layer 2 can be separated from the base sheet 1 by heating.

FIG. 2 is a cross-sectional view showing another embodiment of the protective layer transfer sheet 7 of the present invention. The base sheet 1 has a heat-resistant lubricating layer 3 on one surface. A heat transferable protective layer 2 is provided on the other surface of the substrate 1, and the heat transferable protective layer 2 includes a release layer 6, a sealable / writable protective layer 4, and an adhesive layer 5 in this order from the base sheet 1. The heat transferable protective layer 2 is easily separated from the base sheet 1 by heating by separating the release layer 6 and the sealable / writable protective layer 4 from each other.

Hereinafter, each layer constituting the protective layer transfer sheet of the present invention will be described. (Base Sheet) As the base sheet 1 used in the protective layer transfer sheet of the present invention, the same base sheet as used in the conventional thermal transfer sheet can be used as it is, and the surface of the sheet can be used. A material which has been subjected to an easy adhesion treatment or another material can be used, and there is no particular limitation.

Specific examples of preferable base sheets include, for example, polyesters such as polyethylene terephthalate, polycarbonate, polyamide, polyimide, and the like.
There are plastic films such as cellulose acetate, polyvinylidene chloride, polyvinyl chloride, polystyrene, fluororesin, polypropylene, polyethylene, and ionomer; papers such as glassine paper, condenser paper, and paraffin paper; and cellophane. A composite film in which more than one kind are laminated can also be used. The thickness of these substrate sheets is appropriately changed depending on the material so that the strength and heat resistance are appropriate, but usually the thickness is 2.5 to 10
About 0 μm is preferable.

(Thermal Transferable Protective Layer) In the protective layer transfer sheet of the present invention, a thermal transferable protective layer 2 is provided on at least a part of the substrate sheet so as to be peelable. -It has writing performance, and the outermost surface layer after transfer is composed of an acrylic resin and at least one of hydroxymethylcellulose and carboxymethylcellulose. The heat transferable protective layer can be composed of a sealable / writable protective layer 4 and an adhesive layer 5 from the substrate sheet side. The heat transferable protective layer has a structure in which a release layer 6, a marking / writing protection layer 4, and an adhesive layer 5 are formed in this order from the substrate sheet side. And the thermal transferable protective layer 2 can be easily separated from the base sheet 1 by heating.

(Seal / Writable Protective Layer)
Alternatively, the marking / writing protection layer 4 provided on the release layer is a layer having a water absorbing property, and has a marking / writing property at the same time as water absorption, and has water resistance, solvent resistance, and alcohol resistance. It is preferable to have both solvent resistance such as acetone resistance and performance such as plasticizer resistance. This seal / writable protective layer is located as the outermost surface layer of the protective layer after thermal transfer, and includes an acrylic resin,
It is composed of at least one of hydroxymethylcellulose and carboxymethylcellulose. As the acrylic resin, those in which a polymer is dispersed in an aqueous solution obtained by emulsion polymerization of an acrylate such as methyl acrylate or ethyl acrylate or a methacrylate such as methyl methacrylate or ethyl methacrylate are preferably used.
Particularly, a copolymer of methyl methacrylate and ethyl acrylate or butyl acrylate is preferably used.

Various cellulose ethers can be contained in addition to the hydroxymethyl cellulose and carboxymethyl cellulose contained in the protective layer for marking and writing. That is, methyl cellulose, ethyl cellulose,
Cellulose ethers such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylhydroxyethylcellulose can be added. Further, the sealable / writable protective layer is mainly composed of the above-mentioned acrylic resin, at least one of hydroxymethylcellulose and carboxymethylcellulose. Other resins include polyvinyl alcohol (PVA) -based resin, urethane-based resin, and water-soluble resin. Polyester resin, alkyl vinyl ether resin,
It is possible to add a maleic acid copolymer resin, a polyvinylpyrrolidone-based resin, a water-soluble alkyd resin, a non-cellulosic water-soluble polysaccharide, or the like.

The sealable / writable protective layer of the present invention is located as the outermost surface layer of the protective layer after thermal transfer and has a cracked shape or a shape having micropores. As one embodiment showing the shape, there is an enlarged photograph (magnification: 800 times) by a microscope as shown in FIG. When viewed from the surface of the sealable / writable protective layer after the thermal transfer, cracks having a width of several μm are spread in irregular directions in a leaf vein shape, and the porosity of the surface shape is 5% to 40%. The degree is preferred. The ink of the marking ink and various writing instruments penetrates into the voids of the cracks and the fine pores, and becomes easy to dry and fix. If the above porosity is too low, the writeability and the sealability corresponding to various writing tools will be reduced. On the other hand, if the porosity is too high, the transparency of the protective layer is reduced, and the clarity of the underlying thermal transfer image is deteriorated (the image is concealed).

Such a cracked shape or a shape having micropores is a coating liquid obtained by adding a water-soluble cellulose ether such as hydroxymethylcellulose or carboxymethylcellulose to an emulsion in which an acrylic resin is dispersed in an aqueous solution. Is applied to a substrate sheet and dried. The cause of the formation cannot be determined, but the acrylic resin and cellulose ether in the coating liquid are dry films, and due to the difference in thermal shrinkage of both resins, cracking phenomena and fine It is believed that pore formation occurs. The mixing ratio of at least one of the above-mentioned hydroxymethylcellulose and carboxymethylcellulose to the acrylic resin is preferably 0.1% to 50% by mass, and depending on the mixing ratio, cracks as described above, or A shape having fine holes can be formed. If the above mixing ratio is less than 0.1%, the writeability and the sealability corresponding to various writing implements decrease. On the other hand, if the above mixing ratio exceeds 50%, the porosity of the layer surface becomes too large, the transmittance as the protective layer is reduced, and the sharpness of the underlying thermal transfer image is deteriorated. (Hiding the image) is not preferable.

[0017] For example, gravure printing method,
It can be applied by a conventionally known forming means such as a screen printing method, a reverse coating method using a gravure plate, or the like, and dried to form a sealable / writable protective layer. The thickness of the sealing / writing protective layer is 0.5 μm to 5% in solid content.
It is preferably about μm. Its thickness. If it is thinner than this, water absorption performance and durability are insufficient, and if it is larger than this, problems occur in terms of transparency and transferability.

(Adhesive Layer) In the present invention, an adhesive layer 5 is preferably provided on the outermost surface of the transferable protective layer of the protective layer transfer sheet in order to improve the adhesion of the protective layer to the image receiving sheet. For the adhesive layer, any of conventionally known adhesives and heat-sensitive adhesives can be used, but the glass transition temperature is 50 ° C. to 80 ° C.
C. It is more preferred to be formed from a thermoplastic resin, for example, an ultraviolet absorbing resin, an acrylic resin, vinyl chloride-
Select a resin having an appropriate glass transition temperature from resins with good adhesiveness when heated, such as vinyl acetate copolymer resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, polyamide resin, vinyl chloride resin, etc. Is preferred.

As the ultraviolet absorbing resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber to a thermoplastic resin or an ionizing radiation curable resin can be used. More specifically, salicylates, benzophenones, benzotriazoles, substituted acrylonitriles,
Conventionally known non-reactive organic ultraviolet absorbers such as nickel chelate type and hindered amine type may be added with an addition polymerizable double bond (for example, vinyl group, acryloyl group, methacryloyl group, etc.), alcoholic hydroxyl group, amino group Those into which a reactive group such as a group, a carboxyl group, an epoxy group, and an isocyanate group are introduced can be exemplified. The adhesiveness with the base sheet is that the adhesive layer contains at least one resin of an ultraviolet absorbing resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, a polyester resin, and a polycarbonate resin. It is particularly preferred because it is excellent.

The adhesive layer is formed of the above resin, an organic ultraviolet absorber such as a benzophenone compound, a benzotriazole compound, an oxalic anilide compound, a cyanoacrylate compound, a salicylate compound, zinc, Additives of inorganic fine particles having an ultraviolet absorbing ability such as oxides of titanium, cerium, tin, iron and the like can be added. Further, as an additive, a color pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent whitening agent, and the like can be appropriately used as needed.
The resin constituting the adhesive layer as described above, and, if necessary,
By applying and drying a coating solution to which the above-described additives are added, preferably in a dry state, 0.5 to 10 μm
An adhesive layer is formed with a thickness of approximately.

(Heat-resistant lubricating layer) The protective layer transfer sheet of the present invention has an adverse effect such as sticking and wrinkling due to heat of the thermal head on the back surface of the base sheet, that is, the surface opposite to the surface provided with the heat transferable protective layer. In order to prevent this, a heat-resistant lubricating layer 3 is provided. As the resin forming the heat-resistant lubricating layer, any conventionally known resin may be used, for example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene. Resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetopropionate resin, cellulose acetate Butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin,
Polycarbonate resins, chlorinated polyolefin resins, and the like are included.

Further, in order to improve the heat resistance of the heat-resistant lubricating layer, the strength of the coating film, and the adhesion to the base sheet, a cured product of a thermoplastic resin having a reactive group in the resin and polyisocyanate, A reaction product with a monomer or oligomer having an unsaturated bond can be used, and a curing method is not particularly limited, for example, heating, irradiating with ionizing radiation, or the like. Added to the heat-resistant lubricating layer composed of these resins,
Alternatively, as a slipperiness imparting agent to be overcoated, phosphate ester, silicone oil, graphite powder, silicone-based graft polymer, fluorine-based graft polymer,
Examples include silicone polymers such as acrylic silicone graft polymers, acrylic siloxanes, and aryl siloxanes, and are preferably polyols, for example, a layer composed of a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate compound, and further a filler. Is more preferably added.

The heat-resistant lubricating layer is prepared by dissolving or dispersing the resin, the lubricity-imparting agent, and the filler described above with an appropriate solvent to prepare an ink for forming a heat-resistant lubricating layer. On the back surface of the above-mentioned substrate sheet, for example, it can be formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, a reverse coating method using a gravure plate or the like. The thickness of the heat-resistant lubricating layer is about 0.1 to 2 μm in solid content.

(Release Layer) When the transferable protective layer is difficult to peel off from the base sheet, a release layer 6 can be formed between the base sheet and the transferable protective layer. The release layer is, for example, waxes, silicone wax, silicone resin, fluorine resin, acrylic resin, polyvinyl alcohol resin, cellulose derivative resin, urethane resin, acetate vinyl resin, acrylic vinyl ether resin, maleic anhydride resin, and It can be formed by applying and drying a coating liquid containing at least one of these resin group copolymers by a conventionally known method such as gravure coating and gravure reverse coating. Among the above resins, as the acrylic resin, a resin such as acrylic acid or methacrylic acid, or a resin copolymerized with another monomer or the like is preferable, and is excellent in adhesion to the base material sheet and releasability from the protective layer. ing.

The release layer can be appropriately selected from those which migrate to the transfer object during thermal transfer, those which remain on the substrate sheet side, and those which undergo cohesive failure. The release layer remains on the base sheet side due to the thermal transfer, and the interface between the release layer and the heat transferable protective layer is made to be the surface of the protective layer after the thermal transfer. Because it is excellent in terms of transfer stability of the layer,
It is preferably performed. The release layer can be formed by a conventionally known coating method, and has a thickness of 0.5 to 5 μm in a dry state.
m is sufficient. If a matte protective layer is desired after the transfer, various particles are included in the release layer, or the surface of the release layer on the protective layer side is matted to form a matte surface. You can do it. In addition, if the releasability from the substrate sheet and the protective layer is good, the protective layer can be directly peeled off from the substrate sheet by thermal transfer without providing the release layer.

In the protective layer transfer sheet, the transferable protective layer described above may be provided alone on the base sheet,
(Yellow), M (magenta), and C (cyan) may be provided in a face-sequential manner together with a dye layer and a hot-melt ink layer. Using the protective layer transfer sheet as described above,
The image receiving sheet on which the protective layer is transferred and on which an image is formed is not particularly limited. For example, any sheet such as plain paper, high-quality paper, tracing paper, plastic film, etc. may be used as the base material, and in terms of shape, any of cards, postcards, passports, stationery, report paper, notes, catalogs, etc. Alternatively, a substrate in which a receptor layer having a dye receptivity is provided on the substrate is applicable. The receiving layer may be provided by a coating method or thermal transfer using a thermal head or a hot roll. Incidentally, if the substrate itself has the acceptability of the dye,
There is no need to provide a receiving layer.

Further, cards such as an ID card, an identification card, a license and the like can be prepared using the protective layer transfer sheet of the present invention. These cards include text information in addition to image information such as photographs. In this case, for example, the formation of character information can be performed by a fusion transfer method, and the formation of an image such as a photograph can be performed by a sublimation transfer method. Further, the card may be provided with an emboss, a sign, an IC memory, a magnetic layer, a hologram, and other printings, and may be provided with an emboss, a sign, a magnetic layer, and the like after the transfer of the protective layer.

A color image and / or a character image is formed by a thermal printer using a thermal transfer sheet on an image receiving sheet or a card, and a thermal transfer protective layer is transferred thereon by using the protective layer transfer sheet of the present invention. To form a protective layer, or use the protective layer transfer sheet of the present invention having a thermal transfer ink layer on the same substrate. When transferring, the thermal transfer printer may set the transfer conditions separately such as for sublimation transfer, for melt transfer, for the transfer of the protective layer, or by appropriately adjusting the printing energy with a common printer You may. In the protective layer transfer sheet of the present invention,
The heating means is not limited to a thermal transfer printer, and other hot plates, hot stampers, heat rolls, line heaters,
It can also be transferred with an iron etc. Further, the protective layer may be transferred to the entire surface of the formed image or may be transferred only to a specific portion.

[0029]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on mass unless otherwise specified. (Example 1) A polyethylene terephthalate film (PET, 6.0 μm thick) having a heat-resistant lubricating layer formed on the back surface
m, manufactured by Toray Co., Ltd.)
Coated by gravure printing at a rate of 0 g / m ² ,
After drying, a release layer is formed, and the following coating liquid for a sealable / writable protective layer is further dried thereon by gravure printing at a speed of 3.0.
g / m ² and dried. Further, the adhesive layer was formed thereon by applying and drying at a rate of 3.0 g / m ^{2 in} the same manner using the following coating liquid for an adhesive layer to form an adhesive layer. A transfer sheet was obtained.

Coating liquid for release layer Silicone-modified acrylic resin 16 parts (Celltop 226, manufactured by Daicel Chemical Industries, Ltd.) Aluminum catalyst 3 parts (Celltop CAT-A, manufactured by Daicel Chemical Industries, Ltd.) Methyl ethyl ketone 8 Parts toluene 8 parts

Coating liquid for sealing / writing protective layer 10 parts polyvinyl alcohol resin (Poval C-318: manufactured by Kuraray Co., Ltd.) Acrylic resin 10 parts (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.) Carboxy 0.5 parts of methylcellulose (CMC Daicel 1260, manufactured by Daicel Chemical Industries, Ltd.) 10 parts of ion-exchanged water 10 parts of isopropyl alcohol

Coating liquid for adhesive layer Polyester resin 11 parts (Vylon 700, manufactured by Toyobo Co., Ltd.) UV absorber acrylic copolymer 4.5 parts (UVA635L, manufactured by BASF Japan) Silica (silicon dioxide) 1 part (Sylysia 310, manufactured by Fuji Silysia Ltd., average particle size 1.4 μm) Methyl ethyl ketone 30 parts Toluene 30 parts

Example 2 In the same manner as in Example 1, a polyethylene terephthalate film coated with a heat-resistant lubricating layer was coated in the following order: release layer / marking / writing protection layer / adhesive layer. The release layer and the adhesive layer were formed under the same conditions as in Example 1, and the seal / writable protective layer was formed in the same manner as in Example 1 except that the following coating solution was used. A layer transfer sheet was prepared.

Coating Liquid for Marking / Writing Protective Layer Polyvinyl alcohol resin 10 parts (Poval C-318: manufactured by Kuraray Co., Ltd.) Acrylic resin 10 parts (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.) Hydroxy 0.5 parts of methyl cellulose (HMC Daicel, manufactured by Daicel Chemical Industries, Ltd.) 10 parts of ion-exchanged water 10 parts of isopropyl alcohol

Example 3 In the same manner as in Example 1, a polyethylene terephthalate film coated with a heat-resistant lubricating layer was coated in the following order: release layer / marking / writing protective layer / adhesive layer. The release layer and the adhesive layer were formed under the same conditions as in Example 1, and the seal / writable protective layer was formed in the same manner as in Example 1 except that the following coating solution was used. A layer transfer sheet was prepared.

The stamping-writability protective layer coating solution 10 parts of the acrylic resin (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.) carboxymethyl cellulose 0.2 parts (CMC Daicel 1260, manufactured by Daicel Chemical Industries, Ltd.) Ion exchange water 10 parts Isopropyl alcohol 10 parts

Example 4 In the same manner as in Example 1, a polyethylene terephthalate film coated with a heat-resistant lubricating layer was coated in the following order: release layer / marking / writing protection layer / adhesive layer. The release layer and the adhesive layer were formed under the same conditions as in Example 1, and the seal / writable protective layer was formed in the same manner as in Example 1 except that the following coating liquid was used. A layer transfer sheet was prepared.

The stamping-writability protective layer coating solution 10 parts of the acrylic resin (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.) carboxymethyl cellulose 0.2 parts (manufactured by CMC Daicel 1140, Daicel Chemical Industries, Ltd.) Ion exchange water 10 parts Isopropyl alcohol 10 parts

Comparative Example 1 In the same manner as in Example 1, a PET film coated with a heat-resistant lubricating layer was coated in the order of a release layer / adhesive layer. The release layer and the adhesive layer were formed as in Example 1.
Then, a protective layer transfer sheet of Comparative Example 1 was produced. (The protective layer transfer sheet of Comparative Example 1 is the same as that of Example 1.
This is a configuration in which the seal / writability protective layer is omitted, as compared with the protective layer transfer sheet of No. )

Next, on a PET film (6.0 μm thick, manufactured by Toray Co., Ltd.) having a heat-resistant lubricating layer formed on the back surface, each coating solution for the dye layer having the following composition was applied to the surface of yellow and magenta by a gravure coating method. And cyan in the order of 1.0 g / m ² (at the time of drying), followed by drying to provide a dye layer. Thus, a sublimation thermal transfer thermal transfer sheet of one set of three colors was prepared.

Yellow Dye Layer Coating Solution Yellow Disperse Dye 5 parts (Macrolex Yellow 6G, manufactured by Bayer) Polyvinyl butyral resin 5 parts (S-lek BX-1, Sekisui Chemical Co., Ltd.) Methyl ethyl ketone 45 parts Toluene 45 parts

The magenta dye layer coating solution is used as a magenta disperse dye as C.I. I. Disperse Red 60,
It has the same composition as the above-mentioned yellow dye layer coating liquid except that Bayer Co. was used. Further, the cyan dye layer coating liquid is Kayaset Blue 714 as a cyan disperse dye.
The composition is the same as that of the above yellow dye layer coating liquid except that Nippon Kayaku Co., Ltd. was used.

As a base material of the image receiving sheet, synthetic paper having a back surface layer on the back surface (thickness: 150 μm, YUPO FPG-1)
50, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) on a surface of a receiving layer coating solution having the following composition, using a bar coater, a coating amount of 4.0 g / m2.
² (at the time of drying), followed by drying to form a receptor layer, thereby producing a thermal transfer image-receiving sheet. The receiving layer of the thermal transfer image receiving sheet and the dye layer surface of the thermal transfer sheet of the above-described sublimation thermal transfer method are overlapped, and a thermal head is used from the back side of the thermal transfer sheet, using a printer that heats, and a printed matter of a full-color image is printed. Was formed. As a sublimation transfer printer, a printer capable of controlling 256 gradations equipped with a thermal head having a recording density of 300 dpi and connected to an electric signal obtained by color separation of a photographic image was used. The printing condition is that the printing speed is 5 ms / line and the applied energy at the maximum gradation is 0.65 mJ / dot.

Further, the protective layer was transferred to the image surface of the print using the above-prepared protective layer transfer sheets of Examples and Comparative Examples by the printer used above. The prints with the respective protective layers thus obtained were evaluated for printability, writability with a water-based pen and a water-resistant pen, cut-off of the protective layer, and gloss of the surface of the print after transfer of the protective layer.
However, each evaluation method and evaluation criteria are as follows.

(Sealability) Stamp Ink 1 (Guten
The stamp with the berg endorsing (manufactured by Berg Endorsing) and stamp ink 2 (manufactured by Shachihata Ink Co., Ltd.) is pressed against the image surface with the protective layer, and left for 10 minutes. Observed.も の indicates that the ink was fixed, X indicates that the ink was not fixed, and XX indicates that the ink was not significantly fixed.

(Water-based pen writability) The above-mentioned printed matter with a protective layer obtained using each of the protective layer transfer sheets of Examples and Comparative Examples using a fluorescent aqueous pen PROPUS2 manufactured by Mitsubishi Pencil Co., Ltd. as an aqueous pen. Was written by hand on the protective layer, and the fixability was visually observed, and evaluated according to the following criteria. (Evaluation criteria) ：: Characters can be read without blurring. ：: The characters are not too blurred and can be read, but if they are lightly rubbed with a finger, they become thin. ×: disappears when lightly rubbed with a finger.

(Water Resistant Pen Writability) With the above protective layer obtained using each protective layer transfer sheet of Examples and Comparative Examples using Sakura Ball Sign Kirara manufactured by Sakura Crepas Co., Ltd. as a water resistant pen. The handwritten characters were written on the protective layer of the print, the fixability was visually observed, and the evaluation was performed in the same manner as the evaluation criteria of the water-based pen for writability.

(Foil-cutting property) On the image surface of the printed matter,
Using the protective layer transfer sheets of the examples and comparative examples prepared above, after transferring the protective layer, the surface of the print and the transfer edge portion of the protective layer transfer sheet were visually observed, and the foil cut was observed. They were checked for uniformity and no tailing.
The evaluation criteria are as follows. ◎: No tailing, no problem. ：: Tail less than 0.5 mm, but no problem in practical use.

(Glossiness) In the above-mentioned prints with a protective layer obtained using the protective layer transfer sheets of Examples and Comparative Examples, the gloss of the surface after the transfer of the protective layer was visually observed. Examined. The evaluation criteria are as follows. A: Excellent surface gloss. ：: There are fine irregularities, but there is no problem in glossiness in practical use. Δ: Some unevenness was observed, and there was a problem in practice.

The above evaluation results are shown in Table 1 below.

[Table 1]

[0051]

As described above, in the present invention, the protective layer in which the heat transferable protective layer is provided on at least a part of the opposite side of the base sheet having the heat-resistant lubricating layer on one side is provided. In the transfer sheet, the outermost surface layer of the protective layer after the transfer is formed of an acrylic resin and at least one of hydroxymethylcellulose and carboxymethylcellulose, and the outermost surface layer of the protective layer after the transfer has a cracked shape or a fine pore. It becomes the retained shape, and the ink of the marking ink and various writing tools penetrates into the voids of the cracks and micropores,
It becomes easy to dry and fix, and a protective layer excellent in writability corresponding to various writing utensils and excellent in sealability can be obtained. Also, as a protective layer transfer sheet, the protective layer has excellent film-cutting properties from the base sheet, and in the resulting printed matter after the protective layer transfer, the gloss of the protective layer surface and the sharpness of the image located under the protective layer sex,
That is, a material having transparency that does not hide the image is obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a protective layer transfer sheet of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of the protective layer transfer sheet of the present invention.

FIG. 3 is an enlarged photograph by a microscope of one embodiment showing a crack shape or a shape having micropores positioned as the outermost surface layer of a protective layer after thermal transfer.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base sheet 2 thermal transferable protective layer 3 heat-resistant lubricating layer 4 sealable / writable protective layer 5 adhesive layer 6 release layer 7 protective layer transfer sheet

 ────────────────────────────────────────────────── ─── Continuing on the front page F term (reference) 2C005 HA30 HB01 HB03 KA29 KA41 2H111 AA01 AA26 AA27 AA52 BA02 BA08 BA21 BA53 BA64 BA73 4F100 AA20H AJ06C AK21 AK23 AK25C AK25J AK42 AL01 AL05C10 BA08 BA10A04 GB90 JJ03A JK14C JK16A JL00 JL01C JL14C JN01 JN21 YY00C

Claims (4)

[Claims] 1. A protective layer transfer sheet having a heat transferable protective layer releasably provided on at least a part of an opposite side of a base sheet having a heat-resistant lubricating layer on one side, wherein the heat transferable protective layer is provided. A protective layer transfer sheet, which has printing performance and writing performance, and wherein the outermost surface layer after transfer is composed of an acrylic resin and at least one of hydroxymethylcellulose and carboxymethylcellulose. 2. The protective layer transfer sheet according to claim 1, wherein the outermost surface layer of the protective layer after the transfer has a crack shape or a shape having micropores. 3. The protective layer transfer sheet according to claim 1, wherein a ratio of at least one of the hydroxymethylcellulose and the carboxymethylcellulose to the acrylic resin is 0.1% to 50%. . 4. The protective layer transfer sheet according to claim 1, wherein the thickness of the outermost protective layer after transfer is 0.5 μm to 5 μm.