JP2002079766A - Protective layer transfer sheet - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a protective layer transfer sheet that has excellent writing properties and sealability corresponding to various writing instruments, does not obscure an image located below, and has excellent transparency of a protective layer. I do. SOLUTION: A heat-resistant lubricating layer 3 is provided on one surface of a base material sheet 1, and at least a part of the opposite surface of the base material sheet 1 is formed of at least one transfer protective layer in a releasable manner. In the protective layer transfer sheet 8 provided with No. 2, at least one layer of the transfer protective layer 2 contains a binder resin, colloidal silica, and alumina, so that the transparency of the protective layer is not impaired and excellent. It has a marking performance and a writing performance. The binder resin is preferably at least one of gelatin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyurethane resin and aqueous silicone resin.

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 releasable transfer protective layer, and more particularly, to an image formed by a thermal transfer recording system, a water-based pen, a fountain pen, and the like. The present invention relates to a protective layer transfer sheet capable of providing the above-described writing property.

[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 printed sheets may be relatively small, such as a printed matter such as the production of an ID card such as an identification card, a business photograph, a printer of a personal computer, a video printer, and the like. 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 thermal transfer sheet, a monotonous image such as a character or a number can be easily formed by using a thermal fusion type thermal transfer sheet. These images suffer from poor durability, especially poor 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 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]

However, the protective layer formed as described above has toughness of the protective layer itself,
As a result of considering the water resistance and the like, it is common to use an organic solvent-based resin as a binder, for example, to form a thermal transfer image as described above for ID photo use or card use, and to thermally transfer a protective layer on the image. When formed, it was difficult to seal or write a signature on the surface of the protective layer. Therefore, a water-soluble resin such as a polyvinyl alcohol resin may be used as the protective layer in some cases. However, the resin alone does not have sufficient water absorption, the foil breaking performance is poor, and the abrasion resistance and water resistance do not satisfy the performance as a protective layer. There is a method of mixing colloidal silica in the resin to make up for this, but in order to impart sufficient water absorption, foil cutting performance, abrasion, water resistance, a large amount of addition is required, and it is required as an overcoat There was a problem that sufficient transparency was lost. Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide excellent writing properties corresponding to various writing instruments, have a sealability, and do not obscure an image located below, without causing the transparency of the protective layer to be lower. It is to provide a protective layer transfer sheet excellent in the above.

[0006]

According to the present invention, in order to solve the above-mentioned problems, a heat-resistant lubricating layer is provided on one side of a base sheet, and at least a part of the opposite side of the base sheet is provided. To
In a protective layer transfer sheet provided with at least one transfer protective layer that is releasably provided, at least one of the transfer protective layers contains a binder resin, colloidal silica, and alumina, so that a protective layer is formed. Has excellent marking performance and writing performance without loss of transparency. The binder resin is gelatin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyurethane resin,
It is preferable that at least one of the aqueous silicone resins is used.

It is preferable that the above-mentioned transfer protective layer is composed of a sealable / writable protective layer and a heat-sealing adhesive layer. Further, it is desirable to provide an intermediate layer for improving interlayer adhesion between the above-described seal / writing protection layer and the adhesive layer. It is preferable that the above-mentioned transfer protective layer is provided on a base material sheet in a releasable manner via a non-transferable release layer. Further, it is preferable that the total content ratio of colloidal silica and alumina to the binder resin of the transfer protective layer is 1/1 ≦ binder resin / colloidal silica and alumina ≦ 1/4 (mass ratio). It is preferable that the mixing ratio of colloidal silica and alumina contained in the transfer protective layer is 1/20 ≦ alumina / colloidal silica ≦ 1/5 (mass ratio).

[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 8 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. Is provided with a transfer protection layer 2. FIG. 2 is a cross-sectional view showing another embodiment which is the protective layer transfer sheet 8 of the present invention. The base sheet 1 has a heat-resistant lubricating layer 3 on one surface. On the other side of the seal, a sealable / writable protective layer 4 and a heat-sealing adhesive layer 5
Are formed in this order, and the seal / writing protection layer 4 is formed.
The transfer protection layer 2 including the adhesive layer 5 and the transfer protection layer 2 can be separated from the base sheet 1 by heating.

FIG. 3 is a cross-sectional view showing another embodiment of the protective layer transfer sheet 8 of the present invention, wherein the base sheet 1 has a heat-resistant lubricating layer 3 on one surface. 1 is provided with a transfer protection layer 2 on the other surface.
The adhesive layer 5 is formed in this order, and the intermediate layer 6 enhances the adhesive force between the seal / write protection layer 4 and the adhesive layer 5. FIG. 4 shows a protective layer transfer sheet 8 of the present invention.
FIG. 9 is a cross-sectional view showing another embodiment in which a heat-resistant lubricating layer 3 is provided on one surface of a base material sheet 1 and transferred to the other surface of the base material sheet 1 via a release layer 7. The protective layer 2 is provided, and the transfer protective layer 2 of the protective layer transfer sheet 8 is heated by heating.
Is peeled and transferred, and the release layer 7 remains on the base sheet 1 side.

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 base sheets is appropriately changed depending on the material so that its strength and heat resistance are appropriate.
About 0 μm is preferable.

(Transfer Protective Layer) In the protective layer transfer sheet of the present invention, a transfer protective layer 2 is provided on at least a part of the base sheet so as to be peelable. The above-mentioned transfer protective layer is composed of at least one or more layers, and a seal / write-protective protective layer is indispensable, and an adhesive layer having heat sealability and an intermediate layer for improving interlayer adhesive strength are added as necessary. It is configured.

(Seal and Writable Protective Layer) The seal and writable protective layer 4 will be described below. The sealable / writable protective layer contains a binder resin, colloidal silica, and alumina. The sealable / writable protective layer comes to the outermost surface after the transfer of the protective layer to the transfer object. Here, the addition of colloidal silica and alumina is for the purpose of forming a porous structure in the resin and improving the water absorption. At the same time, the toughness of the protective layer and the foil breaking performance can be improved.

The protective layer for marking and writing has water-absorbing properties as well as water-absorbing properties, and has properties such as water resistance, solvent resistance, solvent resistance such as alcohol resistance and acetone resistance, and plasticizer resistance. It is preferable to have both. The sealable / writable protective layer of the present invention is to be transferred onto a thermal transfer image as a protective layer, is located on the outermost surface of the transferred protective layer, and does not conceal the thermal transfer image located below, and has high transparency. Writability is required, and it has physical strength. Examples of the binder resin constituting the sealable / writable protective layer include gelatin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyurethane resin, aqueous silicone resin, water-soluble polyester resin, alkyl vinyl ether resin, and maleic acid copolymer. Resins, cellulosic resins, water-soluble alkyd resins, non-cellulosic water-soluble polysaccharides, and the like. Among the above binder resins, it is preferable to use at least one or more of gelatin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyurethane resin, and aqueous silicone resin in terms of stamping and writing.

The average particle diameter of the primary particles of the colloidal silica contained in the sealable / writable protective layer is preferably 0.005 μm or more, and more preferably 0.005 to 0.
07 μm, more preferably 0.005 to 0.05 μm. If the average particle size of the primary particles is less than 0.005 μm, the water absorption will decrease. Further, the alumina contained in the sealable / writable protective layer may be either crystalline or non-crystalline as a sol-like alumina hydrate, and the form thereof may be appropriately selected from irregular particles, spherical particles and the like. . The alumina sol is preferably a sol-like boehmite. The alumina sol used in the present invention has an average particle diameter of 0.001 to 0.04 μm, preferably 0.005 to
One having a range of 0.02 μm is used. If the particle size of the alumina sol is too small, the printability of a stamp or an oil-based pen or the like deteriorates, which is not preferable.

If colloidal silica and alumina are excessively added to the seal / write protection layer, the transparency of the protection layer is lost, which is not preferable for the purpose of overcoating the surface of an image or the like located below. Therefore, it is necessary to minimize the addition amount of both colloidal silica and alumina. In the present invention, the particle diameter of colloidal silica and alumina is fine as described above, and the total content ratio of colloidal silica and alumina with respect to the binder resin of the stamping / writing protection layer is 10/1 ≦ binder resin. / Colloidal silica and alumina ≦ 1/2
0 (mass ratio), and it is particularly preferable to add them in a ratio of 1/1 ≦ binder resin / colloidal silica and alumina ≦ 1/4 (mass ratio). If the content of colloidal silica and alumina is too large, the transparency of the protective layer may be reduced, or the gloss of the surface of the protective layer may be reduced. On the other hand, if the content ratio of colloidal silica and alumina is too small, a porous structure cannot be formed, and the printing and writing properties are lost. In the present invention,
By adding both colloidal silica and alumina,
It was found that even when the total amount of addition was significantly reduced as compared with the case where only a single kind was added, the effect of excellent writing performance corresponding to various writing implements and excellent marking performance was sufficiently obtained.

The mixing ratio of colloidal silica and alumina to be added to the marking / writing protective layer is 1/50 ≦ alumina /
Colloidal silica ≦ 1/1 (mass ratio), especially 1 /
20 ≦ alumina / colloidal silica ≦ 1/5 (mass ratio)
It is preferable that If the content ratio of alumina is too small, the sealability and the writeability of an oil-based pen or the like will decrease. On the other hand, when the content ratio of the colloidal silica is too small, the water absorption decreases. The sealable / writable protective layer was prepared by adding the above-described binder resin, colloidal silica, and alumina to a solvent (water, alcohol, etc.), and further adding a surfactant, a dispersion stabilizer, and the like as necessary. It can be formed by applying and drying a conventionally known coating means such as a gravure printing method, a screen printing method, a reverse coating method using a gravure plate or the like using a coating liquid. The coating amount of the sealable / writable protective layer is 0.1 g / m ^{2 to} 5 g / m ² .
0 g / m ² , particularly preferably 0.7 g / m ^{2 to} 2.0 g / m
About ² m is appropriate. If it is thinner than this, the printability and strength as a protective film are insufficient, and if it is thicker than this, the transparency is reduced or the foil breakability during transfer is poor. Become. In addition, the sealing / writing protection layer is not only composed of one layer, but also has a coating amount of 0.1 g / m ^{2 to} 5.0 g /
If it is m ² , it may be composed of two or more layers.

(Adhesive Layer) In the present invention, an adhesive layer 5 having a heat seal property is provided on the imprint / writability protective layer of the protective layer transfer sheet so as to improve the adhesiveness of the protective layer to an object to be transferred. It is preferably provided for this purpose. This adhesive layer is preferably selected from heat sealing materials according to the material of the transfer object, but is generally preferably formed from a thermoplastic resin having a glass transition temperature of 50 ° C to 80 ° C, For example, heat-absorbing resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, gelatin, cellulose resin, polyamide resin, vinyl chloride resin, etc. Resins having an appropriate glass transition temperature are selected from among resins having good glass transition temperatures.

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 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. In addition, as an additive, a plasticizer, a coloring pigment,
A white pigment, an extender, 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 containing the above-described additives, preferably 0.5 g in a dry state
/ M ^{2 to} 5.0 g / m ² to form an adhesive layer with a coating amount of about.

(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 transfer protective layer. 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,
A silicone polymer such as an acrylic silicone graft polymer, an acrylic siloxane, or an aryl siloxane may be mentioned, but a polyol, 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 a suitable solvent to prepare an ink for forming a heat-resistant lubricating layer. On the back of the material sheet, for example,
Gravure printing method, screen printing method, applied by forming means such as a reverse coating method using a gravure plate,
It can be formed by drying. The coating amount of the heat-resistant lubricating layer is 0.1g / m ² ~2.0g / m ² approximately in solids.

(Release Layer) When the transfer protective layer is difficult to peel off from the substrate sheet, a release layer 7 can be formed between the substrate sheet and the transferable protective layer. The release layer is, for example, waxes, silicone wax, silicone resin, fluororesin, 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 transfer to the transfer object during thermal transfer, those which remain on the substrate sheet side, and those which undergo cohesive failure. The release layer is left on the base sheet side by the thermal transfer, and the interface between the release layer and the transfer protective layer is made to be the surface of the protective layer after the thermal transfer. This method is preferred because of its excellent transfer stability and the like. The release layer can be formed by a conventionally known coating method, and the coating amount is 0.5 g / m2 in a dry state.
^{About 2 to} 5.0 g / m ² 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.

(Intermediate Layer) The protective layer transfer sheet of the present invention comprises:
It is preferable to provide an intermediate layer 6 as a transfer protection layer between the seal / write protection layer and the adhesive layer. The intermediate layer improves the adhesion between the sealing / writing protection layer and the adhesive layer, and further assists in improving the marking / writing performance of the marking / writing protection layer. However, if the seal / write protection layer and the adhesive layer exhibit their respective functions sufficiently and have high adhesiveness to each other, it is not necessary to provide an intermediate layer. As the resin forming the intermediate layer, a water-soluble resin is preferable, and specifically, a polyvinylpyrrolidone-based resin, a polyvinyl alcohol (PVA) -based resin, a water-soluble polyester-based resin, an alkyl vinyl ether resin, a maleic acid copolymer resin, Cellulose-based resins, water-soluble alkyd resins, non-cellulose-based water-soluble polysaccharides and the like can be mentioned. The intermediate layer can be formed by a conventionally known coating method, and the coating amount is 0.3 g / m ² or more in a dry state.
It is about 5.0 g / m ² .

In the protective layer transfer sheet, the above-described transfer protective layer may be provided alone on the substrate sheet, or may be a dye layer of each color of Y (yellow), M (magenta), C (cyan) or heat. It may be configured to be provided in a face-sequential manner together with the meltable ink layer. There is no particular limitation on the image receiving sheet, which is a transfer object on which the protective layer is transferred and the image is formed, using the protective layer transfer sheet as described above. For example, as a base material, plain paper, high-quality paper, tracing paper, plastic film, etc., any sheet may be used, and in terms of shape, cards, postcards, passports, stationery, report paper,
Any material such as a notebook or a catalog may be used, and a material having a substrate having a dye-receiving property on its base material is applicable. How to provide the receiving layer, even in the coating method,
Alternatively, thermal transfer using a thermal head or a thermal roll may be used. If the substrate itself has a dye receptivity, there is no need to provide a receptor layer.

Also, cards such as an ID card, an identification card, and a license 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 the transfer protective layer is transferred thereon by using the protective layer transfer sheet of the present invention. The protective layer transfer sheet of the present invention, which has a protective layer formed thereon or has a thermal transfer ink layer on the same substrate, is used. At the time of transfer, the thermal transfer printer may set transfer conditions separately, such as for sublimation transfer, for melt transfer, and for 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 may be transferred by a hot plate, a hot stamper, a hot roll, a line heater, an iron, or the like. 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. (Examples 1 to 5) Polyethylene terephthalate film (PE
T, thickness 5.2 μm) On the surface, the following coating liquid for a release layer was applied by a bar coater at a rate of 0.7 g / m ² when dried, and dried to form a release layer. The following coating liquid for a marking / writing protective layer was applied thereon by a bar coater at a rate of 1.0 g / m ² when dried, and dried to form a marking / writing protection layer. Further, the adhesive layer was formed by coating and drying at a rate of 1.2 g / m ^{2 in} the same manner using the following coating liquid for an adhesive layer on the stamping / writing protection layer, at the rate of 1.2 g / m ² at the time of drying. A protective layer transfer sheet according to an example of the invention was obtained.

Coating liquid for release layer Silicone-acrylic resin 8 parts (Celltop 226, manufactured by Daicel Chemical Industries, Ltd.) Silicone-acrylic resin 8 parts (Celltop 227, manufactured by Daicel Chemical Industries, Ltd.) Aluminum catalyst 3 parts (Celltop CAT-A, manufactured by Daicel Chemical Industries, Ltd.) Vinyl chloride-vinyl acetate copolymer resin 8 parts (1000ALK, manufactured by Denki Kagaku Kogyo Co., Ltd.) Methyl ethyl ketone 8 parts Toluene 8 parts

Coating Solution for Sealing / Writable Protective Layer Polyvinyl Alcohol Resin A Part (Poval C-318, Kuraray Co., Ltd.) Polyvinyl Pyrrolidone Resin B Part (K-90, ISP) Polyvinyl Acetal Resin C Part (KX-5, manufactured by Sekisui Chemical Co., Ltd.) Colloidal silica (average primary particle diameter of 0.04 μm) D part (Snowtec OL40, manufactured by Nissan Chemical Co., Ltd.) Alumina sol (average pore diameter 0.006 to 0) .02 μm) Part E (CATALOID AS-3, manufactured by Catalysis Kasei Co., Ltd.) 25 parts of ion-exchanged water 25 parts of isopropyl alcohol 25 parts of the polyvinyl alcohol resin, B part of the polyvinylpyrrolidone resin, and polyvinyl acetal resin Table 1 shows the numerical values of each of Examples C, D of colloidal silica, and E of alumina sol in Examples. Ride there. However, all of the above-mentioned parts A, B, C, D and E are values as solid contents.

Coating liquid for adhesive layer Vinyl chloride-vinyl acetate copolymer resin 1 part (1000ALK, manufactured by Denki Kagaku Kogyo KK) Benzophenone-modified acrylic resin 1 part (UVA635L, manufactured by BASF Japan) Methyl ethyl ketone 4 parts Toluene 4 Department

Coating solution for intermediate layer Polyvinyl pyrrolidone resin 50 parts (K-90, manufactured by ISP) 25 parts isopropyl alcohol 25 parts Methyl ethyl ketone 25 parts Toluene 40 parts

Comparative Example 1 In the same manner as in the Example, the following coating liquid for a protective layer was applied to a PET film on which a heat-resistant lubricating layer was coated and easily adhered, using a bar coater at the time of drying at 1.6 g / m 2.
^The composition was applied at a ratio of ² and dried to form a protective layer. Then, the following coating solution for an intermediate layer was applied on the protective layer by a bar coater at a rate of 1.0 g / m ² when dried, and dried to form an intermediate layer. Further, on the intermediate layer, a coating liquid for an adhesive layer used in Examples was applied by a bar coater at a rate of 1.2 g / m ² when dried, and dried to form an adhesive layer. A protective layer transfer sheet of Example 1 was obtained.

Coating liquid for protective layer Polyvinyl alcohol resin (PVA) 1 part (Poval C-318, manufactured by Kuraray Co., Ltd.) Colloidal silica (average primary particle diameter 0.04 μm) 13 parts (Snowtec OL40, Nissan Chemical Co., Ltd.) PVA curing agent 0.05 parts (Sumireze resin 5004, Sumitomo Chemical Co., Ltd.) Ion exchange water 14 parts Isopropyl alcohol 14 parts

Coating liquid for intermediate layer 1 part polyvinylpyrrolidone resin (K-90, manufactured by ISP) 1 part vinyl chloride-vinyl acetate copolymer resin (1000 ALK, manufactured by Denki Kagaku Kogyo KK) Isopropyl alcohol 1 Parts Methyl ethyl ketone 1 part Toluene 1.6 parts

Next, a thermal transfer printer manufactured by Olympus Optical Co., Ltd .;
A sublimation thermal transfer type thermal transfer sheet of one set of color and an overcoat type thermal transfer image receiving sheet for the same printer are prepared, and the receiving layer of the thermal transfer image receiving sheet and the dye layer surface of the sublimation thermal transfer type thermal transfer sheet are overlaid. A full-color image print was formed using a thermal transfer printer (P-330, manufactured by Olympus Optical Co., Ltd.).

At this time, the protective layer transfer sheets of the above-described Examples and Comparative Examples were cut and pasted on the protective layer panel portion of the thermal transfer sheet used above, and the protective layer was transferred. For each of the obtained prints with a protective layer,
The writability with an aqueous pen and a water-resistant pen, the transparency of the protective layer, the gloss of the surface of the print after transfer of the protective layer, and the water resistance were evaluated. However, each evaluation method and evaluation criteria are as follows.

(Sealability) Stamp ink (Gutenb)
erg Endorsing) was pressed against the image surface with the protective layer, left for 1 minute, and the ink was fixed or not and visually observed with a finger.も の indicates that the ink was fixed, and △ indicates that the ink was partially fixed but was almost good.

(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 of No. 1 and left for 1 minute. The written portion was rubbed with a finger, visually observed, and evaluated according to the following criteria. (Evaluation criteria) ：: Characters can be read without blurring. Δ: The characters are not too blurred and can be read, but if they are lightly rubbed with a finger, they become thin.

(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. Handwritten characters were written on the protective layer of the print, and after leaving for 1 minute, the written portion was rubbed with a finger and visually observed, and evaluated in the same manner as the evaluation criteria for the water-based pen. .

(Transparency) The density (optical reflection density) of the black image portion of each of the prints with the protective layer obtained using the protective layer transfer sheets of Examples and Comparative Examples was determined by Macbeth R.
The difference between the measured value of each example and the measured value of Comparative Example 1 was determined, and the numerical value was shown. The higher the value (plus), the higher the transparency of the transfer protective layer. If the value is negative, the transparency is lower than that of the comparative example.

(Glossiness) The glossiness of the surface of the protective layer after the transfer of the protective layer was measured for the prints with the protective layer obtained using the protective layer transfer sheets of Examples and Comparative Examples. Using a gloss meter (GROSS METER100), the glossiness was measured by a 45 ° reflection method, and the measured value of each example was different from the measured value of Comparative Example 1 (measured value of Example—measured value of Comparative Example 1). )(%)showed that. The higher the value (plus), the higher the glossiness of the transfer protective layer. If the value is negative, the glossiness is lower than that of Comparative Example 1.

(Water resistance) One drop of water was dropped with a dropper on the protective layer of the above-mentioned print having a protective layer obtained by using the protective layer transfer sheets of Examples and Comparative Examples, and left for 1 minute. Thereafter, the dropped water was sucked with a cotton swab, and the dropped portion was visually observed and evaluated according to the following criteria. (Evaluation criteria) ：: Water does not permeate under the protective layer and there is no change. Δ: Water permeated a little under the protective layer, but no problem in practical use.

The above evaluation results are as shown in Table 1 below.

[Table 1]

As shown in the above table, the printed matter obtained by using the protective layer transfer sheet according to Example 1 was able to improve gloss and transparency as compared with Comparative Example 1, while maintaining the other properties. there were. In Example 2, the water-resistant pen writing property and glossiness could be improved as compared with Comparative Example 1, and other performances were maintained. In Example 3, Comparative Example 1
In comparison with the above, the glossiness could be improved, and other performances were maintained. In Example 4, as compared with Comparative Example 1, the sealability and the water-resistant pen writing property could be improved, and other performances were maintained. In Example 5, the printability and glossiness could be improved as compared with Comparative Example 1, and other performances were maintained. Thus, the protective layer transfer sheet obtained in Examples of the present invention is
By mixing both colloidal silica and alumina sol into the resin at the same time, the total amount added can be reduced, and as a result,
It has become possible to obtain the desired desired performance.

[0047]

As described above, in the present invention, the heat-resistant lubricating layer is provided on one surface of the base sheet, and at least a part of the opposite surface of the base sheet is detachably provided with at least one surface. In a protective layer transfer sheet provided with a transfer protective layer composed of at least one layer, at least one of the transfer protective layers contains a binder resin, colloidal silica, and alumina, so that the obtained transfer protective layer is excellent. In addition to the water-based ink, oil-based ink and water-resistant pen, etc., are used for the writing performance of various writing instruments. 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 That has transparency, that is, transparency that does not hide the image.

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

FIG. 4 is a cross-sectional view showing another embodiment of the protective layer transfer sheet of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base sheet 2 transfer protective layer 3 heat-resistant lubricating layer 4 sealable / writable protective layer 5 adhesive layer 6 intermediate layer 7 release layer 8 protective layer transfer sheet

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hitoshi Saito 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. (reference) 2H111 BA02 BA32 BA53

Claims (7)

[Claims] Claims: 1. A heat-resistant lubricating layer is provided on one surface of a base sheet, and at least a part of the opposite surface of the base sheet is provided with at least one transfer protective layer in a releasable manner. A protective layer transfer sheet according to claim 1, wherein at least one of the transfer protective layers comprises a binder resin, colloidal silica, and alumina. 2. The protection according to claim 1, wherein the binder resin is at least one of gelatin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyurethane resin and aqueous silicone resin. Layer transfer sheet. 3. The protective layer transfer sheet according to claim 1, wherein the transfer protective layer comprises a sealable / writable protective layer and a heat-sealing adhesive layer. 4. The protective layer transfer sheet according to claim 3, wherein an intermediate layer for improving interlayer adhesion is provided between the sealable / writable protective layer and the adhesive layer. . 5. The transfer protective layer according to claim 1, wherein the transfer protective layer is provided on a base sheet so as to be peelable via a non-transferable release layer. Protective layer transfer sheet. 6. A total content ratio of colloidal silica and alumina to the binder resin of the transfer protective layer is 1/1 ≦ binder resin / colloidal silica and alumina ≦ 1/4 (mass ratio). A protective layer transfer sheet according to any one of claims 1 to 5, characterized in that: 7. The mixing ratio of colloidal silica and alumina contained in the transfer protective layer is 1/20 ≦ alumina /
The protective layer transfer sheet according to any one of claims 1 to 6, wherein colloidal silica ≤ 1/5 (mass ratio).