JP2006327193A - Protective layer transfer film and photographic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protective layer transfer film capable of giving various durabilities to a heat transfer picture or the like and especially capable of keeping an effect for a long period on light fastness, and a photographic material of which the durability is raised thereby. <P>SOLUTION: For the protective layer transfer film which provides a thermal transfer resin layer 2 becoming the protective layer by transfer on a substrate film 1, the photographic material is composed by containing a resin to which a reactive ultraviolet absorber is reaction combined to the thermal transfer resin layer 2. Further, though the thermal transfer resin layer 2 may be a single layer, the layer 2 may be constituted of many layers like a transparent rein layer 4, an ultraviolet isolating layer 5 and a thermally adhesive resin layer 6. Further, as occasion demands, a mold releasing layer 3 is provided between the substrate film 1 and the thermal transfer resin layer 2, a rear surface layer 7 may be provided on its opposite side surface. Further, an integral transfer film wherein one color-four colors thermal transfer ink layers (unillustrated) and the thermal transfer resin layer 2 are repetitively provided at a specific pitch in a face order, may be taken. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermal transfer film, in particular, a protective layer transfer film for thermally transferring a protective layer, and more specifically, excellent durability such as light resistance, weather resistance, friction resistance, chemical resistance, and solvent resistance for thermal transfer images and the like. It is related with the protective layer transfer film which can provide.

  Conventionally, various thermal transfer methods have been widely used as simple printing methods. In these thermal transfer methods, various images are easily formed, so that they are used to create printed materials with a relatively small number of printed sheets, for example, ID cards such as identification cards. In addition, when a color image is preferable as in a face photograph, for example, yellow, magenta, and cyan, and if necessary, a black colored thermal transfer layer on a continuous base film are repeated in a surface sequential manner. A thermal transfer method using a large number of thermal transfer films has been performed.

  Such thermal transfer films can be broadly classified as a so-called melt transfer type thermal transfer film in which the thermal transfer layer is softened by heating according to image information and an image is recorded on the transfer material by thermal transfer, and thermal transfer by heating. The dye in the layer is sublimated (heat transfer), and only the dye is thermally transferred onto the transfer material to form a so-called sublimation transfer type thermal transfer film.

  However, when creating an ID card such as an identification card with such a thermal transfer film, for example, if a melt transfer type thermal transfer film is used, it is easy to form images such as letters and numbers. This image has a drawback that it is inferior in durability, particularly in friction resistance. On the other hand, when a sublimation transfer type thermal transfer film is used, an image with gradation such as a facial photograph can be accurately formed. In contrast, since there is no vehicle, there is a disadvantage that the durability such as light resistance, weather resistance, and friction resistance is inferior.

  As a means for solving the above drawbacks, for example, there is a method of adding an ultraviolet absorber or an antioxidant. Even if such a method is used, the light resistance and the like are improved to some extent. However, in the method of simply adding the ultraviolet absorber to the protective layer constituting resin, the ultraviolet absorber is volatilized or decomposed by heat, and the ultraviolet absorber. There is a problem in that the effect of this decreases with time. As a method for solving the above-mentioned drawbacks, Patent Document 1 discloses that a reactive ultraviolet absorber is reactively bonded in a dye-receiving layer resin of a thermal transfer image-receiving sheet. However, since the dye that forms an image by transferring heat with the sublimation transfer method is present in the vicinity of the surface of the receiving layer resin, it is not effective to impart UV absorbing ability to the entire receiving layer resin. When the amount of the ultraviolet absorber is increased, the original performance of the receiving layer resin is impaired, and other properties such as blurring of the image are impaired. Therefore, the present invention solves the problems of the prior art as described above, and uses a protective layer transfer film excellent in performance capable of maintaining various durability of a thermal transfer image, in particular, light resistance and the like for a long period of time. An object is to provide a printed material with improved durability.

JP-A-5-221974

  The present inventors have found that the ultraviolet absorption effect can be continuously maintained for a long time by reacting the ultraviolet absorber with the resin, and applying this to the heat transferable resin layer of the protective layer transfer film, the present invention Completed.

  That is, the invention of claim 1 is a protective layer transfer film in which a thermal transfer resin layer is provided on a base film, wherein the thermal transfer resin layer is a transparent resin layer, a thermal adhesive resin layer from the base film side. The heat-adhesive resin layer is composed of a reactive ultraviolet absorber represented by the following general formula and at least one of an acrylic monomer, an oligomer, and a reactive polymer. A protection comprising a copolymer and a resin different from the copolymer, and the content of the reactive ultraviolet absorber is 20% by weight or more in the heat-adhesive resin layer It consists of a layer transfer film.

  The invention according to claim 2 is the protective layer transfer film according to claim 1, wherein the copolymer contains a copolymer represented by the following formula.

  The invention of claim 3 has a region of a thermal transfer ink layer comprising at least one color or two or more sublimable dye ink layers and / or a heat-meltable ink layer, and a region of the thermal transfer resin layer. An integrated transfer film of an ink layer and a protective layer sequentially provided on a base film, wherein the thermal transfer resin layer is laminated in the order of a transparent resin layer and a thermal adhesive resin layer from the base film side A copolymer of a reactive ultraviolet absorber represented by the following general formula and at least one of an acrylic monomer, an oligomer, and a reactive polymer; and An ink layer and a protective layer comprising a resin different from the copolymer, and the content of the reactive ultraviolet absorber is 20% by weight or more in the heat-adhesive resin layer The integrated transfer film.

  In the invention of claim 4, the thermal transfer resin layer of the protective layer transfer film according to claim 1 or 2 is laminated on at least a part of a print screen of a printed matter having an image colored with a dye. It consists of prints.

  In the protective layer transfer film of the present invention and a printed product using the same, since at least a part of the heat transferable resin layer contains a resin reactively bonded to the ultraviolet absorber, the conventional benzotriazole type or Compared to benzophenone-based UV absorbers in the thermal transfer resin layer, there is less vaporization, divergence and decomposition due to heat of UV absorbers, or elution by solvents, and a protective layer on the thermal transfer image. When the heat transferable resin layer is transferred, it is excellent in various resistances such as friction resistance, scratch resistance, chemical resistance, and storage resistance, and in particular, has an effect of providing a printed matter excellent in light resistance. Further, the protective layer transfer film has a structure in which a region of the thermal transfer ink layer and a region of the thermal transfer resin layer for the protective layer are provided in the surface sequential order on one surface of the transfer film substrate. Formation and lamination of the protective layer can be efficiently carried out in-line.

  Next, preferred embodiments of the present invention will be described in detail with reference to the drawings. 1, FIG. 2, FIG. 3, and FIG. 4 are schematic cross-sectional views for explaining one embodiment of the protective layer transfer film of the present invention. FIG. 1 is an example of the simplest layer configuration, in which a thermal transfer resin layer 2 containing a resin obtained by reactively bonding a reactive ultraviolet absorber is provided on one surface of a base film 1 as a single layer. . FIG. 2 shows a configuration in which the thermal transfer resin layer 2 is laminated on one surface of the base film 1 in order from the base film side, divided into two layers, a transparent resin layer 4 and a thermal adhesive resin layer 6. The resin that is reactively bonded with the reactive ultraviolet absorber is contained in either the transparent resin layer 4 or the thermal adhesive resin layer 6. In FIG. 3, the thermal transfer resin layer 2 is divided into three layers of a transparent resin layer 4, an ultraviolet blocking layer 5, and a thermal adhesive resin layer 6 in order from the base film side on one surface of the base film 1. And laminated. In this case, the resin in which the reactive ultraviolet absorbent is reactively bonded is, of course, used for the ultraviolet blocking layer 5. In FIG. 4, the release layer 3, the transparent resin layer 4, the ultraviolet blocking layer 5, and the thermal adhesive resin layer 6 are laminated on one surface of the substrate film 1 in this order from the substrate film side. The back surface 7 is provided with heat resistance and slip properties on the surface. The back layer 7 has an action to prevent the thermal head of the printer from sticking, and is not shown in the case of the configuration of FIGS. 1 to 3, but can be provided as necessary. It is not necessary when the heat resistance and slip properties of the material film are good. Moreover, the release layer 3 reduces the adhesiveness between the transparent resin layer 4 and the base film 1 when the peelability between the base film 1 and the transparent resin layer 4 is not appropriate, and the transparent resin The layer 4 is provided to facilitate peeling, and this layer is not shown in the case of FIGS. 1 to 3, but can be provided as necessary. Of course, when the peelability between the base film 1 and the transparent resin layer 4 is good, the release layer 3 is unnecessary. When the release layer 3 is provided, the heat transferable resin layer 2 including the transparent resin layer 4 is peeled off from the release layer 3 by transfer, and the release layer 3 itself remains on the base film side. To do. Below, the constituent material and manufacturing method of the protective layer transfer film of this invention and the printed matter obtained by transferring this are demonstrated.

  First, in the protective layer transfer film of the present invention, a resin in which a reactive ultraviolet absorbent used in the thermal transfer resin layer is reactively bonded will be described. The reactive ultraviolet absorber used in the present invention is a conventionally known organic ultraviolet absorber such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, hindered amine, etc. For example, an additive polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group, or an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group is introduced into the agent. For example, some specific examples that can be suitably used include those represented by the following structural formula, but are not limited thereto.

  As a method for reactively fixing the reactive ultraviolet absorber, various methods can be used. For example, a conventionally known resin component such as a monomer, oligomer or reactive polymer and the reactive ultraviolet absorber are combined. The copolymer of the present invention can be obtained by radical polymerization. As the reactive ultraviolet absorber in this case, it is preferable to use a reactive ultraviolet absorber having an addition polymerizable double bond as shown in Chemical Formula 6 and Chemical Formula 7. Also, if the reactive ultraviolet absorber has a hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group, etc., use a thermoplastic resin having a functional group reactive with the above reactive group. Depending on the reaction, the reactive ultraviolet absorber can be reactively fixed to the thermoplastic resin by heat or the like using a catalyst. In the present invention, the reactive ultraviolet absorber as described above is copolymerized with a resin component such as a monomer, an oligomer, or a reactive polymer to obtain a polymer having ultraviolet absorptivity, which is thermally transferred. It is added to the resin layer or laminated as a layer to constitute the heat transferable resin layer. The following are mentioned as a monomer component copolymerized with the said reactive ultraviolet absorber. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, isodecyl acrylate, Isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, lauryl tridecyl acrylate, lauryl tridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, seryl stearyl acrylate, seryl stearyl methacrylate, stearyl acrylate, stearyl methacrylate, ethyl hexyl acrylate , D Ruhexyl methacrylate, octyl acrylate, octyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate , Dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, tertiary butylaminoethyl acrylate, tertiary butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydride Furfuryl methacrylate.

  And ethylene diacrylate, ethylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol diacrylate Acrylate, Decaethylene glycol dimethacrylate, Pentadecaethylene glycol diacrylate, Pentadecaethylene glycol dimethacrylate, Penta contactor ethylene glycol diacrylate, Penta contactor ethylene glycol dimethacrylate, Butylene diacrylate, Butylene dimethacrylate, Allyl acrylate, allyl methacrylate Rate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol pentaacrylate, neopentyl glycol pentamethacrylate, phosphazene hexaacrylate, phosphazene Hexamethacrylate and the like.

  In addition, the above substances may be used not only as monomers but also as oligomers. Furthermore, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, etc. made of polymers of the above substances or derivatives thereof, etc. An acrylic reactive polymer can also be used. These monomers, oligomers, and acrylic reactive polymers may be used alone or in combination.

  A thermoplastic copolymer resin in which a reactive ultraviolet absorber is reactively bonded by copolymerizing a monomer, an oligomer, or an acrylic reactive polymer and a reactive ultraviolet absorber as described above. The amount of the reactive ultraviolet absorber contained in the copolymer resin is suitably in the range of 10 to 90% by weight, particularly preferably 30 to 70% by weight. If the content is less than 10% by weight, it is difficult to obtain satisfactory light resistance. On the other hand, if it exceeds 90% by weight, problems such as stickiness at the time of coating and image bleeding at the time of transfer to a dye image are not preferable. The molecular weight of the copolymer resin is preferably about 5,000 to 250,000, and particularly preferably about 9,000 to 30,000. When the molecular weight is less than 5,000, the coating film is weak and durability as a protective layer cannot be obtained sufficiently. On the other hand, if it exceeds 250,000, when the protective layer is transferred with a thermal head or the like, the film breakage or the like deteriorates, which is not preferable. An example of the structural formula of a thermoplastic copolymer resin copolymerized with the reactive ultraviolet absorber is as follows. Of course, the structural formula is not limited to this.

Below, a base film and each layer are demonstrated one by one.
1) Base film As the base film 1 used for the protective layer transfer film of the present invention, the same base film as that used in conventional thermal transfer films can be used as it is, and on the surface of the film. Those having an easy adhesion treatment and others can be used, and are not particularly limited. Specific examples of preferable base film include, for example, polyesters such as polyethylene terephthalate, polycarbonate, polyamide, polyimide, cellulose acetate, polyvinylidene chloride, polyvinyl chloride, polystyrene, fluororesin, polypropylene, polyethylene, ionomer, and the like. There are films, papers such as glassine paper, condenser paper, and paraffin paper, cellophane, etc., and composite films in which two or more of these are laminated are also included. Although the thickness of these base film 1 is suitably changed according to material so that the intensity | strength and heat resistance may become appropriate, about 3-100 micrometers is preferable normally.

2) Release layer Usually, a transfer film is prepared by providing the thermal transfer resin layer 2 on one surface of the base film 1, but depending on the combination of the material of the base film 1 and the thermal transfer resin layer 2, the thermal transfer may be performed. In some cases, the releasability of is not sufficient. In such a case, the release layer 3 can be provided in advance on the surface of the base film 1 (FIG. 4). The release layer 3 is used by selecting one or more kinds from resins such as waxes, silicone wax, silicone resin, fluororesin, acrylic resin, polyvinyl alcohol, urethane resin, cellulose resin such as cellulose acetate. In the case where two or more kinds are mixed, a water-soluble resin may be appropriately used. And it can form by apply | coating and drying the coating liquid which has these resin as a main component by methods, such as a conventionally well-known gravure coat and a gravure reverse coat, and the thickness of a coating film is enough at about 0.1-2 micrometers. It is. It should be noted that when selecting a material to be used for the release layer, it should be noted that it has appropriate release properties with the thermal transfer resin layer. It is important to make the adhesive strength with the base film higher than the adhesive strength with the layer. If the adhesive strength with the base film is insufficient, the protective layer is transferred together with the release layer, etc. Cause abnormal transcription. In addition, when a matte protective layer is desirable in the printed matter after transfer, it is possible to include various particles in the release layer, or to use a base film in which the release layer side surface is matted. The surface of the printed material to which the protective layer has been transferred can also be matted.

3) Thermal transferable resin layer In the protective layer transfer film of the present invention, the thermal transferable resin layer 2 is transferred to a printing screen of a transfer object by thermal transfer to form a protective layer. Accordingly, the functions that the heat transferable resin layer 2 should have include that the film is reliably peeled off from the base film 1 or the release layer 3 provided thereon during heat transfer, and the heat to the transfer object Good adhesion, various resistances such as friction resistance and scratch resistance as a protective layer of the stamp screen, especially excellent light resistance can be imparted in the present invention, and transparency is good and the image on the transfer surface is clear. It is not damaged. From this point, the heat transferable resin layer 2 can be provided as a single layer as shown in FIG. 1, but the transparent resin layer 4 and the thermoadhesive resin from the base film 1 side as shown in FIGS. It is also preferable to provide a multilayer structure of two or three layers in the order of the layer 6 or the order of the transparent resin layer 4, the ultraviolet blocking layer 5, and the thermal adhesive resin layer 6. Each layer in such a case will be described below.

3-1) Transparent resin layer The transparent resin layer 4 provided on the substrate film 1 or the release layer 3, that is, the layer on the substrate film side of the heat transferable resin layer 2, has friction resistance and transparency. Resins excellent in hardness, such as polyester, polystyrene, acrylic resin, polyurethane, acrylic urethane resin, silicone-modified resins of these resins, and mixtures of these resins, as well as polymerizable monomers as described above A resin obtained by crosslinking and curing at least one of oligomers, reactive polymers, and the like by ionizing radiation irradiation can be used. Moreover, in order to improve flexibility and adhesiveness, a thermoplastic resin with good compatibility may be mixed and used for the above-mentioned curable resin layer. In the case of crosslinking and curing by ionizing radiation, an intermediate layer (primer layer) made of acrylic resin, urethane resin, polyester, polystyrene, acrylic urethane resin, etc. is used in order to further improve the adhesion to the ultraviolet blocking layer. It may be provided. These resins are excellent in transparency but tend to form a relatively tough film, so that the film is not sufficiently cut off during transfer. Therefore, highly transparent fine particles such as silica, alumina, calcium carbonate, and plastic pigments are used to improve the film breakability of these transparent resins and the friction and scratch resistance of the printing screen coated by transfer. Or wax can be added to such an extent that the transparency of the resin is not impaired. The addition amount is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin solid content. Moreover, in order to further improve friction resistance and scratch resistance, additives such as silicone-modified resins and lubricants may be contained.

  As a method for forming such a transparent resin layer 4, gravure coating, gravure reverse coating, roll coating, and many other means can be used, and the transparent resin layer 4 is formed by applying and drying a coating solution containing the above resin. . The thickness of the transparent resin layer 4 is about 0.1 to 50 μm, preferably about 1 to 10 μm, as a dry film.

3-2) UV blocking layer In the present invention, when the thermal transfer resin layer 2 is composed of multiple layers, the resin to which the reactive UV absorber is reactively bonded is the transparent resin layer 4 and / or the thermal adhesive resin layer 6. However, it may be provided separately as the ultraviolet blocking layer 5. In this case, it is not limited whether it is provided between the transparent resin layer 4 and the thermoadhesive resin layer 6 or between the base film 1 or the release layer 3 and the transparent resin layer 4. It is preferable to provide between the resin layer 4 and the thermoadhesive resin layer 6. The method for forming the ultraviolet blocking layer 5 may be the same as the method for forming the transparent resin layer, and a thickness of about 0.1 to 5 μm is sufficient.

3-3) Thermal adhesive resin layer Next, in order to transfer each of the above layers onto the printing screen with good adhesiveness, the thermal adhesive resin layer 6 can be provided as the uppermost layer. For example, acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acryl copolymer resin, polyester resin, polyamide resin, etc. A resin having good adhesiveness when heated can be used. One or more of these resins in a form that can be applied, such as a solution or an emulsion, is selected from the application methods listed in the transparent resin layer, and then applied and dried. Can be formed. The thickness of the thermoadhesive resin layer 6 is preferably in the range of about 0.1 to 5 μm.

4) Back layer Further, in the protective layer transfer film of the present invention, the opposite surface provided with the heat transferable resin layer 2 is prevented from sticking to the thermal head of the printer or the transfer hot plate, if necessary. And the back surface layer 7 (heat-resistant slip layer) can be provided in order to improve slipperiness (refer FIG. 4). As the material for the back layer 7, conventionally known materials such as a resin obtained by curing a butyral resin or the like with an isocyanate compound, or a silicone resin can be used as they are, and a thickness of about 0.1 to 5 μm is sufficient. Moreover, you may provide a back surface layer through a primer layer as needed.

(Protective layer transfer film production and transfer method, etc.)
As mentioned above, although each layer which comprises the protective layer transfer film of this invention was demonstrated, the whole thickness of the heat transferable resin layer 2 has the preferable range of about 0.5-50 micrometers among these. Such a heat transferable resin layer 2 may be provided alone on the base film to form a transfer film having only a protective layer. For example, a yellow, magenta, cyan sublimation dye ink layer, or a black melt type A transfer ink layer (containing carbon black) and a surface-sequential arrangement may be provided, and the ink layer and the protective layer may be integrated into a transfer film. In the case of an integral transfer film, the pattern of the plate is not particularly limited, and examples thereof include a transfer film in which the following layer pattern is repeatedly provided in the surface order. (Hereinafter, yellow is abbreviated as Ye, magenta as Mg, cyan as Cy, and black as Bk.)
(1) Ye dye layer, Mg dye layer, Cy dye layer, protective layer (2) Ye dye layer, Mg dye layer, Cy dye layer, Bk dye layer, protective layer (3) Ye dye layer, Mg dye layer, Cy Dye layer, Bk molten ink layer, protective layer (4) Bk dye layer, protective layer (5) Bk molten ink layer, protective layer In these plate patterns, the size of the Bk dye layer, Bk molten ink layer, protective layer is It may be formed larger than other layers. The detection mark for detecting each layer may be provided anywhere on each layer, for example, at the head of each layer region or the head of the top color. Moreover, in the transfer film in which the ink layer and the protective layer are integrated as described above, each layer constituting the heat transferable resin layer and the like is a transparent resin layer, and these are printed by aligning them in a predetermined pattern. Since these layers need to be stacked, an additive such as a fluorescent brightening agent is added to each of these layers, and alignment by visual observation or machine detection can be facilitated by ultraviolet irradiation or the like. In addition, regarding the thermal transfer ink layer, the ink and method used for the conventionally known thermal transfer (ink) film can be used as they are for the material of the ink to be used and the method of providing it on the substrate film surface. The image protected using the protective layer transfer film as described above is usually an image formed by a sublimation type thermal transfer method and / or a melt type thermal transfer method, but is not limited to this and can be widely used. It is. In particular, when applied to an image by sublimation thermal transfer, a protective layer is formed on the image, and the dye forming the image is re-colored by heat at the time of transfer, so the image becomes clearer. There is an effect of becoming.

  Sublimation-type thermal transfer images and / or melt-type thermal transfer images include any of image-receiving sheets and card base materials such as polyester resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, and polycarbonate plastic sheets. It may be formed on such a transfer material. For example, a thermal transfer image receiving sheet provided with a dye-accepting resin layer (receiving layer) on a base sheet, or a film, sheet, molded product or the like made of these resins can be used. Examples of resins having dye acceptability include polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and various polyacrylates, polyethylene terephthalate, and polybutylene terephthalate. Polyester resins, polystyrene resins such as polystyrene or copolymers thereof, polyamide resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, and ionomers, cellulose diacetates, cellulose triacetates, etc. Cellulosic resins, polycarbonates and the like can be mentioned, and a release agent such as silicone oil may be added to these resin layers in order to prevent fusion with the thermal transfer sheet.

  The sheet-like base material used for the thermal transfer image receiving sheet as described above includes (1) synthetic paper (polyolefin type, polystyrene type, etc.), (2) fine paper, art paper, coated paper, cast coated paper, wallpaper, backing Paper, synthetic resin solution or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, and other natural fiber paper such as cellulose fiber paper, (3) polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethyl Various plastic films or sheets such as methacrylate and polycarbonate can be used. Among the above, the synthetic paper (1) preferably has a microvoid layer having a low thermal conductivity (in other words, a high heat insulating property) on its surface. Moreover, the laminated body by the arbitrary combinations of said (1)-(3) can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper, or a laminate of cellulose fiber paper and a plastic film or sheet.

  In addition, materials in the case where a card is used as the transfer target will be described. The card substrate used in the card of the present invention has a conventionally known polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, as long as a dye receiving layer on which a sublimation dye is dyed is formed on the surface thereof. Various plastic films or sheets such as polycarbonate can be used, and white opaque films or sheets formed by adding white pigments and fillers to these synthetic resins, or foamed foam sheets can also be used. Furthermore, synthetic paper (polyolefin, polystyrene, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin solution or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal additive Paper, paperboard, other cellulose fiber paper, etc. can be used and are not particularly limited. Moreover, the laminated body by arbitrary combinations, such as the said base film, can also be used.

  An example of a preferable card substrate in the present invention has a configuration in which a transparent polyvinyl chloride layer is laminated on both surfaces of a polyvinyl chloride center layer containing a white pigment, and is at least an image forming surface. The transparent vinyl chloride layer contains an appropriate amount of plasticizer to improve the dyeing property. A preferable range of the amount of these plasticizers is 0.1 to 10 parts by weight per 100 parts by weight of polyvinyl chloride forming the dye receiving surface, and a particularly preferable range is 3 to 5 parts by weight. If the amount of the plasticizer used is too small, the dyeing property to the sublimation dye is insufficient. On the other hand, if the amount of the plasticizer is too large, the dye receiving surface becomes soft and easily adheres to the dye layer of the thermal transfer sheet during thermal transfer. Therefore, an abnormal transfer in which the dye layer is peeled off and transferred as it is is likely to occur, and the printed image is blurred during storage, and a clear image cannot be obtained.

  Further, coloring pigments, white pigments, extender pigments, fillers, ultraviolet absorbers, antistatic agents, thermal stabilizers, antioxidants, fluorescent brighteners, and the like may be optionally used for the dye receiving surface. it can. Such a card substrate may be previously formed with a necessary magnetic recording layer, embossed pattern, other printed pattern, optical memory, IC memory, barcode, etc., or sublimation transfer. These magnetic recording layers and the like may be provided after information such as a facial photograph is formed by a method or the like. The face photograph provided on the card substrate can be formed according to a conventional method using the sublimation type thermal transfer sheet of the present invention. At the same time, information such as characters and barcodes can be formed on a sublimation type thermal transfer sheet, but it is preferable to form such information using a hot melt ink type thermal transfer sheet capable of high density black printing.

  As described above, a color image and / or a character image is formed on an image receiving sheet or a card by a thermal printer, and the protective layer transfer film of the present invention is used to transfer the thermal transfer resin layer thereon to form a protective layer. However, during transfer, the thermal printer may set transfer conditions separately for sublimation transfer, melt transfer, and protective layer transfer, or use a common printer with appropriate printing energy. You may adjust to. In the protective layer transfer film of the present invention, the heating means is not limited to a thermal printer, and other heating plates, hot stampers, hot rolls, line heaters, irons and the like can also be used for transfer. The protective layer may be transferred to the entire surface of the formed image or may be transferred only to a specific portion. Furthermore, although it cannot be said to be a transfer film, it can also be applied as a pouch material made of a laminate sheet used in, for example, a restaurant menu or cards. In this case, the ultraviolet ray blocking layer and the heat-adhesive resin layer of the present invention are provided on one side of a transparent substrate film or a commercially available laminate sheet to form the laminate sheet of the present invention, which is used as a sublimation thermal transfer method and / or Alternatively, it is possible to use heat bonding on an image formed by a melt type thermal transfer method.

The present invention includes the following aspects as particularly preferred embodiments.
(1) A protective layer transfer film in which a thermal transfer resin layer is provided on a base film, wherein the thermal transfer resin layer contains a resin in which a reactive ultraviolet absorbent is reactively bonded. .
(2) A resin obtained by reactively combining a reactive ultraviolet absorber contained in the thermal transfer resin layer is a reactive ultraviolet absorber represented by the following general formula, and a monomer, oligomer, or reactive polymer of a thermoplastic resin. The protective layer transfer film as described in (1) above, which is a copolymer with at least one of the above.

(3) The protective layer transfer according to (2), wherein the copolymer is a copolymer of a reactive ultraviolet absorber and at least one of an acrylic monomer, an oligomer, and a reactive polymer. the film.
(4) Resin in which the thermal transfer resin layer is composed of a laminate in which a transparent resin layer and a thermal adhesive resin layer are laminated in this order from the base film side, and a reactive ultraviolet absorber is reactively bonded to at least one layer The protective layer transfer film according to any one of (1) to (3) above, comprising:
(5) The thermal transfer resin layer is composed of a laminate in which a transparent resin layer, an ultraviolet blocking layer, and a thermal adhesive resin layer are laminated in this order from the base film side, and the ultraviolet blocking layer absorbs the reactive ultraviolet ray. The protective layer transfer film as described in any one of (1) to (3) above, which contains a resin obtained by reactively bonding an agent.
(6) A region of a thermal transfer ink layer composed of a sublimable dye ink layer and / or a heat-meltable ink layer of at least one color or two or more colors and the region of the thermal transfer resin layer are arranged on the base film in the order of surface. The protective layer transfer film as described in (1) to (5) above, which is provided.
(7) The thermal transfer resin layer of the protective layer transfer film according to the above (1) to (6) is laminated on at least a part of a print screen of a printed matter having an image colored with at least a dye. Characteristic prints.

Next, an Example and a comparative example are given and this invention is demonstrated further in detail. In addition, what was displayed by "part" in the sentence means a weight part.
(Creation of sublimation thermal transfer film)
Three colors of ink containing a sublimable dye having the following composition were prepared.
(1) Composition of yellow ink Quinophthalone dye represented by the following structural formula 5.5 parts Polyvinyl butyral (manufactured by S-LEC BX-1 Sekisui Chemical Co., Ltd.) 4.5 parts Methyl ethyl ketone / toluene (weight ratio 1: 1) 90.0 Part

(2) Composition of magenta ink In the composition of yellow ink, only the kind of dye was changed to magenta dye (CI Disperse Red 60), and the other was prepared in the same manner as yellow ink.
(3) Composition of cyan ink In the composition of the yellow ink, only the kind of dye was changed to a cyan dye (CI Solvent Blue 63), and the other was prepared in the same manner as the yellow ink. On the other hand, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET) having a thickness of 6 μm (hereinafter referred to as “Lumirror Toray”) is used as a base film, and a heat-resistant slip layer made of silicone resin is gravure-coated on one side of the film. In the printing method, the entire surface was provided with a thickness of 1 μm, and a primer layer made of urethane resin was provided on the other surface with a thickness of 0.5 μm. Next, the above ink composition is coated on the primer layer by a gravure printing method so that the coating amount is approximately 3 g / m ² (solid content) in order of yellow, magenta, and cyan, respectively, in order of PET film. In the flow direction, each color was repeatedly solid-printed with a length of 15 cm to form an ink layer with three sublimation dyes, and a sublimation type thermal transfer film was prepared.

Example 1
Using a gravure coating method, a PET film (product name: Lumirror Toray) with a thickness of 12 μm is used as a base film, and a heat-resistant slip layer made of silicone resin is used as a back layer on one side so that the dry thickness is 1 μm. Then, a transparent resin layer coating solution having the following composition was applied to the other surface by a gravure coating method so that the coating amount when dried was 3 g / m ² and dried to form a transparent resin layer. .
☆ Composition of coating solution for transparent resin layer Acrylic resin (Dianar BR-83, manufactured by Mitsubishi Rayon) 20 parts Methyl ethyl ketone / toluene (weight ratio 1: 1) 80 parts (hereinafter methyl ethyl ketone is referred to as MEK) On the transparent resin layer, an ultraviolet blocking layer coating solution having the following composition was applied by a gravure coating method so that the coating amount when dried was 1 g / m ² and dried to form an ultraviolet blocking layer. .

☆ Composition of coating solution for UV blocking layer Copolymer resin (UVA-635L, manufactured by BASF Japan) reactively bonded with a reactive UV absorber 20 parts Ethyl acetate 80 parts UVA-635L is represented by the following formula It is a copolymer resin.

Furthermore, on the ultraviolet blocking layer, a thermoadhesive resin layer coating solution having the following composition is applied and dried by a gravure coating method so that the coating amount when dried is 1 g / m ^2. A protective layer transfer film of Example 1 was prepared.
☆ Composition of coating solution for heat-adhesive resin layer Vinyl chloride-vinyl acetate copolymer resin (# 1000ALK, manufactured by Denki Kagaku Kogyo) 20 parts MEK / toluene (weight ratio 1: 1) 80 parts

(Example 2)
The protective layer transfer film of Example 2 was prepared in the same manner as in Example 1 except that only the composition of the coating solution for the ultraviolet blocking layer was changed as described below.
☆ Composition of coating solution for UV blocking layer Copolymer resin reactive UV absorbent (UVA-633L, manufactured by BASF Japan) 20 parts Ethyl acetate 80 parts UVA-633L is represented by the following formula It is a copolymer resin.

(Example 3)
In the configuration of Example 1, all of the processing of Example 3 was performed in the same manner as in Example 1 except that the composition of the coating solution for transparent resin layer was changed to the coating solution having the following composition except for the ultraviolet blocking layer. A protective layer transfer film was prepared.
☆ Composition of coating solution for transparent resin layer Copolymerized resin (UVA-633L, manufactured by BASF Japan) with reactive UV absorbers 20 parts
80 parts of ethyl acetate

Example 4
In the configuration of Example 1, all processes were performed in the same manner as in Example 1 except that the ultraviolet blocking layer was removed and the coating solution for the heat-adhesive resin layer was applied in place of the coating solution having the following composition. A protective layer transfer film was prepared.
☆ Composition of coating solution for heat-adhesive resin layer Acrylic resin (Dianar BR-90, manufactured by Mitsubishi Rayon) 10 parts Copolymer resin reactive UV absorbent (UVA-633L, manufactured by BASF Japan) 20 parts MEK / Toluene (weight ratio 1: 1) 70 parts

(Example 5)
In the structure of Example 1, the coating solution for the transparent resin layer is replaced with a coating solution (ionizing radiation curable resin) having the following composition, and the adhesion between this layer and the ultraviolet blocking layer applied thereon is improved. Therefore, an intermediate layer by the intermediate layer coating solution having the following composition was newly added on the transparent resin layer, and both were processed under the following conditions. A protective layer transfer film was prepared.
☆ Composition of coating solution for transparent resin layer Dipentaerythritol hexaacrylate 7.5 parts Polymethyl methacrylate 15.0 parts MEK / toluene (weight ratio 1: 1) 77.5 parts ☆ Composition of coating solution for intermediate layer Poly Methyl methacrylate 30 parts MEK / toluene (weight ratio 1: 1) 70 parts The processing conditions of the coating solution are as follows. First, the coating amount of the transparent resin layer coating solution is 3 g / m ² (solid content) by the gravure coating method. Then, the intermediate layer coating solution is applied and dried so that the coating amount is 1 g / m ² (solid content) by the gravure coating method, and then in the nitrogen gas atmosphere from the coating surface side. The electron beam accelerated to 175 KV was irradiated with 5 Mrads and cured and crosslinked to form a transparent film.

(Example 6)
In the configuration of Example 1, all the processes were performed in the same manner as in Example 1 except that only the composition of the coating solution for the transparent resin layer was changed as described below (to a composition to which a wax component was added). A protective layer transfer film was prepared.
☆ Composition of coating solution for transparent resin layer Acrylic resin (Dianar BR-83, manufactured by Mitsubishi Rayon) 20 parts Polyethylene wax (average particle size 10 μm) 1 part MEK / toluene (weight ratio 1: 1) 80 parts

(Example 7)
In the configuration of Example 5, everything was processed in the same manner as Example 5 except that only the composition of the coating solution for the transparent resin layer was changed as follows (to a composition in which a wax component and colloidal silica were added). A protective layer transfer film of Example 7 was prepared.
☆ Composition of coating solution for transparent resin layer Dipentaerythritol hexaacrylate 7.5 parts Polymethyl methacrylate 15.0 parts Polyethylene wax (average particle size 10 μm) 1.5 parts Colloidal silica 1.5 parts MEK / toluene (weight) Ratio 1: 1) 77.5 parts

(Example 8)
In the protective layer transfer film of Example 8, the thermal transfer ink layer and the protective layer are arranged in the surface order on the same substrate film instead of the protective layer alone, and the ink layer and the protective layer provided repeatedly are integrated. A transfer film was prepared by the following procedure. A single-sided easy-adhesion treated PET film (Lumirror F54 manufactured by Toray) with a thickness of 6 μm is used as the base film, a heat-resistant slip layer made of silicone resin is used as the back layer on the non-treated side, and the thickness when dried is 1 μm. It was provided on the entire surface by a gravure coating method. On the surface subjected to the easy adhesion treatment, a thermal transfer ink layer (Ye, Mg, Cy, Bk ink layers of four colors arranged in a length of 15 cm) and a protective layer (length of 15 cm) These regions were arranged in a plane sequence in the flow direction of the PET film as one unit, and a thermal transfer ink layer and a protective layer (thermal transfer resin layer) were provided in a configuration in which this region was repeatedly provided. In the above, for the three-color ink layers of Ye, Mg, and Cy, the sublimation dye ink having the composition shown in the section (Preparation of sublimation type thermal transfer film) is used for the easy adhesion treatment surface of the PET film. Printing was performed by arranging Ye, Mg, and Cy in this order so that the coating amount was 3 g / m ² (solid content). At this time, three colors of Ye, Mg, and Cy are repeatedly printed as one set, and a space of 30 cm is provided between each set for the Bk ink layer and the protective layer.

Further, since the Bk ink layer is a heat-melting type, the thermal transfer ink layer has a configuration in which a release layer, a release protective layer, and a Bk colored layer are sequentially laminated on a PET film. Specifically, using a release layer coating solution, a release protective layer coating solution, and a Bk colored layer ink having the following compositions, the coating amount when dried by gravure printing is 1 g / m ^2. The Bk thermal transfer ink layer was formed by printing so as to be adjacent to each of the Cy dye printing layers. In the above, since only the release layer can be used in common with the release layer formed on the lowermost layer of the next protective layer adjacent to the Bk thermal transfer ink layer, the material and coating amount can be shared. It is reasonable to print the release layer coating liquid adjacent to each Cy dye printing layer with the dimensions of the entire space of 30 cm, and this was also performed in this example.

☆ Composition of release layer coating liquid Polyurethane resin (Hydran AP-40, Dainippon Ink & Chemicals) 7.5 parts Polyvinyl alcohol (Gosenol C-500, Nippon Synthetic Chemical Co., Ltd.) 15 parts Fluorescent whitening agent (Uvitex CF Ciba Geigy) ) 0.1 part Water / ethyl alcohol (weight ratio 1: 1) 300 parts ☆ Composition of coating solution for release protective layer Acrylic resin (BR-83, manufactured by Mitsubishi Rayon) 88 parts Polyethylene wax (average particle size 10 μm) 11.5 Part Polyester (Byron 200 manufactured by Toyobo Co., Ltd.) 0.5 part Optical brightener (Uvitex OB manufactured by Ciba Geigy) 0.5 part MEK / toluene (weight ratio 1: 1) 300 parts ☆ Composition of Bk colored layer ink Vinyl chloride- Vinyl acetate copolymer resin 60 parts Carbon black 40 parts MEK / toluene (weight ratio 1: 1) 200 parts

Next, a thermal transfer resin layer serving as a protective layer is provided in a space of 15 cm in length left between each set of the PET film. In this embodiment, as described above, the thermal transfer resin layer is separated in this space. A release layer for improving moldability (transferability) has already been provided, and the structure of the heat transferable resin layer provided thereon is changed from the side in contact with the release layer to the transparent resin layer, the primer layer, and the ultraviolet ray. A blocking layer and a heat-adhesive resin layer were sequentially laminated, and coating solutions having the following compositions were sequentially applied and dried by a gravure printing method and laminated. Incidentally, the coating amount of time each drying, 2 g / m ² transparent resin layer, a primer layer is 1 g / m ^2, the ultraviolet blocking layer is 1 g / m ^2, heat-adhesive resin layer is 1 g / m ² I did it. In addition, since an ionizing radiation curable resin was used for the transparent resin layer, the resin was cured and crosslinked by irradiating 5 Mrads of an electron beam accelerated to 175 KV in a nitrogen gas atmosphere from the coating surface side after application and drying of each layer. went. The integral transfer film of the thermal transfer ink layer and the protective layer prepared as described above was used as the protective layer transfer film of Example 8.

☆ Composition of coating solution for transparent resin layer Dipentaerythritol hexaacrylate 10 parts Polymethyl methacrylate 20 parts Silane coupling agent treated silica 3 parts Polyethylene wax 1 part Fluorescent whitening agent (Uvitex OB manufactured by Ciba Geigy) 0.15 parts MEK / Toluene (weight ratio 1: 1) 70 parts ☆ Composition of primer layer coating solution Polymethylmethacrylate 30 parts Fluorescent whitening agent (Uvitex OB Ciba Geigy) 0.15 parts MEK / toluene (weight ratio 1: 1) 70 parts ☆ Composition of coating solution for UV blocking layer Copolymerized resin with reactive UV absorber (UVA-635L manufactured by BASF Japan) 20 parts MEK / toluene (weight ratio 1: 1) 80 parts ☆ Coating for thermal adhesive resin layer Composition of liquid Vinyl chloride-vinyl acetate copolymer resin (# 1000ALK Denki Kagaku Kogyo) 0 parts optical brightening agent (Uvitex OB manufactured by Ciba Geigy) 0.15 part MEK / toluene (weight ratio 1: 1) 70 parts

Example 9
The protective layer transfer film of Example 9 is a base film, that is, a single-sided easy-adhesion-treated PET film having a thickness of 6 μm in the configuration of the integrated protective layer transfer film of the thermal transfer ink layer and the protective layer of Example 8. In addition, the back layer and the thermal transfer ink layer (four colors) were processed in the same manner as in Example 8, and only the protective layer portion was configured as in Example 6 (however, a transparent resin layer and a heat-adhesive resin layer) Was prepared by replacing the fluorescent brightener as described below. Therefore, the part of the protective layer is first provided with a release layer similar to that in Example 8 on the base film surface, and on that,
(1) As a transparent resin layer, a layer (coating) comprising 20 parts of an acrylic resin (Dianar BR-83), 1 part of polyethylene wax (average particle size 10 μm), and 0.1 part of a fluorescent brightener (manufactured by Uvitex OB Ciba Geigy) The amount 3g / m ²⁾
(2) Layer of copolymer resin (UVA-635L) in which a reactive ultraviolet absorber is reactively bonded as an ultraviolet blocking layer (coating amount 1 g / m ² )
(3) A layer composed of 20 parts of vinyl chloride-vinyl acetate copolymer resin (# 1000ALK) and 0.1 part of a fluorescent brightening agent (Uvitex OB manufactured by Ciba Geigy) as a heat-adhesive resin layer (application amount: 1 g / m ² )
Are sequentially laminated. Moreover, since no ionizing radiation curable resin is used for the transparent resin layer, the electron beam irradiation after coating and drying is not performed. In the protective layer transfer films of Examples 6 to 9, the film transferability during transfer and the transferred image surface with respect to the transparent resin layer that becomes the outermost layer after transfer in the heat transferable resin layer. In order to further improve the scratch resistance, polyethylene wax, colloidal silica, silane coupling agent-treated silica and the like are added. From this point, apart from the comprehensive tests such as light resistance and image blurring after high-temperature storage, the image surface prepared with the thermal transfer film prepared in the first section (Creation of sublimation type thermal transfer film) In addition, when the thermal transfer resin layer of each example was transferred with a solid pattern with a thermal head printer and the film breakability and the scratch resistance of the surface of the transferred material were tested, the wax component and various silicas corresponding to each were tested. In contrast to the structure not contained in the transparent resin layer, that is, Examples 6 and 9 are compared with those of Example 1, and Examples 7 and 8 are those of Example 5. In contrast, it was confirmed that both the film breakability and the scratch resistance of the surface of the transferred material were improved.

(Comparative Example 1)
In the configuration of Example 1, the protective layer transfer film of Comparative Example 1 was prepared by processing in the same manner as in Example 1 except that only the ultraviolet blocking layer was excluded.

(Comparative Example 2)
In the structure of Example 1, except that the ultraviolet blocking layer was removed and the coating solution for the heat-adhesive resin layer was applied in place of the coating solution having the following composition, all the processes were performed in the same manner as in Example 1, and Comparative Example 2 was performed. A protective layer transfer film was prepared.
☆ Composition of coating solution for heat-adhesive resin layer Acrylic resin (Dianar BR-90, manufactured by Mitsubishi Rayon) 20 parts Benzotriazole-based UV absorber (Tinuvin 328, manufactured by Ciba Geigy) 1 part MEK / toluene (weight ratio 1: 1) 80 parts

(Comparative Example 3)
In the configuration of Example 1, except that the ultraviolet blocking layer was removed and the coating solution for the heat-adhesive resin layer was applied in place of the coating solution having the following composition, all the processing was performed in the same manner as in Example 1, and Comparative Example 3 was performed. A protective layer transfer film was prepared.
☆ Composition of coating solution for heat-adhesive resin layer Acrylic resin (Dianar BR-90, manufactured by Mitsubishi Rayon) 20 parts Benzophenone ultraviolet absorber (Chemsorb 112, manufactured by Chemipro Kasei) 1 part MEK / toluene (weight ratio 1: 1) 80 parts

(Comparative Example 4)
In the configuration of Example 1, except that the ultraviolet blocking layer was removed and the coating solution for the heat-adhesive resin layer was applied in place of the coating solution having the following composition, all the processing was performed in the same manner as in Example 1, and Comparative Example 3 was performed. A protective layer transfer film was prepared.
☆ Composition of the coating solution for the heat-adhesive resin layer Acrylic resin (Dianar BR-90, manufactured by Mitsubishi Rayon) 20 parts Benzotriazole-based UV absorber (Tinuvin 328, manufactured by Ciba Geigy) 10 parts MEK / toluene (weight ratio 1: 1) 70 parts

(Comparative Example 5)
Comparative Example 5 compares the effect of using a resin reactively bonded to the ultraviolet absorber used on the transfer film side in the present invention not on the transfer film side but on the receiving layer of the image receiving sheet. Therefore, synthetic paper (YUPO FRG-150, thickness 150 μm, manufactured by Oji Oil Chemical Co., Ltd.) is used as the base sheet of the image-receiving sheet that is the transfer material, and the coating for the dye-receiving layer having the following composition is applied to one surface The liquid was applied with a bar coater so that the coating amount when dried was 4.0 g / m ² and dried to form a dye-receiving layer, thereby preparing a thermal transfer image-receiving sheet.
☆ Composition of the dye receiving layer coating solution
Copolymerized resin reactive UV absorber (UVA-633L, manufactured by BASF Japan) 20 parts Amino-modified silicone (X-22-343, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Epoxy-modified silicone (KF-393, Shin-Etsu Chemical) 5 parts MEK / toluene (weight ratio 1: 1) 80 parts A color image is transferred to the dye-receiving layer of the thermal transfer image-receiving sheet obtained above by the same method as described below, and the structure of Comparative Example 1 is applied to the image surface. A protective layer (a protective layer excluding the ultraviolet blocking layer) was transferred, and the light resistance and blurring test described later were conducted for evaluation.

(Transfer of image and protective layer to card substrate and image receiving sheet)
As a material to be transferred to the protective layer transfer films of Examples 1 to 9 and Comparative Examples 1 to 4, a card base made of polyvinyl chloride having the following material composition (image receiving sheet in the case of Comparative Example 5) is used. On one side (the receiving layer side in the image receiving sheet), the dye-coated surface of the sublimation type thermal transfer film (the surface of the thermal transfer ink layer of the protective layer transfer film in Examples 8 and 9) previously superimposed is superimposed, Thermal energy was applied through a printer thermal head connected to an electrical signal obtained by color separation to form a full-color image.
☆ Material composition of card substrate
Polyvinyl chloride compound (degree of polymerization 800) (containing about 10% of additives such as stabilizer) 100.0 parts White pigment (titanium oxide) 10.0 parts Plasticizer (DOP) 0.5 parts Subsequently, the card Using the protective layer transfer films of Examples 1 to 9 and Comparative Examples 1 to 4 on the color image forming surface of the substrate (Comparative Example 5 is the image receiving sheet), and also to the image forming surface of the image receiving sheet of Comparative Example 5 On the other hand, using the protective layer transfer film of Comparative Example 1, each thermal transfer resin layer was transferred with the thermal head of the same printer to form a color image with a protective layer.

(Light resistance test of transferred images)
Using the color image obtained above and each card substrate to which the protective layer has been transferred and the image receiving sheet as samples, the light resistance of the image surface was measured with a xenon fade meter (Ci-35A manufactured by Atlas Co., Ltd.) at 200 KJ / m ² and 300 KJ. / M ^{2 was} irradiated, and the change in the optical density before and after the irradiation was measured with an optical densitometer (RD-918 manufactured by Macbeth Co.), and the residual ratio of the optical density was calculated by the following formula.
Residual rate (%) = (optical density after irradiation / optical density before irradiation) × 100
In addition, as a result of the light resistance test, the residual ratio is shown in Table 1 in place of the following classification symbols.
◎: Residual rate is 80% or more ○: Residual rate is 70% or more and less than 80% △: Residual rate is 60% or more and less than 70% ×: Residual rate is less than 60%

(Bleeding test of transferred image)
The color image obtained above and each card substrate to which the protective layer was transferred and the image receiving sheet were used as samples, and after observing the bleeding of the image surface at 60 ° C. for 100 hours, the results were determined based on the following criteria: The symbols are shown in Table 1.
Explanation of symbols ○: No dot bleeding is observed.
X: Dot blur is observed.

FIG. 1 is a schematic cross-sectional view for explaining one embodiment of the protective layer transfer film of the present invention. FIG. 2 is a schematic cross-sectional view for explaining another embodiment of the protective layer transfer film of the present invention. FIG. 3 is a schematic cross-sectional view illustrating still another embodiment of the protective layer transfer film of the present invention. FIG. 4 is a schematic cross-sectional view illustrating still another embodiment of the protective layer transfer film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Thermal transfer resin layer 3 Release layer 4 Transparent resin layer 5 Ultraviolet ray blocking layer 6 Thermal adhesive resin layer 7 Back layer

Claims (4)

In the protective layer transfer film formed by providing a heat transferable resin layer on the base film, the heat transfer resin layer is composed of a laminate in which a transparent resin layer and a heat adhesive resin layer are stacked in this order from the base film side, The thermal adhesive resin layer is a copolymer of a reactive ultraviolet absorber represented by the following general formula and at least one of an acrylic monomer, an oligomer and a reactive polymer, and the copolymer A protective layer transfer film comprising a different resin, and the content of the reactive ultraviolet absorber is 20% by weight or more in the heat-adhesive resin layer.

The protective layer transfer film according to claim 1, wherein the copolymer contains a copolymer represented by the following formula.

A region of a thermal transfer ink layer comprising a sublimable dye ink layer and / or a heat-meltable ink layer of at least one color or two or more colors and a region of the thermal transfer resin layer are provided on a base film in the order of planes. An integrated transfer film of an ink layer and a protective layer, wherein the thermal transfer resin layer is composed of a laminate in which a transparent resin layer and a thermal adhesive resin layer are laminated in this order from the base film side, and the thermal adhesive resin The layer contains a copolymer of a reactive ultraviolet absorber represented by the following general formula and at least one of an acrylic monomer, an oligomer, and a reactive polymer, and a resin different from the copolymer An integral transfer film of an ink layer and a protective layer, wherein the content of the reactive ultraviolet absorber is 20% by weight or more in the heat-adhesive resin layer.

3. A print product comprising the thermal transfer resin layer of the protective layer transfer film according to claim 1 or 2 laminated on at least a part of a print screen of a print product having an image colored with at least a dye.

Images