THERMAL TRANSFER COVER FILM

Abstract: A thermal transfer cover sheet comprising a transparent resin layer (2) and, if necessary a heat-sensitive adhesive layer (5), formed on a base film (1) with a release layer (3) interposed therebetween, and a thermal transfer process using this sheet. A preferable material for the transparent resin layer is ionizing radiation-curing resin, silicone-modified resin and wax-containing resin. When this sheet is laid on the surface of a picture image (7Y, 7M, 7C) and heated, the transparent resin layer is transferred onto the image to form an image protecting layer, thus giving an article having a picture image formed thereon, which is excellent in durability, luster and color development and is free from curling. When most of a parting agent is incorporated in a thermal transfer dye layer in forming a picture image (7Y, 7M, 7C) by sublimation transfer, it becomes possible to prevent the dye layer from using with an image accepting layer and to improve the adhesion of the transparent resin layer to the image accepting layer.

Description: The present invention relates to a heat transfer cover film. More particularly, the present invention relates to a heat transfer cover film enabling heat transferred images to be improved in terms of such durability as rub-resistance and allowing them to develop color and luster as well. So far, heat transfer techniques have been widely used for simple and expeditious printing. Allowing various images to be produced expeditiously, these heat transfer techniques have incidentally been employed for prints usually made in a small number, e.g. for preparing ID or other cards. Where it is desired to obtain color images like photographs of face, another type of heat transfer technique is now available, making use of heat transfer films of continuous length comprising a continuous substrate film on which a number of heat transfer layers colored in yellow, magenta and cyan (and black, if necessary) are formed successively and repeatedly. Such heat transfer sheets are generally broken down into two types, one referred to as a so-called wax type of heat transfer film in which a heat transfer layer is thermally softened and transferred onto an image-receiving material in an imagewise manner and the other a so-called sublimation type of heat transfer film in which only a dye sublimes (migrates) thermally from within a heat transfer layer onto an image-receiving sheet after an imagewise pattern. When ID or other cards are to be produced with such heat transfer films as mentioned above, the wax type of heat transfer film has the advantage of being capable of forming verbal, numerical or other images, but involves the disadvantage that such images are poor in durability, esp., rub resistance. With the sublimation type of heat transfer film, on the other hand, it is possible to obtain gray scale images, i.e., gradation pattern, like photographs of face. Unlike those obtained with ordinary ink, however, the formed images are less lustrous for lack of any vehicle and, by the same token, are poor in durability, e.g. rub resistance. In order to solve such problems, it has been proposed so far to laminate transparent films on the surfaces of the images. However, this is not only cumbersome to handle but gives rise to card curling as well, because the cards are laminated all over the surfaces. What is more, too thin films cannot be used in view of lamination work, thus posing a problem that the overall thickness of cards increase. As an alternative to the above-mentioned lamination technique, it has been proposed to coat the surfaces of images with heat- or ionizing radiation-curable resins and cure them. However, this is not only troublesome to handle but also brings about a possibility that the images may be attacked by solvents in coating materials. With the heat-curable resins, there is another possibility that the dyed images may discolor or fade due to the heat used for curing. JP-A-01/58 590 discloses a heat transfer sheet comprising inter alia a protective layer with an ionizing radiation-curable resin, an intermediate layer and at least one solvent evaporation type film-forming resin, the layers being sequentially provided in a laminate form on a releasable sheet. JP-A-01/202 492 discloses a transfer sheet comprising a protective layer made of a half-cured layer of an ionizing radiation-curable resin and at least a metallic film layer provided sequentially on a releasable side of a releasable sheet. US-A-4,704,310 discloses a release coating for a heat transferable laminate wherein the release is composed of a carrier web, typically paper, overcoated with a non-wax release layer, overcoated with an ink design layer and a heat activatable adhesive layer. A barrier layer is preferably included between the non-wax layer and the ink design layer. The release contains UV curable components which are cured by exposure to ultraviolet light. JP-A-59/106 997 discloses a sublimable layer containing coloring matter and a heat meltable layer provided on a support. The sublimable layer and the heat meltable layer are preferrably applied onto the support in this order. It is therefore an object of this invention to provide a heat transfer cover film which can solve the above-mentioned problems of the prior art and so can expeditiously give excellent, curl-free images that are improved in terms of such properties as durability, esp. rub resistance, luster, color development. The above-mentioned and other objects and features of the invention are achievable by the following invention. This invention concerns a heat transfer cover film according to claim 1. By forming an ionizing radiation-cured resin layer on a substrate film in a releasable manner and transferring that layer onto the surface of a transfer image, it is possible to provide expeditious production of an excellent, curl-free image representation which is improved in terms of such properties as durability, esp. rub resistance, gloss and color development. Transparent particles are incorporated in the ionizing radiation-cured resin layer, whereby a protective layer having a much more improved rub resistance is heat transferable, because the film can be well cut during heat transfer. There is a heat transfer process disclosed in which (a) a dye layer of a heat transfer sheet including a substrate film having said dye layer on its surface is overlaid on (b) a dye-receiving layer of a heat transfer image-receiving sheet including a substrate film having said dye-receiving layer on its surface in opposite relation; heat is applied from the back surface of said heat transfer sheet according to an imagewise pattern to form an image; and a transparent protective film is laminated on the surface of said image, wherein said dye layer contains a releasant, while said dye-receiving layer is releasant-free or contains a releasant in such an amount as to offer no impediment to the lamination of said transparent protective layer. The laminating of the transparent protective layer is carried out with the heat transfer cover film according to the present invention By allowing the dye layer to contain the releasant in an amount sufficient to ensure easy release of it from the dye-receiving layer during heat transfer while permitting the dye-receiving layer to be releasant-free or contain the releasant in such an amount as to offer no impediment to the lamination of the transparent protective layer, it is possible to laminate the transparent protective layer easily on the surface of the image formed by heat transfer and thereby produce an image representation which is improved in terms of such properties as durability, esp. rub resistance, resistance to staining, light fastness, resistance to discoloration and fading in the dark and storability. There is disclosed a heat transfer sheet in which a substrate sheet is provided on the same surface with a first heat transfer layer comprising a thermally migratable dye and an untransferable binder and a second heat transfer layer comprising a dyed or pigmented, heat-meltable binder, wherein said substrate sheet is made of a polyester film treated on at least its surface to be provided with said heat transfer layers in such a way that said surface is made easily bondable. By using as a substrate sheet a polyester film made readily bondable to heat transfer layers, it is possible to provide a heat transfer sheet enabling a clear gray scale image and a clear verbal or other image to be made at the same time. Such a heat transfer sheet as described above is especially useful for forming the images required to have a cover film. For that purpose, this heat transfer sheet may also have a transparent layer for a cover film according to the invention. Figure 1 is a sectional view of the heat transfer cover film according to this invention, Figures 2 and 3 each are a sectional view of how a transparent resin layer has been formed on a heat transfer image with the heat transfer cover film of this invention, and Figure 4 is a plan view of one embodiment of the heat transfer cover film of this invention. Heat Transfer Cover Film This invention will now be explained more illustratively with reference to the drawings attached hereto to illustrate the preferred embodiments diagrammatically. Referring now to Fig. 1, there is diagrammatically shown a section of the heat transfer cover film according to this invention, wherein an ionizing-radiation-cured resin layer 2 is releasably formed on a substrate film 1. A release layer, shown at 3 in Fig. 1, is provided to decrease the adhesion between the resin layer 2 and the substrate film 1, thereby making release of that layer 2 easy. This layer 3 may be unnecessary when the film 1 is well releasable from the resin layer 2. A back layer, shown at 4, is provided to prevent a printer's thermal head from sticking to the film 1. This layer 4 may again be dispensed with when the properties of the film 1 such as heat resistance and slip properties are satisfactory. The heat transfer cover film of this invention will now be explained in greater detail with reference to what it is made of and how to produce it. No particular limitation is imposed upon the material of which the substrate film 1 is made. Any material so far available for conventional heat transfer films may be used as such to this end. Other materials may, of course, be employed. Illustrative examples of the material of which the substrate film 1 is made include tissues such as glassine paper, condenser paper and paraffin paper. Besides, use may be made of plastics such as polyester, polypropylene, cellophane, polycarbonate, cellulose acetate, polyethylene, polyvinyl chloride, polystyrene, nylon, polyimide, polyvinylidene chloride, and ionomer or their composite materials with said papers. The substrate film 1 may vary in thickness to have proper strength, heat resistance, etc., but should preferably have a thickness ranging generally from 3 µm to 100 µm. In this invention, the ionizing radiation-cured resin layer 2 is formed of an ionizing radiation-curable resin. Ionizing radiation-curable resins so far known in the art may be used, if they are polymers or oligomers having a radically polymerizable double bond in their structure, e.g. those comprising (meth)acrylates such as polyester, polyether, acrylic resin, epoxy resin and urethane resin, all having a relatively low molecular weight, and radically polymerizable monomers or polyfunctional monomers optionally together with photopolymerization initiators, and capable of being polymerized and crosslinked by exposure to electron beams or ultraviolet rays. The radically polymerizable monomers, for instance, may include (meth)acrylic ester, (meth)acrylamide, allyl compounds, vinyl ethers, vinyl esters, vinyl cyclic compounds, N-vinyl compounds, styrene, (meth)acrylic acid, crotonic acid and itaconic acid. The polyfunctional monomers, for instance, subsume diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris-(β-(meth)acryloxyethyl)isocyanurate. According to this invention, suitable solvents, non-reactive transparent resins or the like, if required, may be added to the ionizing radiation-curable resin comprising the above-mentioned components to prepare ink whose viscosity, etc. are regulated. This ink is then coated on the substrate film by numerous means such as gravure coating, gravure reverse coating or roll coating. Subsequent drying and curing gives the ionizing radiation-cured resin layer 2, which has preferably a thickness of about 0.5 µm to about 20 µm. The transparent resins used, for instance, may include polyester resin, polystyrene resin, acrylic resin, epoxy resin, cellulose resin, polyvinyl acetal resin and vinyl chloride/vinyl acetate copolymer resin. These resins excel in transparency but tend to form films so relatively tough that they cannot be well cut at the time of transfer. Also, they are so less than satisfactory in slip properties that they are likely to be injured by surface rubbing, thus decreasing in surface gloss. According to the 2nd aspect of this invention, such transparent resins are improved in terms of the "film cutting" at the time of transfer and slip properties by mixing them with wax. Radiations such as ultraviolet rays or electron beams are used for curing the ionizing radiation-curable resin layer. For irradiation, all conventional techniques may be used as such. For electron beam curing as an example, use may be made of electron beams having an energy of 50 to 1,000 KeV, preferably 100 to 300 KeV, emitted from various electron beam accelerators such as those of Cockroft-Walton type, van de Graaff type, resonance transformation, insulating core transformer, linear, electrocurtain, dynamitoron and high-frequency types, and so on. For ultraviolet curing, use may be made of ultraviolet rays emanating from such light sources as ultra-high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs or metal halide lamps. It is understood that curing by ionizing radiations may be carried out just after the formation of the curable layer or after the formation of all the layers. When forming the aforesaid ionizing radiation-cured resin layer, particles of high transparency are added to said cured resin layer. These particles may embrace such inorganic particles as silica, alumina, calcium carbonate, talc or clay particles or such organic particles such as acrylic, polyester, melamine or epoxy resin particles, all being divided to as fine as submicrons or a few µm. Such particles are used in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the ionizing radiation-curable resin so that the transparency of the layer may substantially be obtained. In too small amounts insufficient "film cutting" can take place during heat transfer, whereas in too large amounts the protective layer is lacking in transparency. Various images to be covered may be further improved in terms of such properties as slip properties, gloss, light fastness, weather-resistance and whiteness by incorporation of other additives, e.g. waxes, slip agents, UV-absorbers, antioxidants and/or fluorescent brighteners. Prior to forming the ionizing radiation-cured resin layer, it is preferred to provide the release layer 3 on the surface of the substrate film. Such a release layer is made of such releasants as waxes, silicone wax, silicone resin, fluorocarbon resin and acrylic resin. The release layer 3 may be formed in similar manners as applied for forming the aforesaid ionizing radiation-cured resin layer, except curing. When it is desired to obtain a matted protective layer after transfer, various particles may be incorporated in the release layer. Alternatively, use may be made of a substrate film matted on its surface on which the release layer is to be provided. When the heat transfer film used in this invention is particularly made of a polyester film made easily bondable, a water soluble polymer is used as the release layer. As such a water soluble polymer, use is preferably made of polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, carboxymethylcellulose, methylcellulose, polyethylene oxide, gum arabic, water soluble butyral, water soluble polyester, water soluble polyurethane, water soluble polyacrylic and water soluble polyamide, which may be used in combination of two or more to control releasability. The release layer may then have a thickness of about 0.01 µm to about 5 µm. In order to make these layers more transferable, a heat-sensitive adhesive layer 5 may be additionally provided on the surface of the ionizing radiation-cured resin layer. Such an adhesive layer, for instance, may be formed by coating on that surface resins of improved hot adhesiveness such as acrylic resin, vinyl chloride resin, vinyl chloride/vinyl acetate copolymer resin and polyester resin, followed by drying, and may preferably have a thickness of about 0.5 µm to about 10 µm. While the heat transfer cover film of the 1st aspect of this invention is constructed as mentioned above, it is understood that the ionizing radiation-cured resin may be provided on the substrate film independently or successively in combination with a sublimation type of dye layer and a wax ink layer. This layer 5 may be formed by the coating and drying of a solution of a thermoplastic resin whose Tg lies in the range of 40-75°C, preferably 60-70°C, e.g. a resin having an improved hot adhesiveness such as acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride/vinyl acetate copolymer resin and polyester resin, and may preferably have a thickness of about 0.1 µm to about 10 µm. At a Tg lower than 40°C, the aforesaid heat-sensitive adhesive layer is softened when the resulting image is used at a relatively high temperature, so that micro-cracking can occur in the transparent resin layer, resulting in degradation of its chemical resistance, esp. its resistance to plasticizers. At a Tg higher than 75°C, on the other hand, not only is the image to be covered made less adhesive to the transparent resin layer even with the heat emitted from a thermal head, but the "foil cutting" of the transparent resin layer also drops, making it difficult to perform transfer with high resolution. Of the aforesaid heat-sensitive adhesives, the most preference is given to polyvinyl chloride resin, polyvinyl acetate resin and vinyl chloride/vinyl acetate copolymer resin, all having a polymerization degree of 50-300, preferably 50-250. At a polymerization degree lower than 50 such difficulties as is the case with low Tg's are experienced, whereas at higher than 300 such problems as is the case with high Tg's arise. Preferably, such a heat transfer cover film as mentioned above is used specifically, but not exclusively, to protect images obtained with the transfer and/or wax types of heat transfer techniques. Especially when applied to sublimation transfer images, it does not only provide a protective layer for said images but makes them clearer as well, because the dyes forming them are again allowed to develop color due to the heat at the time of heat transfer. It is also noted that the sublimation and/or wax types of transfer images may have been formed on any one of image-receiving materials heretofore known in the art. However, images formed on card materials made of polyester resin, vinyl chloride resin, etc. are preferably protected by a heat transfer cover film of this invention. Such card materials may be provided with embossments, signatures, IC memories, magnetic layers or other prints. Alternatively, they may be provided with embossments, signatures, magnetic layers, etc. after the heat transfer of the cover film. How to produce a card with the heat transfer cover film according to this invention will now be explained illustratively with reference to Figure 2. First, an yellow dye layer of a sublimation type of heat transfer sheet is overlaid on the surface of a card material 6 to transfer an yellow image 7Y thereonto with a thermal printer operating according to chromatic separation signals. Likewise, magenta and cyan images 7M and 7C are transferred onto the same region to produce a desired color image 7. Then, characters, signs and the like, shown at 8, are printed as desired, with a wax ink type of heat transfer sheet. Subsequently, the ionizing radiation-cured resin layer is transferred onto the color image 7 and/or verbal image 8 to form a protective film 2, using the heat transfer cover film of this invention. In this manner, a desired card is obtained. The thermal printer used for the aforesaid heat transfer may be independently (or, preferably, continuously) accommodated to sublimation transfer, wax ink transfer and heat transfer covering. Alternatively, these transfer operations may be performed at properly regulated energy levels with a common printer. It is noted that as the heating means suitable for this invention, not only are thermal printers applicable but hot plates, hot rolls, irons or other units are also usable. According to this invention wherein a substrate film is releasably provided thereon with an ionizing radiation-cured resin layer, which is in turn transferred onto the surface of a transfer image, it is possible to provide expeditious production of an excellent, curl-free image representation which is improved in terms of such properties as durability, esp. rub resistance, gloss and color development. A protective layer having a improved rub resistance is transferred onto a transfer image by incorporating particles in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the ionizing radiation curable resin in the ionizing radiation-cured resin layer, because the "film cutting" at the time of transfer takes place so well. Heat Transfer Process using a heat transfer cover film according to the present invention Similar to those so far known in the art, the heat transfer sheet may include a substrate film having a thickness of about 0.5 µm to about 50 µm, preferably about 3 µm to about 10 µm, for instance, a film made of polyethylene terephthalate, polystyrene, polysulfone and cellophane, and a dye layer formed thereon, comprising a sublimable dye, preferably a dye having a molecular weight of about 250 or higher and a binder resin based on, e.g. cellulose, acetal, butyral and polyester. This film is only different from the conventional ones in that said dye layer is permitted to contain a relatively large amount of a releasant. It is noted that a releasant is added to both the dye layer and the dye-receiving layer in conventional ones so as to prevent their fusion at the time of heat transfer. In the present disclosure, however, the wording "a relatively large amount" is understood to mean that a substantial portion or 100% by weight to 50% by weight of the releasant added is contained in the dye layer. The releasant for instance, may be wax, silicone oil, surfactants based on phosphates and solid slip agents such as polyethylene powders, Teflon® powders, talc and silica, all generally available and heretofore known in the art. However, preference is given to silicone resins. As the aforesaid silicone resins, it is desired to use those modified by epoxy, long-chain alkyl, alkyl, amino, carboxyl, higher alcohols, fluoro-fatty acids, fatty acids, alkylaralkyl polyether, epoxy-polyether, polyether and the like by way of example. The more preferable releasants used are silicone-modified resins in which silicone resins are bonded to vinylic, acrylic, polyester type and cellulosic resins by blocking or grafting. With these modified resins well compatible with the binder of the dye layer, it is possible to leave the migration, stability, capability of forming coats, etc. of the dye intact and make the transfer of it onto the dye-receiving layer less likely to occur at the time of heat transfer, thus doing no damage to the capability of the transparent protective layer of being laminated on the surface of the dye-receiving layer. The aforesaid releasants may be used alone or in admixture, preferably accounting for 0.1 to 30% by weight, particularly 0.1 to 20% by weight of the dye layer. In too small amounts they fail to produce sufficient release effects, whereas in too large amounts they give rise to a drop of dye migration or coat strength and offer some problems in connection with dye discoloration and storability. The heat transfer image-receiving sheet used to make images with such a heat transfer sheet as aforesaid may be made of any material with the recording surface being able to receive the aforesaid dye such as vinyl chloride resin. When made of dye receptivity-free materials such as films or sheets of pater, metals, glass or synthetic resins, it may provided on at least its one side with a dye-receiving layer made of a resin capable of receiving dyes satisfactorily such as polyester resin or vinylic resin, e.g. vinyl chloride/styrene copolymers or vinyl chloride/vinyl acetate copolymers. Such a dye-receiving layer may contain such a releasant as aforesaid so as to facilitate sheet feeding and releasing and provide surface protection or for other purposes. However, that releasant should be used in small amounts, because it is difficult to laminate the transparent protective layer on the dye-receiving layer containing a large amount of the releasant. The amount of the releasant, when added, should be not higher than 50% by weight, preferably 30% by weight of the amount of the releasant which has been contained in both the dye layer and the dye-receiving layer so as to improve the releasability therebetween. More specifically, that releasant has to be used in an amount of not higher than 1 part by weight, preferably 0.5 parts by weight per 100 parts by weight of the resin forming the dye-receiving layer. According to the heat transfer process, the aforesaid heat transfer sheet and image-receiving sheet are used to laminate the transparent protective layer on the resulting image which is carried out with a heat transfer cover film of this invention. The present process using the heat transfer cover film of the present invention will now be explained with reference to Figure 3. For instance, an yellow dye layer of the heat transfer sheet is first overlaid on the surface of a heat transfer image-receiving sheet 15 to transfer an yellow image 16Y thereonto with a thermal printer operating according to color separation signals. Likewise, magenta and cyan images 16M and 16G may be transferred to form a desired color image 16. Then, a transparent protective layer 12 is transferred onto the image 16 with the heat transfer cover film of the present invention. In this manner, the color image 16 having the desired transparent protective layer 12 laminated thereon is obtained. Other embodiments are also envisioned. For instance, the transparent protective layer 12 may be located adjacent to the dye layer 17 of the heat transfer sheet, as illustrated in Figure 5. It is also understood that the lamination of the transparent protective layer may be achieved not only through the thermal head of the thermal printer used for heat transfer but also with laminators, hot rolls, irons or other known equipment or, possibly, in coating manners. As aforesaid, the dye layer is allowed to contain a substantial portion of the releasant in such an amount as to assure easy separation of the dye layer from the dye-receiving layer at the time of heat transfer, while the dye-receiving layer is releasant-free or permitted to contain the releasant in such an amount as to offer no impediment to the lamination of the transparent protective layer, the transparent protective layer can be easily transferred onto the surface of the image formed by heat transfer, thus making it possible to make an image representation improved in terms of such properties as durability, esp. rub resistance, resistance to staining, light fastness, resistance to discoloration and fading in the dark and storability. Production of Heat Transfer Sheet and Card by using a heat transfer cover film of the present invention Such items of information as characters, signs and bar codes carried on cards, e.g. ID cards are required to be recorded in black at high density rather than on a gray scale. Thus such items of information are desired to be recorded with a heat meltable type of heat transfer sheet. With that purpose in mind, there has been proposed a mixed type of heat transfer sheet in which a sublimation type of dye layer and a heat meltable type of ink layer are successively provided on the same substrate sheet (see Japanese Patent Laid-Open Publication (KOKAI) No. 63-9574). With this mixed type of heat transfer sheet, excellent gray scale images for photographs for faces, etc. are formed together with monochromic, high-density images for characters, signs and the like. In the case of such a mixed type of heat transfer sheet as aforesaid, it is required for the sublimation type of dye layer that only the dye migrate onto the image-receiving material while the binder remain on the substrate sheet. In other words, the dye layer is required to be well adhesive to the substrate sheet. For the wax type of ink layer, it is required that the ink layer be transferred onto the image-receiving material in its entirety. To put it another way, the ink layer should be well-releasable from the substrate sheet. Such requirements may possibly be met by forming a heat-meltable type of ink layer with a well-releasable substrate sheet and forming an adhesive layer on its region to be provided with a sublimation type of dye layer or, alternatively, providing a substrate sheet including an adhesive layer with a release layer and forming a heat-meltable ink layer on that release layer. A problem with forming such an adhesive layer, however, is that the heat-sensitivity of the sublimable dye layer is so decreased that no satisfactory gray scale image can be obtained, because more energy is generally required for the heat transfer of the sublimable dye layer than for the transfer of the heat meltable ink layer. To avoid this, the adhesive layer should be made as thin as possible. Still, some difficulty has been involved so far in providing an adhesive layer of the order of submicrons uniformly, thus offering such problems as unevenness of printing and unusual (or overall) transfer of dye layers. In order to provide a solution to such difficulties, there is provided a heat transfer sheet including a substrate sheet having on the same surface a first heat transfer layer comprising a thermally migrating dye and a non-transferable binder and a second heat transfer layer comprising a dyed or pigmented, heat-meltable binder, wherein the substrate sheet is formed of a polyester film made easily-bondable on at least the surface to be provided with the heat-transfer layers. By using this heat transfer sheet in combination with the aforesaid heat transfer cover film according to the present invention, it is possible to obtain high-quality image representations. The aforesaid heat transfer sheet will now be explained more illustratively with reference to its preferred embodiments. In the present disclosure, the "polyester film made easily bondable" refers to a polyester film provided thereon with a very thin, uniform adhesive layer. In order to obtain such an adhesive layer, it is preferred that heat-, catalyst- and ionizing radiation-curable type of crosslinked resins, for instance, polyurethane, acrylic, melamine or epoxy resins are first dispersed in water or dissolved in organic solvents to prepare coating solutions. They may then be coated on the aforesaid polyester film by any desired coating means, for instance, blade coating, gravure coating, rod coating, knife coating, reverse roll coating, spray coating, offset gravure coating or moss coating, followed by drying. Of importance in this case is the thickness of the adhesive layer formed. At too large a thickness the heat sensitivity of the sublimation type of dye layer drops, whereas at too small a thickness such unusual transfer of dye layers as mentioned above takes place. Thus the adhesive layer should have a thickness lying in the range of 0.001 to 1 µm, preferably 0.05 to 0.5 µm. It is particularly preferred that the adhesive layer formed be of uniform thickness. For instance, this is achieved by forming a few-µm thick adhesive layer before stretching the polyester film and then biaxially stretching that film, whereby the adhesive layer can be made uniform and reduced to as thin as 1 µm or less in thickness. Particularly preferable as the aforesaid polyester film is a film of polyethylene terephthalate or polyethylene naphthalate, which is commercially available or may be prepared by known methods (see, for instance, Japanese Patent Laid-Open Publication Nos. 62-204939 and 62-257844). Such a substrate sheet as aforesaid may have a thickness enough to assure some heat resistance and strength, say, 0.5 to 50 µm, preferably about 3 µm to about 10 µm. The sublimation type of dye layer that is the first heat transfer layer formed on the surface of the substrate sheet contains a sublimable dye carried by any desired binder resin. Any dye so far used for conventional known heat transfer sheets may be effectively applied to this end without exception. By way of example alone, use may be made of dye reds such as MS Red G, Macrolex Red Violet R, Ceres Red 7B, Samaron Red HBSL and Resolin Red F3BS; yellow dyes such as Foron Brilliant Yellow 6GL, PTY-52 and Macrolex Yellow 6G; and blue dyes such as Kayaset Blue 714, Vacsolin Blue AP-FW, Foron Brilliant Blue S-R and MS Blue 100. Known resins may all be used as the binders for carrying such dyes as aforesaid. By way of example, preferable are cellulosic resins such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, hydroxypropylcellulose, methylcellulose, cellulose acetate and cellulose acetate butyrate; vinylic resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone and polyacrylamide; polyester; and the like. Of these resins, preference is given to resins based on cellulose, acetal, butyral and polyester in consideration of such properties as heat resistance and dye migration. Such a dye layer may preferably be formed by dissolving or dispersing the aforesaid sublimable dye and binder resin as well as other components, e.g. releasants in suitable solvents to prepare a coating or ink material for forming the dye layer and coating it on the aforesaid substrate sheet, followed by drying. The dye layer formed in this manner may have a thickness of 0.2 to 5.0 µm, preferably about 0.4 to about 2.0 µm, and the sublimable dye may preferably account for 5 to 90% by weight, preferably 10 to 70% by weight of the dye layer. When it is desired to obtain a monochromic image, the dye layer may be made from one selected from the group consisting of the aforesaid dyes. When it is desired to obtain a full-color image, on the other hand, the dye layer may be formed choosing suitable cyan, magenta and yellow (and, if necessary, black) dyes. The heat meltable ink layer is located in parallel to the aforesaid sublimable dye layer or layers. In what order these dye layers are arranged is not critical. For instance, yellow, magenta and cyan dye layers and a heat-meltable, black ink layer may be successively formed according to an A4 size. The aforesaid ink layer comprises a dyed or pigmented, heat-meltable binder. A preferable colorant is carbon black, but other dyes or pigments of different hues may be used as well. The binder used may be a thermoplastic resin or wax having a relatively low melting point or their mixture, but care should preferably taken of its adhesion to the associated image-receiving material. For instance, when the image-receiving material is a vinyl chloride resin often used for ID cards, thermoplastic resins such as (meth)acrylic ester, vinyl chloride/vinyl acetate copolymer resin, ethylene/vinyl acetate copolymer resin and polyester resin are preferable. In order to form the heat meltable ink layer on the substrate sheet, the aforesaid ink materials may be coated thereon by not only hot melt coating but also a number of other coating means as well, inclusive of hot melt coating, hot lacquer coating, gravure coating, gravure reverse coating and roll coating. Required to be determined with harmony between the required density and heat sensitivity in mind, the ink layer formed preferably lies in the range of 0.2 to 3.0 µm. At too small a thickness the reflection density of the transfer image is insufficient, whereas at too large a thickness the "foil cutting" at the time of printing degrades, resulting in a drop of the sharpness of the printed image. The substrate sheet has preferably included a release protective layer on its surface before forming the aforesaid ink layer. This release protective layer serves to improve the releasability of the ink layer and is transferred along with the ink layer, giving a surface protective layer on the transfer image and thereby improving its rub resistance, etc. Such a release protective layer may be made of (meth)acrylic resin, silicone-based resin, fluorine-based resin, cellulosic resin (such as cellulose acetate), epoxy-based resin, polyvinyl alcohol and the like, which contain waxes, organic pigments, inorganic pigments and the like, and may preferably have a thickness of 0.2 to 2.5 µm. At too small a thickness it fails to produce sufficient protective effects such as scratch-resistance, whereas at too large a thickness the "foil cutting" at the time of printing gets worse. It is preferred that a heat-sensitive adhesive layer be additionally provided on the aforesaid ink layer. This adhesive layer should again be chosen in consideration of its adhesion to the associated image-receiving material. For instance, when the image-receiving material is a card material made of a resin based on vinyl chloride, it is preferable to use such a well-adhesive thermoplastic resin as aforesaid. The adhesive layer formed should preferably have a thickness lying in the range of 0.05 to 1.0 µm. At too small a thickness no desired adhesion is obtained, whereas at too large a thickness the "foil cutting" at the time of printing gets worse. The aforesaid heat transfer sheet also includes such a cover film as illustrated according to the present invention. It is further preferred that the aforesaid substrate sheet be provided on its back surface with a heat-resistant slip layer adapted to prevent a thermal head from sticking to it and improve its' slip properties. The image-receiving material used to make images with such a heat transfer sheet as aforesaid may be made of any material with the recording surface showing dye-receptivity with respect to the aforesaid dye. When made of a dye-receptivity-free material such as paper, metals, glass or synthetic resin, it may have been provided with a dye-receiving layer on at least its one surface. The heat transfer sheet is particularly fit for the preparation of cards made of polyvinyl chloride resin. With no need of forming any special dye-receiving layer, a gray scale image comprising the sublimable dye layer and characters, signs, bar codes, etc. comprising the meltable ink layer may be printed directly on these card materials. A particularly preferable card material contains a plasticizer in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight per 100 parts by weight of polyvinyl chloride. Moreover, it should be well-receptible with respect to the sublimable dye and well-adhesive to the meltable ink. In a more preferred embodiment, the card material contains, in addition to the aforesaid plasticizer, a slip agent in an amount of 0.1 to 5 parts by weight per 100 parts by weight of polyvinyl chloride. According to that embodiment, it is found that even when a relatively large amount, e.g. 1 to 5 parts by weight of the plasticizer is incorporated in the polyvinyl chloride, the card material offers no blocking problem with respect to the heat transfer sheet, and is improved in terms of its receptivity with respect to the sublimable dye. Such a polyvinyl chloride card material as aforesaid may be obtained by blending together the required components and forming the blend into a sheet of, e.g. about 0.05 mm to about 1 mm in thickness by known means such as calendering or extrusion, and may be in the form of either a card or a sheeting which will be cut into card size. Also, the card material may be of a monolayer or multilayer structure, in which latter case, for instance, a white pigment-containing center core is provided with a transparent resin layer on at least its one surface. It is understood that the heat transfer sheet is never limited to preparing polyvinyl chloride cards. For instance, it is not only suited for making image-receiving materials other than cards, e.g. passports, to say nothing of polyester cards, but is also useful for producing various prints inclusive of less sophisticated catalogs, for which gray scale images and monochromic images for characters, signs, bar codes, etc. are required at the same time. Energy applicator means so far known in the art may all be used to apply heat energy to carry out heat transfer with such heat transfer sheet and image-receiving material as mentioned above. For instance, the desired images may be obtained by the application of a heat energy of about 5 mJ/mm² to about 100 mJ/mm² for a time controlled by recording hardware such as a thermal printer (e.g. Video Printer VY-100 made by Hitachi, Ltd. ) The substrate sheet used is a polyester film made easily bondable, as described above, there is provided a heat transfer sheet capable of forming clear gray scale images and clear verbal or other images at the same time. With this heat transfer sheet, it is possible to provide an excellent card. The present invention will now be explained more illustratively with reference to the reference examples, examples, application examples and comparative examples, wherein unless otherwise stated, the "parts" and "%" are given by weight. Preparation Example A1 Three ink compositions containing sublimable dyes of different colors were prepared with the components mentioned just below. Yellow Ink Disperse dye (Macrolex® Yellow 6G made by Bayer Co., Ltd.) 5.5 parts Polyvinyl butyral resin (Eslec® BX-1 made by Sekisui Chemical Co., Ltd.) 4.5 parts Methyl ethyl ketone/toluene (at a weight ratio of 1:1) 89.5 parts Magenta Ink This ink was similar to the yellow ink with the exception that a magenta disperse dye (Disperse Red 60) was used. Cyan Ink This ink was similar to the yellow ink, provided that a cyan disperse dye (Solvent Blue 63) was used. Provided as a substrate film was a 6.0 µm thick polyester film Lumirror made by Toray Industries, Ltd.) having on its back surface a heat-resistant slip layer (of 1 µm in thickness) and on its front surface a primer layer (of 0.5 µm in thickness) comprising a polyurethane base resin. Using gravure coating, the aforesaid ink compositions were successively and repeatedly coated on the front surface of the substrate film in the order of yellow, magenta and cyan, at a width of 15 cm and to a coverage of about 3 g/m². Subsequent drying gave a sublimation type of heat transfer sheet containing sublimable dye layers of three different colors. Preparation Example A2 The following wax ink composition, heated at a temperature of 100°C, was coated on the same substrate film as used in Reference Ex. A1 but including no primer layer, to a coverage of about 4 g/m² by hot melt roll coating, thereby preparing a wax type of heat transfer sheet. Wax Ink Ester wax 10 parts Wax oxide 10 parts Paraffin wax 60 parts Carbon black 12 parts Example A1 Using gravure coating, the following ink composition was coated on the same substrate film as used in Reference Ex. A2 at a ratio of 1 g/m² on dry solid basis. Subsequent drying gave a release layer. Ink for Release Layer Silicone base resin 10 parts Vinyl chloride/vinyl acetate copolymer 10 parts Methyl ethyl ketone 100 parts Toluene 100 parts Then, the following ink was coated on the surface of the aforesaid release layer at a ratio of 10 g/m² on dry solid basis. Subsequent drying gave an ionizing radiation-curable resin layer. Ink for Ionizing Radiation-Curable Resin Layer Dipentaerythritol hexacrylate 40 parts Hydrophobic colloidal silica 40 parts Polymethyl methacrylate 20 parts Polyethylene wax 3 parts Methyl ethyl ketone 250 parts Toluene 250 parts Then, the following ink composition was coated on the surface of the aforesaid resin layer at a ratio of 1 g/m² on dry solid basis, followed by drying which gave an adhesive layer. After that, the product was exposed to electron beams of 180 kV at a dose of 5 Mrad in a nitrogen atmosphere of 10⁻⁷ Torr with an electron beam irradiator made by Nisshin High Voltage Co., Ltd. to cure the ionizing radiation-curable resin layer, thereby obtaining a heat transfer cover film according to this invention. Ink for Adhesive Layer Vinyl chloride/vinyl acetate copolymer 10 parts Methyl ethyl ketone 100 parts Toluene 100 parts Example A2 The procedures of Example A1 were followed with the exception that the following ionizing radiation-curable ink was used, thereby obtaining a heat transfer cover film according to this invention. Ink for Ionizing Radiation-Cured Resin Layer Trimethylolpropane triacrylate 60 parts Talc (Microace L-1 made by Nippon Talc Co., Ltd.) 10 parts Polymethyl methacrylate 30 parts Fluorine base surfactant (Flow Lard 432 made by Sumitomo 3M Co., Ltd.) 3 parts Methyl ethyl ketone 200 parts Toluene 200 parts Application Example A1 The sublimable dye layer of the sublimation type of heat transfer film of Reference Ex. A1 was overlaid on the surface of a card material comprising 100 parts of a compound of polyvinyl chloride - having a polymerization degree of 800 - containing about 10% of such additives as a stabilizer, 10 parts of a white pigment (titanium oxide) and 0.5 parts of a plasticizer (DOP), and heat energy was then applied thereto through a thermal head connected to electrical signals obtained by the chromatic separation of a photograph of face to form a full-color image thereof. Subsequently, characters and signs were reproduced with the wax type of heat transfer film of Reference Ex. A2. Finally, a transferable protective layer was transferred onto the respective imaged regions with the heat transfer cover film according to Example A1 of this invention to obtain a card bearing the photograph of face and the required pieces of information. Application Example A2 The procedures of Application Ex. A1 were followed with the exception that the heat transfer cover film of Example A2 was used, thereby preparing a card. Comparative Example A1 The procedures of Application Example A1 were followed with the exception that no ionizing radiation-cured resin layer was transferred, thereby preparing a card. Comparative Example A2 A cover film was prepared by following the procedures of Example A1 provided that the following ink was used in place of the ink for the ionizing radiation-cured resin layer. With this cover film, a card was made by following the procedures of Application Example A1. Ink for Protective Layer Polyester resin (U-18 made by Arakawa Kagaku K.K.) 20 parts Methyl ethyl ketone 50 parts Toluene 50 parts Comparative Example A3 A cover film was prepared by following the procedures of Example A1 provided that the following ink was used in place of the ink for the ionizing radiation-cured resin layer. With this cover film, a card was made by following the procedures of Application Example A1. Ink for Protective Layer Cellulose resin (CAB381-0.1) 20 parts Methyl ethyl ketone 50 parts Toluene 50 parts Results of Estimation The cards obtained as aforesaid were estimated. The results are reported in Table 1 given just below. Film Cutting Rub Resistance Gloss Pencil Hardness A.Ex. A1 O ○ O ○ 72% 2H A2 O ○ O ○ 81% 2H C.Ex. A1 - X 14% 4B A2 X ○ 59% H A3 X ○ 28% H A.Ex: Application Example C.Ex: Comparative Example Film Cutting: Determined in terms of the releasability of films after transfer and by observing the transfer images under a microscope. O ○: Releasing is very easy and the ionizing radiation-cured resin layers are sharply cut along the contours of the the images. X: There is considerable resistance to releasing with the edges of the resin layers lacking uniformity. Rub Resistance: Measured by rubbing the surfaces of the images 100 times with gauze impregnated with isopropyl alcohol. O ○: The gauze is not stained at all. ○: The gauze is somewhat stained. X: The gauze is badly stained. Gloss: Determined in terms of gloss value in %. Example B1 A heat transfer cover sheet was prepared by following the procedures of Example A1 with the proviso that the following water soluble polymer composition was used as the ink for the release layer. Ink for Release Layer Polyvinyl alcohol AH-26 (made by Nippon Gosei Kagaku K.K.) 2.0 parts Ethyl alcohol 49.0 parts Pure water 49.9 parts Example B2 A heat transfer cover sheet was prepared by following the procedures of Example A1 with the proviso that the following water soluble polymer composition was used as the ink for the release layer. Ink for Release Layer Polyvinyl alcohol C-500 (made by Nippon Gosei Kagaku K.K.) 2.0 parts Ethyl alcohol 49.0 parts Pure water 49.9 parts Example B3 A heat transfer cover sheet was prepared by following the procedures of Example A1 with the proviso that the following water soluble polymer composition was used as the ink for the release layer. Ink for Release Layer Polyvinyl alcohol KL-05 (made by Nippon Gosei Kagaku K.K.) 2.0 parts Polyvinyl alcohol L-5407 (made by Nippon Gosei Kagaku K.K.) 1.8 parts Ethyl alcohol 49.0 parts Pure water 49.9 parts The present invention may find wide applications in preparing objects on which prints or images are formed by heat transfer techniques, for instance, ID cards.

Claims: A heat transfer cover film comprising a substrate film and an ionizing radiation-cured resin layer releasably formed on the substrate film, characterized in that said ionizing radiation-cured resin layer contains particles in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the ionizing radiation-curable resin so that the transparency of the layer may substantially be obtained. A heat transfer cover film as claimed in Claim 1, wherein a release layer is interleaved between the substrate film and the ionizing radiation-cured resin layer. A heat transfer cover film as claimed in Claim 1, wherein the ionizing radiation-cured resin layer contains a wax, a slip agent, an ultraviolet absorber, an antioxidant and/or a fluorescent brightener. A heat transfer cover film as claimed in Claim 1, wherein the ionizing radiation-cured resin layer is made of a polymer or oligomer having a radically polymerizable double bond in its molecule. A heat transfer cover film as claimed in Claim 1, wherein the substrate film is provided thereon with a dye layer. A heat transfer cover film as claimed in Claim 2, wherein the release layer comprises a water soluble polymer.

Inventors: ANDO J DAI NIPPON INSATSU KABU, OSHIMA K DAI NIPPON INSATSU KA, TORII M DAI NIPPON INSATSU KAB, ANDO, J. DAI NIPPON INSATSU KABUSHIKI KAISHA, OSHIMA, K. DAI NIPPON INSATSU KABUSHIKI KAISHA, TORII, M. DAI NIPPON INSATSU KABUSHIKI KAISHA
Applicants: DAINIPPON PRINTING CO LTD, DAI NIPPON INSATSU KABUSHIKI KAISHA
Application year: 1990
Main classification: B41M5
IPC codes: B41M5, B41M7