Thermal transfer image receiving sheet and thermal transfer sheet

Abstract: A thermal transfer image receiving sheet includes substrate sheet and a dye receptor layer disposed on at least one surface side of the substrate sheet, wherein the dye receptor layer has been formed on the substrate sheet by superposing the substrate sheet on to a receptor layer transfer film comprising a substrate film and the. dye receptor layer disposed on one surface side thereof which is peelable from the substrate film, so that the receptor layer transfer film is bonded to the substrate sheet to form a laminate, and peeling the substrate film from the laminate. The thermal transfer sheet also includes a substrate film, an intermediate layer disposed on the substrate film, and a dye layer disposed on the substrate film by the medium of the intermediate layer, wherein the dye layer comprises a dye and a binder resin, and at least one of the intermediate layer and the dye layer contains bubbles.

Description: BACKGROUND OF THE INVENTION The present invention relates to a thermal transfer image receiving sheet and more particularly to a thermal transfer image receiving sheet having a dye receptor layer which is capable of forming a good image by using a thermal transfer system. Heretofore, various thermal transfer methods have been known. Among these, there has been proposed a method wherein a sublimable dye (or subliming dye) is used as a recording agent, and is carried on a substrate film such as paper and plastic film to obtain a thermal transfer film and various full colour images are formed on an image receiving sheet such as paper and plastic film having thereon a dye receptor layer, by using the resultant thermal transfer film. In such a case, a thermal head of a printer is used as heating means so that a large number of colour dots of three or four colours are transferred to the image receiving sheet under heating in a very short period of time. As a result, a full colour image of an original is reproduced by using the multicolour colour dots. The thus formed images are very clear and are excellent in transparency, since the dyes are used therein as a colorant. Accordingly, these images are excellent in half tone reproducibility and gradation characteristic, and are substantially the same as the images formed by the conventional offset printing and gravure printing. Further, when the above image forming method is used, there can be formed images of high quality which are comparable to full colour photographic images. As the thermal transfer image receiving sheet to be used in the above sublimation type thermal transfer system, there has been used one comprising a substrate sheet and a dye receptor layer disposed thereon. However, since the image receiving sheet is heated at the time of the transfer operation, it causes considerable curl. In addition, in a case where such an image receiving sheet is left standing at a higher or lower temperature before it is used for the thermal transfer operation, it also causes curl, and cannot be fed to a printer in some cases. As a method for solving such a problem of curl production, there has been proposed a method wherein a back coating layer is bonded to a surface of a substrate sheet reverse to the surface thereof on which a dye receptor layer is formed (Japanese Laid Open Patent Application (JP A, KOKAI) No. 214484/1988), a method wherein an ionisation radiation curing adhesive is disposed between a substrate sheet and a dye receptor layer (Japanese Laid Open Patent Application No. 24794/1989), etc. In these methods, however, the problem of curl production has not sufficiently been solved yet. SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal transfer image receiving sheet having a dye receptor layer which is capable of forming a good image by using a thermal transfer system. According to the invention, there is provided a thermal transfer image receiving sheet comprising a substrate sheet and a dye receptor layer disposed on at least one surface side of the substrate sheet, wherein the substrate sheet has been formed by laminating at least two heat-shrinkable sheet materials so that the difference between the heat shrinkage directions thereof corresponds to an angle of 45 degrees or below. According to this embodiment, the occurrence of curl in the thermal transfer image receiving sheet can effectively be prevented at the time of thermal transfer operation. These and other objects, features and advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic sectional view showing an embodiment of the thermal transfer image receiving sheet according to the present invention. Figure 2 is a schematic sectional view showing another embodiment of the thermal transfer image receiving sheet according to the present invention. Figure 3 is a view for illustrating a shrinkage direction in a thermal transfer image receiving sheet. Figure 4 is a schematic sectional view showing another embodiment of the thermal transfer image receiving sheet according to the present invention. Figure 5 is a schematic sectional view showing another embodiment of the thermal transfer image receiving sheet according to the present invention. Figure 6 is a schematic sectional view showing a transparent type thermal transfer image receiving sheet according to the present invention. DESCRIPTION OF PREFERRED EMBODIMENTS Hereinbelow, the present invention will be described in more detail with reference to preferred embodiments thereof. Referring to Figure 1, the thermal transfer image receiving sheet according to the present invention comprises a substrate sheet 1, and a dye receptor layer 2 disposed on at least one surface side of the substrate sheet 1. In this embodiment, the dye receptor layer 2 is disposed on one surface side of the substrate sheet 1. Substrate sheet The substrate sheet comprises a laminate for the purpose of preventing the occurrence of curl in the thermal transfer image receiving sheet. Figure 2 is a schematic sectional view showing an embodiment of the thermal transfer image receiving sheet according to the present invention wherein such a substrate film of a laminate type is used. Referring to Figure 2, the substrate sheet 1 comprise a laminate comprising a core material 11 of paper, etc., and heat shrinking (or heat shrinkable) sheet material layers 12 and 12' disposed on both surface sides of the core material 10, and a dye receptor layer 13 is formed on at least one surface side of such a laminate. A laminate comprising an optional combination of the substrate films set out below may be used as the substrate sheet 1. Specific examples of the substrate sheet to be used in the present invention may include various papers such as synthetic paper (polyolefin type, polystyrene type, etc.), paper of fine quality or wood free paper, art paper or coated paper, cast coated paper, wall paper, backing paper, synthetic resin impregnated paper or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin containing paper, paper board, cellulose fiber paper, and the like; and various sheets of films of plastics such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, and the like. Further, the substrate film 1 may also comprise a white opaque film formed from a mixture of the above synthetic resin and white pigment or filler, or a foamed sheet which has been subjected to foaming operation. However, the substrate sheet 1 usable in the present invention should not be restricted to the above specific examples. Representative examples of such a laminate may include: a combination of cellulose fiber paper and synthetic paper, and a cellulose fiber paper and a plastic film or sheet. The above substrate film may have an appropriate thickness, and for example, it may generally have a thickness of about 10 to 300µm. In a case where the thermal transfer image receiving sheet is disposed (or scrapped) or cut into an appropriate size after the use thereof, etc., when the image receiving sheet is torn by hand or cut by means of a knife, scissors, a shredder and the like, the substrate sheet may preferably have a tear strength (or tear propagation strength) in the range of about 15 to 185 as measured according to JIS P 8116, in consideration of a balance between the strength thereof and easiness in the tearing or cutting thereof. When such a substrate sheet is used, the entirety of the thermal transfer image receiving sheet may have a tear strength of 20 to 200, so that it may easily be torn by hands or cut by means of various machines. In a case where the thermal transfer image receiving sheet is further subjected to folding or filing operation, the substrate sheet may preferably have a rigidity in the range of about 7 to 95 m 3 as measured according to JIS P 8143, in consideration of the easiness in folding and prevention of bulkiness thereof after the filing. When such a substrate sheet is used, the entirety of the thermal transfer image receiving sheet may have a rigidity in the range of 10 to 100 m 3 , so that it may easily be subjected to folding or filing operation. Figure 3 is a schematic view for illustrating the direction of the heat shrinkage of the two heat shrinking sheet 12 and 12' of the above thermal transfer image receiving sheet. The direction of the heat shrinkage is defined as a direction wherein the largest shrinkage of the heated material is observed. In Figure 3, the direction of the heat shrinkage of the sheet disposed on the front side is denoted by an arrow of a solid line, and the direction of the heat shrinkage of the sheet disposed on the back side is denoted by an arrow of a broken line. In Figure 3A, the directions of the heat shrinkage of the films disposed on front and back sides are perpendicular to each other. In such a case, the resultant thermal transfer image receiving sheet causes considerable curl. In Figure 3B, the directions of the heat shrinkage of the films disposed on front and back sides form an angle of about 25° (25 degrees) therebetween. In such a case, the resultant thermal transfer image receiving sheet causes a little curl, which is in a practically tolerable range. In Figure 3C, the directions of the heat shrinkage of the films disposed on front and back sides are substantially the same as each other. In such a case, in the resultant thermal transfer image receiving sheet, the occurrence of curl is prevent most effectively. The core material 11 to be used for such a purpose may be selected from various films and sheets for substrate film as described above. In consideration of the cost, nerve, etc., of the core material, preferred examples thereof may include various papers such as paper of fine quality or wood free paper, art paper or coated paper, cast coated paper, wall paper, backing paper, synthetic resin impregnated paper or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin containing paper, and paper board. The above core material may have an appropriate thickness, but it may generally have a thickness of about 30 to 200 µm. As the heat shrinking sheet materials 12 and 12' to be laminated on both sides of the above core material 11, there may be used synthetic paper, synthetic resin sheet, foamed polypropylene, foamed polyethylene, foamed polystyrene, etc. Among these, synthetic paper or foamed polypropylene is preferred in view of various strengths and cushion property. The heat shrinking sheet material may preferably have a thickness of 30 µm to 80 µm. It is preferred that the heat shrinking sheet materials 12 and 12' comprising the same material and having the same thickness are laminated on both sides of the core material 11. However, it is possible that heat shrinking sheet materials comprising different materials and having different thicknesses are laminated on both sides of the core material, as long as the difference (or deviation) between the directions of the heat shrinkage thereof is in the range of 45 degrees or smaller, more preferably 30 degrees or smaller. The resultant laminate (substrate sheet) having a three layer structure may preferably have a total thickness in the range of 100 to 300 µm, which may appropriately be determined in consideration of its nerve, curl, weight, cost, conveying property, etc. In the above embodiment, two heat shrinking sheet materials are bonded to both surfaces of the core material. However, a similar effect may be obtained when the core material is omitted and the two sheet materials are directly laminated on each other. The substrate sheet to be used in the present invention may also comprise a heat resistant synthetic paper having a porosity. Such a heat resistant synthetic paper may be obtained by stretching a composition comprising a porous synthetic resin and a filler to form a porous synthetic paper, and subjecting the resultant porous synthetic paper to crosslinking treatment by means of an electron gun, etc. The porous synthetic paper to be used in the present invention may be obtained by melt kneading a composition comprising a thermoplastic resin such as polypropylene and an inorganic filler, forming the resultant kneaded product into a film by an extrusion film formation process, and then stretching the film in the longitudinal direction thereof to form a core material, extrusion laminating films comprising a similar composition as described above on both sides of the core material, and stretching the resultant laminate in the lateral direction thereof. The porous synthetic paper per se and the production process therefor per se may be those know in the prior art. In the electron beam crosslinking treatment of the above porous synthetic paper, known synthetic paper as such may be irradiated with an electron beam. In such a case, however, the resultant degree of crosslinking (or crosslinking degree) is relatively low as compared with the electron beam irradiation dose. Accordingly, it is preferred to preliminarily incorporate an electron beam crosslinking component in the porous synthetic paper before the electron beam irradiation. Specific examples of such a crosslinking component may include polymers, oligomers and/or monomers having a radical polymerizable double bond in the structure thereof. More specifically, such polymers may include: polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin, polythiol polyene resin, etc. The above oligomers may include: polyfunctional (meth)acrylates comprising polyhydric alcohols, etc. The above monomers may include: monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N vinylpyrrolidone; and polyfunctional monomers such as divinylbenzene, trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)-acrylate, and neopentyl glycol di(meth)acrylate. Specific examples of a peroxide capable of providing a radical under the action of an electron beam may include organic peroxide such as acetyl cyclohexyl peroxide, isobutyl peroxide, diisopropyl peroxide carbonate, di-n-propyl peroxide carbonate, dimyristyl peroxide carbonate, di(2-ethoxyethyl)peroxide carbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, 3,5,5-trimethyl hexanonyl peroxide, octanonyl peroxide, lauroyl peroxide, acetyl peroxide, m-toluoyl peroxide, benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and cumene hydroperoxide. In general, the above crosslinking component is added to a resin composition before the film formation of the porous synthetic paper. It is generally preferred to prepare a synthetic paper which contains a non volatile crosslinking component in advance. However, it is also possible to use a method wherein commercially available porous synthetic paper is impregnated with an oligomer or monomer (particularly, a polyfunctional monomer) having a relatively low molecular weight, or with a solution prepared by dissolving the above peroxide in an organic solvent. Since the crosslinking component to be contained in a resin may be changed corresponding to the kind, molecular weight, number of functional groups thereof, it is difficult to determine the addition amount therefore in a single way. However, in general, the addition amount of the crosslinking component may be in the range of 0.5 to 50 wt.parts with respect to 100 wt.parts of the thermoplastic resin such as polypropylene. The electron beam to be used for the crosslinking of the synthetic paper containing the crosslinking component may be one having an energy of 50 to 1,000 KeV, more preferably 100 to 300 KeV, which may be emitted from various electron beam accelerator such as Cockroft Walton type, Van de Graf type, resonance transformer type, insulating core transformer type, linear type, Dynamitron type, and high frequency type. The thus obtained heat resistant synthetic paper may have an appropriate thickness, and for example, it may generally have a thickness of about 10 to 300 µm. When the above substrate film shows a poor adhesion with respect to the dye receptor layer to be formed thereon, it is preferred to subject the surface of the film to primer treatment or corona discharge treatment. Dye receptor layer The dye receptor layer to be formed on the surface of the above substrate film is one such that it may receive a sublimable dye migrating from (or transferring from) the thermal transfer sheet and may retain the thus formed image. For the purpose of forming the dye receptor layer, there may be used a method wherein a receptor layer transfer sheet is superposed on the above substrate film for the thermal transfer image receiving sheet, and thereafter the substrate film of the receptor layer transfer sheet is peeled from the resultant superposition thereby to transfer the dye receptor layer to the above substrate. Further, there may also be used a method wherein a coating material for forming the dye receptor layer is applied on to the substrate film for the thermal transfer image receiving sheet. (Formation of dye receptor layer by transfer method) The receptor layer transfer film to be used in the present invention comprises a substrate film and a dye receptor layer disposed on one side thereof, wherein the dye receptor layer is peelable from the substrate film. In a preferred embodiment, a heat sensitive or pressure sensitive adhesive layer is disposed on the surface of the receptor layer. According to an embodiment of the present invention, the above receptor layer transfer film is superposed on a substrate sheet for an image receiving sheet, these sheets are pressed by appropriate pressing means thereby to bond these sheets to each other, and then the substrate film is peeled from the resultant superposition, thereby to obtain a desired thermal transfer image receiving sheet. In another embodiment of the present invention, when the substrate of the image receiving sheet comprises a plastic sheet, the surface of the receptor layer may be extrusion coated with the above plastic material, thereby to omit a step of forming a heat sensitive or pressure sensitive adhesive layer on the surface of the receptor layer constituting the receptor layer transfer film. The thickness of the substrate sheet may appropriately be changed corresponding to the material constituting it so as to provide suitable strength and heat resistance thereof, but the thickness may preferably be 3 to 100 µm. It is preferred to form a release layer on the surface of the substrate film, prior to the formation of the receptor layer. Such a release layer may be formed from a release agent such as waxes, silicone wax, silicone resins, fluorine containing resins, and acrylic resins. The release layer may be formed in the same manner as that for a receptor layer as described hereinbelow. It is sufficient that the release layer has a thickness of about 015 to 5 µm. When a matte (or matted) receptor layer is desired after the transfer operation, it is possible to incorporate various particles in the release layer, or to use a substrate film having a matted surface on the release layer side thereof so as to provide a matted surface. As a matter of course, when the above substrate sheet has an appropriate releasability, it is not necessary to form the release layer. The dye receptor layer to be formed on the surface of the above substrate film is one such that it may receive a sublimable dye migrating from (or transferring from) the thermal transfer film after it is transferred to an arbitrary (or optional) transfer receiving material, and may retain the thus formed image. Specific examples of the resin for forming the dye receptor layer may include: polyolefin type resin such as polypropylene; hologenated polymer such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, and polyvinylidene chloride; vinyl type polymers such as polyvinyl acetate and polyacrylic acid esters; polyester type resin such as polyethylene terephthalate and polybutylene terephthalate; polystyrene type resins; polyamide type resins; copolymer resins comprising olefin such as ethylene and propylene, and another vinyl monomer; ionomers, cellulose type resins such as cellulose diacetate; polycarbonate; etc. Particularly preferred examples thereof may include vinyl type resins and polyester type resins. Preferred examples of the release agent to be used as a mixture with the above resin may include: silicone oil, phosphoric acid ester type surfactants, fluorine containing surfactants, etc. Particularly preferred examples thereof may include silicone oil. Such a silicone oil may preferably be a modified silicone oil such as epoxy modified silicone oil, alkyl modified silicone oil, amino modified silicone oil, carboxyl modified silicone oil, alcohol modified silicone oil, fluorine modified silicone oil, alkylaralkylpolyether modified silicone oil, epoxy polyether modified silicone oil, and polyether modified silicone oil. The release agent may be used either singly or as a combination of two or more species thereof. The release agent may preferably be added to the dye receptor layer in an amount of 0.5 to 30 wt.parts with respect to 100 wt.parts of the resin constituting the dye receptor layer. If such an addition amount is not in the above range, there occurs a problem such that the thermal transfer film sticks to the dye receptor layer or the printing sensitivity can be lowered, in some cases. When the above release agent is added to the dye receptor layer, the release agent is bled or exuded to the surface of the receptor layer after the transfer operation so as to form thereon a release layer. The receptor layer may be formed by applying a solution or dispersion to one side surface of the above substrate film and then drying the resultant coating. The dispersion may be prepared by adding an additive such as release agent; to the resin as described above, as desired, and dissolving the resultant mixture in an appropriate organic solvent, or by dispersing the mixture in an organic solvent or water. The resultant solution or dispersion may be applied on to the substrate sheet, e.g. by a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, etc. When the above receptor layer is formed, a fluorescent brightening agent, a pigment or filler such as titanium oxide, zinc oxide, kaolin clay, calcium carbonate and silica fine powder can be added to the receptor layer for the purpose of improving the whiteness of the dye receptor layer to further improve the clarity (or colour definition) of the resultant transferred image. The dye receptor layer to be formed in the above manner can have an arbitrary thickness, but may generally have a thickness of 1 to 50 µm. Such a dye receptor layer may preferably comprise a continuous coating but may also be formed as a discontinuous coating by using a resin emulsion or resin dispersion. It is preferred to further dispose a heat-sensitive or pressure-sensitive adhesive layer on the surface of the above receptor layer so as to improve the transferability of the above layers. After the dye receptor layer is transferred to the substrate, the adhesive layer may also function as an intermediate layer with respect to the resultant image receiving sheet. In the formation of the above adhesive layer, it is preferred to use adhesives for dry laminating such as two component type polyurethane type adhesive or epoxy type adhesive which have been used in the lamination of films in the prior art; adhesives for wet laminating such as vinyl acetate resin emulsion and acrylic resin emulsion; and hot melt adhesive such as ethylene-vinyl acetate copolymer type, polyamide type, polyester type, and polyolefin type. The adhesive layer may preferably have a thickness of about 0.5 to 40 µm. When good cushion property or good heat insulating property at the time of image formation are required to be imparted to the thus obtained image receiving sheet, it is preferred to incorporate a foaming agent in the above adhesive. The foaming agent to be used for such a purpose may be one which is capable of being decomposed under heating to generate a gas such as oxygen, carbonic acid gas, and nitrogen. Specific examples of such a foaming agent may include: decomposition type foaming agents such as dinitropentamethylenetetramine, diazoaminobenzene, azobisisobutyronitrile, and azodicarboamide; and known foaming agent (or foaming material) such as so-called micro balloon which may be prepared by microencapsulating a low-boiling point liquid such as butane and pentane, with a resin such as polyvinylidene chloride and polyacrylonitrile. Further, it is also possible to use a foaming material which is prepared by subjecting the above micro balloon to foaming operation in advance, or the above "micro balloon" coated with a white pigment. The above foaming agent or foaming material may preferably be used in an amount such that the layer containing the bubbles may provide a foaming magnification (or expansion coefficient) in the range of about 1.5 to 20. For example, it is preferred to use the foaming agent or foaming material in an amount of 0.5 to 30 wt.parts with respect to 100 wt.parts of the resin constituting the adhesive layer functioning as an intermediate layer. The foaming agent may be subjected to a foaming operation at the time of the formation of the dye receptor layer transfer film, or at the time of the transfer of the dye receptor layer. In addition, it is possible that the receptor layer (and optionally, the intermediate layer) which is not subjected to the foaming operation is transferred to the substrate, and the receptor layer is subjected to the foaming operation under heating due to a thermal head at the time of image formation. The time of the foaming operation may arbitrarily be effected by selecting the kind of the foaming agent, the temperature used for transferring the dye receptor layer, etc. In the above embodiment, the microcapsule type foaming agent such as "microsphere" has an outer wall even after the foaming operation, and therefore such a foaming agent is particularly preferred since it does not provide a defect such as a pin hole in the adhesive layer, tackiness agent layer, or receptor layer. When a fluorescent brightening agent or a white pigment selected from various species thereof such as titanium oxide is added to the intermediate layer, in place of or in addition to the above foaming agent, the whiteness of the receptor layer after the transfer operation may be improved. In addition, when the substrate sheet for the thermal transfer image receiving sheet comprises paper, the yellowish hue of the paper may be hidden by the above agent or pigment. As a matter of course, another optional additive such as extender pigment and filler may be added to the intermediate layer, as desired. Particularly, when the substrate for the thermal transfer image receiving sheet comprises a plastic sheet, the pressure sensitive adhesive layer may be omitted by adopting an extrusion laminating method as the film formation method therefor, and extruding the plastic sheet by extrusion coating on to the surface of the receptor layer constituting the dye receptor layer transfer film. It is also possible that the receptor layer surface of the receptor layer transfer film is subjected to laminating while a thermoplastic resin such as polyethylene is extruded to the above surface of the substrate for the thermal transfer image receiving sheet by using the above method, and then the substrate film of the receptor layer transfer film is peeled from the resultant laminate. As the use of the thermal transfer method is widened, it has been desired that an image receiving paper which is similar to plain paper is used, and pulp paper such as plain paper is used as the substrate of the image receiving sheet. In such a case, it is possible to obtain an image receiving sheet (plain paper like image receiving sheet) which is similar to plain paper by regulating the Bekk smoothness of the paper to 100 to 20,000 sec. Further, when the transfer surface of the receptor layer is caused to have a smoothness in the above range and the surface thereof reverse to the transfer surface is caused to have a smoothness of 5 to 400 sec. which is the same as that of plain paper, it is possible to obtain an image receiving sheet having a receptor layer excellent in smoothness while the entirety thereof is kept more plain paper like. In the above method, static electricity is considerably generated when the substrate film is peeled after the receptor layer is transferred to the substrate for the image receiving sheet. As a result, a defect such as blister is caused in the transfer receptor layer to lower the resultant yield, the operability of the peeling, etc., is impaired, and further fire can be caused in some cases. Particularly, when a matted film is used as the substrate film or a matted release layer is disposed on the substrate film for the purpose of obtaining the plain paper like transfer receptor layer surface, the above problem of electrification becomes more serious. In such a case, it is preferred to incorporate an antistatic agent in at least one layer selected from the substrate film, release layer, mat layer, dye receptor layer and adhesive layer constituting the receptor layer transfer film, and the substrate for the image receiving sheet. Preferred examples of such an antistatic agent may include fatty acid esters, sulfuric acid esters, phosphoric acid esters, amides, quaternary ammonium salts, betaines, amino acid salts, ethylene oxide adducts, etc. The amount of the antistatic agent to be used for such a purpose can vary depending on the kind of the antistatic agent and the kind of the layer to which the antistatic agent is to be added. In all cases, the addition amount (or usage) thereof may preferably be 0.01 to 0.5 g/m 2 so as to provide a surface resistance of the receptor layer transfer film or the substrate for the image receiving sheet in the range of 10 8 to 10 12 Ω. cm. If the amount of the antistatic agent to be used for such a purpose is too small, the resultant antistatic effect is not sufficient. On the other hand, the addition amount thereof is too large, such a usage is not economical and a problem of stickiness (or tackiness) can occur. In order to transfer the receptor layer, there may preferably be used an ordinary laminator. As the lamination means to be used for such a purpose may include, e.g. dry lamination, wet lamination, extrusion lamination, hot melt lamination, etc. (Formation of dye receptor layer by coating method) In order to form the dye receptor layer by a coating method, it is possible to use the same as that selected from various resins as described above with reference to the transfer method. The dye receptor layer may be formed by applying a solution or dispersion to at least one side surface of the above substrate film for the thermal transfer image receiving sheet and then drying the resultant coating. The solution or dispersion may be prepared by adding an additive to the resin as describe above, as desired, and dissolving the resultant mixture in an appropriate organic solvent, or by dispersing the mixture in an organic solvent or water. The resultant solution or dispersion may be applied on to the substrate film, e.g. by a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, etc. When the above dye receptor layer is formed, a pigment or filler such as titanium oxide, zinc oxide, kaolin clay, calcium carbonate and silica fine powder can be added to the dye receptor layer for the purpose of improving the whiteness of the dye receptor to further improve the clarity (or colour definition) of the resultant transferred image. The dye receptor layer to be formed in the above manner can have an arbitrary thickness, but may generally have a thickness of 1 to 50 µm. Such a dye receptor layer may preferably comprise a continuous coating but may also be formed as a discontinuous coating by using a resin emulsion or resin dispersion. Hereinbelow, there is described an embodiment which is commonly applicable to the above transfer method and coating method. First, in the present invention, it is possible to add a fibrous inorganic filler (whisker) to the above dye receptor layer. Specific examples of the whisker may include: potassium titanate whisker, zinc oxide whisker, graphite whisker, silicon nitride whisker, silicon carbide whisker, etc. Such a whisker may preferably be added to the dye receptor layer in amount of 1.0 to 50 wt.parts with respect to 100 wt.parts of the resin constituting the dye receptor layer. The whisker may preferably have an average length of 5 to 50 µm, and may preferably have an average diameter of 0.1 to 1 µm. It is also possible to treat the surface of the whisker with an amino type or epoxy type silane coupling agent, titanate, etc., as desired, or to subject the surface to metallizing. It is also possible to cause the dye receptor layer formed in the above manner to have a glossiness of 30% or lower, substantially without incorporating filler therein. For such a purpose, it is possible to use a method wherein the image receiving sheet is passed between a heated embossing roller and a nip roller, a method wherein the image receiving sheet is passed between heated nip rollers with a shaping sheet having surface unevenness configuration, etc. In the above method using the embossing roller, when the surface unevenness of the embossing roller has a height of convexity (or depth of concavity) in the range of about 1 to 500 µm, and a pitch of the unevenness in the range of about 1 t0 500 µm, the resultant shaped dye receptor layer may have a glossiness of 30% or lower. In a case where the above shaping sheet is used, the shaping sheet may preferably have a surface unevenness having the above parameters in the same range as described above. When a texture similar to that of paper is imparted to the dye receptor layer, plain paper, etc., may be used on the shaping sheet. In the present invention, the above glossiness may be measured by means of a gloss meter (trade name: KY5, mfd, by Asahi Seiko K.K.). Basically, the thermal transfer image receiving sheet according to the present invention having the above structure will sufficiently be used for an intended purpose. In the present invention, however, a release agent can be contained in the dye receptor layer so as to impart thereto good releasability with respect to the thermal transfer sheet. Preferred examples of the release agent to be used for such a purpose may include: silicone oil, phosphoric acid, ester type surfactants, fluorine containing surfactants, etc. Particularly preferred examples thereof may include silicone oil. Such a silicone oil may preferably be a modified silicone oil such as epoxy modified silicone oil, alkyl modified silicone oil, amino modified silicone oil, carboxyl modified silicone oil, alcohol modified silicone oil, fluorine modified silicone oil, alkylaralkylpolyether modified silicone oil, epoxy polyether modified silicone oil, and polyether modified silicone oil. The release agent may be used either singly or as a combination of two or more species thereof. The release agent may preferably be added to the dye receptor layer in an amount of 0 to 20 wt.parts, particularly 3 to 12 wt.parts, with respect to 100 wt.parts of the resin constituting the dye receptor layer. If such an addition amount of the release agent is too small, there can occur a problem such that the thermal transfer sheet sticks to the dye receptor layer or the printing sensitivity can be lowered, while good adhesion property of the ink can be provided. On the other hand, the addition amount of the release agent is too large, good releasability with respect to the thermal transfer sheet may be obtained but the adhesion property of the ink is unsatisfactory. The image receiving sheet according to the present invention is applicable to various uses such as transfer receiving sheet or card on which thermal transfer recording can be effected, and sheet for forming transmission type manuscript to be used for such a purpose. In the image receiving sheet according to the present invention, it is also possible to dispose a primer layer or cushion layer, as desired, between the substrate film and the dye receptor layer. Particularly, when the cushion layer is disposed therebetween, noise produced at the time of printing can be suppressed and an image corresponding to image information can reproducibly be formed by transfer recording operation. Figure 4 and Figure 5 are schematic sectional views showing embodiments of the thermal transfer image receiving sheet according to the present invention, respectively. Referring to Figure 4 the thermal transfer image receiving sheet comprises a substrate sheet 21, and a dye receptor layer 23 disposed on the substrate sheet 21 through the medium of a bubble containing layer (a cushion layer) 22. Referring to Figure 5, the thermal transfer image receiving sheet comprises a substrate sheet 31, and a dye receptor layer 34 disposed on the substrate sheet 31 through the medium of a bubble containing layer (a cushion layer) 32 and an intermediate layer 33. In order to form the bubble containing layer 22 or 32, it is possible to use the same as that selected from various foaming agents and resins as described above. The bubble containing layer may preferably have a thickness of about 5 to 50 µm. Specific examples of the material constituting the intermediate layer may include: polyurethane resin, acrylic resin, polyethylene type resin, epoxy resin, etc. Among these, for example, a hard resin mixed with a curing agent is preferred for the purpose of improving the surface strength of the dye receptor layer. The intermediate layer may preferably have a thickness of about 0.1 to 25 µm. Further, it is possible to add a filler to the above bubble layer 22 or intermediate layer 33 for the purpose of improving the surface strength of the dye receptor layer. As the filler, any of known fillers such as titanium oxide can be used. It is also possible to dispose of lubricant layer (or lubricating layer) on the back side of the substrate film. Specific examples of the materials for constituting the lubricant layer may include methacrylate resins such as methyl methacrylate, acrylate resins corresponding to such a methacrylate resin, vinyl type resins such as vinyl chloride-vinyl acetate copolymer, etc. In the thermal transfer image receiving sheet according to the present invention as described above, when at least one layer constituting the sheet, e.g. dye receptor layer, adhesive layer (primer layer), substrate sheet, back coating sheet, etc., is coloured pale blue, the quality of the formed image may be retained for a long period of time. Particularly, in the case of a transparent type thermal transfer image receiving sheet, the discernibleness of the formed image may be improved in addition to the above maintenance of the image quality. Hereinbelow, there is described an embodiment wherein the above at least one layer is coloured pale blue, with reference to the transparent type thermal transfer image receiving sheet. Referring to Figure 6, the transparent type thermal transfer image receiving sheet according to the present invention comprises a transparent substrate sheet 41, and a dye receptor layer 42 disposed on a surface of the substrate sheet 41. The image receiving sheet in this embodiment may further comprise an adhesive layer 43 and/or a back coating layer 44, as desired. The transparent substrate sheet 41 may comprise a material selected from those for the substrate sheet as described above which is capable of providing transparency. Specific examples of such a transparent sheet may include films or sheets of various plastics such as acetylcellulose, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate and polycarbonate, which are the same as those used for a film which is to be used in a conventional OHP (overhead projector) or Schaukasten for the purpose of observing an image. The dye receptor layer 42 may be formed in the same manner as described hereinabove. The colorant to be used for the above colouring may be one selected from various blue pigments and dyes. Among these, anthraquinon type dyes or phthalocyanine type dyes are preferred in view of the resultant transparency, heat resistance thereof, etc. As a matter of course, it is possible to use another dye or pigment such as cerulean blue and cobalt blue. The colouring density may vary depending on the kind of the dye or pigment to be used therefor, but may preferably be such that it does not substantially lower the transparency of the image receiving sheet, and a light bluish hue is discernible when the resultant sheet is observed with naked eyes. The concentration of the colorant may preferably be about 0.01 to 0.5 wt.%. The hue of the blue colour is also important. When the discernibleness and durability of the image are comprehensively considered, it is preferred that the chromaticity is in the region surrounded by the three points of (x=0.310, y=0.316), (x=0.285, y=0.280) and (x=0.275, y=0.320) in CIE 1931 colorimetric system. Specific examples of the dye suitably used for such colouring may include the following dyes: When the image receiving sheet is coloured by using the above colorant, the method used for the colouring, per se may be a conventional method. For example, when the dye receptor layer, adhesive layer, or back coating layer is coloured, it is possible to dissolve or dispose an appropriate colorant in a coating liquid for forming such a layer. Further, when the substrate sheet is coloured, it is possible to use a so-called mass coloration (or mass colouring) method wherein an appropriate colorant is dissolved or dispersed in a resin for forming the substrate. In the above embodiment, a transparent type image receiving sheet is described. However, the above description is also applicable to an opaque type thermal transfer image receiving sheet. In the present invention, it is possible to dispose a detection mark in the image receiving sheet. The detection mark is very useful, e.g., in a case where the thermal transfer sheet is subjected to positioning operation with respect to the image receiving sheet. For example, it is possible to dispose a detection mark which is detectable by means of a phototube detection device, on the back surface of the substrate film by printing, etc. When thermal transfer operation is effected by using the above thermal transfer image receiving sheet according to the present invention, the thermal transfer sheet to be used in combination therewith is one comprising a sheet such as paper and polyester film, and a dye layer disposed thereon containing a sublimable dye. Any of the conventional thermal transfer sheet as such may be used in the present invention. In this case, when the whisker as described above is also added to the dye layer of the thermal transfer sheet, there can be provided a matted image having better quality. Hereinbelow, there is described a thermal transfer sheet which is capable of forming good images in combination with the thermal transfer image receiving sheet according to the present invention as described above. The thermal transfer sheet basically comprises a substrate film and a dye layer disposed thereon by the medium of an intermediate layer, as desired, in the same manner as in the prior art. However, the thermal transfer sheet is characterised in that bubbles are incorporated in the dye layer and/or the intermediate layer. The substrate film may preferably have a thickness of, e.g. about 0.5 to 50 µm, more preferably about 3 to 10 µm. Specific examples of the substrate film may include: various papers, various coated papers, polyester film, polystyrene film, polypropylene film, polysulfone film, aramide film, polycarbonate film, polyvinyl alcohol film, cellophane, etc. Particularly preferred examples thereof may include polyester film. The substrate film may be either in a sheet form or a continuous film form, and should not be particularly restricted. The dye layer to be formed on the above substrate film comprises, at least, an appropriate binder resin, and a dye and bubbles carried therein. The dye to be used for such a purpose may be any of dyes usable in the conventional thermal transfer sheet, and is not particularly restricted. Preferred examples of such a dye may include: red dyes such as MS Red G, Macrolex Red Violet R, Ceres Red 7B, Samaron Red HBSL, Resolin Red F3BS; yellow dyes such as Horon Brilliant Yellow 6GL, PTY-52, Macrolex Yellow 6G; and blue dyes such as Kayaset Blue 714, Wacsorin Blue AP-FW, Horon Brilliant Blue S-R, and MS Blue 100. As the binder for carrying the above mentioned dye, any of known binders can be used. Preferred examples of the binder resin may include: cellulose resins such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, hydroxypropylcellulose, methycellulose, cellulose acetate, and cellulose acetate butyrate; vinyl type resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, and polyacrylamide; and polyester resin. Among these, cellulose type resins, acetal type resins, butyral type resins, and polyester type resins are particularly preferred in view of heat resistance, migration property of the dye, etc. The dye layer can further contain an additive selected from various additives known in the prior art, as desired. Such a dye layer may preferably be formed by dissolving or dispersing the above mentioned sublimable dye, binder resin and another optional component in an appropriate solvent to prepare a coating material or ink for forming the dye layer; sequentially applying the coating material(s) or ink(s) on to the above mentioned substrate film; and drying the resultant coating. The thus formed dye layer may generally have a thickness of about 0.2 to 5.0 µm, preferably about 0.4 to 2.0 µm. The sublimable dye content in the dye layer may preferably be 50 to 90 wt.%, more preferably 10 to 70 wt.% based on the weight of the dye layer. In the formation of the dye layer, when a mono colour image is desired, a dye of one colour selected from the above dyes is used for such a purpose. When a full colour image is desired, for example, appropriate dyes of cyan, magenta and yellow colours (and further black colour, as desired) are selected to form dye layers of cyan, magenta and yellow colours (and further black colour, as desired). It is also possible to dispose an intermediate layer between the substrate film and the dye layer, for the purpose of improving the adhesion property, cushion property, etc. Specific examples of the material constituting the intermediate layer may include: polyurethane resin, acrylic resin, polyethylene type resin, butadiene rubber, epoxy resin, etc. The intermediate layer may preferably have a thickness of about 0.1 to 5 µm, and may be formed in the same manner as in the case of the above dye layer. The thermal transfer sheet is mainly characterised in that bubbles are incorporated in at least one layer of the dye layer and the intermediate layer to be formed in the manner as described above. The method of incorporating the bubble in the above layer, may be one wherein a foaming agent is incorporated in a coating liquid to be used at the time of the formation of each of the respective layers, and the foaming agent is subjected to foaming operation at an appropriate temperature at the time of or after the drying of the coating formed by the application of the coating liquid. The foaming agent to be used for such a purpose may be one which is capable of being decomposed at a high temperature to generate a gas such as oxygen, carbonic acid gas, and nitrogen. Specific examples of such a foaming agent may include: decomposition type foaming agents such as dinitropentamethylenetetramine, diazoaminobenzene, azobisisobutyronitrile, and azodicarboamide; and known foaming agent (or foaming material) such as so-called micro balloon which may be prepared by microencapsulating a low boiling point liquid such as butane pentane, with a resin such as polyvinylidene chloride and polyacrylonitrile. Further, it is also possible to use a foaming material which is prepared by subjecting the above micro balloon to foaming operation in advance. The above foaming agent or foaming material may preferably be used in an amount that the layer containing the bubbles may provide a foaming magnification (or expansion coefficient) in the range of about 1.5 to 20. Particularly preferred examples of the foaming agent may include the above micro balloon which can be subjected to the foaming operation at a relatively low temperature. Samples thereof of various grades are available from Matsumoto Yushi Seiyaku K.K. and each of them may be used. When the thermal transfer sheet is used, good dye migrating property may be obtained and high quality images having no defect such as white dropout or image incompleteness may be formed, even in combination with a matted image receiving sheet prepared by matting the dye receptor layer thereof. When thermal transfer operation is effected by using the thermal transfer image receiving sheet according to the present invention in combination with the above thermal transfer sheet, or a conventional thermal transfer sheet, the means for applying heat energy to be used for such a thermal transfer operation may be any of various known heat energy application means. For example, when a recording time is controlled by using a recording apparatus such as a thermal printer (e.g. Video Printer VY 100, mfd. by Hitachi K.K.), so as to provide a heat energy of about 5 to 100 mJ/mm 2 , a desired image may be formed. Hereinbelow, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the description appearing hereinafter, part(s) and % of part(s) by weight and wt.%, respectively, unless otherwise noted specifically. (Example C) Example C-1 Two sheets of 50 µm thick foamed polypropylene (Toyopearl SS, mfd. by Toyobo K.K.) were bonded to both surfaces of a 60 µm thick coated paper (Newtop, mfd. by Kanzaki Seishi K.K., basis weight: 72.3 g/m 2 ) by using an adhesive so that the heat shrinkage directions of the above polypropylene sheets were parallel to each other. A coating liquid having the following composition was applied on to one side surface of the thus prepared sheet by means of a bar coater so as to provide a coating amount of 5.0 g/m 2 (after drying), and the resultant coating was dried by means of a dryer, and then dried in an oven for 10 min at 80°C, whereby a dye receptor layer was formed. Composition of coating liquid for receptor layer Polyester (Vylon 600, mfd. by Toyobo K.K.) 4.0 parts Vinyl chloride/vinyl acetate copolymer (#1000A, mfd. by Denki Kagaku Kogyo K.K.) 6.0 parts Amino modified silicone (X-22-3050C, mfd. by Shinetsu Kagaku Kogyo K.K.) 0.2 part Epoxy modified silicone (X-22-3000E, mfd. by Shinetsu Kaguku Kogyo K.K.) 0.2 part Methyl ethyl ketone/toluene (wt.ratio = 1/1) 89.6 parts Then, a coating liquid having the following composition was applied on to the surface of the above sheet reverse to the receptor layer surface side by means of a bar coater so as to provide a coating amount of 1.0 g/m 2 (after drying), and the resultant coating was dried to form a slip layer, whereby a thermal transfer image receiving sheet according to the present invention was obtained. Acrylic resin 10 parts Teflon filler (particle size = 2 µm) 5 parts Toluene 50 parts Methyl ethyl ketone 50 parts Example C-2 A thermal transfer image receiving sheet according to the present invention was prepared in the same manner as in Example C-1, except that two sheets of 60 µm thick polypropylene type synthetic paper (Upo, mfd. by Oji Yuka K.K.) were bonded to both surfaces of a 75 µm thick polyethylene terephthalate film (Lumirror, mfd. by Toray K.K.) by using an adhesive so that the heat shrinkage directions of the two synthetic paper sheets were parallel to each other. Example C-3 A thermal transfer image receiving sheet according to the present invention was prepared in the same manner as in Example C-1, except that a sheet of 50 µm thick polypropylene type synthetic paper (Upo, mfd. by Oji Yuka K.K.) was bonded to one surface side of a to 60 µm thick coated paper (Top Coat, mfd. by Kanzaki Seishi K.K., basis weight: 72.3 g/m 2 ) as a core material, and a sheet of 50 µm thick foamed polypropylene (Toyopearl SS, mfd. by Toyobo K.K.) was bonded to the other surface side of the above synthetic paper by using an adhesive so that the heat shrinkage directions of the two sheets of the synthetic paper and foamed polypropylene were parallel to each other. Example C-4 A thermal transfer image receiving sheet according to the present invention was prepared in the same manner as in Example C-1, except that two sheets of 50 µm thick polyethylene terephthalate type synthetic paper (K1553, mfd. by Toyobo K.K.) were bonded to each other by using an adhesive so that the heat shrinkage directions of the two synthetic paper sheets were parallel to each other. Comparative Example C-1 A thermal transfer image receiving sheet of Comparative Example was prepared in the same manner as in Example C-1, except that two sheets of foamed polypropylene were bonded so that the heat shrinkage directions of the two foamed polypropylene sheets were at right angles to each other. Then, a sublimation type thermal transfer sheet for yellow colour (mfd. by Dai Nippon Printing K.K.) was superposed on each of the above thermal transfer image receiving sheets of Examples C-1 to C-4 and Comparative Example C-1 so that the dye layer of the thermal transfer sheet contacted the dye receptor layer of the image receiving sheet, and printing operation was effected by supplying printing energy of 90 mJ/mm 2 by means of the thermal head of a sublimation type thermal printer (VY-50, mfd. by Hitachi Seisakusho K.K.) from the back surface side of the thermal transfer sheet thereby to form yellow images. Then, magenta, cyan and black images were sequentially superposed on the resultant yellow images in the same manner as described above, thereby to form full colour images. The thus obtained results are shown in the following Table 1. Image receiving sheet Dot dropout Density non uniformity Curl Paper feeding property 60°C 0°C Example C-1      Example C-2      Example C-3      Example C-4      Comparative Example C-1   X X X  : Good ○ : Practically no problem Δ : Somewhat poor X : Poor

Claims: A thermal transfer image receiving sheet comprising a substrate sheet and a dye receptor layer disposed on at least one surface side of the substrate sheet, wherein the substrate sheet has been formed by laminating at least two heat-shrinkable sheet materials so that the difference between the heat shrinkage directions thereof corresponds to an angle of 45° or below. A thermal transfer image receiving sheet according to Claim 1, wherein heat shrinkage directions of the two heat shrinkable sheet materials are substantially parallel to each other. A thermal transfer image receiving sheet according to Claim 1, wherein the substrate sheet comprises a laminate having a three layer structure which comprises a core material and the heat-shrinkable sheet materials laminated on both sides of the core material. A thermal transfer image receiving sheet according to Claim 1, wherein the heat-shrinkable sheet material has a thickness of 30 to 80 µm, and the substrate sheet has a thickness of 100 to 300 µm. A thermal transfer image receiving sheet according to Claim 1, wherein the dye receptor layer has been formed on the substrate sheet by superposing the substrate sheet on to a receptor layer transfer film comprising a substrate film and the dye receptor disposed on one surface side thereof which is peelable from the substrate film so that the receptor layer transfer film is bonded to the substrate sheet to form a laminate, and peeling the substrate film from the laminate.

Inventors: ASAJIMA MIKIO, EGUCHI HIROSHI, FUJIMURA HIDEO, IMOTO KAZUNOBU, OSHIMA KATSUYUKI, SAITO HITOSHI, SATO HIDEAKI, UENO TAKESHI, YAMAUCHI MINEO, ASAJIMA, MIKIO, EGUCHI, HIROSHI, FUJIMURA, HIDEO, IMOTO, KAZUNOBU, OSHIMA, KATSUYUKI, SAITO, HITOSHI, SATO, HIDEAKI, UENO, TAKESHI, YAMAUCHI, MINEO
Applicants: DAINIPPON PRINTING CO LTD, DAI NIPPON PRINTING CO., LTD.
Application year: 1991
Main classification: B41M5
IPC codes: B41M5, B32B27