JP4984249B2 - Intermediate transfer recording medium - Google Patents

Description

  The present invention relates to an intermediate transfer recording medium, and more particularly, when transferring a coloring material of a thermal transfer sheet to a receiving layer of the intermediate transfer recording medium and transferring the receiving layer having the formed thermal transfer image to a transfer target, In particular, the present invention relates to an intermediate transfer recording medium in which a printed matter with good heat resistance, transfer defect prevention, and thermal transfer image durability can be easily obtained.

  Conventionally, a thermal transfer method has been widely used as a simple printing method. In the thermal transfer method, a thermal transfer sheet provided with a color material layer on one surface of a base sheet and a thermal transfer image receiving sheet provided with an image receiving layer as necessary are superposed, and the thermal transfer sheet is heated by a heating means such as a thermal head. In this method, an image is formed on a thermal transfer image receiving sheet by heating the back surface of the image to an image and selectively transferring the color material contained in the color material layer.

  Thermal transfer methods are classified into a melt transfer method and a sublimation transfer method. The melt transfer method uses a thermal transfer sheet in which a heat melt ink layer in which a color material such as a pigment is dispersed in a binder such as a heat meltable wax or resin is supported on a base sheet such as a PET film, and heats a thermal head or the like. In this image forming method, energy is applied to the means in accordance with image information, and a color material is transferred together with a binder onto a thermal transfer image receiving sheet such as paper or a plastic sheet. An image obtained by the melt transfer method has a high density and excellent sharpness and is suitable for recording binary images such as characters.

  On the other hand, the sublimation transfer method uses a thermal transfer sheet in which a dye layer in which a dye that transfers heat by sublimation is dissolved or dispersed in a resin binder is supported on a base sheet such as a PET film, and is used as a heating means such as a thermal head. In this image forming method, energy is applied according to image information, and only a dye is transferred onto a thermal transfer image receiving sheet in which a dye receiving layer is provided on a base sheet such as paper or plastic as required. In the sublimation transfer method, the amount of dye transfer can be controlled in accordance with the amount of energy applied, so that it is possible to form a gradation image in which the image density is controlled for each dot of the thermal head. Further, since the color material to be used is a dye, the formed image is transparent, and the reproducibility of intermediate colors when dyes of different colors are superimposed is excellent. Therefore, when using thermal transfer sheets of different colors such as yellow, magenta, cyan, black, etc., and transferring each color dye on the thermal transfer image receiving sheet, high-quality photographic tone full-color images with excellent reproducibility of intermediate colors can be obtained. Formation is possible.

  Due to the development of various hardware and software related to multimedia, this thermal transfer method is a full-color hard copy system for analog images such as digital graphics and video such as still images by computer graphics, satellite communications and CD-ROM. As the market is expanding. The specific application of the thermal transfer image receiving sheet by this thermal transfer method is diverse. Typical examples include printing proofs, image output, CAD / CAM design and design output, various medical analytical instruments such as CT scans and endoscopic cameras, measuring instrument output applications and instant As an alternative to photos, output of ID cards, ID cards, credit cards, other face photos on cards, etc., as well as composite photos and amusement photos at amusement facilities such as amusement parks, game centers, museums, and aquariums Etc.

  With the diversification of uses of the above-mentioned thermal transfer image receiving sheet, there is an increasing demand for forming a thermal transfer image on an arbitrary object. Normally, a dedicated thermal transfer image-receiving sheet provided with a receiving layer on a base material is used as an object for forming a thermal transfer image. However, there are limitations on the base material and the like, as shown in Patent Document 1 and the like. An intermediate transfer recording medium with a layer that can be peeled off on a substrate. Using a thermal transfer sheet that has a dye layer on its receiving layer, the dye is transferred to form an image, and then the intermediate transfer recording medium is heated. A method of transferring the receiving layer onto an arbitrary transfer target has been proposed.

  As described above, there are many advantages of the thermal transfer method, but when an image is formed with a melt transfer type thermal transfer sheet, there is a weak point that lacks durability against friction, and image formation with a sublimation transfer type thermal transfer sheet. In such a case, a gradation image such as a face photograph can be accurately formed, but there is a weak point that lacks durability such as weather resistance, friction resistance, and chemical resistance. Even in the system using the above intermediate transfer recording medium, the image formed product finally obtained still lacks the image durability described above. On the other hand, Patent Document 2 describes an intermediate transfer sheet (intermediate transfer recording medium) in which a release layer, a curable protective layer, an intermediate adhesive layer, and an image receiving and adhesive layer are provided on a substrate. Durability is provided by a protective layer of resin or UV curable resin. However, in this curable protective layer, the foil breakability of the protective layer is not good, and transfer failure occurs at the end of the transfer portion.

JP-A-62-238791 JP 2004-351656 A

  Therefore, the present invention has been made in view of such a situation, and the coloring material of the thermal transfer sheet is transferred to the receiving layer of the intermediate transfer recording medium, and the receiving layer having the formed thermal transfer image is transferred. It is an object of the present invention to provide an intermediate transfer recording medium that has a good foil cutting property when transferred to a body, prevents a transfer failure, and can easily obtain a printed matter with durability of a thermal transfer image.

The intermediate transfer recording medium of the present invention is the intermediate transfer recording medium according to claim 1, wherein at least a protective layer and a receiving layer are sequentially laminated on one surface of the base sheet, and the protective layer is made of an ionizing radiation curable resin. An adhesive layer made of vinyl chloride-vinyl acetate copolymer resin is partially provided between the base sheet and the protective layer, and a release layer made of cellulose acetate propionate resin is formed on the receiving layer. partially provided, peeling said, the region E between the adhesive layer and partially provided with a release layer which partially provided without peeling from the substrate, the region F except the region E from the base sheet It is possible. In the region F except an area E located on this partially provided adhesive layers, also receiving layer in the region F except the region E located below the releasing layer, a protective layer may foil cutting, Can be transferred to the transfer target.

As claim 2, in the intermediate transfer recording medium according to claim 1, between the substrate sheet and the protective layer, characterized in that a detection mark. By reading this detection mark with a printer, the color material is transferred from the thermal transfer sheet to the receiving layer at an accurate position to form a thermal transfer image, and the receiving layer and the protection are accurately positioned relative to the transfer target. A layer stack of layers can be transferred. A primer layer may be provided between the protective layer and the receiving layer.

The intermediate transfer recording medium of the present invention is an intermediate transfer recording medium in which at least a protective layer and a receiving layer are sequentially laminated on one surface of a base sheet. The protective layer is made of an ionizing radiation curable resin. An adhesive layer made of vinyl chloride-vinyl acetate copolymer resin is partially provided between the protective layer, and a release layer made of cellulose, acetate, propionate resin is partially provided on the receiving layer. the, in the region E between the adhesive layer and partially provided with a release layer partially provided without peeling off from the substrate, the region F except the region E is peelably become consists substrate sheet is there. By adopting such a configuration, when the coloring material of the thermal transfer sheet is transferred to the receiving layer of the intermediate transfer recording medium and the receiving layer having the formed thermal transfer image is transferred to the transfer target, the receiving layer (protection) A printed matter having good foil cutting property in transfer (including the layer), preventing transfer failure, and excellent thermal transfer image durability.

  FIG. 1 is a schematic cross-sectional view showing an intermediate transfer recording medium 1 according to an embodiment of the present invention before transfer to a transfer medium and during transfer. FIG. 1 (1) shows an intermediate transfer recording medium 1 before being transferred to a transfer medium, in which a protective layer 3, a primer layer 4, and a receiving layer 5 are sequentially laminated on one surface of a base sheet 2. The protective layer 3 is made of an ionizing radiation curable resin, and the adhesive layer 6 is partially provided between the base sheet 2 and the protective layer 3. FIG. 1 (2) shows the intermediate transfer recording medium 1 shown in FIG. 1 (1) being transferred to the transfer target 10, and the receiving layer 5 of the intermediate transfer recording medium 1 and the transfer target 10 are shown. When the intermediate transfer recording medium 1 is heated so as to be in contact with each other, the region B located above the partially provided adhesive layer 6 does not peel from the substrate sheet 2, The region A remaining on the sheet 2 side and excluding the region B is peeled off from the base material sheet 2 and transferred and adhered to the transfer target 10. Therefore, the area A is a transfer portion having a size and a shape to be transferred to the transfer target 10. Region B is a laminate of an adhesive layer, a protective layer, a primer layer, and a receiving layer.

  In the case of FIG. 1, since the adhesive layer 6 adheres the base sheet 2 and the protective layer 3, the protective layer 3, the primer layer 4, and the receiving layer 5 in the region B located above the adhesive layer 6 are based. Does not peel from the material sheet. In FIG. 1, the detection mark 7 is provided between the base sheet 2 and the protective layer 3 or between the base sheet 2 and the adhesive layer 6. Not specified. Although not shown in FIG. 1 (2), a thermal transfer image is formed on the surface of the receiving layer 5, and the primer layer 4 and the protective layer 3 cover the imaged receiving layer 5. The transferred object 10 becomes a printed matter.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the intermediate transfer recording medium 1 of the present invention before transfer to a transfer medium and during transfer. FIG. 2 (1) shows an intermediate transfer recording medium 1 before being transferred to a transfer medium, in which a protective layer 3, a primer layer 4, and a receiving layer 5 are sequentially laminated on one surface of a base sheet 2. The protective layer 3 is made of an ionizing radiation curable resin, the release layer 8 is partially provided on the receiving layer 5, and the detection mark 7 includes the base sheet 2, the protective layer 3, The position is not specified if it can be detected in the printer. FIG. 2 (2) shows the intermediate transfer recording medium 1 shown in FIG. 2 (1) in the middle of transfer to the transfer target 10, and the receiving layer 5 of the intermediate transfer recording medium 1 and the transfer target 10 are shown. When the intermediate transfer recording medium 1 is heated so as to be in contact with each other, the region D located below the partly provided release layer 8 is released from the transfer target 10. The region C, which is a portion excluding the region D, is not peeled off from the base material sheet 2 and is peeled off from the base material sheet 2 and transferred and adhered to the transfer target 10. Therefore, the region C is a transfer portion having a size and a shape to be transferred to the transfer target 10. Region D is a laminate of a protective layer, a primer layer, a receiving layer, and a release layer.

  In the case of FIG. 2, since the adhesiveness between the release layer 8 and the transfer target 10 is low, the release layer 8, the receiving layer 5, the primer layer 4, and the protective layer in the region D located below the release layer 8. 3 is not transferred to the transfer target 10 but remains on the substrate sheet 2, and the receiving layer 5, the primer layer 4, and the protective layer 3 in the region C excluding the region D are removed from the substrate sheet 2. It peels and adheres to the transfer object 10. In FIG. 2, the detection mark 7 is formed in a region D located below the release layer 8 between the base sheet 2 and the protective layer 3. Although not shown in FIG. 2 (2), a thermal transfer image is formed on the surface of the receiving layer 5, and the primer layer 4 and the protective layer 3 cover the imaged receiving layer 5. The transferred object 10 becomes a printed matter.

  FIG. 3 is a schematic cross-sectional view showing another embodiment of the intermediate transfer recording medium 1 of the present invention before transfer to a transfer medium and during transfer. FIG. 3 (1) shows an intermediate transfer recording medium 1 before being transferred to a transfer medium, in which a protective layer 3, a primer layer 4, and a receiving layer 5 are sequentially laminated on one surface of a base sheet 2. The protective layer 3 is made of an ionizing radiation curable resin, the adhesive layer 6 is partially provided between the base sheet 2 and the protective layer 3, and the release layer 8 is further provided on the receiving layer 5. Is partially provided. 3 (2) shows the intermediate transfer recording medium 1 shown in FIG. 3 (1) in the middle of transfer to the transfer target 10, and the receiving layer 5 of the intermediate transfer recording medium 1 and the transfer target 10 are shown. When the intermediate transfer recording medium 1 is heated so as to be in contact with each other, the region E between the partially provided adhesive layer 6 and the partially provided release layer 8 is a base sheet. The region F remaining on the base sheet 2 side without being peeled off 2 and excluding the region E is peeled off from the base sheet 2 and transferred and adhered to the transfer target 10. Therefore, the region F is a transfer portion having a size and a shape to be transferred to the transfer target 10.

  In the case of FIG. 3, since the adhesive layer 6 adheres the base sheet 2 and the protective layer 3, the protective layer 3, the primer layer 4, the receiving layer 5, the release layer 5 in the region E located above the adhesive layer 6. The mold layer 8 does not peel from the base sheet. In FIG. 3, the detection mark 7 is provided between the base sheet 2 and the protective layer 3 or between the base sheet 2 and the adhesive layer 6. Not specified. Although not shown in FIG. 3 (2), a thermal transfer image is formed on the surface of the receiving layer 5, and the primer layer 4 and the protective layer 3 cover the imaged receiving layer 5. The transferred object 10 becomes a printed matter.

  FIG. 4 is a schematic plan view showing an example of arrangement when the intermediate transfer recording medium 1 of the present invention is manufactured with multiple impositions. The intermediate transfer recording medium has four rows in the flow direction and three units per row. A 4 × 3 12-unit intermediate transfer recording medium 1 having a transfer recording medium 1 is shown, and a detection mark 7 is provided at the head in the flow direction of each unit. A cross-sectional view taken along P and Q shown in the drawing corresponds to FIG. A region B located on the partially provided adhesive layer is a portion other than the region A. Only the portion indicated by the region A is transferred and adhered from the intermediate transfer recording medium 1 to the transfer target 10.

  FIG. 5 is a schematic plan view showing an example of the arrangement when the intermediate transfer recording medium 1 of the present invention is produced by multi-sided attachment, and has four rows in the flow direction and three units per row. A 4 × 3 12-unit intermediate transfer recording medium 1 having a transfer recording medium 1 is shown, and a detection mark 7 is provided at the head in the flow direction of each unit. A cross-sectional view taken along the line R and S shown in FIG. 2 corresponds to FIG. A region located under the partly provided release layer is D, and a portion excluding the region D is a region C. Only the portion indicated by the region C is transferred and adhered from the intermediate transfer recording medium 1 to the transfer target 10.

  FIG. 6 is a schematic plan view showing an example of the arrangement when the intermediate transfer recording medium 1 of the present invention is manufactured by multi-sided attachment, and has four rows in the flow direction and three units per row. A 4 × 3 12-unit intermediate transfer recording medium 1 having a transfer recording medium 1 is shown, and a detection mark 7 is provided at the head in the flow direction of each unit. A cross-sectional view taken from the T and U shown in the drawing corresponds to FIG. A region located under the partly provided release layer is E, and a portion excluding the region E is a region F. Only the portion indicated by the region F is transferred and adhered from the intermediate transfer recording medium 1 to the transfer target 10.

Hereinafter, each layer constituting the intermediate transfer recording medium of the present invention will be described in detail.
(Base material sheet)
The substrate sheet 2 of the intermediate transfer recording medium used in the present invention may be any material as long as it has a conventionally known degree of heat resistance and strength, for example, 0.5 to 50 μm, preferably 15 to 30 μm. Polyethylene terephthalate film of about thickness, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, Examples thereof include cellulose derivatives such as cellophane and cellulose acetate, polyethylene films, polyvinyl chloride films, nylon films, polyimide films, ionomer films, and the like.

(Protective layer)
The protective layer 3 in the intermediate transfer recording medium of the present invention is formed on the base sheet with a configuration made of an ionizing radiation curable resin, that is, an ionizing radiation curable resin as a main component. In the present specification, the “ionizing radiation curable resin” refers to a material obtained by irradiating and curing an ionizing radiation curable resin that is a precursor or a composition before curing without irradiating with ionizing radiation. means. This protective layer is formed on the printed material in a state in which, after the thermal transfer image is formed on the receiving layer of the intermediate transfer recording medium, the intermediate transfer recording medium is heated and the image-formed receiving layer is transferred to the transfer medium. Located on the resurface of the form. Therefore, the protective layer is peeled off from the base material sheet of the intermediate transfer recording medium by heating with a thermal head, a heat roll or the like, and transferred to the transfer target.

  This protective layer mainly exhibits a function of imparting various durability to the thermal transfer image, and is made of an ionizing radiation curable resin. Specifically, it is as shown below. As the ionizing radiation curable resin before curing of the ionizing radiation curable resin, (meth) acryloyl group, (meth) acryloyloxy group ((meth) acryloyl means acryloyl or methacryloyl) in the molecule, (Met) has the same meaning as the above), and a composition obtained by appropriately mixing a polymerizable unsaturated bond or an epoxy group-containing prepolymer, oligomer, and / or monomer is used. Examples of these prepolymers and oligomers include acrylates such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate, silicon resins such as siloxane, unsaturated polyester, and epoxy.

  Examples of monomers include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate, trimethylolpropane tri (meth) acrylate, and / or a polyol compound having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, penta Examples include erythritol tetrathioglycol. The above compounds are used alone or in combination of two or more as required. In order to impart ordinary coating suitability to the resin composition, 5% by mass or more of the prepolymer or oligomer is used as the monomer. And / or polythiol is preferably 95% by mass or less.

  When selecting the monomer, if the flexibility of the cured product is required, the amount of the monomer can be reduced in a range that does not hinder various durability points of the protective layer and coating suitability, A monofunctional or bifunctional acrylate monomer is used to obtain a structure having a relatively low crosslinking density. In addition, when the cured product is required to have heat resistance, hardness, solvent resistance, etc., the amount of monomer is increased within a range that does not hinder coating suitability, or an acrylate monomer having three or more functions. It is preferable to use a high crosslink density structure. A monofunctional monomer and a trifunctional or higher monomer can be mixed to adjust the coating suitability and the physical properties of the cured product.

  Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, and the like. Examples of bifunctional acrylate monomers include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. Examples of trifunctional or higher acrylate monomers include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipenta Examples include erythritol hexaacrylate.

  In order to adjust the physical properties such as flexibility and surface hardness of the cured product, the following non-curable resin of ionizing radiation is used for at least one of the prepolymer, oligomer and monomer. About 50 mass% can be mixed and used. As the non-curable resin for ionizing radiation, thermoplastic resins such as urethane-based, fiber-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate can be used.

  The protective layer of the intermediate transfer recording medium of the present invention is excellent in various durability and has an appropriate flexibility (influencing the ease of handling and appearance of the printed product after transfer). It is preferable to use an ionizing radiation curable resin. Furthermore, an ionizing radiation curable resin containing 5 to 40 parts by mass of oligomer per 100 parts by mass of the urethane-modified acrylic resin is suitable. The urethane-modified acrylic resin is one in which a hydroxyl group (—OH) present in the acrylic resin and isocyanate (—NCO) react to have a urethane bond in the resin. It is preferable to contain an oligomer at a ratio of 5 to 40 parts by mass per 100 parts by mass of the resin, thereby having an excellent function of combining flexibility and durability as a protective layer.

  In the above expression, it is apt to be considered that only the oligomer is added, but it is natural that not only the oligomer but also a monomer may be added. When the amount of oligomer used is small, the strength, durability, etc. of the resulting protective layer are not sufficient, and when the amount of oligomer is too large, the tackiness of the surface of the protective layer is increased and blockage is likely to occur. Absent.

  When the ionizing radiation curable resin as described above is cured by ionizing radiation irradiation, it is necessary to use a transparent resin. In addition, as a photopolymerization initiator in the ionizing radiation curable resin composition, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylmeurum monosulfide, thioxanthones, and / or photosensitization. As the agent, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used. In consideration of releasability, a silicone resin, wax, fluororesin, melanin resin, surfactant or the like may be added as an additive.

  In the present invention, ultraviolet rays are mainly used as a method for completely curing the protective layer formed on the base sheet with a resin composition containing an ionizing radiation curable resin. Visible rays, electron beams, gamma rays, and X-rays can be used as ionizing radiation having energy quanta capable of polymerizing and crosslinking molecules. As the ionizing radiation irradiation apparatus, an ultraviolet irradiation apparatus is usually used. As the ultraviolet irradiation device, a light source such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light, a metal halide lamp or the like is used. The apparatus irradiates electrons having energy of 100 to 1000 KeV, preferably 100 to 300 KeV. The irradiation dose is usually about 5 to 300 KGy (kilo gray).

The protective layer is prepared by dissolving or dispersing the protective layer composition containing the ionizing radiation curable resin described above in an appropriate solvent to prepare a protective layer forming ink. Further, for example, it can be formed by applying, drying and curing by a forming means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate. Although a protective layer can be formed in arbitrary thickness on a base material sheet, it is 0.1-50 g / m < ² > by the thickness after drying, Preferably it is about 1-20 g / m < ² >.

(Primer layer)
In the intermediate transfer recording medium of the present invention, a primer layer 4 is provided between the receiving layer and the protective layer for the purpose of ensuring the adhesion between them. Since this primer layer has a role of holding the receiving layer and the protective layer, even when the protective layer 3, the primer layer 4 and the receiving layer 5 are heated when transferred to the transfer target, It is preferable to have a mechanical strength that does not hinder.

  Examples of the material constituting the primer layer include polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic polymer, and polyvinyl chloride. , Polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer Such as tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, etc. Resins. Moreover, a white pigment, a filler, a conductive material, and the like may be added to these synthetic resins as long as the transparency is not impaired.

The primer layer can be formed by the same method as in the case of the protective layer, and the primer layer coating amount is about 0.2 to 5.0 g / m ² (solid content), preferably 0. .5 to 2.0 g / m ² (solid content).

(Receptive layer)
The receiving layer 5 formed on the primer layer has a function of receiving a color material transferred from the thermal transfer sheet by heating. In particular, in the case of a sublimation dye, it receives and develops color. At the same time, it is desirable not to resublimate once received dye. An intermediate transfer recording medium is used to form a transfer image on the receiving layer, and the receiving layer including the image-formed portion, the primer layer, and the protective layer are transferred to the transfer target. In general, the receiving layer is provided with transparency so that the image transferred to the transfer target can be clearly observed from above. However, it is also possible to characterize the retransfer image by artificially making the receiving layer turbid or lightly colored.

  The receiving layer is generally composed mainly of a thermoplastic resin. Examples of the material for forming the receiving layer include polyolefin resins such as polypropylene, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, halogenated polymers such as polyvinylidene chloride, polyvinyl acetate, and polyacrylic. Examples include polyester resins such as esters, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, cellulose resins such as ionomers and cellulose diacetates, and polycarbonate resins. Particularly preferred among these are polyester resins, vinyl chloride-vinyl acetate copolymers, and mixtures thereof.

  In sublimation transfer recording, a release agent is mixed in the receiving layer for the purpose of preventing fusion between the thermal transfer sheet having the colored transfer layer and the receiving layer of the intermediate transfer recording medium or a decrease in printing sensitivity during image formation. be able to. Preferable release agents used in combination include silicone oil, phosphate ester surfactants, fluorine surfactants, and the like, among which silicone oil is desirable. As the silicone oil, modified silicone oils such as epoxy modification, vinyl modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are desirable.

  One or more release agents are used. Moreover, the addition amount of the release agent is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the receiving layer forming resin. When the range of the addition amount is not satisfied, problems such as fusion between the sublimation type thermal transfer sheet and the receiving layer of the intermediate transfer recording medium or a decrease in printing sensitivity may occur. By adding such a releasing agent to the receiving layer, the releasing agent bleeds out on the surface of the receiving layer after the transfer to form a releasing layer. Further, these release agents may not be added to the receiving layer but may be separately applied on the receiving layer.

The receptor layer is a dispersion in which a resin obtained by adding a necessary additive such as a release agent to the above-described primer layer is dissolved in an appropriate organic solvent or dispersed in an organic solvent or water. Is applied by a known forming means such as gravure coat, gravure reverse coat, roll coat and the like, and dried to form. In forming the receiving layer, the receiving layer may have any coating amount, but is generally 1 to 50 g / m ² in a dry state. Such a receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating using a resin emulsion, a water-soluble resin, or a resin dispersion. Furthermore, an antistatic agent may be coated on the receiving layer in order to stabilize the conveyance of the thermal transfer printer.

(Adhesive layer)
Further, the adhesive layer 6 is partially provided between the base material sheet and the protective layer of the intermediate transfer recording medium of the present invention to enhance the adhesiveness between the base material sheet and the protective layer, and is provided partially. The region B composed of the protective layer, the primer layer, and the receiving layer located on the adhesive layer does not peel from the base sheet. As the adhesive layer, any conventionally known pressure-sensitive adhesive or heat-sensitive adhesive can be used, but it is preferably formed from a thermoplastic resin having a glass transition temperature (Tg) of 50 ° C. to 80 ° C., for example, polyester resin, chloride It is possible to select a resin having an appropriate glass transition temperature from a resin having a good adhesive property when heated, such as a vinyl-vinyl acetate copolymer resin, an acrylic resin, a butyral resin, an epoxy resin, a polyamide resin, and a vinyl chloride resin. preferable. In addition, in the case where a part of the adhesive pattern and a heating means such as a thermal head are formed in a pattern instead of the entire surface, it is preferable that the resin mentioned above has a smaller molecular weight. If necessary, a coating solution in which an additive such as an inorganic or organic filler is added to the resin constituting the adhesive layer as described above is applied and formed by the same forming means as in the case of the receiving layer. By drying, it is preferably formed to a thickness of about 0.5 to 10 g / m ² during drying.

(Release layer)
In the intermediate transfer recording medium of the present invention, the release layer 8 is partially provided on the receiving layer, and the release layer portion (the portion indicated by region D in FIG. 2) is peeled from the base sheet. Do not. On the other hand, the region C excluding the part of the release layer is peeled off from the substrate sheet, and transferred and adhered to an arbitrary transfer target. The release layer is, for example, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, one Heat of wax such as partially modified wax, fatty acid ester, fatty acid amide, silicone wax, silicone resin, fluorine resin, acrylic resin, polyester resin, polyurethane resin, cellulose resin, vinyl chloride-vinyl acetate copolymer, nitrified cotton, etc. It can be formed using a plastic resin.

The release layer can be formed from a binder resin and a release material. As the binder resin, thermoplastic resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate and other acrylic resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl butyral, etc. Vinyl-based resins, cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, unsaturated polyester resins that are thermosetting resins, polyester resins, polyurethane resins, amino alkyd resins, and the like can be used. As the releasable material, waxes, silicone waxes, silicone resins, melamine resins, fluorine resins, fine powders of talc and silica, lubricants such as surfactants and metal soaps, and the like can be used. The release layer is prepared by dissolving or dispersing the above-mentioned necessary materials with an appropriate solvent to prepare a release layer coating solution, and this is a gravure printing method, screen printing method or reverse coating method using a gravure plate It can be formed by coating and drying by means such as. The thickness after the drying is usually 0.1 to 10 g / m ² .

(Detection mark)
In the intermediate transfer recording medium of the present invention, it is preferable to provide a detection mark 7 between the base sheet and the protective layer. By reading this detection mark with a printer, the color material is transferred from the thermal transfer sheet to the receiving layer at an accurate position to form a thermal transfer image, and the receiving layer and primer are accurately positioned relative to the transfer target. A layer in which a layer and a protective layer are laminated can be transferred.

  The shape and color of the detection mark are not limited as long as it can be detected by the detector. In addition, the position of the detection mark is the shape of the detection mark that can be provided between the base material sheet and the protective layer in the region B located on the adhesive layer or in the region D located below the release layer. In FIG. 4, for example, as shown in FIGS. 4 and 5, the shape may be a rectangle or an ellipse, or may be a shape such as a round shape or a barcode. In the case of a line shape, it may be formed over the entire width of the intermediate transfer recording medium. The color of the detection mark only needs to be detectable by a detector. For example, in the case of a light transmission type detector, silver or black having high concealment properties may be used. Further, in the case of a light reflection type detector, the color tone of metallic luster having high reflectivity can be given.

  The detection mark can be formed by gravure printing or offset printing. Although not formed between the base sheet and the protective layer, the detection mark may be formed by penetrating a hole from the front surface to the back surface of the intermediate transfer recording medium.

(Image forming method)
The intermediate transfer recording medium of the present invention forms a final printed matter by an image forming method as described below. 1) First, a thermal transfer sheet having a hot melt ink layer containing a color material on a base material or a dye layer containing a dye (color material) that transfers heat by sublimation in the receiving layer of the intermediate transfer recording medium of the present invention. Then, the color material is transferred to the receiving layer of the intermediate transfer recording medium by a heating means such as a thermal head to form a thermal transfer image.

  2) Next, an intermediate transfer recording medium having a receiving layer on which the thermal transfer image is formed and a transfer target are prepared, and stacked so that the receiving layer and the transfer target are in contact with each other. Heating and pressing with a roll are performed to transfer the receiving layer having the thermal transfer image together with the primer layer and the protective layer to the transfer target, thereby obtaining a printed material with excellent durability of the thermal transfer image.

  By performing the above-mentioned 1) thermal transfer image forming step and 2) transferring the receiving layer having the thermal transfer image onto the transfer target, the foil breakage is good, transfer failure can be prevented, and the thermal transfer image. Thus, a printed matter having the above durability can be easily obtained. As shown in FIG. 1, in the form in which the adhesive layer 6 is partially provided between the base sheet 2 and the protective layer 3, the region B positioned on the partially provided adhesive layer 6 is Without being peeled from the substrate sheet 2, the receiving layer 5, the primer layer 4, and the protective layer 3 in the region A excluding the region B are transferred to the transfer target 10 with good foil breakage. In the above case, it goes without saying that the thermal transfer image is formed in the region A of the receiving layer in the step 1), but the thermal transfer image may extend from the region A to the region B. In the step 2), as shown in FIG. 1B, the adhesive layer 6 of the intermediate transfer recording medium is formed so that the area of the region A is smaller than the area of the transfer target 10 on the transfer side. It is preferable to set the pattern to be applied and select the size of the transfer target 10 to transfer the receiving layer having the thermal transfer image to the transfer target. When the area A and the size of the transfer surface of the transfer target are the same, it is difficult to align the intermediate transfer recording medium and the transfer target. Further, when the area A is larger than the area on the transfer side of the transfer target, transfer defects are likely to occur in the transfer of the receiving layer.

  Further, as shown in FIG. 2, a release layer 8 is partially provided on the receiving layer 5, and the release layer 8 is not peeled off from the base sheet 2, and the release layer 8 is not peeled off. The receiving layer 5, primer layer 4, and protective layer 3 in the region C excluding the portion of FIG. In this case, it goes without saying that the thermal transfer image is formed in the area A of the receiving layer in the step 1), but the thermal transfer image may extend from the area A to the area B. In the step 2), as shown in FIG. 2B, the release layer 8 of the intermediate transfer recording medium is set so that the area of the region C is smaller than the area of the transfer target 10 on the transfer side. It is preferable to set the pattern to be applied and to select the size of the transfer target 10 and transfer the receiving layer having the thermal transfer image to the transfer target. When the size of the area C and the transfer surface of the transfer target are the same, it is difficult to align the intermediate transfer recording medium and the transfer target. Further, when the area C is larger than the area on the transfer side of the transfer target, transfer defects tend to occur in the transfer of the receiving layer.

Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, parts or% is based on mass.
( Reference Example 1)
On the one side of a 25 μm-thick polyethylene terephthalate film base sheet, the following detection mark ink is applied by a gravure printer in the arrangement shown in FIGS. A detection mark of / m ² was formed. On the base material sheet on the surface where the detection mark is formed, as shown in FIG. 1, the following coating liquid for the adhesive layer is applied by a gravure printing machine so that the coating amount when dried is 1.0 g / m ² . An adhesive layer was formed. On the base material sheet on the surface on which the adhesive layer is formed, as shown in FIG. 1, the following coating liquid for protective layer is applied by a gravure printing machine so that the coating amount when dried is 5.0 g / m ² . A protective layer was formed.

<Ink for detection mark>
Carbon black 8.0 parts Urethane resin 5.0 parts Methyl ethyl ketone part Toluene 100 parts

<Coating liquid for adhesive layer>
20 parts of vinyl chloride-vinyl acetate copolymer resin (Solvine CNL, manufactured by Nissin Chemical Industry Co., Ltd.)
Methyl ethyl ketone 40 parts Toluene 40 parts

<Coating liquid for protective layer>
Urethane acrylic resin 100 parts Dipentaerythritol hexaacrylate 20 parts Photopolymerization initiator 5 parts Methyl ethyl ketone 100 parts Toluene 100 parts

On the above protective layer, a primer layer having a coating amount of 1.5 g / m ² at the time of drying was formed by a gravure printing machine using the following primer layer coating solution. Further, a receiving layer having a coating amount of 4.0 g / m ² upon drying was formed on the primer layer by a gravure printing machine using the following receiving layer coating solution, and the intermediate transfer recording of Reference Example 1 was performed. A medium was made. However, the detection mark of the intermediate transfer recording medium and the drying after coating each layer are usually used hot air drying. However, in the case of the protective layer, the coating is dried with hot air, and then the ultraviolet irradiation device ( UV light was irradiated with ozone using a high pressure mercury lamp with an output of 120 W / cm.

<Primer layer coating solution>
Acrylic polyol resin 60 parts (U-245B / isocyanate crosslinking agent 10/1, manufactured by Soken Chemical Co., Ltd.)
20 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

<Coating liquid for receiving layer>
Vinyl chloride-vinyl acetate copolymer (Solvine C, manufactured by Nissin Chemical Industry Co., Ltd.) 60 parts Epoxy-modified silicone (X-22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.2 parts Methyl ethyl ketone / toluene (mass) Ratio 1/1) 5 parts

( Reference Example 2)
On one surface of a 25 μm thick polyethylene terephthalate film base sheet, the amount of coating for the detection mark ink used in Reference Example 1 in the arrangement as shown in FIGS. Formed a detection mark of 2.0 g / m ² . On the substrate sheet on the surface where the detection mark is formed, the protective layer coating liquid used in Reference Example 1 is coated with a protective layer having a coating amount of 5.0 g / m ² when dried using a gravure printing machine. Formed. On the protective layer, the primer layer coating solution used in Reference Example 1 was formed with a gravure printing machine to form a primer layer having a coating amount of 1.5 g / m ² when dried. Further, a receiving layer having a coating amount of 4.0 g / m ² when dried was formed on the primer layer by a gravure printing machine using the receiving layer coating solution used in Reference Example 1. Further, on the receiving layer, a coating solution for a release layer having the following composition with a disposition as shown in FIGS. 2 and 5 is 1.0 g / m ² when dried by a gravure printing machine. A release layer was formed to produce an intermediate transfer recording medium of Reference Example 2.

<Release layer coating solution>
Cellulose acetate propionate resin 100 parts (CAP482-0.5, manufactured by Eastman Chemical)
20 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

Example 3
On the one side of a 25 μm thick polyethylene terephthalate film base sheet, the coating amount at the time of drying was applied to the detection mark ink used in Reference Example 1 with a gravure printer in the arrangement as shown in FIGS. Formed a detection mark of 2.0 g / m ² . As shown in FIG. 3, the adhesive layer coating liquid used in Reference Example 1 was applied onto the base material sheet on the surface on which the detection mark was formed by a gravure printing machine so that the coating amount when dried was 2.0 g. An adhesive layer of / m ² was formed. As shown in FIG. 3, the protective layer coating solution used in Reference Example 1 was applied onto the base material sheet having the adhesive layer formed thereon with a gravure printing machine to give a coating amount of 5.0 g when dried. A protective layer of / m ² was formed.

On the protective layer, a primer layer having a coating amount of 1.5 g / m ² at the time of drying was formed using a gravure printing machine with the primer layer coating solution used in Reference Example 1. Further, a receiving layer having a coating amount of 4.0 g / m ² when dried was formed on the primer layer by a gravure printing machine using the receiving layer coating solution used in Reference Example 1. Further, on the receiving layer, the release layer coating liquid used in Reference Example 2 was placed in the arrangement as shown in FIGS. An m ² release layer was formed to produce the intermediate transfer recording medium of Example 3.

(Comparative Example 1)
On the one side of a 25 μm thick polyethylene terephthalate film base sheet, the amount of coating for the detection mark ink used in Reference Example 1 in the arrangement as shown in FIGS. Formed a detection mark of 2.0 g / m ² . On the substrate sheet on the surface where the detection mark is formed, the protective layer coating liquid used in Reference Example 1 is coated with a protective layer having a coating amount of 5.0 g / m ² when dried using a gravure printing machine. Formed. On the protective layer, the primer layer coating solution used in Reference Example 1 was formed with a gravure printing machine to form a primer layer having a coating amount of 1.5 g / m ² when dried. Further, on the primer layer, the receiving layer coating solution used in Reference Example 1 was formed with a gravure printing machine to form a receiving layer having a coating amount of 4.0 g / m ² when dried. No. 1 intermediate transfer recording medium was produced.

(Comparative Example 2)
The intermediate transfer recording medium of Comparative Example 2 was prepared in the same manner as Comparative Example 1 except that the protective layer coating liquid was changed to a coating liquid having the following composition in the intermediate transfer recording medium of Comparative Example 1.
<Coating liquid for protective layer>
20 parts of polymethyl methacrylate resin (BR-87, manufactured by Mitsubishi Rayon Co., Ltd.)
80 parts of methyl ethyl ketone

  Using the above-prepared intermediate transfer recording medium of each example, the evaluation of foil breakage was performed by the following method. First, the following card base materials were prepared as transfer objects. A card substrate comprising 100 parts of a polyvinyl chloride (polymerization degree 800) compound containing about 10% of an additive such as a stabilizer, 10 parts of a white pigment (titanium oxide) and 0.5 part of a plasticizer (DOP) was prepared. .

(Foil cutting property)
Using the intermediate transfer card printer of HDP600 (manufactured by FARGO) and the thermal transfer ink ribbon for HDP600, an image is formed on the receiving layer of the intermediate transfer recording medium using the intermediate transfer recording medium produced in the above-described examples and comparative examples, and a heat roller The receiving layer, the primer layer, and the protective layer are transferred to the entire surface of the card to be transferred on the surface to be transferred under the conditions of a surface temperature of 190 ° C. and a speed of 3 sec / inch. The foil transferability of the intermediate transfer recording medium was examined.

The criteria for evaluation of foil breakage are as follows.
A: The foil transferability of the intermediate transfer recording medium is very good, and the receiving layer formed with the image, together with the primer layer and the protective layer, has a defined area (areas A and C) with an outline to the transfer target, The transfer is very sharp.
○: The foil transfer property of the intermediate transfer recording medium is good, and the receiving layer on which the image has been formed, together with the primer layer and the protective layer, the defined areas (areas A and C) are sharply transferred to the transfer target. is doing.
×: The foil transferability of the intermediate transfer recording medium is not good, and the imaged receiving layer together with the primer layer and the protective layer protrudes from the determined area (area A, C) and is transferred to the entire surface of the card. The transferred edge is not sharp and is a problem.

(durability)
Furthermore, the durability of the following conditions was evaluated for the printed matter obtained by the evaluation of the foil breakability of the above Examples and Comparative Examples.
Durability was evaluated with a wear wheel CS-10F and a load of 500 gf using a rotary ablation tester manufactured by Toyo Seiki Seisakusho.

  The criterion for evaluating durability was to count the number of rotations at an end point where the image formed by the thermal transfer ink ribbon disappeared due to the wear ring.

Table 1 shows the evaluation results of the above-mentioned foil breakability and durability.

FIG. 2 is a schematic cross-sectional view showing an intermediate transfer recording medium according to an embodiment of the present invention before transfer to a transfer medium and during transfer. FIG. 6 is a schematic cross-sectional view showing the intermediate transfer recording medium according to another embodiment of the present invention before transfer to a transfer medium and during transfer. FIG. 6 is a schematic cross-sectional view showing the intermediate transfer recording medium according to another embodiment of the present invention before transfer to a transfer medium and during transfer. FIG. 3 is a schematic plan view showing an example of arrangement when the intermediate transfer recording medium of the present invention is manufactured by multi-sided attachment. FIG. 3 is a schematic plan view showing an example of arrangement when the intermediate transfer recording medium of the present invention is manufactured by multi-sided attachment. FIG. 3 is a schematic plan view showing an example of arrangement when the intermediate transfer recording medium of the present invention is manufactured by multi-sided attachment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Intermediate transfer recording medium 2 Base material sheet 3 Protective layer 4 Primer layer 5 Receptive layer 6 Adhesive layer 7 Detection mark 8 Release layer 10 Transfer object A Area except area B B Area located on adhesive layer C area Area excluding D D Area located under the release layer E Area located between the adhesive layer and the release layer F Area excluding area E

Claims (2)

In an intermediate transfer recording medium in which at least a protective layer and a receiving layer are sequentially laminated on one surface of a base sheet, the protective layer is made of an ionizing radiation curable resin, and vinyl chloride is interposed between the base sheet and the protective layer. -The adhesive layer made of vinyl acetate copolymer resin is partially provided, and the release layer made of cellulose acetate propionate resin is partially provided on the receiving layer. An intermediate transfer recording medium, wherein the region E between the layer and the partly provided release layer does not peel from the substrate, and the region F excluding the region E can be peeled from the substrate sheet. The intermediate transfer recording medium according to claim 1, wherein a detection mark is provided between the base sheet and the protective layer.

Images