JP4221745B2 - Protective layer transfer sheet and printed matter - Google Patents

Description

  The present invention relates to a protective layer transfer sheet and a printed matter.

  Conventionally, an image such as a gradation image, a monotonous image such as a character, a symbol, or the like is formed on a base material using a thermal transfer method. As the thermal transfer system, a thermal sublimation transfer system and a thermal melt transfer system are widely used.

  Among these, the heat-sensitive sublimation transfer method uses a thermal transfer sheet in which a dye layer in which a sublimable dye used as a coloring material is melted or dispersed in a binder resin is supported on a base material, and this thermal transfer sheet is superimposed on an image receiving sheet to form a thermal head. By applying energy corresponding to image information to a heating device such as a sublimation dye contained in the dye layer on the thermal transfer sheet, the image is formed by transferring the dye to the image receiving sheet.

  This heat-sensitive sublimation transfer method can control the amount of dye transfer in dot units according to the amount of energy applied to the thermal transfer sheet, and is therefore excellent in forming gradation images, and has the advantage of easy formation of characters, symbols, etc. Have.

  By the way, various cards such as an identification card, a driver's license, a membership card, and an ID card are widely used. These cards record various information that reveals the identity of the owner. In particular, in an ID card or the like, an image of a face photograph is important together with character information such as an address and name, and the image is required to have a property (durability) that does not change or deteriorate over a long period of time. The

  Currently, the heat-sensitive sublimation transfer method is employed for recording information on such cards. However, the gradation image and the monotonic image formed by the heat-sensitive sublimation transfer method are inferior in resistance to solvents, plasticizers and the like because the transferred dye exists on the surface of the transfer target. For this reason, attempts have been made to improve the durability of images in cards that require durability, such as ID cards on which facial photographic images are recorded.

  Patent Document 1 is provided with a heat transferable protective layer on at least a part of one surface of a base sheet so as to be peelable, and the base sheet side of the protective layer that becomes the outermost surface after thermal transfer is methyl methacrylate, methacrylamide and A protective layer thermal transfer sheet containing a copolymer of at least two components of methacrylic acid is disclosed.

  The transfer sheet disclosed in Patent Document 1 is used to transfer a protective layer to a transfer target (image receiving sheet) on which an image is formed and to improve the durability of the image.

By using the transfer sheet described in Patent Document 1, the durability of the image can be improved to a practical level, but the image with the protective layer (protective image) is further improved in durability. It is requested to do. For example, when a protective image is brought into contact with a plasticizer-containing soft vinyl chloride film for a long period of time, it is desired that the image does not shift to the film and the image does not deteriorate.
JP 2003-80844 (Claims)

  It is an object of the present invention to provide a protective layer transfer sheet that can further improve the durability of an image formed on a transfer target.

As a result of repeating various studies to solve the above problems, the present inventor used a protective layer transfer sheet in which the resin constituting the plasticizer layer is a methacrylic copolymer having specific SP and Tg. In some cases, it has been found that a further excellent durability can be imparted to an image formed on a transfer medium. The present invention has been completed based on such findings.
1. The present invention provides a protective layer transfer sheet in which a heat transferable resin layer is provided on one surface of a base sheet so as to be peelable,
The thermal transfer resin layer is composed of at least a plasticizer layer and a thermal adhesive resin layer from the base sheet side,
The plasticizer layer is composed of an acrylic copolymer having a solubility parameter of 11 or more, a glass transition temperature of 70 ° C. or less, and containing at least two components of methyl methacrylate, methacrylamide and methacrylic acid. A protective layer transfer sheet is provided.
2. The present invention provides the protective layer transfer sheet according to 1 above, wherein the thermal transfer resin layer is composed of a release layer, a plasticizer layer and a thermal adhesive resin layer from the base sheet side.
3. In the present invention, at least one color material layer selected from the group consisting of a heat-sublimable color material layer and a heat-meltable color material layer is provided on one surface of the base sheet in the surface order together with the heat transferable resin layer. The protective layer transfer sheet according to 1 or 2 above is provided.
4). In the present invention, the protective layer transfer sheet according to any one of 1 to 3 above and a printed material are superposed so that the thermal transfer resin layer of the transfer sheet and the image of the printed material are in contact with each other. A print obtained by thermally transferring the heat transferable resin layer is provided.
5. The present invention provides the printed matter according to 4 above, wherein the image of the printed matter is one of an electrophotographic method, an inkjet recording method, and a thermal transfer recording method.

Protective layer transfer sheet The protective layer transfer sheet of the present invention is obtained by laminating a thermal transfer resin layer on one surface of a base sheet.

  The said heat transferable resin layer is comprised from the base material sheet side by the plasticizer layer and the heat-adhesive resin layer. The said heat transferable resin layer is formed on the base material sheet so that peeling from a base material sheet is possible.

  In this invention, the heat transferable resin layer may be comprised from the base material sheet side by the peeling layer, the plasticizer layer, and the heat bondable resin layer.

  In the present invention, a release layer may be provided between the heat transferable resin layer and the base sheet.

  Moreover, in this invention, the back layer may be formed in the other surface of the said base material sheet. The back layer is a substrate that comes into contact with the heating device for the purpose of preventing thermal fusion with a heating device such as a thermal head or a line heater when the thermal transfer resin layer is transferred onto the print, and for smooth running. It can be provided on the other surface of the material sheet on the heat transferable resin side.

  The protective layer transfer sheet of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of the protective layer transfer sheet of the present invention. In FIG. 1, the protective layer transfer sheet 1 of the present invention has a plasticizer layer 4 and a thermoadhesive resin layer 5 sequentially laminated on one surface of a substrate sheet 2.

  FIG. 2 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. In FIG. 2, the protective layer transfer sheet 1 of the present invention has a release layer 3, a plasticizer layer 4, and a thermal adhesive resin layer 5 sequentially laminated on one surface of a substrate sheet 2.

  FIG. 3 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. In FIG. 3, the protective layer transfer sheet 1 of the present invention has a release layer 3, a plasticizer layer 4, and a thermoadhesive resin layer 5 sequentially laminated on one surface of a substrate sheet 2. The back layer 6 is formed on the surface.

  FIG. 4 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. In FIG. 4, the protective layer transfer sheet 1 of the present invention has a release layer 7, a release layer 3, a plasticizer layer 4, and a thermal adhesive resin layer 5 sequentially laminated on one surface of a base sheet 2. A back surface layer 6 is formed on the other surface of the material sheet 2.

The same base material sheet as that widely used in this field can be used as the base material sheet, and it is not particularly limited. Specific examples of the base sheet include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ketone, polyether sulfone, and other highly heat-resistant polyesters; polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, Examples thereof include plastic films such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, and ionomer, and laminates thereof. The plastic film may be stretched or unstretched.

  Although the thickness of a base material sheet can be suitably selected in consideration of strength, heat resistance and the like, it is usually about 1 to 100 μm.

Release layer The release layer is composed of a binder resin.

  As the binder resin, known thermoplastic resins and thermosetting resins used in this field can be widely used.

  Examples of the thermoplastic resin include acrylic resins such as polymethacrylic acid, polymethacrylamide, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate; polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl Examples thereof include vinyl resins such as alcohol and polyvinyl butyral; cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate.

  Examples of the thermosetting resin include unsaturated polyester resins, polyester resins, polyurethane resins, amino alkyd resins, and the like.

  Among these binder resins, acrylic resins are preferable.

  These binder resins may be used alone or in combination of two or more.

  The release layer may contain a wax together with the binder resin. When the wax is contained, the scratch resistance and foil breakability of the release layer are improved.

  Examples of the wax include polyethylene wax, polyester wax, polystyrene powder, olefin powder, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, wool wax, Examples include shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide.

  Wax is usually contained in the release layer in an amount of about 0.1 to 30% by weight, preferably about 0.1 to 10% by weight.

  In the present invention, the release layer may contain an ultraviolet absorber. By blending the ultraviolet absorber, it is possible to improve the light resistance and weather resistance of the image of the transferred material covered with the protective layer after being transferred.

  As the ultraviolet absorber, conventionally known organic ultraviolet absorbers such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, hindered amine and the like can be widely used. Also, for example, addition polymerizable double bonds such as vinyl groups, acryloyl groups, and methacryloyl groups, or functional groups such as alcoholic hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups are introduced into these ultraviolet absorbers. An ultraviolet absorbing resin may be contained in the release layer.

  Furthermore, you may contain various additives, such as antioxidant and a fluorescent whitening agent, in the said peeling layer.

  The release layer is a gravure printing method, a screen printing method, which is obtained by adding a necessary additive such as wax to the binder resin and dissolving or dispersing in water, an organic solvent or the like on the binder resin. It is formed by applying and drying according to a normal coating method such as a reverse roll coating method using a gravure plate.

  The thickness of the release layer is usually about 0.1 to 10 μm, preferably about 0.5 to 5 μm.

Release layer The release layer adjusts the adhesiveness between the base sheet and the heat transferable resin layer to improve the release of the heat transferable resin layer when the peelability between the base sheet and the heat transferable resin layer is not appropriate. Provided to do.

  The release layer is, for example, various waxes such as silicone wax, silicone resin, fluororesin, acrylic resin, water-soluble resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acrylic vinyl ether resin, maleic anhydride resin. It is comprised from various resins etc., such as these, and these mixtures.

  The release layer can be formed by applying a coating liquid containing at least one selected from the group consisting of the above waxes and the above resin onto a base sheet according to a conventionally known coating method and drying. . The thickness of the release layer is usually about 0.5 to 5.0 μm.

  When the release layer is provided, it is desirable to form the thermal transfer resin layer so that the release layer is peeled off from the release layer by transfer, and the release layer itself remains on the substrate sheet side.

Plasticizer layer In the present invention, the plasticizer layer is composed of a methacrylic copolymer composed of two or more monomers selected from the group consisting of methyl methacrylate, methacrylamide and methacrylic acid. It is essential that the coalescence SP is 11 or more and Tg is 70 ° C. or less (preferably 50 to 70 ° C.).

  The plasticizer layer is an ink prepared by dissolving or dispersing the methacrylic copolymer resin or other additives in a solvent such as water or an organic solvent on a base sheet or a release layer formed on the base sheet. It is formed by applying and drying according to a usual coating method such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate.

  The thickness of the plasticizer layer is usually about 0.1 to 10 μm, preferably about 0.5 to 5 μm.

Thermal Adhesive Resin Layer The thermal adhesive resin layer is provided on the opposite surface of the thermal transferable protective layer to the substrate sheet side in order to improve the transferability and adhesion to a printed material that is a transfer target.

  As the resin constituting the heat-adhesive resin layer, any resin that is blended in conventionally known pressure-sensitive adhesives, heat-sensitive adhesives, etc. can be used, but the glass transition temperature (Tg) is 50 to 80 ° C. A plastic resin is preferred. Specific examples of such thermoplastic resins include polyester resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, butyral resins, epoxy resins, polyamide resins, vinyl chloride resins, and the like.

  If necessary, the heat-adhesive resin layer can contain additives such as inorganic fillers and organic fillers together with the resin.

  For the heat-adhesive resin layer, an ink obtained by dissolving or dispersing the above resin and other additives in a solvent such as water or an organic solvent is used on the plasticizer layer, using a gravure printing method, a screen printing method, or a gravure plate. It is formed by applying and drying in accordance with a normal coating method such as a reverse roll coating method.

  The thickness of the heat-adhesive resin layer is usually about 0.1 to 10 μm, preferably about 0.5 to 5 μm.

  The protective layer thermal transfer sheet of the present invention is not limited to the above-described embodiment, and is a composite type protective layer thermal transfer sheet of a thermal transferable protective layer and a heat-meltable color material layer, a thermal transferable protective layer and a dye layer. It can be set arbitrarily according to the purpose of use, such as a protective layer thermal transfer sheet of a composite type comprising a heat melting colorant layer. In particular, by using a composite type protective layer thermal transfer sheet, it is possible to simultaneously perform image formation by the thermal transfer method and transfer of the protective layer to the transfer target.

  As an example of such a protective layer transfer sheet, at least one color selected from the group consisting of a heat transferable resin layer and a heat sublimable color material layer and a heat meltable color material layer on one surface of the base sheet. Examples thereof include a protective layer transfer sheet in which the material layers are provided in the surface order.

  FIG. 5 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. In FIG. 5, the protective layer transfer sheet 1 of the present invention has a heat sublimable color material layer Y, a heat sublimation color material layer M, a heat sublimation color material layer C, and a heat transfer resin on one surface of a base sheet 2. The layers 8 are formed in the surface order, and the back layer 6 is formed on the other surface of the base sheet 2. The heat transferable resin layer 8 includes a plasticizer layer 4 and a heat adhesive resin layer 5.

  FIG. 6 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. In FIG. 6, the protective layer transfer sheet 1 of the present invention has a heat sublimable color material layer Y, a heat sublimation color material layer M, a heat sublimation color material layer C, a heat meltability on one surface of a substrate sheet 2. The color material layer 9 and the heat transfer resin layer 8 are formed in the surface order, and the back layer 6 is formed on the other surface of the base sheet 2. The heat transferable resin layer 8 includes a plasticizer layer 4 and a heat adhesive resin layer 5.

  In the present invention, a primer layer may be provided between the base sheet 2 and the heat sublimable color material layer Y, the heat sublimation color material layer M, or the heat sublimation color material layer C.

  In the present invention, a release layer may be provided between the base sheet 2 and the heat-meltable color material layer 9. This release layer may be the same as the release layer described above.

Thermal sublimation color material layer The heat sublimation color material layer is obtained, for example, by supporting a dye that transfers heat by sublimation mainly in a binder resin.

  As the dye, any of the conventionally used dyes used in thermal transfer sheets can be used effectively, and is not particularly limited. Preferable dyes include magenta dyes such as MS RedG, Macrolex Red Violet R, Ceres Red 7B, Samalon Red HBSL, and Resolin Red F3BS. Examples of yellow dyes include Holon Brilliant Yellow 6GL, PTY-52, Macrolex Yellow 6G, and the like. Examples of the cyan dye include Kayaset Blue 714, Waxoline Blue AP-FW, Holon Brilliant Blue S-R, MS Blue 100, and the like.

  Any conventionally known binder resin for supporting the dye can be used. Examples of preferred binder resins include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and cellulose acetate butyrate; polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone And vinyl resins such as polyacrylamide; polyester resins and the like. Of these, cellulose resins, polyvinyl resins such as polyvinyl butyral and polyvinyl acetal, and polyester resins are preferred from the viewpoints of heat resistance, dye transferability, and the like.

  Furthermore, conventionally well-known various additives may be mix | blended in the heat sublimable color material layer as needed.

  The content of the dye is usually about 5 to 90% by weight, preferably about 10 to 70% by weight, based on the total amount of the heat sublimable color material layer.

  The heat sublimable color material layer is preferably formed by adding the sublimation dye, binder resin and other optional components in an appropriate solvent, and dissolving or dispersing each component to form a heat sublimable color material layer forming paint. Alternatively, it is carried out by preparing an ink, applying it surface-sequentially on the substrate sheet and drying it.

  The thickness of the heat sublimable color material layer is usually about 0.2 to 5 μm, preferably about 0.4 to 2 μm.

Heat-meltable color material layer The heat-meltable color material layer is obtained by supporting a colorant on a binder.

  As the colorant, among organic or inorganic pigments and dyes, those having good characteristics as a recording material, for example, those having a sufficient color density and not discolored by light, heat, temperature, etc. are preferable. As such a colorant, for example, those having a hue such as black, cyan, magenta, and yellow are used.

  As the binder, for example, a mixture in which a wax is a main component and a drying oil, a resin, a mineral oil, a cellulose derivative, a rubber derivative, or the like is blended with the wax is used.

  Examples of the wax include 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, polyester wax. Various waxes such as partially modified waxes, fatty acid esters, and fatty acid amides are used.

  Further, as the binder, vinyl chloride / vinyl acetate copolymer resin, acrylic resin, chlorinated rubber, vinyl chloride / vinyl acetate copolymer resin, cellulose resin, and the like can be used.

  The formation of the heat-meltable color material layer is carried out by preparing a composition for forming a heat-meltable color material layer to which the colorant, binder resin, and other additives as necessary are added, and applying this to the above base sheet. Further, it is carried out by applying a hot melt coat, a hot lacquer coat, a gravure coat, a gravure reverse coat, a knife coat, an air coat, a roll coat method, and the like, followed by drying.

  The thickness of the heat-meltable color material layer is usually about 0.1 to 8 μm, preferably about 0.4 to 2 μm.

  The hot-melt colorant layer formed on the base sheet may consist of one layer, or may consist of two or more layers.

As the resin constituting the back layer back layer, for example, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose resins such as nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl Vinyl resins such as acetal and polyvinylpyrrolidone; Acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, and acrylonitrile-styrene copolymer; Polyamide resin; Polyvinyl toluene resin; Coumarone indene resin; Polyester resin Polyurethane resins; natural or synthetic resins such as silicone-modified or fluorine-modified urethane.

  These resins are used singly or in combination of two or more.

  From the viewpoint of further improving the heat resistance of the back layer, among the above resins, a resin having a reactive group such as a hydroxyl group (for example, butyral resin, acetal resin, etc.) is used, and a polyisocyanate is used as a crosslinking agent. Is preferably used in combination as a crosslinked resin layer.

  Furthermore, for the purpose of imparting slidability with the thermal head, a solid or liquid release agent or lubricant may be blended in the back layer.

  Examples of release agents or lubricants include various waxes such as polyethylene wax and paraffin wax; higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants Examples thereof include various surfactants such as an activator and a fluorosurfactant; fine particles of inorganic compounds such as organic carboxylic acids and derivatives thereof, fluororesins, silicone resins, talc, and silica.

  The amount of lubricant contained in the back layer is usually about 5 to 50% by weight, preferably about 10 to 30% by weight in the back layer.

  The back layer is a reverse roll coating method using a gravure printing method, a screen printing method, and a gravure plate, which is obtained by dissolving or dispersing the above resin and other additives in a solvent such as water or an organic solvent on a base sheet. It is formed by applying and drying according to a normal coating method such as.

  The thickness of the back layer is usually about 0.1 to 10 μm, preferably about 0.5 to 5 μm.

To-be-transferred body There is no restriction | limiting in particular as a to-be-transferred body which transfers a protective layer using this invention protective layer transfer sheet.

  The transfer target may be, for example, a sheet made of any base material such as plain paper, high-quality paper, tracing paper, and plastic film. Further, the transfer object may have any shape such as a card, a postcard, a passport, a notepaper, a report sheet, a notebook, a catalog, and the like.

  If the substrate itself has dye acceptability, it is not necessary to provide a receptor layer, but if the substrate itself does not have dye acceptability, it has dye acceptability on the substrate. It is common to provide a receiving layer. The receiving layer may be provided by a coating method or a thermal transfer method using a thermal head, a hot roll or the like.

  Specific examples of the transfer object of the present invention include, for example, stock certificates, securities, certificates, passbooks, boarding tickets, car horse tickets, stamps, stamps, appreciation tickets, admission tickets, tickets, etc .; cash cards, credit cards , Prepaid cards, members cards, greeting cards, postcards, business cards, driver's licenses, IC cards, optical cards, etc .; cartons, cases such as containers; bags, etc .; forms, envelopes, tags, OHP sheets, slide films , Bookmarks, calendars, posters, brochures, menus, passports, POP supplies, coasters, displays, nameplates, keyboards, cosmetics, watches, lighters, and other accessories; stationery, report paper, and other stationery; building materials, panels, emblems, keys , Cloth, clothing, footwear, radio, TV, calculator, OA equipment, etc. Sample book, mention may be made of the album, the output of computer graphics, the medical image output, and the like.

  The image on the transfer medium may be formed by any method such as an electrophotographic method, an ink jet recording method, or a thermal transfer recording method.

  In using the protective layer transfer sheet of the present invention, conventionally known methods for using the protective layer transfer sheet can be employed as they are. For example, the heat-adhesive resin layer surface of the protective layer transfer sheet of the present invention may be superposed on the transfer target, and the thermal transfer resin layer may be thermally transferred onto the transfer target.

  If the protective layer transfer sheet of the present invention is used, it is possible to impart further excellent durability to the image formed on the transfer target. Therefore, even when the transferred body having this image is brought into contact with a film such as a soft vinyl chloride film containing a plasticizer for a long time, there is no possibility that a part of the image is transferred to the film. The transferred material on which the protective layer is formed does not crack for a long period of time and can maintain the same quality image for a long period of time.

  The present invention will be further clarified by the following examples.

Example 1
Manufacture of protective layer transfer sheet
(1) Preparation of back layer forming ink The following components were mixed to prepare a back layer forming ink.
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., ESREC BX-1): 15 parts by weight Polyisocyanate (manufactured by Dainippon Ink and Chemicals, Barnock D450): 35 parts by weight Phosphate ester surfactant (No. Ichi Kogyo Seiyaku Co., Ltd., Price Surf A208S): 10 parts by weight Talc (Nihon Talc Co., Ltd., Microace P-3): 3 parts by weight
(2) Preparation of Release Layer Forming Ink Each component shown below was mixed to prepare a release layer forming ink.
Silicone-modified acrylic resin (Daicel Chemical Industries, Cell Top 226, solid content 50%): 16 parts by weight Aluminum catalyst (Daicel Chemical Industries, Cell Top CAT-A, solid content 10%) ): 3 parts by weight, methyl ethyl ketone: 8 parts by weight, toluene: 8 parts by weight
(3) Preparation of release layer forming ink The components shown below were mixed to prepare a release layer forming ink.
Acrylic resin (Mitsubishi Rayon Co., Ltd., BR-85): 40 parts by weight Polyester resin (Toyobo Co., Ltd., Byron 200): 2 parts by weight Methyl ethyl ketone: 50 parts by weight Toluene: 50 parts by weight
(4) Preparation of plasticizer layer forming ink Eight types of copolymers shown in Table 1 below (Copolymer 1 to Copolymer 8) were synthesized, and using these copolymers, the following composition was obtained. Eight types of plasticizer layer forming inks 1 to 6 were prepared. In addition, about said copolymer (copolymer 1-copolymer 8), a glass transition temperature (Tg) and a solubility parameter (SP) value are combined with following Table 1, and are shown.

上記表１において、ＭＭＡはメタクリル酸メチル、ＭＡはメタクリル酸、ＭＡＡはメタクリルアミドである。共重合体成分の項において、○はその共重合体成分が含まれていることを、×はその共重合体成分が含まれていないことを意味する。

In Table 1 above, MMA is methyl methacrylate, MA is methacrylic acid, and MAA is methacrylamide. In the term of the copolymer component, “◯” means that the copolymer component is contained, and “x” means that the copolymer component is not contained.

The following components were mixed to prepare a plasticizer layer forming ink.
-Copolymer (any one of copolymer 1 to copolymer 8): 100 parts by weight-Methyl ethyl ketone: 50 parts by weight-Isopropyl alcohol: 50 parts by weight
(5) Preparation of thermal adhesive resin layer forming ink The following components were mixed to prepare a thermal adhesive resin layer forming ink.
-Vinyl chloride-vinyl acetate copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., 1000 ALK): 40 parts by weight-Methyl ethyl ketone: 50 parts by weight-Toluene: 50 parts by weight.

The back layer forming ink prepared in (1) above was applied to one surface of a 6 μm thick polyethylene terephthalate film (Toray Industries, Inc., easy-adhesion treated product) by the gravure coating method (coating amount 1.0 g / m ² (during drying)), and after drying, heat aging was performed to form a back layer.

Next, the release layer-forming ink prepared in (2) above was applied to the other surface of the polyethylene terephthalate film on which the back layer was formed by the gravure coating method (coating amount 0.7 g / m ² (when dry)). And dried to form a release layer.

  Next, on the release layer formed above, the release layer forming ink prepared in (3) above by gravure coating is applied so that the film thickness after drying is 1.0 μm, and dried. A release layer was formed.

  Next, on the release layer formed above, the ink for forming a plasticizer layer prepared in (4) above by gravure coating is applied so that the film thickness after drying is 1.5 μm, and dried. Thus, a plasticizer layer was formed.

  Furthermore, on the plasticizer layer formed as described above, the thermal adhesive resin layer forming ink prepared in (5) above by gravure coating is applied so that the film thickness after drying becomes 1.5 μm. And dried to form a heat-adhesive resin layer.

  Thus, a back layer is formed on one surface of the polyethylene terephthalate film, and a release layer, a release layer, a plasticizer layer, and a heat-adhesive resin layer are sequentially formed on the other surface from the polyethylene terephthalate film side. A protective layer transfer sheet was produced.

Example 2
Manufacture of printed matter An image was formed on a card made of vinyl chloride by thermal transfer using a thermal transfer sheet provided with each color material layer of yellow, magenta and cyan.

Next, each protective layer transfer sheet produced in Example 1 above is overlaid on the image forming portion of the vinyl chloride card, and the protective layer is transferred from the protective layer transfer sheet using a printer (ELTRON, card printer P310). The image was printed so as to cover the image forming portion, and a printed material coated with a protective layer was produced.
Evaluation of Durability The protective layer side of the printed matter produced above was superposed on a plasticized soft vinyl chloride sheet (Mitsubishi Chemical Corporation, Altron # 480, thickness 400 μm), and 70.2 g / m ² The sample was stored under an environment of 82 ° C. for 32 hours under a load, and the deterioration of the image by the plasticizer was observed.
Observation items:
(a) Transfer of image to plasticized soft vinyl chloride sheet No when image transfer to plasticized soft vinyl chloride sheet is not observed at all, ○ when transfer of image is recognized over the entire image × As evaluated.
(b) The presence or absence of cracks in the printed material ○ When the crack is not recognized in the printed material, ○ when the crack is recognized in a part of the printed material (image), and when the crack is recognized throughout the printed material. XX was evaluated.

  The results are shown in Table 2.

表２から、溶解度パラメーターが１１以上、ガラス転移温度が７０℃以下であるメタクリル系共重合体（共重合体１〜３）を用いた保護層転写シートを使用することにより、印画物に優れた耐久性を付与できることが明らかである。

From Table 2, the use of a protective layer transfer sheet using a methacrylic copolymer (copolymers 1 to 3) having a solubility parameter of 11 or more and a glass transition temperature of 70 ° C. or less was excellent in printed matter. It is clear that durability can be imparted.

FIG. 1 is a cross-sectional view showing an example of the protective layer transfer sheet of the present invention. FIG. 2 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. FIG. 3 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. FIG. 4 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. FIG. 5 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention. FIG. 6 is a cross-sectional view showing another example of the protective layer transfer sheet of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Protective layer thermal transfer sheet 2 Base material sheet 3 Release layer 4 Plasticizer layer 5 Thermal adhesive resin layer 6 Back layer 7 Release layer 8 Thermal transfer resin layer 9 Hot melt colorant layer Y Thermal sublimation colorant layer M Thermal sublimation color material layer C Thermal sublimation color material layer

Claims (5)

In the protective layer transfer sheet in which the heat transferable resin layer is detachably provided on one side of the base sheet,
The thermal transfer resin layer is composed of at least a plasticizer layer and a thermal adhesive resin layer from the base sheet side,
The plasticizer layer is composed of an acrylic copolymer having a solubility parameter of 11 or more, a glass transition temperature of 50 to 70 ° C. , and containing at least two components of methyl methacrylate, methacrylamide and methacrylic acid. Protective layer transfer sheet.   The protective layer transfer sheet according to claim 1, wherein the thermal transfer resin layer comprises a release layer, a plasticizer layer, and a thermal adhesive resin layer from the base sheet side.   At least one color material layer selected from the group consisting of a heat-sublimable color material layer and a heat-meltable color material layer is provided in one surface of the base sheet in the surface order together with the heat transferable resin layer. The protective layer transfer sheet according to claim 1 or 2.   The protective layer transfer sheet according to any one of claims 1 to 3 and the printed material are superposed such that the thermal transfer resin layer of the transfer sheet and the image of the printed material are in contact with each other, and the thermal transfer is performed on the image of the printed material. Printed matter obtained by thermal transfer of the photosensitive resin layer.   The printed matter according to claim 4, wherein the image of the printed matter is one of an electrophotographic method, an inkjet recording method, and a thermal transfer recording method.

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