JP2008173980A - Transfer film for curved surface printing and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer film for curved surface printing capable of being obtained quickly and at a low cost so that a curved surface printing body capable of coping with requests of a small lot or multiple kinds in recent years. <P>SOLUTION: The transfer film for the curved surface printing, as given in Figure 1, is formed of laminating an image layer 3 constituting a pattern printed by an on-demanding system printing method on one surface of a substrate film 1 swelling in a specific solvent as given in Figure 1. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention mainly includes curved surfaces of various printed materials such as metal products, plastic molded products, and ceramic molded products (the “curved surface” in this specification includes not only non-planar portions such as curved surfaces but also flat portions. In addition, the present invention relates to a transfer film for curved surface printing for printing by a transfer method and a method for producing the same.

  Conventional methods for printing on various printed materials with curved surfaces include dry offset printing suitable for printing on simple shapes such as cones and boxes, flat shapes not suitable for this dry offset printing, etc. Screen printing suitable for printing that requires a thick ink layer, and further, using transfer paper consisting of a base material, a wax layer, a printing ink layer, and a thermoplastic resin layer, and making it adhere to the substrate Transfer printing that transfers the ink layer by heating from the substrate side, and the method of copying the ink from the intaglio to the silicone rubber pad and pressing it against the substrate (a type of offset printing) The pad printing etc. which are used also for precision goods, such as part marking, can be mentioned.

Among such printing methods on curved surfaces, a curling fit (special curved surface printing) can be mentioned as a printing method capable of attaching a picture (printing) to a substrate having a complicated shape. Printing on a curved surface by this curl fit is performed so that a transfer film having an image layer constituting a pattern activated by an activator on a support film made of a water-soluble or water-swellable film is the upper surface of the image layer. The printed material is floated on the water surface, and the printed material is pushed in from above, and the image layer of the transfer film is transferred to the outer peripheral surface of the printed material using water pressure (for example, Patent Document 1, 2).
Japanese Patent Publication No. 52-41683 JP 54-33115 A

  In the curl-fit printing process, a printing process for forming an image layer on a support film has been conventionally performed by gravure printing. However, in order to form an image layer for painting by gravure printing as described above, it is necessary to produce a printing plate, and there is a problem that it takes time, labor, and cost. Therefore, there is a problem that it is difficult to use a curved printed body in a short time and at a low cost, for example, when a prototype is created and evaluated at the development stage.

  On the other hand, on-demand printing capable of printing without using a printing plate has been attracting attention in the recent trend of small lots and various types, and various printed materials have been produced by on-demand printing such as the inkjet method and electrophotographic method. Have been made. However, there has never been an example in which such an on-demand printing method is incorporated in curved surface printing.

  In the curl-fit printing process, when an ink of a different type from the ink used in the conventional curl-fit is used, the ink or the like may not be fixed to the support film. Furthermore, when such a new type of ink or the like is printed on the support film as it is, there may be a problem that the support film swells. Furthermore, when such a new type of ink is used, the image layer formed with these inks may be washed away at the same time when the support film is finally transferred to the printing medium and removed. There is also a problem that there is. These problems are problems that may occur even when conventional inks are used when it is necessary to change a conventionally used water-soluble support film to another solvent-swellable film.

  Furthermore, when an ink of a different type from the ink used in such a conventional curl fit is used, there is a problem in adhesiveness when a transfer film printed with these inks is transferred to a printing medium. May occur. Further, when printing is attempted on a new material to be printed, there may be a problem in adhesion even when conventional ink is used.

  The present invention has been accomplished in view of the above-mentioned actual situation, and a curved surface obtained quickly and at low cost so that a curved printed body capable of meeting the demands of small lots and various types in recent years can be produced. The provision of a transfer film for printing, and the fixing property of these inks to a support film and the coverage of the transfer film on which these inks are printed, even under various circumstances such as when new types of inks are used, for example. The main object of the present invention is to provide a transfer film for curved surface printing which does not deteriorate the adhesiveness to the printed body.

  In order to achieve the above object, according to the present invention, in claim 1, an image layer constituting a picture printed by an on-demand printing method is laminated on one surface of a support film that swells in a predetermined solvent. A transfer film for curved surface printing is provided, and a process of preparing a support film that swells in a predetermined solvent according to claim 9, and a picture is formed on one surface of the support film by an on-demand printing method. A method for producing a transfer film for curved surface printing comprising at least a step of printing an image layer.

  In this way, by printing the image layer constituting the pattern on the support film by the on-demand printing method, it takes less time, labor, and cost to produce a printing plate than the conventional gravure printing method. Therefore, it is possible to obtain a curved surface transfer film quickly and at low cost, and by performing curved surface printing by curl fitting using this curved surface printing transfer film, it is possible to obtain a curved surface printed body quickly and at low cost. it can.

  Further, in the present invention, as described in claim 2, an intermediate layer is disposed on one surface of a support film that swells in a predetermined solvent, and an image layer constituting a pattern is disposed on the surface or inside of the intermediate layer. It is a transfer film for curved surface printing characterized by being formed.

  Thus, when the intermediate layer is formed, it is possible to fix any kind of ink by selecting the material of the intermediate layer, and from the solvent contained in the ink when printing. It is also possible to protect the support film. Furthermore, the image layer made of ink or the like can be protected in the cleaning / removal process of the support film after the transfer process.

  In the present invention, as described in claim 3, an image layer constituting a pattern is disposed on one surface of a support film that swells in a predetermined solvent, and an adhesive layer is disposed on the surface of the image layer. It is a transfer film for curved surface printing characterized by these. By forming a transfer film on the image layer in this way, for example, due to characteristics such as ink forming the image layer and the material of the curved surface printed body, even when the adhesion between the image layer and the curved surface printed body is poor, An image layer having a pattern can be bonded onto the curved printed body.

  In this case, as described in claim 4, it is also possible to provide both an intermediate layer and an adhesive layer.

  In the present invention, it is particularly preferable that the image layer constituting the pattern is a layer printed by an on-demand printing method (claims 5, 10, and 11). This is because, in particular, when an image layer is printed by an on-demand printing method, the image layer is often printed with an ink or the like different from the conventional one. Problems often occur. Therefore, it is particularly effective when the image layer is printed on-demand.

  In the present invention, the step of printing the image layer is to print the pattern by an ink jet method (Claim 6 and Claim 12) or to print the pattern by an electrophotographic method (Claim 7 and Claim 13). preferable. This is because it is preferable in terms of cost among the on-demand printing methods.

  In the curved surface printing transfer film of the present invention, as described in claim 8, the support film that swells in a predetermined solvent is preferably a water-soluble film. By using a water-soluble film as the support film in this way, water can be used as a predetermined solvent when performing curved surface printing by curl fitting, which is preferable in terms of cost and safety.

  Furthermore, as described in claim 14, the present invention includes (1) a step of preparing a transfer film for curved printing by the manufacturing method according to any one of claims 7 to 11, and (2) the image layer. A step of applying an active agent capable of swelling at least one of the intermediate layer and the adhesive layer to the surface on the image layer side of the transfer film for curved printing obtained in the previous step, and (3) an image of the transfer film for curved printing A step of floating on the predetermined solvent with the surface on which the layer is printed, and (4) lowering the curved printed body from above the transfer film for curved printing swollen in the solvent, A step of allowing the curved surface printing transfer film to spread and adhere to the surface of the curved printed body by the pressure of the solvent; (5) taking out the curved printed body from the solvent; Remove from washing A step for a method of manufacturing a curved printed body characterized by having a step of forming a protective layer on the curved surface printing material which is removed (6) support film.

  In this way, a curved surface printed body is produced without using a printing plate by producing a curved surface printed body using a curved surface printing transfer film having an image layer constituting a picture printed by the above-described on-demand printing method. Therefore, it is possible to produce a curved printed body quickly and at a low cost. Therefore, the curved surface printed body obtained by this manufacturing method as set forth in claim 15 can quickly respond to the customer's request, and can respond to the recent trend of many kinds and small lots. Have advantages.

  The present invention provides a transfer film for curved surface printing, wherein an image layer constituting a picture printed by an on-demand printing method is laminated on one surface of a support film that swells in a predetermined solvent. Is. Therefore, compared to the conventional gravure printing method, it is possible to obtain a curved surface printing transfer film quickly and at low cost because it does not take time, labor, and cost to produce a printing plate. By performing curved surface printing by curl fitting using a film, a curved surface printed body can be obtained quickly and quickly. Therefore, it is possible to respond flexibly to requests such as trial production of various curved surface printed materials, preparation of samples for presentations thereof, and launch of a variety of products in small quantities.

  Hereinafter, the curved surface printing transfer film of the present invention will be described in detail.

  The transfer film for curved surface printing of the present invention is characterized in that an image layer constituting a pattern printed by an on-demand printing method is laminated on one surface of a support film that swells in a predetermined solvent. In particular, it has a great feature in that the image layer constituting the pattern is printed by an on-demand printing method.

  As described above, by printing the image layer constituting the pattern by the on-demand printing method, the image layer constituting the pattern can be printed on the support film without producing a printing plate. Therefore, compared with the transfer film for curved surface printing printed by the gravure which requires the conventional printing plate, the transfer film for curved surface printing can be obtained at low cost and in a short time. Therefore, since the finally obtained curved printed body can be provided at low cost and in a short time, it can be used for prototypes and the like, and can sufficiently cope with the recent trend of many kinds and small lots. .

  The on-demand printing method used in the present invention means a printing method that can be performed without using a printing plate, and specifically includes, for example, an inkjet method, an electrophotographic method, a thermal melting type, or Examples of the printing method include a dye sublimation thermal transfer method, a magnetic head recording method, and a magnetography method for thermomagnetic recording. In the present invention, an ink jet method or an electrophotographic printing method is particularly preferable. This is because these methods are preferable in terms of cost.

  The support film used in the present invention is sufficiently swollen on the solvent and has multicolor printing suitability during the transfer on the solvent in the curl-fit printing step, and further has transferability, that is, the surface of the curved printed body. On the other hand, it is preferable that it has the property which is sufficiently confused. In the present invention, “swelling in a predetermined solvent” means having either a property of being dissolved in a predetermined solvent or swelling.

  Specific examples of such a support film include, for example, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyvinyl alcohol, polyacrylic acid amide, polyacrylic acid soda, polyvinyl methyl ether, and methyl vinyl ether. Mention of maleic anhydride copolymer, copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, or cellulose derivatives such as cellulose, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate, etc. These can be used alone or in combination.

  In the present invention, the above-mentioned predetermined solvent, that is, the solvent that floats and swells the transfer film in the curl fit is not particularly limited, but is preferably water from the viewpoint of cost and safety.

  When the predetermined solvent is water as described above, it is preferable to use a film that swells in water as the support film. Specifically, among the above-mentioned films, starch-based films, polyvinyl alcohol-based films, polyvinyl alcohol and starch are used. Or a film obtained by coating the above material on a liquid-permeable base such as paper, nonwoven fabric, and various porous films, or a laminated film.

  In the present invention, a film containing a polyvinyl alcohol resin as a main component is most preferable. This polyvinyl alcohol resin-based film has a mechanical strength required for on-demand printing by changing various conditions such as the degree of polymerization, the degree of saponification, and the addition of additives such as starch. It is possible to control the hygroscopicity during handling, the speed of softening due to water absorption after floating in water, the time required for spreading or spreading, the ease of deformation during transfer, and the like. An example of a preferable film mainly composed of polyvinyl alcohol (PVA) resin is composed of 80% by weight of PVA, 15% by weight of a high-molecular water-soluble resin, and 5% by weight of starch, and has an equilibrium water content of about 3%.

  The thickness of such a support film is preferably in the range of 10 to 100 μm, more preferably in the range of 20 to 60 μm.

  The transfer film for curved surface printing of the present invention is formed by laminating an image layer constituting a pattern on one surface of such a support film. Here, the pattern is not limited to those having design properties, and includes various patterns and solid coating.

  The ink or toner used in the image layer is not particularly limited as long as it is an ink or toner that can be applied to on-demand printing, but it is temporarily attached to the support film, and a dry film can be easily formed. Further, it is preferable that the vehicle contains a resin that adheres to the surface of the transfer body and easily swells with an activator described later.

  For example, in the case of an electrophotographic system, wet and dry toners are used. Here, the wet toner is basically one in which toner particles composed of a resin and a colorant are dispersed in a dispersion medium. Accordingly, when the support film is printed by an electrophotographic method using such a wet toner, the image layer is composed of toner particles composed of the resin and the colorant. Examples of resins used for such toner particles include styrene-butadiene copolymer resins, styrene-isoprene copolymer resins, styrene-acrylonitrile copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-acrylate copolymer resins, Ethylene-acrylic acid copolymer resin, ethylene-methacrylate copolymer resin, ethylene-ethyl acrylate copolymer resin, vinyl acetate-methyl methacrylate copolymer resin, acrylic acid-methyl methacrylate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, And acrylic resins such as 2-ethylhexyl acrylate / methacrylic acid copolymer, lauryl methacrylate / 2-hydroxyethyl methacrylate copolymer, 2-ethylhexyl methacrylate / diacetone acrylamide copolymer, etc. It can be used in the thermoplastic resin.

  Moreover, as a coloring agent, a well-known organic pigment or an inorganic pigment is used normally. Moreover, when the molecule | numerator of copolymer resin has a colored atomic group, copolymer resin itself or a colored atomic group can be utilized as a coloring agent. That is, the colorant may be an independent component, or the copolymer resin may function as a colorant.

  As the black colorant, for example, an inorganic colorant such as carbon black or iron trioxide or an organic colorant such as cyanine black can be used.

  As the yellow colorant, inorganic pigments such as chrome lead, cadmium yellow, yellow iron oxide, titanium yellow and ocher can be used. As the yellow colorant, the following hardly soluble metal salt (azo lake) can also be used. In other words, acetoacetyl allylide monoazo pigments such as Hansa Yellow G (CI No. pigment Yellow 1), Hansa Yellow 10G (CI No. pigment Yellow 3), Hansa Yellow RN (CI No. pigment Yellow 65), Hansa Brilliant Yellow 5GX (CI No. pigment Yellow 74), Hansa Brilliant Yellow 10GX (CI No. pigment Yellow 98), Permanent Yellow FGL (CI No. pigment Yellow 97), Shimura Lake Fast Yellow 6G (CI No. pigment Yellow 133), Rio Nord yellow K-2R (CI No. pigment Yellow 169); disazo yellow G (CI No. pigment Yellow 12), disazo yellow GR (CI No. pigment Yellow 13), disazo yellow 5G (CI No. pigment Yellow 14), Disazo Yellow 8G (CI No. pigment Yellow 17), Disua Yellow R (CI No. pigment Yellow 55), Permanent yellow HR (CI No. pigment Yellow 83); Condensed azo pigments, chromophthal yellow 3G (CI No. pigment Yellow 93), chromophthal yellow 6G (CI No. pigment Yellow 83) pigment yellow 94), chromophthal yellow GR (CI No. pigment Yellow 95); benzimidazolone monoazo pigments, Hosta Palm Yellow H3G (CI No. pigment Yellow 154), Hosta Palm Yellow H4G (CI No. pigment Yellow 151), Hosta Palm Yellow H2G (CI No. pigment Yellow 120), Hosta Palm Yellow H6G (CI No. pigment Yellow 175), Hosta Palm Yellow HLR (CI No. pigment Yellow 156); Irgadine Yellow 3RLTN (CI No. pigment Yellow 110), Irgadine Yellow 2RLT, Irgadine -2GLT (CI No. pigment Yellow 109), Fast Gen Super Yellow GROH (CI No. pigment Yellow 137), Fast Gen Super Yellow GRO (CI No. pigment Yellow 110), Sandrin Yellow 6GL (CI No. pigment Yellow 173) ) Etc. can be used.

  Examples of other yellow colorants include the following. That is, selenium pigments such as flavantron (CI No. pigment Yellow 24), anthramimidine (CI No. pigment Yellow 108), phthaloylamide type anthraquinone (CI No. pigment Yellow 123), heliofast yellow E3R (CI No. pigment Yellow 99); azo-based nickel complex pigment (CI No. pigment Green 10), nitroso-based nickel complex pigment (CI No. pigment Yellow 153), azomethine-based copper complex pigment (CI No. pigment) Yellow 117); a quinophthalone pigment such as phthalimidoquinophthalone pigment (CI No. pigment Yellow 138) can be used.

  As the magenta colorant, inorganic pigments such as cadmium red, bengara, silver vermilion, red lead, and antimony vermilion can be used. The following azo lake pigments can also be used as the magenta colorant. Specifically, Brilliant Carmine 6B (CI No. pigment Red 57: 1), Lake Red (CI No. pigment Red 53: 1), Permanent Red F5R (CI No. pigment Red 48), Resol Red (CI No. pigment Red 49) ), Persian orange (CI No. pigment Orange 17), Kurosei orange (CI No. pigment Orange 18), Helio Orange TD (CI No. pigment Orange 19), Pigment Scarlet (CI No. pigment Red 60: 1), Brilliant Scarlet G (CI No. pigment Red 64: 1), Helio Red RMT (CI No. pigment Red 51), Bordeaux 10B (CI No. pigment Red 63), Helio Bordeaux BL (CI No. pigment Red 54), etc. Can be used.

  As the magenta colorant, the following insoluble azo pigments (monoazo, disazo, and condensed azo) can also be used. That is, mono-azo or disazo pigments such as Para Red (CI No. pigment Red 1), Lake Red 4R (CI No. pigment Red 3), Permanent Orange (CI No. pigment Orange 5), Permanent Red FR2 (CI No. pigment Red 2), Permanent Red FRLL (CI No. pigment Red 9), Permanent Red FGR (CI No. pigment Red 112), Brilliant Carmine BS (CI No. pigment Red 114), Permanent Carmine FB (CI No. pigment Red 5), P.I. V. Carmin HR (CI No. pigment Red 150), Permanent Carmine FBB (CI No. pigment Red 146), Nova Palm Red F3RK-F5RK (CI No. pigment Red 170), Nova Palm Red HFG (CI No. pigment Orange 38) , Nova Palm Red HF4B (CI No. pigment Red 187), Nova Palm Orange HL. HL-70 (C.I. No. pigment Orange 36), P.I. V. Carmin HF4C (CI No. pigment Red 185), Hosta Balm Brown HFR (CI No. pigment Brown 25), Vulcan Orange (CI No. pigment Orange 16), Pyrazolone Orange (CI No. pigment Orange 13), Pyrazolone Red (CI No. pigment Red 38); chromophthal orange 4R (CI No. pigment Orange 31), chromophthal scarlet R (CI No. pigment Red 166), chromophthal red BR (CI No.) pigment Red 144) can be used.

  As the magenta colorant, the following condensed polycyclic pigments can also be used. That is, anthraquinone pigments such as pyranthrone orange (CI No. pigment Orange 40), anthanthrone orange (CI No. pigment Orange 168), dianthraquinonyl red (CI No. pigment Red 177); thioindigo pigments Thioindigo magenta (CI No. pigment Violet 38), thioindigo violet (CI No. pigment Violet 36), thioindigo red (CI No. pigment Red 88); perinone orange (CI No. pigment Violet 36); pigment Orange 43); perylene pigments such as perylene red (CI No. pigment Red 190), perylene vermilion (CI No. pigment Red 123), perylene maroon (CI No. pigment Red 179), perylene scarlet (CI No. pigment Red 149), perylene red (CI No. pigment Red 178); quinacridone red (CI) No. pigment Violet 19), quinacridone magenta (CI No. pigment Red 122), quinacridone maroon (CI No. pigment Red 206), quinacridone scarlet (CI No. pigment Red 207); pyrocholine pigments; red fluorvin pigments Can be used.

  As other magenta colorants, rhodamine 6G lake (C.I. No. pigment Red 81), which is a dyed lake pigment, can be used. The dyed lake pigment reacts with a water-soluble dye and a precipitant to form a lake and fix it.

  As the cyan colorant, inorganic pigments such as ultramarine blue, bitumen, cobalt blue and cerulean blue can be used. The following can be used as the cyan colorant. That is, phthalocyanine-based pigments such as Fast Genble-BB (CI No. pigment Blue 15), Sumiton Cyanine Blue HB (CI No. pigment Blue 15), Cyanine Blue 5020 (CI No. pigment Blue 15: 1) Monastral Blue FBR (CI No. pigment Blue 15: 2), Palomar Blue B-4810 (CI No. pigment Blue 15: 3), Monastral Blue FGX (CI No. pigment Blue 15: 4), Lionol Blue ES (CI No. pigment Blue 15: 6), Heliogen Blue L6700F (CI No. pigment Blue 15: 6), Sumika Print Cyanine Blue GN-O (CI No. pigment Blue 15), Heliogen Blue L7560 ( CI No. pigment Blue 16), Fast Sky Blue A-612 (CI No. pigment Blue 17), Cyanine Green GB (CI No. pigment Green 7), Cyanine Green S537-2Y CI No. pigment Green 36), Sumiton Fast Violet RL (CI No. pigment Violet 23); Indanthrone blue (PB-60P, PB-22, PB-21, PB-64), a selenium pigment; base Methyl violet / phosphorus / molybdic acid lake (PV-3), which is a reactive dye lake pigment, can be used.

  In addition, a bright pigment or a mat pigment can be used if necessary.

  Examples of the glitter pigment include (1) a so-called pearl pigment, more specifically, a scaly shape obtained by baking titanium oxide or iron oxide on the inner part of a shell, pulverized pearls, or mica fine particles. Foil pieces (titanium dioxide-coated mica), etc .; (2) Metal powder, more specifically, powders of aluminum, brass, bronze, gold, silver, etc., preferably 1-120 μm fine particles or scaly foil pieces (3) Deposition of vapor deposited plastic film, more specifically, silver powder obtained by vapor-depositing the above metal, usually aluminum, on polyethylene terephthalate film, transparent yellow after vapor deposition (4) Two or more types of resin layers having different refractive indexes, for example, a polyester resin layer and an acrylic resin layer, each having a thickness of several μm or less. Examples thereof include foil powder obtained by laminating a large number and finely cutting a composite film that produces an iris color due to light interference.

  Examples of the mat pigment include clay minerals such as kaolinite, halosite, muscovite, and talc, and synthetic achromatic pigments such as anhydrous silica, anhydrous alumina, calcium carbonate, magnesium carbonate, and barium carbonate.

  Such toner particles may contain additives such as a charge control agent, a dispersant, and a fixing agent as required.

  On the other hand, as the dry toner material, either a two-component toner or a one-component toner can be suitably used. Two-component toner and non-magnetic one-component toner are basically composed of binder resin, colorant, charge control agent and additive, and magnetic one-component toner contains magnetic powder such as iron and magnetite in addition to the above materials. . The binder resin needs to be selected in consideration of the charging property and heat fixing property of the toner. Main binder resins include polystyrene, hydrogenated styrene resin, styrene / isobutylene copolymer, styrene / butadiene copolymer, polystyrene resin such as styrene / butadiene / chlorinated paraffin copolymer; polymethyl methacrylate, polyethyl Acrylic resins such as methacrylate, polybutyl methacrylate, polyglycidyl methacrylate, methyl methacrylate / butyl methacrylate copolymer, ethyl methacrylate / acrylic acid copolymer; styrene / n-butyl methacrylate copolymer, styrene / diethylaminoethyl methacrylate copolymer Styrene / methyl methacrylate copolymer, styrene / glycidyl methacrylate copolymer, styrene / methyl methacrylate / n-butyl acrylate copolymer, styrene・ Methyl methacrylate / butyl acrylate / N-ethoxymethyl acrylamide copolymer, styrene / (meth) acryl such as styrene / n-butyl methacrylate / maleic anhydride copolymer, styrene / n-butyl methacrylate / acrylic acid copolymer Acid ester copolymer resin: polyester resin such as fumaric acid / etherified diphenol polyester; epoxy resin; polyurethane resin; silicone resin; butyral resin; low molecular weight polyethylene, ethylene / vinyl acetate copolymer, low molecular weight polypropylene Polyolefin resins such as: Polyamide resins; Polyvinyl alcohol resins; Fluorine resins such as polyvinylidene fluoride, terpene resins, imide resins, ketone resins, ethyl cellulose, rosin, alkyd resins It can be used.

  The charge control agent is used for positive charging, electron donating dye such as nigrosine dye, alkoxylated amine, quaternary ammonium salt, alkylamide, phosphorus and tungsten simple substance and compound, molybdate chelate pigment, fluorine based activator Hydrophobic silica or the like is used. On the other hand, for negative charging, electron accepting dyes such as metal complex salts of monoazo dyes, electron accepting organic complexes, chlorinated polyolefins, chlorinated polyesters, polyesters with excess acid groups, sulfonylamines of copper phthalocyanine, oil black, naphthenic acid Metal soap such as metal salt is used.

  As the colorant, the same material as the wet toner can be used. Other additives include cleaning agents (fatty acid metal salts, fluorosurfactants, silicon oxide derivatives, etc.), fluidizing agents (colloidal silica, silicon varnish, metal soap, nonionic surfactants, etc.), fillers (calcium carbonate) , Clay minerals, mica, etc.) are added to the toner as necessary.

  Next, when the image layer is formed by ink jet printing, the image layer is composed of ink used in the ink jet method. The ink used in such an ink jet system is largely classified into water-based and oil-based inks, and either one is selected according to the physical properties of the support film or an intermediate layer described later. In the water-based ink used in the present invention, the solvent is water alone or a mixed solvent of water and a water-soluble organic solvent. The water is preferably pure water or ultrapure water that has undergone a purification process such as ion exchange or distillation.

  The above water-soluble organic solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and other high-boiling low-volatility polyhydric alcohols. Used, or monoetherified products, dietherified products, esterified products thereof such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Others N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, tetrahydroph Water-soluble organic solvents such as nitrogen-containing organic solvents, such as nitrogen, monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, NNbutyldiethanolamine, triisopropanolamine, and triethanolamine. It can be added within a range where no printing flow or bleeding occurs.

  In addition, for the purpose of improving dryability and permeability with respect to water as the main solvent, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol, etc. Volatile monohydric alcohols can be added.

  On the other hand, the oil-based ink is preferably based on a solvent having a high boiling point in order to prevent clogging of the head. High boiling point solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and other high-boiling low-volatility polyhydric alcohols Monoetherified products, dietherified products, esterified products such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin; Paraffin hydrocarbons such as G and Isopar H: Petroleum naphtha solvents such as Shellsol manufactured by Shell Sekiyu; Naphthenic hydrocarbons And the like aromatic hydrocarbons.

  In the case where quick drying is important, more volatile solvents, for example, alkyl alcohols such as ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; Esters such as ethyl acetate; amides such as dimethylformamide and dimethylacetamide; ethers such as dioxane and tetrahydrofuran can be mixed with the above solvents or used alone.

  Known colorants and dyes are widely used as colorants used in ink jet inks. As the pigment, those described as the colorant of the wet toner can be similarly used. As the dye, water-soluble direct dyes, acid dyes, basic dyes, food dyes, reactive dyes, water-insoluble oil-soluble dyes, and disperse dyes can be used in a form dispersed or dissolved in a solvent.

  As water-soluble dyes mainly used in water-based inks, for example, the following dyes indicated by a color index are used.

  C. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254, 289 , C.I. I. Acid Blue 9, 29, 45, 92, 249, C.I. I. Acid Black 1, 2, 7, 24, 26, 94, C.I. I. Food Yellow 3, 4, C.I. I. Food Red 7, 9, 14, C.I. I. Food Black 2, C.I. I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 142, 144, 86, C.I. I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227, C.I. I. Direct Orange 26, 29, 62, 102, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202, C.I. I. Direct plaques 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, C.I. I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 65, 67, 70, 73, 77, 87, 91, C.I. I. Basic Red 1, 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 14, 109, 112, C.I. I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155, C.I. I. Basic black 2,8.

  Examples of water-insoluble dyes include diarylmethane, triarylmethane, thiazole, methine, azomethine, xanthine, oxazine, azo and azo derivatives, anthraquinone derivatives, quinophthalone derivatives, spirodipyrans, Isodolinosviropyran and fluoran dyes are preferably used. For example, C. I. Disperse yellow 51, 3, 54, 79, 60, 23, 7, 141, C.I. I. Day Sparse Blue 24, 56, 14, 301, 334, 165, 19, 72, 87, 287, 154, 26, 359, C.I. I. Disperse thread 135, 146, 59, 1, 73, 60, 167, C.I. I. Disperse violet 4, 13, 26, 36, 56, 31, C.I. I. Solvent Violet 13, C.I. I. Solvent Black 3, C.I. I. Solvent Green 3, C.I. I. Solvent Yellow 66, 14, 16, 29, 105, C.I. I. Solvent Blue 70, 35, 63, 36, 50, 49, 111, 105, 97, 11, C.I. I. Solvent red 135, 81, 18, 25, 19, 23, 24, 143, 146, 182 and the like.

  Further, in order to improve dispersibility and fixability, resins that are soluble or insoluble in a solvent can be contained. Examples of such resins include polyvinyl alcohols: polyvinyl pyrrolidone; ethylene resins such as ethylene / vinyl acetate copolymers; acrylic resins such as polyacrylic acid and acrylic acid / acrylonitrile copolymers; vinyl acetate / acrylate esters Polymers, vinyl acetate copolymer resins such as vinyl acetate / fatty acid vinyl ethylene copolymer; proteins; natural rubbers; glucosides; cellulose derivatives; polyamide resins; rosin and rosin esters; Resins; alkyd resins; styrene resins; melamine resins and the like.

  Other nonionic surfactants such as polyoxyethylene compound fatty acid ester type and polyethylene oxide condensation type, higher fatty acid salts, higher alkyl dicarboxylates, higher alcohol sulfates, higher alkyl sulfonates, condensation of higher fatty acids and amino acids Products, anionic surfactants such as sulfosuccinic acid ester salts and naphthenic acid salts, cationic surfactants such as fatty acid amine salts, quaternary ammonium salts, sulfonium salts and phosphonium salts, and amphoteric surfactants such as betaine type An activator; an antiseptic; an antifungal agent; a pH adjuster; an antifoaming agent; an ultraviolet absorber; a viscosity adjuster: a surface tension adjuster and the like may be added as necessary.

  Ordinary inkjet inks cannot contain a large amount of binder resin due to their low appropriate viscosity. Therefore, the ink layer formed in an image shape often disappears without being retained in the course of the transfer process in the present invention. This problem can be solved by providing an intermediate layer for fixing the ink layer on the support film as described later. However, as a method for fixing without providing the intermediate layer, the colorant particles in the ink are wrapped with a resin. It is effective to granulate with. According to this method, the colorant itself can be provided with fixing ability without greatly increasing the ink viscosity. The resin for this purpose is a copolymer of at least two types of monomers A and B, and the sp value of each monomer and ing composition is:

の関係を満たすように選択される。例えば水性インクに用いる顔料粒子を造粒樹脂で被覆する方法は、以下の通りである。
１．顔料分散工程
造粒樹脂が可溶で、かつ水との相溶性がある有機溶媒中に造粒樹脂を溶解させ、さらに、顔料を添加する。この液をビーズミル、ボールミル、ハイスビードディスパーザー等で数時問処理し、顔料を粉砕する。
２．溶媒置換工程
上記の分散液を水と混合する。添加時の凝集を防ぐために超音波ホモジナイザー等による分散を行う。
３．有機溶媒除去工程
上記の分散液からロータリーエバポレーター等により顔料分散に用いた有機溶媒を除去する。有機溶媒の減少につれて造粒樹脂の疎水性モノマーに起因する部位は疎水性の着色剤表面に析出し、着色剤を被覆する。同時に造粒樹脂の親水性モノマーに起因する部位は水に膨潤し、被覆した着色剤粒子を分散安定化する。
４．後分散工程
超音波ホモジナイザー等で後分散し、粒径を均一化する。

Selected to satisfy the relationship. For example, a method of coating pigment particles used in water-based ink with a granulating resin is as follows.
1. Pigment dispersing step The granulating resin is dissolved in an organic solvent in which the granulating resin is soluble and compatible with water, and a pigment is further added. This liquid is treated for several hours with a bead mill, ball mill, high speed bead disperser or the like, and the pigment is pulverized.
2. Solvent replacement step The above dispersion is mixed with water. In order to prevent aggregation at the time of addition, dispersion with an ultrasonic homogenizer or the like is performed.
3. Organic solvent removal step The organic solvent used for pigment dispersion is removed from the above dispersion by a rotary evaporator or the like. As the organic solvent decreases, the portion of the granulated resin due to the hydrophobic monomer is deposited on the surface of the hydrophobic colorant and coats the colorant. At the same time, the part resulting from the hydrophilic monomer of the granulated resin swells in water, and the coated colorant particles are dispersed and stabilized.
4). Post-dispersing step After-dispersing with an ultrasonic homogenizer or the like, the particle size is made uniform.

  In this case, the granulated resin is obtained by copolymerization of one or more types of hydrophilic monomers and one or more types of hydrophobic monomers. Those which are soluble in organic solvents and insoluble or hardly soluble in water are preferred.

  Examples of the hydrophilic monomer used include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and salts thereof.

  Further, examples include vinyl alcohol, ethylene glycol, vinyl pyrrolidone, acrylamide, methacrylamide, and monomers having a salt of a cationic functional group such as quaternary ammonium or amino group.

  The hydrophobic monomer is not particularly limited. Those that dissolve well in the organic solvent are preferred. A solubility parameter value (hereinafter referred to as SP value) is used as the solubility index.

  In general, the SP value is known to show compatibility and incompatibility between substances, but taking the relationship between the resin and its solvent as an example, the SP value indicates the degree of solubility of the resin in that solvent. If the difference between the SP values of the two is small, the solubility of the resin in the solvent is large. If the difference is large, the solubility is small and the resin becomes insoluble.

  For example, when tetrahydrofuran is used as the organic solvent, a preferable hydrophobic monomer is such that the SP value of the homopolymer of the hydrophobic monomer is close to the SP value (9.1) of tetrahydrofuran. Such homopolymers include, for example, polyethyl methacrylate (9.1), polypropyl methacrylate (9.0), polyethyl acrylate (9.2), polymethyl methacrylate (9.3), Examples include polypropyl acrylate (9.0), polystyrene (9.1), and polyvinyl acetate (9.4).

  In addition, so-called hot melt inks and UV curable inks can also be used to form a good image on a support film with poor solvent absorption.

  Hot melt inks are solid or high-viscosity liquids at normal temperatures, but are melted and reduced in viscosity by heating during recording. Solvents therefor include paraffin wax, carnapa wax, candelilla wax, wood wax, beeswax, lanolin, whale wax, paraffin Fuchs derivatives, microcrystalline wax, Fischer-Tropsch wax, α-olefin maleic anhydride copolymer wax, etc. And other fatty acids such as stearic acid, myristic acid and palmitic acid; higher alcohols such as nutaryl alcohol and polypinyl ether; polyhydric alcohol fatty acid esters such as sorbitan monostearate; polyolefin Resins; Epoxy resins; Polyamide resins; Polyester resins; Urethane resins.

  On the other hand, the UV curable ink contains a prepolymer, a monomer, a photoinitiator, and a colorant as main components. As the prepolymer, any of prepolymers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, polyol acrylate, and silicon acrylate can be used without any particular limitation.

  Monomers include vinyl monomers such as styrene and vinyl acetate; monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate; diethylene glycol diacrylate, 1,6-hexanediol diacrylate, hydroxypiperic acid ester neopentyl glycol diacrylate Polyfunctional acrylic monomers such as trimethylolpropane triacrylate and dipentaerystol hexaacrylate can be used. The prepolymer and the monomer may be used alone or in combination of two or more.

  Photopolymerization initiators are isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, 1-phenyl-1,2-propadion-2-oxime, 2,2-dimethoxy-2-phenylacetophenone, benzyl, hydroxy Cyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methylthioxanthone, chlorine-substituted benzophenone, halogen-substituted alkyl -From among allyl ketones, etc., those which can obtain desired curing characteristics and recording characteristics are selected and used.

  In addition, photoinitiators such as aliphatic amines and aromatic amines; and photosensitizers such as Chi Xanson may be added as necessary.

  On the other hand, when the image layer is printed by the thermal transfer method, the image layer is made of ink used for the thermal transfer method. Ink materials used in such a thermal transfer method can be divided into materials used for thermal melt transfer and materials used for thermal sublimation transfer.

  First, an ink ribbon used for heat-melt transfer includes an ink layer, a base film, and a heat-resistant (sliding) layer. The ink layer is basically composed of various additives such as a colorant, a wax / mature plastic resin binder, a softener, a dispersant, etc., but its heat melting property is almost due to the binder occupying 60 to 80% of the ink component. It is determined. The thermoplastic resin binder used is polyester resin; polyolefin resin such as polyethylene or polypropylene; ethylene copolymer resin such as ethylene / vinyl acetate copolymer or ethylene / ethyl acrylate copolymer; vinyl chloride resin; methyl methacrylate (Meth) acrylic resins such as a combination of acrylic acid and acrylic acid; polyamides; ketone resins; various cellulose derivatives; polyurethanes; polystyrene resins; polyacetal resins; epoxy resins;

  Also, animal waxes such as beeswax and whale wax for the purpose of lowering the melting temperature; plant waxes such as carnauba wax, candelilla wax and wax wax; petroleum waxes such as paraffin wax and microcrystalline wax; Fischer-Tropsch Synthetic hydrocarbons such as wax and low molecular weight polyethylene; wax compounds such as n-paraffins having 21 or more carbon atoms can also be used. As the colorant, the same material as the wet toner can be used.

  The ink ribbon used for thermal sublimation transfer is a base film coated with an ink thin film mixed with a binder with a large thermal diffusivity in the binder. Like the thermal fusion transfer, the ink ribbon, base film, and heat-resistant (sliding) layer are used. Composed.

  As the dye, a disperse dye, an oil-soluble dye, or a basic dye is preferably used. These dyes have a molecular weight of about 150 to 550, and are selected in consideration of sublimation or melting temperature, hue, light resistance, resin, solubility in a developer, and the like. For example, diarylmethane, triarylmethane, thiazole, methine, azomethine, xanthine, oxazine, azo and azo derivatives, anthraquinone derivatives, quinophthalone derivatives, spirodipyran, indolinospiropyran, fluorane, rhodamine Lactam dyes are preferably used. For example, CI indicated by the color index: Disper Yellow 51, 3, 54, 79, 60, 23, 7, 141; CI Disperse Blue 24, 56, 14, 301, 334, 165, 19, 72, 87, 287, CI: Disperse Thread 135, 146, 59, 1, 73, 60, 167; CI: Disperse Violet 4, 13, 26, 36, 56, 31; CI: Solvent Violet 13; CI: Solvent CI: Solvent Green 3; CI: Solvent Yellow 56, 14, 16, 29, 105; CI: Solvent Blue 70, 35, 63, 36, 50, 49, 111, 105, 97, 11; CI: Solvent Red 135, 81, 18, 25, 19, 23, 24, 143, 146, 18 And the like.

  Other examples include 3,3-diethyloxacyanine iodide, Astrazone Pink FG (CI: 48015 manufactured by Bayer), 2,2-carbocyanine (CI: 808), Astraphyloxin FF (CI: 1) 48070), Astrazone Yellow 70LL (CI: Basic Yellow 21), Eisencarotene Yellow 3GLH (Hodogaya Chemical Co., C1: 48055), Eisencarotene Red 6BH (CI: 48020), etc., monomethine, dimethine or trimethine Methine (cyanine) basic dyes such as diphenylmethane basic dyes such as auramine (CI: 655), malachite green (Cl: 42000), brilliant green (CI: 42040), magenta (CI: 42510), methyl violet C1: 42535), Crystal Violet (C1: 42555), Methyl Green (CI: 684), Victorian Blue B (CI: 44045) and other triphenyllemethane basic dyes, pyronin G (C1: 739), rotamine Xanthene basic dyes such as B (Cl: 45170), rotamine 6G (C1: 45160), acridine yellow G (CI: 785), Leonin AL (CI: 46075), benzoflavin (CI: 791), affine (C1) : 46045) and other basic dyes, neutral red (CI: 50040), astrazone blue BGE / X125% (CI: 51005), quinone imine basic dyes such as methylene blue (CI: 52015), and other quaternary Anthraquinone bases with amines And basic dyes such as ionic dyes. These dyes can be used as they are or in the form in which these dyes are treated with alkali, and counterion exchangers or leuco bodies of these dyes can also be used. In the case of using a leuco dye or the like that is normally colorless or light in color, a developer may be included on the image forming film side.

  Further, these disperse dyes are not used alone, but are used even when two or more kinds are mixed. In particular, when mixed and melted, the thermal behavior differs greatly depending on what kind of mixture the two form, and the vapor pressure also varies with the composition ratio. When it occurs, the activation energy is small and the sublimation sensitivity can be improved.

  As the binder resin, a resin having suitable heat resistance and dye transferability is selected from vinyl chloride resin, polyamide, polycarbonate, polystyrene, acrylic resin, phenol resin, polyester, epoxy resin, polyacetal resin, cellulose resin, and the like.

  Finally, the magnetic toner used in the magnetography method is composed of a thermoplastic resin, a magnetic material, and a color pigment, and the same thermoplastic resin and color pigment as those for the dry toner for electrophotography can be used. In addition, a conductivity imparting agent such as tin oxide; a lubricant such as polytetrafluoroethylene; a wax; a magnetic aggregation inhibitor and the like are added as necessary.

Fe ₃ 0 ₄ , γ-Fe ₂ O ₃ , various ferrites, iron powders, etc. are mainly used as magnetic materials, but the magnetic properties differ depending on the particle shape even with the same composition. Select particles.

  Next, a curved surface printing transfer film provided with an intermediate layer which is a different aspect of the present invention will be described. This is a curved surface printing transfer film characterized in that an intermediate layer is provided between the support film and the image layer.

  This intermediate layer is provided to fix and fix the image layer on the support film when the image layer is directly printed on the support film, when the image is not fixed or fixed on the support film. It is provided to prevent the support film from swelling or the like due to the solvent contained in the ink or toner when the image layer is printed on the support film. As will be described later, the intermediate layer of the present invention is used when the image layer is not resistant to the solvent used when removing the support film after adhering the curved surface printing transfer film to the curved surface printing body. It may be provided for protection.

  The curved surface printing transfer film provided with such an intermediate layer is not limited to the printing method in which the image layer is formed, but is particularly effective when the image layer is formed by on-demand printing. . This is because the ink or toner used in the on-demand system is highly likely to cause the above-described problems such as fixability on the support film. However, the present invention is not limited to those printed on-demand. For example, when the curl-fit transfer process currently performed with water needs to be performed with another solvent, the type of the support film is changed. In such a case, the intermediate layer may be required even for the ink used in current gravure printing.

  In the present invention, the intermediate layer is not limited to one layer, and two or more layers may be provided. In this case, one layer is intended to fix the ink, the other layer is provided to prevent swelling of the support film due to printing, and to protect the image film in the cleaning and removal process of the support film after transfer, etc. May be provided for different purposes.

  In view of the above, such an intermediate layer must have either a property capable of fixing the ink, toner or colorant used for image recording on the surface or inside thereof, or a property insoluble in a predetermined solvent. is there. Furthermore, it is preferable to have a swelling property with respect to an activator, which will be described later, and an adhesive property with respect to a curved printed body.

  The intermediate layer provided in the present invention contains a resin as a main component, and various additives are mixed as necessary. Examples of the resin used for the intermediate layer include celluloses such as ethyl cellulose, nitrocellulose, cellulose acetate, and hydroxyethyl cellulose and derivatives thereof; alkyd resins; polymethacrylic acid, polymethyl methacrylate, 2-ethylhexyl methacrylate / methacrylic acid copolymer, lauryl (Meth) acrylic resins such as methacrylate / 2-hydroxyethyl methacrylate copolymers and metal salts thereof; poly (meth) acrylamide resins such as poly N-isopropylacrylamide and poly N, N-dimethylacrylamide; polystyrene, acrylonitrile / styrene Styrene resins such as polymers, styrene / maleic acid copolymers, styrene / isoprene copolymers; styrenes such as styrene / n-butyl methacrylate copolymers Acrylic resins; Saturated and unsaturated polyester resins; Polyolefin resins such as polypropylene; Halogenated polymers such as polyvinyl chloride and polyvinylidene chloride; Vinyl resins such as polyvinyl acetate and vinyl chloride / vinyl acetate copolymers; Polycarbonate resin; Epoxy resin; Polyurethane resin; Polyacetal resin such as polyvinyl formal, polyvinyl butyral and polyvinyl acetal; Polyethylene resin such as ethylene / vinyl acetate copolymer and ethylene / ethyl acrylate copolymer resin; Amide resin such as benzoguanamine Urea resin; melamine resin; polyvinyl alcohol resin and its anionic cation modification; polyvinyl pyrrolidone and copolymer thereof; polyethylene oxide, carboxylated polyethylene oxide, etc. Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyether polyols; SBR, NBR latex; dextrin; sodium alginate; gelatin and its derivatives, casein, trooaoi, tragacanth gum Natural or semi-synthetic resins such as pullulan, gum arabic, locust bean gum, guar gum, pectin, carrageenin, glue, albumin, various starches, corn starch, konjac, fungi, agar, soy protein; terbene resin; ketone resin; Rosin ester; polyvinyl methyl ether, polyethyleneimine, polystyrene sulfonic acid, polyvinyl sulfonic acid and the like can be used. These resins may be used not only as a homopolymer but also blended within a compatible range.

  Furthermore, in order to improve the absorbability and fixability of the ink, toner or colorant, an appropriate gap can be provided in the intermediate layer. In order to provide a void, a filler is mixed into the intermediate layer. Examples of the filler used include silica; alumina; kaolinite; smectite clay minerals such as bentonite and organic bentonite and derivatives thereof: talc; calcium carbonate; magnesium carbonate; calcium sulfate; barium sulfate; zeolite; Magnesium oxide; Zirconium oxide; Sodium silicate; Calcium silicate; Potassium silicate; Magnesium silicate; Aluminum silicate; Diatomaceous earth; Zinc sulfide; Zinc hydroxide; Zinc carbonate; Zinc oxide; Light; Hydrotalcite; Pseudoboehmite; Inorganic pigments such as litbon and carbon resin pigments; Polystyrene resins; Urea resins; Benzoquaminamine plastic pigments; Melamine resins; Silicon resins; And organic pigments such as polyvinylidene chloride; polyester resins; fluorine resin; polyacrylic resins; polyacrylamide-based resin; polypropylene; poly (vinyl chloride).

  Which of the above materials is selected and what kind of intermediate layer is to be configured must be designed according to the type of on-demand method used for image formation.

  The intermediate layer for printing using the heat-sensitive sublimation transfer method must accept the dye transferred from the ink ribbon when heated and maintain the formed image. Furthermore, in order to prevent these intermediate layer resins from being fused to the ink ribbon by heat during image formation, phosphoric acid esters, surfactants, fluorine compounds, fluorine resins, silicone inclusions, silicone oils, silicone resins It is preferable to internally add various release agents such as the above to the intermediate layer.

  On the other hand, the intermediate layer suitable for the ink jet system is composed of a resin having a high affinity for ink or a resin having a high affinity for ink and a filler in order to have a high ink absorbability. The filler can be contained in a range of 10 to 80% with respect to the entire intermediate layer, but in order to have an appropriate ink absorbability and retain an image at the time of swelling, the content is made 15 to 60%. More preferred.

Means for forming such an intermediate layer on the support film is not particularly limited, and examples thereof include gravure coating, offset gravure, roll coating, bar coating, spray coating, and ultrasonic coating. It can be formed by dissolving a forming material such as the above-described resin in an appropriate solvent. The thickness of such an intermediate layer varies greatly depending on the type of material used for the intermediate layer, but is preferably in the range of ^{2 to} 30 g / m ² .

  Furthermore, as another aspect of the present invention, a curved surface printing transfer film in which an adhesive layer is provided on an image layer can be exemplified. When transferring the transfer film for curved surface printing to the curved surface printed body by curl fitting, depending on the type of ink or the like constituting the image layer, the adhesion to the curved surface printed body may be poor. In such a case, by providing an adhesive layer on the image layer, it is possible to maintain good adhesion to the curved printed body.

  Also in this invention, the printing method of the image layer of the transfer film for curved surface printing on which the adhesive layer is formed is not particularly limited. However, when there is no vehicle binder resin in the image layer when the image layer is formed by an inkjet method, for example, there are many inks used for on-demand printing that have problems with adhesiveness. This is particularly effective when the image layer is formed by demand printing. This adhesive layer may have not only the property of improving the adhesion to the above-mentioned curved printed body but also the property of improving the ink fixing property of the image layer, for example.

  Such an adhesive layer is composed of one or more kinds of resin materials that swell in a specific solvent and exhibit adhesiveness to a curved printed body. Examples of such resins include cellulose derivatives such as ethyl cellulose, nitrocellulose and cellulose acetate; pure frame or modified alkyd resins such as fatty acid-modified phthalic acid alkyd and maleic acid alkyd; polymethacrylic acid, polymethyl methacrylate, (Meth) acrylic resins such as 2-ethylhexyl methacrylate / methyl methacrylate copolymer, lauryl methacrylate / N, N-dimethylacrylamide copolymer; styrene / n-butyl methacrylate copolymer, polyvinyltoluene, styrene / isoprene copolymer Polystyrene resin such as styrene resin such as polyester resin, epoxy resin, polyurethane resin, polyacetal resin, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer resin, etc. ; Amide resin; can be used rosin, and rosin esters, polyvinyl alcohol resins; gelatin, casein, starch, natural or semi-synthetic resin such as soybean protein; terpene resins; ketone resin. When used in combination with the intermediate layer, it is preferable to select one that can swell in the same solvent as the intermediate layer resin.

Means for forming such an adhesive layer on the image layer is not particularly limited, and examples thereof include gravure coating, offset gravure, roll coating, bar coating, spray coating, and ultrasonic coating. it can. In forming the adhesive layer, the above resin or the like may be dissolved in an appropriate solvent. Further, the thickness of the adhesive layer varies depending on the type of material of the adhesive layer, but is preferably in the range of ^{2 to} 30 g / m ² .

  Next, a method for producing the above-described curved surface printing transfer film will be described.

  The method for producing a transfer film for curved printing according to the present invention comprises at least a step of preparing a support film that swells in a predetermined solvent and a step of printing a pattern on one surface of the support film by an on-demand printing method. It is.

  Since the support film that swells in the predetermined solvent is as described above, the description of the process of preparing the support film is omitted. Hereinafter, a process of printing an image layer constituting a pattern on the support film by an on-demand printing method will be described by taking an inkjet method as an example.

  FIG. 1 illustrates the process of forming an image layer on a support film by an inkjet method. First, as shown to Fig.1 (a), the support film 1 is prepared. Next, as shown in FIG. 1B, printing is performed on the support film 1 with the ink A using the ink jet printer 2. FIG. 1 (c) shows a state where printing is performed and drying is performed. An image layer 3 constituting a pattern is provided on a support film 1, thereby forming a curved surface printing transfer film 4. Here, when there is no or insufficient adhesion between the image layer 3 and the curved surface printed body described later, such as the binder resin not mixed with the ink constituting the image layer 3, FIG. As shown in d), the adhesive layer 5 may be provided on the image layer 3, and this may be used as the curved surface printing transfer film 4.

  The transfer film 4 for curved surface printing thus formed is coated with an activator 6 described later (FIGS. 1 (e) and (f)) and sent to a transfer process by curl fitting.

  FIG. 2 shows a process for manufacturing a transfer film for curved surface printing by forming an image layer by an ink jet method as in FIG. 1. In this example, an intermediate layer for fixing and fixing the image layer is shown. It differs in that it is formed.

  FIG. 2A shows a state in which the intermediate layer 7 is provided on the support film 1. In the support film 1 provided with the intermediate layer 7 as described above, an image layer is printed on the intermediate layer 7 side using the ink A by the ink jet printer 2 as shown in FIG. The curved surface printing transfer film 4 in a dried state after printing is shown in FIGS. FIG. 2 (c) shows a state where the ink penetrates only into the intermediate layer 7, and FIG. 2 (d) shows a state where the ink penetrates through the intermediate layer 7 to the support film 1. Show. Further, when the image layer 3 has no or weak adhesion to the printed surface, the adhesive layer 5 is formed on the image layer 3 as shown in FIG. It is good.

  Similarly to the case of FIG. 1, the transfer film 4 for curved surface printing thus formed is coated with an activator 6 described later (FIGS. 2 (f) and (g)), and sent to the transfer process by curl fitting. It is done.

  Next, an example of producing a transfer film for curved surface printing by printing an image layer by an electrophotographic method will be described with reference to FIG. First, a support film 1 is prepared as shown in FIG. Next, an electrostatic latent image on the photoconductor 10 formed by a laser 13 using an electrophotographic printer 12 including a toner tank 8, a developer 9, a photoconductor 10 and an impression cylinder 11 as shown in FIG. The toner B attached according to the image is printed on the support film 1. In this way, the curved surface printing transfer film 4 having the image layer 3 formed on the support film 1 as shown in FIG. 3C is formed. Also in this example, as shown in FIG. 3D, the activator 6 is applied onto the image layer 3 and sent to the transfer process by curl fitting.

  As described above, the method for producing a transfer film for curved surface printing according to the present invention includes at least a step of preparing a support film and a step of printing an image layer constituting a pattern on one surface of the support film by an on-demand printing method. However, if necessary, an intermediate layer may be formed between the support film and the image layer, and an adhesive layer may be formed on the image layer as necessary.

  Next, a method for producing a curved surface printing body using the above-described curved surface printing transfer film will be described.

  In the method for producing a curved printed body of the present invention, as shown in FIGS. 1 (e) and (f), FIGS. 2 (f) and (g), and FIG. 3 (d), a curved surface printing transfer film 4 was prepared. Thereafter, the activator 6 is first applied to the image layer 3 side of the transfer film 4 for curved surface printing. Here, when the adhesive layer 5 is formed on the image layer 3, the activator 6 is applied on the adhesive layer 5.

  The activator is applied in this way unless the activator is applied to swell the image layer or the like, and then the curved print transfer film is floated on the solvent to swell, and then the curved printed body is formed. This is because the curved surface printing transfer film cannot be brought into close contact with the surface of the curved surface printing body when it is pressed from above and transferred to the curved surface printing transfer film, and the transfer is not successful. Such an activator is not limited as long as it can swell at least one of the image layer, the intermediate layer, and the adhesive layer, does not dissolve the ink of the image layer, does not evaporate until transfer is performed, When the surface of the curved printed body is eroded, or when the curved printed body is undercoated with a paint, it is desirable that the paint is not rapidly dissolved during transfer in contact with the paint. In some cases, for example, when the transfer is performed by floating the transfer film for curved printing on a solvent before the image layer is completely dried, the application step of the activator may not be necessary.

  Examples of such activators include, for example, pentane, hexane, heptane, octane, etc., or mixed hydrocarbons such as gasoline, petroleum, benzine, mineral spirits, petroleum hydrocarbons such as petroleum naphtha, benzene, toluene, Aromatic hydrocarbons such as xylene, cyclohexane, ethylbenzene, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chloroform, carbon tetrachloride, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, benzyl alcohol Monohydric alcohols such as ethylene glycol, propylene glycol, glycerin and other polyhydric alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, isophor Ketones such as ethyl ether, isopropyl ether, ethylene glycol, mono-methyl ether, ethylene glycol, mono-ethyl ether, diethylene glycol and other ethers, acetate esters, butyric acid esters, nitro hydrocarbons, Nitriles, amines, other acetals, acids, furans and the like can be mentioned, and these are used alone or as a mixed solvent.

  Moreover, what added resin which has affinity with a solvent to such a solvent can be used as an activator. Examples of such resins include vinyl halide monomers such as vinyl chloride and vinylidene chloride, styrene and derivatives thereof, vinyl ester monomers such as vinyl acetate, allyl alcohol and allyl esters, acrylic acid, methacrylic acid, N-unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid or fumaric acid, ester derivatives of the above unsaturated carboxylic acids, nitrile derivatives or acid amide derivatives thereof, acid amide derivatives of the above unsaturated carboxylic acids Methylol derivatives and N-alkylmethylol ether derivatives, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl-acrylate, 2-hydroxyethyl-methacrylate 2-hydroxypropyl-acrylate, 2-hydroxypropyl-methacrylate, ethylene glycol-monoacrylate, ethylene glycol-monomethacrylate, ethylene glycol-diacrylate, ethylene glycol-dimethacrylate, maleic anhydride, itaconic anhydride, methyl vinyl ketone , Thermoplastic resins such as homopolymers or copolymers of monomers such as butadiene ethylene, propylene, dimethylaminoethyl methacrylate, vinyl pyridine, tert-butylaminoethyl methacrylate, monoallyl ether of polyhydric alcohol, polyamides Thermosetting resins such as resin, polyester resin, phenol resin, melamine resin, urea resin, epoxy resin, diallyl phthalate resin, silicon resin, polyurethane resin Or it can be given their modified resins or precondensates, natural resins, rosins and derivatives thereof, cellulose derivatives, natural or synthetic rubber, a petroleum resin or the like.

  These resins are preferably added to the above solvent as an activator for reasons such as easy viscosity adjustment, no application method, long ink retention time, long transfer time, etc. The amount is preferably in the range of 5 to 60% by weight.

Preferred examples of such an activator composition are shown below, but the composition of this activator is designed according to the material to be swollen, and the activator of the present invention is not limited thereto. .
(Activator composition example 1)
-Xylene: 5-10 parts by weight-Ethylene glycol monobutyl ether: 20-30 parts by weight-Butyl carbitol acetate: 30-40 parts by weight-Phthalate ester (DBP): 20-30 parts-Cellulose acetate butyrate (CAB) : 0.9 parts by weight-Ethyl acetate: 1 to 5 parts by weight (Activator composition example 2)
-Alkyd resin: 15 parts by weight-Nitrocellulose: 2 parts by weight-Barium bicarbonate: 30 parts by weight-Phthalate ester (DBP): 35 parts by weight-Ethylene glycol monobutyl ether: 14 parts by weight-Butyl cellosolve acetate: 52 parts by weight- Maleic acid: small amount As a means for applying such an activator, gravure coating, offset gravure, roll coating, bar coating, spray coating, ultrasonic coating, etc. can be applied, and the coating amount of the active agent is 2 to 30 g / m. ² , preferably 3 to 15 g / m ² .

  Next, the curved surface printing transfer film thus coated with the activator is floated on a solvent, preferably on water. This state is shown in FIG. A curved surface printing transfer film 4 on which an image layer 3 constituting a pattern is printed on a support film 1 is floated on a solvent. Since the support film 1 swells in this solvent, the support film 1 swells and spreads as shown in FIG. At this time, the image layer 3 on the support film 1 is spread in the same manner as the support film 1 spreads because the activator is applied. Thereby, the transfer film for curved surface printing is in a spread state.

  Then, with the curved surface printing transfer film 4 spread in this manner, as shown in FIG. 4B, the curved surface printing body 15 is lowered from above the curved surface printing transfer film 4 on the solvent 14, Part or all of them are allowed to settle in the solvent 14, and the curved surface printing transfer film 4 is spread and adhered to the surface of the curved surface printing body 15 by the pressure of the solvent 14.

  Here, the curved printed body is not particularly limited in terms of material and form as long as it is formed of a material to which the image layer or adhesive layer of the transfer film for curved surface printing can adhere. Examples of materials that can be used for the curved printed body include, for example, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene resin, polycarbonate resin, AES resin (ABS resin with improved weather resistance), polypropylene resin, polyethylene resin, Injection molded products such as synthetic resins, melamine resins, phenolic resins, formalin resins, urea resins, and fiber-based resins composed of homopolymers such as polyolefin oxide resins and polyvinyl chloride resins, copolymers, or mixtures selected from these. In addition to various synthetic resin molded products such as extrusion molded products, hollow molded products, vacuum molded products, etc., metal products, ceramic molded products, and the like can be mentioned.

  In addition, in terms of form, almost all forms such as those having concave or convex parts, flat ones, two-dimensional or three-dimensional curved surfaces, those having through holes, and lattice-like ones can be applied. it can. Furthermore, the thing etc. with which the fine embossing for producing the textures, such as a tree, a stone, and a textiles, are provided in the surface are applicable.

  Next, the curved printed body 15 is taken out from the solvent 14 and the support film is removed. In order to remove the support film, as shown in FIG. 4C, it is preferable to shower-wash the swollen support film using the same solvent as the solvent 14 because it is most efficient. By performing shower cleaning in this manner, the support film can be completely removed, and dirt generated during transfer can also be removed. The temperature of the solvent, the washing time, and the like here vary greatly depending on the solvent and the support film to be used. For example, when polyvinyl alcohol (PVA) is used as the support film and water is used as the solvent, in general, It is preferable to wash at a water temperature of 15 to 60 ° C. for about 1 to 10 minutes.

  Then, as shown in FIG. 4 (d), the curved surface molded body 15 from which the support film has been removed is dried by means such as air blow or a drying furnace. After drying, a protective layer is formed on the curved printed body to obtain a curved printed body. For example, when the intermediate layer is formed and the image layer is sufficiently protected by this, the step of forming the protective layer may not be performed.

  Here, the material used for the protective layer may be a thermoplastic resin or a curable resin. Specifically, thermosetting resins such as thermosetting acrylic resins, polyurethane resins, epoxy resins, melamine resins, polyester resins, prepolymers or oligomers having an ethylenically unsaturated bond in the molecule, or ethylenically unsaturated in the molecule An ionizing radiation curable composition composed of a composition containing a monomer having a bond or a mixture thereof as a main component can be exemplified.

  Examples of the prepolymer or oligomer having an ethylenically unsaturated bond in the molecule used in the ionizing radiation curable composition described above include unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyol acrylates. , Various acrylates such as melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyol methacrylate, various methacrylates such as melamine methacrylate, etc., and monomers having an ethylenically unsaturated bond in the molecule include, for example, styrene, Styrene monomers such as α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxy acrylate Acrylic esters such as chill, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, methacrylic esters such as propyl methacrylate, acrylamide, methacrylamide, etc. Of unsaturated acids such as saturated carboxylic acid amide, 2- (N, N-dibenzylamino) ethyl acrylate, (N, N-dimethylamino) methyl methacrylate and 2- (N, N-diethylamino) propyl acrylate Substituted amino alcohol esters, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol Polyfunctional compounds such as diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane Examples include trithioglycolate, trimethylolpropane trithiopropionate, and pentaerythritol tetrathioglycolate.

  Furthermore, examples of the thermoplastic resin used in the protective layer include nitrified cotton, acetate fiber, butyrate fiber, acrylic resin, vinyl chloride resin, vinyl acetate resin, and vinyl butyral resin.

  As described above, since the method for producing a curved printed body of the present invention can be obtained without preparing a printing plate, a curved printed body can be obtained quickly and at low cost. Therefore, for example, it can be used for the production of various prototypes, and is a manufacturing method that can sufficiently cope with the recent trend of small lots and various types. This effect is also exhibited by the curved printed body obtained by this manufacturing method.

  Hereinafter, the present invention will be described in more detail through examples.

[Example 1]
(Formation of intermediate layer)
A coating liquid in which the following composition was sufficiently mixed and dissolved was applied onto a thin film film of polyvinyl alcohol as a support film with a wire bar. The coating amount was set so that the dry coating amount was 8 g / m ² . As a result, an intermediate layer compatible with the oil-based inkjet was formed on the support film.
2-ethylhexyl methacrylate / methyl methacrylate copolymer resin (2-ethylhexyl methacrylate / methyl methacrylate (weight ratio) = 70/30, weight average molecular weight 383,000): 4 parts by weight Hydrophobic silica (primary particle diameter 12 μm, BET specific surface area 150m ² / g)
: 1 part by weight · Toluene: 6 parts by weight · Methyl ethyl ketone: 9 parts by weight (production of transfer film for curved surface printing)
On this intermediate layer, full-color printing was performed at 360 dpi by an ink jet printer (PJ3600, manufactured by Olympus Optical Co., Ltd.) using an oil-based ink to form an image layer to obtain a transfer film for curved surface printing. The obtained image layer was not blurred and excellent in dot resolution, and it was confirmed that the intermediate layer had excellent ink absorbability.

[Example 2]
(Formation of intermediate layer)
Polyvinyl alcohol (PVA) thin film is used as a support film. ・ Nitrocellulose: 14 parts by weight ・ Alkyd resin: 5 parts by weight ・ Phthalate ester: 6 parts by weight ・ Ethyl acetate: 22 parts by weight ・ Toluene: 26 A coating solution prepared by thoroughly mixing and dissolving 17 parts by weight of isopropyl alcohol: 17 parts by weight is coated and dried with a wire bar so that the dry coating amount is 5 g / m ² . A first intermediate layer was formed.

continue,
A coating liquid in which a composition comprising 4 parts by weight of styrene / acrylic acid copolymer resin, 2 parts by weight of calcium carbonate, and 15 parts by weight of ion exchange water was sufficiently mixed and dissolved was formed on the polyvinyl film. The coated surface of the first intermediate layer was coated with a wire bar so that the dry coating amount was 10 g / m ^2, and dried to form a second intermediate layer compatible with water-based inkjet printing. .
(Manufacture of transfer film for curved surface printing)
Full-color printing was performed on the intermediate layer coated surface of the PVA film using an inkjet printer (PM750C manufactured by Seiko Epson Corporation) to produce a curved surface printing transfer film. The obtained film did not bleed, and no swelling of the support film was observed due to the action of the water-resistant intermediate layer.

[Example 3]
(Preparation of water-soluble pigment ink for inkjet)
1. Preparation of cyan ink C.I. I. Pigment Blue 15: 4: 5 parts by weight (MONASTRAL BLUE FGX, manufactured by Geneca Corporation)
-Polymer dispersing agent (styrene / acrylic acid copolymer): 1 part by weight-Glycerin: 6 parts by weight-Ethanol: 8 parts by weight-Ion exchange water: 80 parts by weight Mixing container with 80 g of glass beads And dispersed for 2 hours with a disperser (RC-5000 manufactured by Red Devil) to obtain an aqueous pigment cyan ink.
2. Preparation of magenta ink C.I. I. Pigment Blue 15: 4 to C.I. I. An aqueous pigment magenta ink was prepared in the same manner except that Pigment Red 176 (PV Carmine HF-3C, manufactured by Hoechst) was used.
3. Preparation of yellow ink C.I. I. Pigment Blue 15: 4 to C.I. I. An aqueous facial yellow ink was prepared in the same manner except that Pigment Yellow 109 (Irgazine Yellow 2GLTE, manufactured by Chipa Specialty Chemicals Co., Ltd.) was used.
4). Preparation of black ink C.I. I. An aqueous pigment black ink was prepared in the same manner except that Pigment Blue 15: 4 was replaced with carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation).
(Manufacture of transfer film for curved surface printing)
Using the aqueous pigment ink, full-color printing was performed on the PVA film using an inkjet printer (MJ800C manufactured by Seiko Epson Corporation). Immediately after recording, the water in the ink caused swelling of the PVA film, but after drying, it returned to its original state and no effect on the image was observed. The obtained image had a tendency to be slightly poor in fixability, and peeled off when rubbed with an eraser or the like.

On the image layer thus formed,
Nitrocellulose: 12 parts by weight Alkyd resin: 4 parts by weight Phthalate ester: 6 parts by weight Ethyl acetate: 32 parts by weight Toluene: 33 parts by weight Isopropyl alcohol: 13 parts by weight -The dissolved coating solution was coated and dried with a wire bar so that the dry coating amount was 5 g / m ² to form an adhesive layer. No image distortion or discoloration due to application of the adhesive layer was observed.

  The transfer film for curved surface printing thus obtained has a good fixability of the image layer and has no problem in resolving power.

[Example 4]
(Preparation of granulated water-based pigment ink for inkjet)
1. Preparation of granulated cyan ink A resin granulated pigment ink was prepared in order to give the pigment particles fixability.

First,
・ Dimethylacrylamide-methyl methacrylate copolymer resin: 12.5 parts by weight (dimethylacrylamide / methyl methacrylate (weight ratio) = 95/15)
・ C. I. Pigment Blue 15: 4: 5 parts by weight (MONASTRAL BLUE FGX, manufactured by Geneca Corporation)
Tetrahydrofuran: 67.5 g of a composition consisting of 50 parts by weight was placed in a mixing container together with 130 g of glass beads and dispersed with a disperser (RC-5000 manufactured by Red Devil) for 3 hours. Subsequently, 219 g of ion-exchanged water was added while irradiating an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Seisakusho Co., Ltd.), and tetrahydrofuran was removed by evaporation using a rotary evaporator. The dispersion was again treated with an ultrasonic homogenizer to obtain a cyan pigment dispersion. The obtained pigment dispersion was filtered through a mesh, and cyan ink was obtained by adding 10 parts by weight of polyethylene glycol and 5 parts by weight of ethanol to 85 parts by weight of cyan dispersion.
2. Preparation of granulated magenta ink C.I. I. Pigment Blue 15: 4 to C.I. I. A granulated magenta ink was prepared in the same manner except that Pigment Red 176 (PV Carmine HF-3C, manufactured by Hoechst) was used.
3. Preparation of granulated yellow ink C.I. I. Pigment Blue 15: 4 to C.I. I. A granulated yellow ink was prepared in the same manner except that Pigment Yellow 109 (Irgazine Yellow 2GLTE, manufactured by Chipa Specialty Chemicals Co., Ltd.) was used.
4). Preparation of granulated black ink C.I. I. An aqueous pigment black ink was prepared in the same manner except that Pigment Blue 15: 4 was replaced with carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation).
(Manufacture of transfer film for curved surface printing)
Using the granulated water-based pigment ink, full-color printing was performed on a PVA film with an ink jet printer (MJ800C, manufactured by Seiko Epson Corporation) to produce a transfer film for curved surface printing. The PVA film was slightly swollen by water in the ink immediately after recording, but returned to its original state after drying and had no effect on the image.

[Example 5]
(Preparation of wet toner)
1. Preparation of cyan wet toner: 2-etherhexyl acrylate / methacrylic acid copolymer resin: 15 parts (2-ethylhexyl acrylate / methacrylic acid (weight ratio) = 75/25)
・ C. I. Pigment Blue 15: 4: 15 parts by weight (MONASTRAL BLUE FGX, manufactured by GENECA)
Isolper L (manufactured by Exxon Corporation): 500 g of a composition consisting of 30 parts by weight is kneaded for 3 hours with a double planetary mixer while ripening to 120 ° C., followed by stirring at room temperature at a rate of 0.5 ° C./min. The paste was gradually cooled to obtain a paste-like facial dispersion. Isopar L was added at a ratio of 25 parts by weight with respect to 15 parts by weight of the pigment dispersion, and the beads were dispersed with a disperser (RC-5000 manufactured by Red Devil) for 12 hours to obtain a master toner. Mastona-400g soy lecithin (manufactured by Junsei Chemical Co., Ltd.) 2.5g and basic calcium petronate (manufactured by Witco) 2.5g as a charge control agent, further diluted to 3500g with Isopar L, cyan wet A toner was obtained.
2. Preparation of magenta wet toner C.I. I. Pigment Blue 15: 4 to C.I. I. A magenta toner was prepared in the same manner except that Pigment Red 176 (PV Carmine HF-3C, manufactured by Hoechst) was used.
3. Preparation of yellow wet toner C.I. I. Pigment Blue 15: 4 to C.I. I. A yellow wet toner was prepared in the same manner except that Pigment Yellow 109 (Irgazine Yellow 2GLTE, manufactured by Chipa Specialty Chemicals Co., Ltd.) was used.
4). Preparation of black wet toner C.I. I. A black wet toner was prepared in the same manner except that Pigment Blue 15: 4 was replaced with carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation).

All of the obtained toners were uniformly negatively charged and exhibited good dispersion stability.
(Preparation of transfer film for curved surface printing)
An electrostatic latent image of −200 V was formed in a pattern on the dielectric drum with a needle electrode, and roller development was performed using the toner. The toner image on the drum was sequentially transferred onto the PVA film by electrostatic transfer, and this process was repeated for four colors to obtain a transfer film for full-color curved surface printing. The obtained image was excellent in resolving power and was firmly fixed on the PVA film.

[Example 6]
(Manufacture of curved prints)
On the image layer on which the curved surface printing transfer film obtained in Examples 1 to 5 was printed, an activator (Ohashi Chemical Co., Ltd. C, P, AH NORMAL EX) was applied at 13 g / m ² using a wire bar. Coated in proportion and floated with the image layer on top of the water surface at a temperature of 25 ° C. before the activator dried.

  Next, after confirming that this curved surface printing transfer film was sufficiently swollen by water and the activator, the curved surface printing body made of ABS resin was pushed in from above the curved surface printing transfer film, and the outer surface of the curved surface printing body The transfer film for curved surface printing was closely attached to. The printed surface to be curved was pulled up from the water, the polyvinyl alcohol remaining on the outermost surface was washed away with water at 40 ° C., and dried at 70 ° C. for 20 minutes. In order to protect the image layer on the curved printed body after drying, a two-component urethane paint was spray-coated and then dried at 70 ° C. for 40 minutes to obtain a curved printed body.

  All of the obtained curved surface prints were less divided and did not form a printing plate as compared with those produced by a conventional method, and the production time was also short. Furthermore, it had the same designability and durability as a conventional curved printed body.

It is explanatory drawing which shows an example of the process of forming the transfer film for curved surface printing by inkjet printing. It is explanatory drawing which shows the other example of the process of forming the transfer film for curved surface printing by inkjet printing. It is explanatory drawing which shows an example of the process which forms the transfer film for curved surface printing by electrophotographic printing. It is explanatory drawing which shows an example of the printing process by curl fitting.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Support film 2 ... Inkjet printer 3 ... Image layer 4 ... Curve transfer printing film 5 ... Adhesive layer 6 ... Activator 7 ... Intermediate layer 8 ... Toner tank 9 ... Developer 10 ... Photoreceptor 11 ... Impression cylinder 12 ... Electrophotography Printer 13 ... Laser 14 ... Solvent,
15 ... curved surface A ... ink B ... toner

Claims (15)

  A transfer film for curved surface printing, wherein an image layer constituting a picture printed by an on-demand printing method is laminated on one surface of a support film that swells in a predetermined solvent.   A transfer film for curved surface printing, wherein an intermediate layer is disposed on one surface of a support film that swells in a predetermined solvent, and an image layer constituting a pattern is disposed on the surface or inside of the intermediate layer.   A transfer film for curved surface printing, wherein an image layer constituting a pattern is disposed on one surface of a support film that swells in a predetermined solvent, and an adhesive layer is disposed on the surface of the image layer.   An intermediate layer is disposed on one surface of a support film that swells in a predetermined solvent, an image layer constituting a pattern is disposed on the surface of the intermediate layer, and an adhesive layer is disposed on the surface of the image layer. Characteristic transfer film for curved printing.   5. The transfer film for curved surface printing according to any one of claims 2 to 4, wherein the image layer constituting the pattern is a layer printed by an on-demand printing method. .   6. The transfer film for curved surface printing according to claim 1 or 5, wherein the image layer is an image layer on which a pattern is printed by an inkjet method.   The curved image printing transfer film according to claim 1, wherein the image layer is an image layer on which a pattern is printed by an electrophotographic method.   The transfer film for curved surface printing according to any one of claims 1 to 7, wherein the support film swelled in the predetermined solvent is a water-soluble film.   Curved surface printing transfer comprising: a step of preparing a support film that swells in a predetermined solvent; and a step of printing an image layer constituting a pattern on one surface of the support film by an on-demand printing method. A method for producing a film.   10. The method for producing a transfer film for curved surface printing according to claim 9, further comprising a step of forming an intermediate layer between a step of preparing the support film and a step of printing the image layer.   The method for producing a transfer film for curved surface printing according to claim 9, further comprising a step of forming an adhesive layer after the step of printing the image layer.   The method for producing a transfer film for curved surface printing according to any one of claims 9 to 11, wherein the step of printing the image layer is a step of printing a pattern by an inkjet method.   The method for producing a transfer film for curved surface printing according to any one of claims 9 to 11, wherein the step of printing the image layer is a step of printing a pattern by an electrophotographic method. . (1) a step of preparing a transfer film for curved surface printing by the production method according to any one of claims 9 to 13;
(2) a step of applying an active agent capable of swelling at least one of the image layer, the intermediate layer, and the adhesive layer to the surface on the image layer side of the transfer film for curved printing obtained in the previous step;
(3) a step of floating the curved surface printing transfer film on the predetermined solvent with the surface on which the image layer is printed facing upward;
(4) The curved surface printed body is lowered from above the transfer film for curved surface printing swollen on the solvent, and a part or all of it is settled in the solvent, and the curved surface is applied to the surface of the curved surface printed body by the pressure of the solvent. The process of spreading and adhering the transfer film for printing,
(5) removing the curved printed body from the solvent, and washing and removing the support film from the curved printed body;
(6) A process for producing a curved printed body, comprising a step of forming a protective layer on the curved printed body from which the support film has been removed.   A curved printed body obtained by the production method according to claim 14.

Images