JP6155756B2 - Image receiving sheet and manufacturing method thereof - Google Patents

Description

  The present invention relates to an image receiving sheet, and more particularly to an image receiving sheet suitably used for a card substrate on which an IC chip or the like is mounted and a method for manufacturing the image receiving sheet.

  For identification cards (ID cards) and credit cards, magnetic cards that record data using the magnetic recording method have been widely used. However, the security of personal information stored in the magnetic card is further improved, and In recent years, IC cards with built-in IC chips have begun to spread in order to increase the data recording capacity. Since such an IC card has a structure in which an IC chip is embedded in a part of the card base, the surface of the card base is more likely to be uneven than the conventional magnetic card. The print quality printed on the surface of this was not always satisfactory.

  Therefore, an IC card having a structure in which a cushion layer capable of absorbing the thickness of the IC chip is provided between the card substrate in which the IC chip is embedded and the image receiving layer has been proposed (for example, JP-A-7-088974). Publication). However, since the cushion layer which is the base of the image receiving layer (surface layer) has flexibility, there is a problem that the scratch resistance of the surface of the IC card is insufficient. Further, since a polyolefin resin or the like is used as a cushion layer, the chemical resistance is low, and there is a problem of durability that the IC card enters from the edge when it comes into contact with chemicals or water. In addition, in order to suppress unevenness generated on the card surface, the IC chip embedded in the card base is made to have a predetermined thickness, or the adhesive used to hold the IC chip between the card base is made to have a predetermined thickness. This has also been proposed (for example, Japanese Patent Application Laid-Open No. 2000-2111278). However, even if the surface of the card base is smooth, if the surface of the IC card surface (image receiving layer) is hard, it can receive information such as image information and text information that has gradation characteristics like a face photograph. When printing on a layer by a thermal transfer method, the print quality may be insufficient.

  In addition, as described above, when printing on the image receiving layer is performed by the thermal transfer method, due to the heat at the time of printing, it is caused by the difference in thermal shrinkage between the part where the IC chip of the card base is embedded and the other part. There arises a problem that unevenness and non-uniformity of the surface to be generated easily occur. For this reason, an attempt has been made to form an image receiving layer provided on a card substrate with an actinic ray curable resin (Japanese Patent Laid-Open No. 2000-298714). However, when the image receiving layer is provided on the entire surface of the card substrate, there is a problem that the IC card is curled due to curing shrinkage of the resin due to irradiation of actinic rays when forming the image receiving layer.

  Japanese Patent Application Laid-Open No. 2002-222403 discloses that a cushion layer made of actinic ray curable resin is provided between a card base and an image receiving layer so that the card can be deformed even during printing by a thermal transfer method or during hot pressing. It is proposed that an IC card having excellent durability such as chemical resistance can be realized.

JP 7-088974 A JP 2000-2111278 A JP 2000-298714 A JP 2002-222403 A

  In the IC card base material provided with a cushion layer between the image receiving layer and the base material described in JP-A-2002-222403 described above, the present inventors recently used an actinic ray curable resin to form a cushion layer. When forming the resin, the ordinary actinic ray irradiation improves the cushioning properties (that is, the print quality), but the chemical resistance and scratch resistance are still insufficient, and the exposure amount of actinic rays is increased to increase the resin. Although the chemical resistance is improved even if the degree of polymerization is increased, the hardness of the cushion layer is not further increased, and it has been found that the scratch resistance is insufficient. And the knowledge that an IC card substrate with an image receiving layer that is excellent in any of print quality, chemical resistance and scratch resistance can be realized by irradiating actinic rays in two specific steps to form a cushion layer. Obtained. The present invention is based on such knowledge.

  Accordingly, an object of the present invention is to provide a method for producing an image receiving sheet which is excellent in all of print quality, chemical resistance and scratch resistance.

The method for producing an image receiving sheet according to the present invention comprises at least a base sheet, an actinic ray curable resin layer provided on the substrate sheet, and an image receiving layer provided on the actinic ray curable resin layer. A method for producing an image receiving sheet comprising:
Apply the actinic ray curable resin composition on the base sheet to form a coating film,
By irradiating the coating film with actinic rays, the coating film is cured or semi-cured,
Forming an image receiving layer on the cured or semi-cured coating;
Comprising
The actinic ray irradiation to the coating film is carried out at least twice to form an actinic ray curable resin layer.

  In the method for producing an image receiving sheet according to the present invention, it is preferable that the actinic ray irradiation is performed at least twice in a separate step.

  In the method for producing an image receiving sheet according to the present invention, it is preferable that the actinic rays at the first irradiation are ultraviolet rays.

In the method for producing an image receiving sheet according to the present invention, the first actinic ray irradiation is preferably performed with an integrated exposure amount of 50 to 500 mJ / cm ² .

  In the method for producing an image receiving sheet according to the present invention, the actinic ray at the second irradiation is preferably ultraviolet light.

In the method for producing an image receiving sheet according to the present invention, the second actinic ray irradiation is preferably performed with an integrated exposure amount of 50 to 500 mJ / cm ² .

  Further, in the method for producing an image receiving sheet according to the present invention, after the actinic ray curable resin composition is irradiated with the first actinic ray, an image receiving layer is formed on the coating film, and then the image receiving layer is interposed therebetween. Then, it is preferable to irradiate the coating film with the second actinic ray.

  In the method for producing an image receiving sheet according to the present invention, the image receiving layer preferably includes an intermediate layer and a metal compound-containing layer.

  In the method for producing an image receiving sheet according to the present invention, the image receiving layer preferably includes an intermediate layer, a metal compound-containing layer, and a top layer.

  In the method for producing an image receiving sheet according to the present invention, it is preferable that the second irradiation is performed after at least one hour has elapsed after the first irradiation.

  Moreover, in the manufacturing method of the image receiving sheet by this invention, it is preferable to apply | coat the said actinic-light curable resin composition so that the thickness of the said coating film may be 3-20 micrometers.

  In the present invention, an image receiving sheet obtained by the above production method and a card substrate provided with the image receiving sheet are also provided.

  According to the present invention, when an actinic ray curable resin composition of an image receiving sheet is irradiated with actinic rays to form an actinic ray curable resin, the coating film comprising the actinic ray curable resin composition is active at least twice or more. By irradiating with a light beam, an image receiving sheet having excellent printing quality, chemical resistance and scratch resistance can be obtained.

It is a cross-sectional schematic diagram of the image receiving sheet obtained by the method by this invention. It is the schematic process drawing which showed each process by one Embodiment of the manufacturing method of the image receiving sheet of this invention. It is the schematic process drawing which showed each process by other embodiment of the manufacturing method of the image receiving sheet of this invention. It is the schematic process drawing which showed each process by other embodiment of the manufacturing method of the image receiving sheet of this invention.

<Definition>
In this specification, an actinic ray curable resin composition means a precursor or a composition before irradiating actinic rays, and an actinic ray curable resin composition cured by irradiating actinic rays is active. It shall be called a light curable resin.

  Moreover, in this specification, an actinic ray means the radiation which acts on actinic-light curable resin chemically, and accelerates | stimulates polymerization, specifically, infrared rays, visible rays, ultraviolet rays, X-rays, It means electron beam, α ray, β ray, γ ray and the like.

<Method for producing image receiving sheet>
The method for producing an image receiving sheet according to the present invention is provided on a substrate sheet 1, an actinic ray curable resin layer 2 provided on the substrate sheet 1, and an actinic ray curable resin layer 2 as shown in FIG. An image receiving sheet 10 comprising at least the image receiving layer 3 is manufactured. The image receiving sheet 10 may include an intermediate layer 3A and a metal compound-containing layer 3B as the image receiving layer 3, and may further include a top layer 3C on the metal compound-containing layer 3B. Hereafter, each process of the manufacturing method of the image receiving sheet by this invention is demonstrated.

(I) Base Sheet Preparation Step FIG. 2 is a schematic process diagram showing each step of the image receiving sheet manufacturing method according to the present invention. In the method for producing an image receiving sheet according to the present invention, as shown in FIG. Examples of the sheet substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, and poly-4. Polyfluorinated ethylene resins such as ethylene fluoride and ethylene-tetrafluoroethylene copolymer, polyamides such as nylon 6 and nylon 6.6, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate Copolymers, ethylene / vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon, cellulose resins such as cellulose triacetate and cellophane, polymethyl methacrylate, polyethyl methacrylate, poly Acrylic resins such as ethyl acrylate and polybutyl acrylate, synthetic resin sheets such as polystyrene, polycarbonate, polyarylate, and polyimide, or single-layer paper such as fine paper, thin paper, glassine paper, sulfate paper, and metal foil Or a laminate of two or more layers. The base sheet may have a single layer structure or a multilayer structure. In the present invention, the fluorescent material can be contained in the base sheet. Further, in order to improve the sharpness of the image formed on the image receiving sheet, a white pigment (for example, titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, calcium carbonate is included in the base sheet in advance. Etc.) is preferably added. When the image receiving sheet is used for an ID card such as an automobile license or an identification card, the base sheet is generally composed of a sheet or film made of a vinyl chloride resin containing a white pigment. . It is preferable that the thickness of a base material sheet is 30-300 micrometers, More preferably, it is 50-200 micrometers.

(Ii) Actinic ray curable layer forming step Next, an actinic ray curable resin composition is applied on the substrate sheet 1 to form a coating film 2 '(FIG. 2 (b)). As described above, the actinic ray curable resin layer 2 is formed by curing the coating film 2 ′ by irradiation with actinic rays. The actinic ray curable resin layer 2 is disposed between the base sheet 1 and the image receiving layer 3 on which an image is formed, and plays a role of alleviating the unevenness of the base sheet due to electronic components. As such an actinic ray curable resin composition, a composition containing a compound having addition polymerization property or ring-opening polymerization property can be used. Examples of addition polymerizable compounds include radical polymerizable compounds (for example, described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, etc.). Photopolymerizable compounds) and cationic polymerization photocurable compounds are known, and recently photocationic polymerization photocurable compounds (for example, sensitized to a long wavelength region above visible light) JP-A-6-43633, JP-A-8-324137, etc.) may be used.

  As the radically polymerizable compound, a normal photopolymerizable compound or a thermally polymerizable compound can be used. The radically polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and can be used without particular limitation as long as it is a compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. The thing of various forms, such as an oligomer and a polymer, can be used. Only 1 type of radically polymerizable compound may be used, and 2 or more types may be used together by arbitrary ratios.

  Examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts, esters, urethanes and amides thereof. And radically polymerizable compounds such as unsaturated monomers, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Is mentioned. More specifically, Shinzo Yamashita, “Cross-linking agent handbook” (1981 Taiseisha); Kato Kiyomi ed., “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the industry can be suitably used. The content of the radical polymerizable compound is preferably 1 to 97% by mass and more preferably 30 to 95% by mass with respect to the actinic ray curable resin composition.

  When the actinic ray curable resin composition contains a radical polymerizable compound, it is necessary to use a radical polymerization initiator in combination. Examples of the radical polymerization initiator include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, JP-A-60-60104, JP-A-59-1504 and JP-A-61. No. 243807, etc., Japanese Patent Publication No. 43-23684, Japanese Examined Publication No. 44-6413, Japanese Examined Publication No. 44-6413, Japanese Examined Publication No. 47-1604, etc. Diazonium compounds described in US Pat. No. 3,567,453, organic azide compounds described in US Pat. Nos. 2,848,328, 2,852,379, and 2,940,853 Ortho-quinonediazides described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015, JP-B 45-9610, etc. Various onium compounds described in JP-A-55-39162, JP-A-59-14023, and the like, and “Macromolecules, Vol. 10, page 1307 (1977),” JP-A-59-142205. Azo compounds described in Japanese Patent Publication No. 1-54440, European Patent Nos. 109,851, 126,712 and the like, “Journal of Imaging Science” (J. Imag. Sci.) ", Vol. 30, page 174 (1986), (oxo) sulfonium organoboron complexes described in JP-A-5-213861 and JP-A-5-255347. And titanocenes described in JP-A No. 61-151197, “Coordination Chemistry Review ( ordinance Chemistry Review), 84, 85-277 (1988), and transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, JP-A-3-209477 2,4,5-triarylimidazole dimer, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344. These polymerization initiators are preferably contained in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  In order to form the actinic ray curable resin layer, a polymerization accelerator, a chain transfer agent, a polymerization inhibitor, an antistatic agent, a surfactant, other resins, etc. are included in the actinic ray curable resin composition as necessary. These additives may be appropriately added.

  Examples of polymerization accelerators and chain transfer catalysts include amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, US Pat. No. 4,414,312 and JP-A No. 64-13144. Thiols, disulfides described in JP-A-2-291561, thiones described in U.S. Pat. No. 3,558,322 and JP-A-64-17048, and o-acylthiohydroxy described in JP-A-2-291560. Examples thereof include samates and N-alkoxypyridinethiones.

  When a radically polymerizable compound is contained, a polymerization inhibitor can be contained for the purpose of preventing polymerization during storage of the liquid. Specific examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine and the like.

  Examples of the antistatic agent include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a polymer antistatic agent, and conductive fine particles, as well as “11290 Chemical Products”, Chemical Industry Daily, p875. Compounds described in 876 and the like.

  As the surfactant, nonionic surfactants as described in JP-A-62-251740, JP-A-3-208514 and the like, or JP-A-59-121044, JP-A-4 Amphoteric surfactants as described in each publication such as No. 13149 can be added.

  Surfactants such as silicone oils, silicone-alkylene oxide copolymers (for example, L-5410 commercially available from Union Carbide), silicone-based active agents such as Nippon Unicar, silicone oil-containing aliphatic epoxides, Examples thereof include silicon-containing monoepoxides. It is also possible to use Si-based additives described in “New Silicone and its Applications” published by Toshiba Silicone Corporation in 1994, “Special Silicone Reagent Catalog” published in 1996 by Asmax Corporation.

  The actinic ray curable resin composition may contain a resin other than those described above, for example, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, styrene, paramethylstyrene, You may use together other arbitrary high molecular polymers, such as vinyl monomers, such as methacrylic acid ester and acrylic acid ester, a cellulose type, thermoplastic polyester, a natural resin. In addition, the industry known in Kiyoshi Akamatsu's supervision, “New Technology of Photosensitive Resins” (CMC, 1987) and “Chemical Products of 10188”, pages 657-767 (Chemical Industry Daily, 1988) These organic polymer polymers may be used in combination.

  Of these, resins containing unsaturated groups that can be polymerized by radicals or acids are preferred, and resins such as those described in JP-A-9-134011 can be used. Specifically, a resin having an unsaturated group such as a glycidyl group, a (meth) acryloyl group, or a vinyl group can be given here. The content of these high molecular polymers in the actinic ray curable resin composition is preferably in the range of 0.01 to 70% by mass, and more preferably in the range of 0.05 to 50% by mass.

  Furthermore, depending on the purpose, sensitizers, coating solvents, antifoaming agents, plasticizers, etc., light stabilizers, ultraviolet absorbers, antioxidants, stabilizers such as corrosion inhibitors, dyes, organic and inorganic pigments, Oxygen scavengers and reducing agents such as phosphines, phosphonates, phosphites, fluorescent brighteners, colorants, flame retardants, foaming agents, fungicides, magnetic substances and other additives that give various properties, dilution solvents, etc. You may mix and use. Alternatively, Si-based compounds, waxes, and the like can be added to modify the coating surface and improve leveling.

  The use of coating solvents is detailed in the “Solvent Handbook” issued by Kodansha. There are no particular restrictions on the use of these organic solvents.

  In order to impart cushioning properties, the actinic ray curable resin composition preferably contains a polymerizable compound having high flexibility and rubber elasticity. For example, urethane-based polymerizable compounds, alkyl glycol-based polymerizable compounds, propylene glycol-based polymerizable compounds, ethylene glycol-based polymerizable compounds, and long-chain alkyl group-containing polymerizable compounds can be preferably used.

  A cushioning aid may be added. As the cushioning aid, it is possible to add a material having high flexibility, a material having a low elastic modulus, or a material having rubber elasticity. Specifically, a) a thermoplastic resin, b) a thermoplastic elastomer, c) a hot melt adhesive, d) a rubber elastic resin, etc. can be preferably used. This improves the printability, point pressure strength, and curling properties.In addition, when an image receiving layer for receiving an image is formed, the adhesion to the image receiving layer is improved, and a surface protective layer is formed on the image recording body. When formed, it is also effective for improving the adhesion to the surface protective layer.

  Examples of the thermoplastic resin include polyacetoacetal, butyral resin, polyurethane resin, cellulose resin, polystyrene resin, acrylic resin, and polycarbonate resin. In these thermoplastic resins, a resin having a heat softening point of 150 ° C. or higher is preferable. In the present invention, urethane resin and acrylic resin are particularly preferable. Specifically, Dainippon Ink, Nippon Run series, polybutyl acrylate, and the like.

  The thermoplastic elastomer has the same properties as vulcanized rubber at room temperature and is elastic, and represents the same properties as ordinary thermoplastic resins at high temperatures. Thermoplastic elastomers generally have both a soft segment (soft phase) having elasticity in the molecule and a hard segment (hard phase) for preventing plastic deformation.

  Specific examples of thermoplastic elastomers include styrene (styrene block copolymer (SBC)), olefin (TP), polystyrene and polyolefin block polymer, urethane (TPU), polyester (TPEE), and polyamide. (TPAE), 1,2-polybutadiene, vinyl chloride (TPVC), fluorine, ionomer resin, chlorinated polyethylene, silicone and the like. Specifically, the 1996 edition of “12996 Chemical Products” (Chemical Industry) Nikkansha), “Polyfile” p. 77-P112 etc. The block polymer thermoplastic elastomers of polystyrene and polyolefin include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / block polymers having a polystyrene phase and a hydrogenated phase of polyolefin. Examples include butylene-styrene (SEBS), styrene-ethylene / propylene-styrene (SEPS), and styrene-ethylene / propylene (SEP) block polymers. Specifically, they are Shell Chemical Co., Califlex TR / Clayton D and G series, Asahi Kasei Co., Ltd., Tuftec H and M series, Kuraray, Septon series, Daicel Chemical Industries, and Epofriend series.

  As the hot melt adhesive, those commonly used can be used. Examples of the main component of the hot melt adhesive include ethylene / vinyl acetate copolymer (EVA), polyester, polyamide, thermoplastic elastomer, and polyolefin. Examples of polyamide hot melt adhesives include the Macromelt series manufactured by Henkel. In the present invention, a thermoplastic elastomer hot melt adhesive is preferred. Examples include Califlex TR and Clayton series manufactured by Shell Chemical Co., Ltd., Tough Plain manufactured by Asahi Kasei Co., Ltd., Toughden manufactured by Firestone Synthetic Rubber and Latex, and Solprene 400 Series manufactured by Phillips Petroleum. Polyolefin-based hot melt adhesives include Sumitomo Chemical Sumitick, Chisso Petrochemical Bistack, Mitsubishi Yuka Yucatac, Henkel Macromelt Series, Mitsui Petrochemical Tuffmer, Ube Lexen APAO, Eastman Chemical There are East Bond and A-FAX manufactured by Hercules.

  The rubber elastic resin generally represents a resin. Specifically, crosslinked rubber particles, natural rubber, acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, fluorine rubber, neoprene rubber, chloro Sulfonated polyethylene, epichlorohydrin, EPDM (ethylene propylene diene rubber), elastomers such as urethane elastomer, polyethylene, polypropylene, polybutadiene, polybutene, impact-resistant ABS resin, polyurethane, ABS resin, acetate, cellulose acetate, amide resin, polytetra Fluoroethylene, nitrocellulose, polyester, impact-resistant acrylic resin, styrene-butadiene copolymer, styrene TPE, ethylene-vinyl acetate copolymer Acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, plasticized vinyl chloride resin, vinylidene chloride resin, polyvinyl chloride, polyvinylidene chloride, long chain alkyl group-containing (meth) acrylic monomer Among the vinyl copolymer resins, resins having a high penetration are listed. In order to increase the penetration, a plasticizer or the like can be added to the various polymers.

  The coating film 2 ′ coated with the actinic radiation curable resin composition described above is a known actinic radiation curable resin composition such as roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat and the like. It can form by apply | coating on a base material sheet by a means. The thickness of the coating film is preferably 3 to 20 μm, more preferably 5.0 to 12.0 μm. When the coating film is less than 3 μm, the function of alleviating the unevenness of the substrate sheet may be impaired, and when the coating film exceeds 20 μm, it is completely active even by irradiation with two actinic rays described later. The photocurable resin composition may be difficult to completely cure. The coating film may be dried or aged at a temperature of 30 ° C. to 120 ° C. before being irradiated with actinic rays.

  Subsequently, when the coating film 2 'made of the actinic ray curable resin composition obtained as described above is irradiated with actinic rays to polymerize and cure the resin composition, the actinic ray is at least twice or more. Is applied to cure the actinic ray curable resin composition. That is, the actinic ray curable resin composition is semi-cured by the first actinic ray irradiation (FIG. 2 (c)), and then the actinic ray curable resin composition that has been semi-cured is irradiated with the actinic ray for the second time. Thus, the actinic ray curable resin layer 2 is formed (FIG. 2D).

  The inventors of the present invention conventionally used an actinic ray curable resin layer (cushion layer) formed by a single actinic ray irradiation as described above, but at least two actinic ray irradiations as described above. It has been found that the image quality, chemical resistance and scratch resistance of the obtained image-receiving sheet can be improved by forming. The reason for this is not clear, but is considered as follows. In the conventional single exposure, when the coating film has a certain thickness, the monomer and polymerization initiator in the actinic ray curable resin composition existing in the vicinity of the coating film surface undergo polymerization reaction, but the deep part (active In the light irradiation direction depth), the unsaturated group of the monomer may remain unreacted or the polymerization initiator may remain as a raw material. Therefore, a difference has occurred in the physical properties of the actinic ray curable resin in the thickness direction of the coating film. Although the monomer in the deep part of the coating film is polymerized by increasing the exposure amount or increasing the exposure time, the physical property difference of the actinic ray curable resin cannot be eliminated in the thickness direction of the coating film. Moreover, when the exposure amount is increased too much, there is a problem that the actinic ray curable resin is yellowed. On the other hand, when the second exposure is performed, the unreacted monomer and the polymerization initiator remaining at the first exposure are applied to the entire coating film by molecular motion (thermal fluctuation) until the second exposure. Since it is diffused, a more uniform polymerization reaction is performed in the direction of the coating film. As a result, it is considered that the printing quality and chemical resistance are improved. The above is only an assumption, and the present invention is not bound by the above theory.

  Irradiation of actinic rays is preferably performed intermittently two times or more, rather than continuously twice or more. After the first actinic ray irradiation, the second actinic ray irradiation is performed in a separate step. It is more preferable. In the case where the first and second actinic ray irradiations are intermittently performed, for example, after forming the coating film 2 ′ on the production line (FIG. 2B), the first actinic ray irradiation is subsequently performed ( 2 (c)), the second irradiation of active light (FIG. 2 (d)) can be performed on the same production line. In addition, when performing the second actinic ray irradiation in a separate process, in a state where the resin is semi-cured by the first actinic ray irradiation (the state of FIG. 2 (c)), it is once wound into a roll shape, It may be supplied to the second actinic ray irradiation step in a roll form, and the second actinic ray irradiation may be performed on the semi-cured resin (coating film) (FIG. 2D).

As described above, various rays such as infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used as described above. When the actinic ray irradiation is performed, the first actinic ray irradiation is preferably infrared rays, visible rays, ultraviolet rays, or electron beams, more preferably ultraviolet rays or electron beams, and still more preferably ultraviolet rays. When irradiation is performed first active light in the ultraviolet, the peak irradiance of the ultraviolet is preferably 500~4000mW / cm ^2, more preferably 500-3000 mW / cm ^2. Further, the accumulated exposure amount at the time of first ultraviolet irradiation is preferably from 50 to 500 mJ / cm ^2, more preferably 100~300mj / cm ^2. By irradiating ultraviolet rays under the irradiation conditions as described above, the actinic ray curable resin can be kept in a semi-cured state without being completely cured.

The second irradiation with actinic rays is preferably infrared rays, visible rays, ultraviolet rays, or electron beams, more preferably ultraviolet rays or electron beams, and even more preferably ultraviolet rays. When irradiation is performed for the second time to actinic rays in UV peak irradiance of ultraviolet rays preferably 500~4000mW / cm ^2, more preferably 500-3000 mW / cm ^2. Moreover, 50-500 mj / cm < ² > is preferable and, as for the integrated exposure amount in the time of the 1st ultraviolet irradiation, More preferably, it is 50-300 mj / cm < ² >. By irradiating ultraviolet rays under the irradiation conditions as described above, an image receiving sheet excellent in all of print quality, chemical resistance and scratch resistance can be realized without yellowing the actinic ray curable resin.

  For the irradiation of ultraviolet rays, a conventionally known ultraviolet irradiation device can be used. For example, various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED are used without limitation. be able to.

  The second and subsequent actinic ray irradiations may be performed before forming the receiving layer 3 described later (FIG. 2 (e)) as shown in FIG. 2, but as shown in FIG. By actinic ray irradiation, the coating film 2 ′ (actinic ray curable resin composition) is left in a semi-cured state (FIG. 3C), and an intermediate layer is formed on the coating film 2 ′ as described later. After the formation of 3A (FIG. 3 (d)), the second and subsequent actinic rays may be irradiated through the intermediate layer 3A (FIG. 3 (e)), and as shown in FIG. The coating film 2 'is in a semi-cured state by the second irradiation with actinic rays (FIG. 4C), and an intermediate layer 3A, a metal compound-containing layer 3B and a top layer 3C are formed on the coating film 2'. (FIG. 4 (d)), the second and subsequent actinic ray irradiation may be performed (FIG. 4 (e)).

  In addition, the second and subsequent actinic ray irradiation is preferably performed after 1 hour or more has passed since the first actinic ray irradiation, and more preferably after 2 hours. By performing the second and subsequent actinic ray irradiation after 1 hour or more has passed since the first actinic ray irradiation, it is possible to obtain an image receiving sheet that is further excellent in printing quality, chemical resistance, and scratch resistance.

(Iii) Receiving Layer Formation Step The image receiving layer 3 is for receiving a sublimation or heat diffusible dye image by a thermal transfer recording method and printing character information and image information on the image receiving sheet 10. As a material for forming the image receiving layer, a conventionally known resin material that can easily accept a heat transferable color material such as a sublimation dye or a heat-meltable ink can be used. For example, polyolefin resin such as polypropylene, vinyl chloride resin such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or polyacrylate Vinyl resins, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene or propylene and other vinyl polymers, celluloses such as ionomers or cellulose diastases Examples thereof include resins and polycarbonates, and vinyl chloride resins, acrylic-styrene resins or polyester resins are particularly preferable.

  In the present invention, the image receiving layer 3 preferably includes a layer (metal compound-containing layer 3B) containing a metal ion-containing compound that can form a chelate by reacting with a dye compound that is a coloring material described later. That is, in the present invention, a dye compound as a coloring material is thermally transferred to an image receiving layer, and then a metal ion-containing compound in the image receiving layer is reacted with the dye compound to form a chelate complex. The light resistance of images and characters transferred to the sheet can be improved.

As the metal ion-containing compound to be contained in the metal compound-containing layer, conventionally known compounds can be used, and inorganic or organic salts and metal complexes of divalent and polyvalent metals belonging to Groups I and VIII Can be preferably used. For example, the following general formula containing Ni ²⁺ , Cu ⁺ , Co ²⁺ , Cr ²⁺ and Zn ²⁺ :
[M (Q1) k (Q2 ) m (Q3) n] p + p (L -)
(In the formula, M represents a metal ion, Q1, Q2, and Q3 each represent a coordination compound capable of coordination with the metal ion represented by M, L represents a counter anion that can form a complex, and k Represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. In these, the complex represented by the above general formula is tetradentate or hexadentate. Or a complex represented by the number of ligands of Q1, Q2 and Q3, and p represents 1, 2 or 3. Among these, a coordination compound having at least one amino group coordinated to a metal is preferable, and specific examples include ethylenediamine and derivatives thereof, glycinamide and derivatives thereof, picolinamide and derivatives thereof. Examples of the counter anion L that can form a complex include inorganic compound anions such as Cr, SO ₄ , and ClO ₄ , and organic compound anions such as a benzenesulfonic acid derivative and an alkylsulfonic acid derivative pair, and tetraphenyl is particularly preferable. Boron anions and their derivatives, and alkylbenzene sulfonate anions and their derivatives. Examples of such metal ion-containing compounds include those exemplified in US Pat. No. 4,987,049.

The addition amount of the above-mentioned binder resin of the metal ion-containing compound is preferably from 0.5 to 20 g / ^{m 2,} more preferably 1 to 15 g / ^{m 2.}

  In the receiving layer 3, an intermediate layer 3 </ b> A may be included in order to improve adhesion with the actinic ray curable resin described above. As a material constituting the intermediate layer, for example, vinyl chloride resin, polyester resin, acrylic resin, polyvinyl acetal resin, polyvinyl alcohol, polycarbonate, cellulose resin, styrene resin, urethane resin, urethane acrylate resin, Resins such as amide resin, urea resin, epoxy resin, phenoxy resin, polycaprolactone resin, polyacrylonitrile resin, styrene resin (styrene block copolymer (SBC)), olefin resin (TP), urethane resin (TPU) And thermoplastic elastomers such as polyester (TPEE), polyamide (TPAE), 1,2-polybutadiene, vinyl chloride (TPVC), fluorine, ionomer resin, chlorinated polyethylene, and silicone. Specific examples of the thermoplastic elastomer include SEBS resins, SEPS resins, and modified products thereof described in the 1996 edition of “12996 Chemical Products” (Chemical Industry Daily). The above-described resins may be used alone or in combination of two or more.

  Among the above-described resins, thermoplastic resins made of polystyrene and polyolefin block polymers, polyvinyl butyral resins, and the like are preferable. As a polyvinyl butyral resin, SRECIK BH-3, BX-1, BX-2, BX-5, BX-55, BH-S, BL-S manufactured by Sekisui Chemical Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. Commercially available products such as Denkabutyral # 4000-2, # 5000-A, # 6000-EP may be used. These polybutyral resins are not particularly limited in the degree of polymerization before thermosetting. Further, from the viewpoint of film strength, a thermosetting compound may be added to the above-described resin. Specifically, an isocyanate curing agent, an epoxy curing agent, or the like can be used, and the thermosetting conditions are preferably 50 to 90 ° C. and 1 to 72 hours.

  The intermediate layer may contain additives such as an ultraviolet absorber, an antioxidant, and a light stabilizer. These additives need to be added to such an extent that the function of the intermediate layer is not impaired. Specifically, the content of the additive is preferably 0.05 to 20% by mass, more preferably 0.05% to 10% by mass with respect to 100% by mass of the total solid content of the resin.

  The ultraviolet absorber added to the intermediate layer is not particularly limited as long as it functions as an ultraviolet absorber for dye images and can be thermally transferred. For example, JP-A-59-158287, 63-74666, and 63. -145089, 59-196292, 62-229594, 63-122596, 61-283595, JP-A-1-204788, and the like, and Known compounds can be used to improve the image durability in photographs and other image recording materials. Specific examples include salicylic acid type, benzophenone type, benzotriazole type, and cyanoacrylate type. For example, Tinuvin P, Tinuvin 123, 234, 320, 326, 327, 328, 312, 315, 384, 400 (manufactured by Ciba Geigy) ), Sumisorb-110, 130, 140, 200, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.), MarkLa-32, 36, 1413 (manufactured by Adeka Gas Chemical Co., Ltd.) A commercially available product such as can be suitably used. A pendant polymer having a benzophenone derivative or the like in the side chain is also preferably used. In addition, inorganic fine particles having absorption in the ultraviolet region, ultrafine metal oxide powder dispersants and the like can also be used. Examples of inorganic fine particles include titanium oxide, zinc oxide, and silicon compounds. Examples of the ultrafine metal oxide powder dispersant include ultrafine zinc oxide powder, ultrafine titanium oxide powder, and the like, water or alcohol mixed liquids or various oil dispersion media, surfactants, water-soluble polymers, and solvent-soluble polymers. And those made using a dispersing agent such as

  Examples of the antioxidant added to the intermediate layer include the antioxidants described in JP-A-59-182785, JP-A-60-130735, JP-A-1-127387, and the like. Known compounds can be used to improve the image durability of the image recording material. Specific examples include primary antioxidants such as phenols, monophenols, bisphenols, and amines, or secondary antioxidants such as sulfurs and phosphoruss. For example, Sumizer BBM-S, BHT, BP -76, MDP-S, GM, WX-R, BP-179, GA, TPM, TP-D, TNP (manufactured by Sumitomo Chemical Co., Ltd.), Irganox-245, 259, 565, 1010, 1035, 1076, Commercially available products such as 1081, 1098, 3114 (manufactured by Ciba Geigy), MarkAQ-20, AO-30, AO-40 (manufactured by Adeka Argus Chemical Co., Ltd.) can be suitably used.

  As the light stabilizer added to the intermediate layer, JP-A-59-158287, JP-A-63-74666, JP-A-63-145089, JP-A-59-196292, JP-A-62-229594, The compounds described in JP-A-63-122596, JP-A-61-283595, JP-A-1-204788, and the like, and compounds known as those for improving image durability in photographs and other image recording materials are used. Can be mentioned. Specific examples include hindered amines, such as Tinuvin 622LD, 144, Chimassob 944 LD (manufactured by Ciba Geigy), Sanol LS-770, LS-765, LS-292, LS-2626, LS-114, LS-774. (Sankyo Co., Ltd.), Mark LA-62, LA-67, LA-63, LA-68, LA-82, LA-87 (Adeka Argus Chemical Co., Ltd.) and other commercially available products are preferably used. it can.

  A release agent may be added to the image receiving layer 3. As the release agent, those compatible with the binder to be used are preferable, and specifically, modified silicone oils and modified silicone polymers are typical, for example, amino-modified silicone oil, epoxy-modified silicone oil, polyester-modified silicone oil, An acrylic modified silicone resin, a urethane modified silicone resin, etc. are mentioned. Of these, the polyester-modified silicone oil is particularly excellent in that it prevents fusion with the ink sheet but does not hinder the secondary processability of the image receiving layer. As other mold release agents, fine particles such as silica, curable silicone compounds, and the like can also be used.

  An image-receiving layer coating solution is prepared by dispersing or dissolving each of the above-described components in a solvent, and the image-receiving layer coating solution is applied onto one sheet member of the IC card substrate and dried to form the image-receiving layer. Can be formed. The thickness of the image receiving layer is generally about 1 to 50 μm, preferably about 2 to 10 μm.

  The receiving layer 3 may have a top layer 3C on the outermost surface. As the top layer, vinyl chloride resin, polyester resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol, polycarbonate, cellulose resin, styrene resin, urethane resin, amide resin, urea Resin, epoxy resin, phenoxy resin, polycaprolactone resin, polyacrylonitrile resin, SEBS resin, SEPS resin, and modified products thereof can be used. Among these resins, preferred are vinyl chloride resin, polyester resin, acrylic resin, polyvinyl butyral resin, styrene resin, epoxy resin, urethane resin, urethane acrylate resin, SEBS resin, and SEPS resin. These resins can be used alone or in combination of two or more.

  A release agent may be added to the image receiving layer 3. As the release agent, those compatible with the binder to be used are preferable, and specifically, modified silicone oils and modified silicone polymers are typical, for example, amino-modified silicone oil, epoxy-modified silicone oil, polyester-modified silicone oil, An acrylic modified silicone resin, a urethane modified silicone resin, etc. are mentioned. Of these, the polyester-modified silicone oil is particularly excellent in that it prevents fusion with the ink sheet but does not hinder the secondary processability of the image receiving layer. As other mold release agents, fine particles such as silica, curable silicone compounds, and the like can also be used.

  The image receiving layer may be preliminarily printed in a format such as ruled lines before printing image information or character information. The format printing can be formed by any method such as offset printing, gravure printing, silk printing, screen printing, intaglio printing, letterpress printing, ink jet method, sublimation transfer method, electrophotographic method, and thermal melting method.

<Image-receiving sheet and card substrate provided with the same>
The image receiving sheet 10 obtained by the manufacturing method described above includes a base sheet 1, an actinic ray curable resin layer 2 provided on the substrate sheet 1, and an image receiving layer 3 provided on the actinic ray curable resin layer 2. , At least. By attaching the sheet member 20 to the base sheet 1 side of the image receiving sheet 10 with the adhesive 30, the card base 100 can be obtained. Further, by embedding an electronic component 40 composed of an IC chip that electrically stores user information and a coiled antenna body connected to the IC chip in the adhesive 30, a card with an IC chip can be obtained. Can be formed. In the present invention, even with such a card with an IC chip, since the image receiving sheet is produced by the manufacturing method as described above, with an IC chip that is excellent in any of print quality, chemical resistance and scratch resistance. You can get a card.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Unless otherwise specified, “%” means mass%.

(1) Preparation of actinic ray curable resin composition Three types of actinic ray curable resin compositions having the following compositions were prepared.
<Actinic ray curable resin composition 1>
Urethane acrylate oligomer (160TM, Shin-Nakamura Chemical Co., Ltd.) 5.5%
Acrylate compound (DCP, Shin-Nakamura Chemical Co., Ltd.) 1.5%
Reactive binder (P1002S, Shin-Nakamura Chemical Co., Ltd.) 2.5%
Polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 0.5%
Solvent (Methyl ethyl ketone) 70.0%

<Actinic ray curable resin composition 2>
Urethane acrylate oligomer (UA-1280T, Shin-Nakamura Chemical Co., Ltd.) 4.0%
Acrylate compound (DCP, Shin-Nakamura Chemical Co., Ltd.) 3.0%
Reactive binder (P1002S, Shin-Nakamura Chemical Co., Ltd.) 2.5%
Polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 0.5%
Solvent (Methyl ethyl ketone) 70.0%

<Actinic ray curable resin composition 3>
Photo-curing resin (UV3810, manufactured by Toagosei Co., Ltd.) 7.7%
Thermoplastic resin (Epoblend, manufactured by Daicel Industries) 2.0%
Polymerization initiator (Irgacure 127, manufactured by Ciba Specialty Chemicals) 0.3%
Solvent (Toluene) 70.0%

(2) Preparation of image receiving layer forming composition The following three types of receiving layer forming compositions were prepared as coating liquids for forming the receiving layer. In addition, as a metal ion containing compound used for preparation of the following receiving layer forming composition 2, compound MS-7 described in JP-A-2008-170772 was used.
<Receptive layer forming composition 1>
Polyvinyl butyral resin (ESREC BL-1, manufactured by Sekisui Chemical Co., Ltd.) 9%
Isocyanate (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1%
Solvent (methyl ethyl ketone / butyl acetate = 8: 1 solution) 90%

<Receptive layer forming composition 2>
Polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 6%
Metal ion-containing compound 4%
Solvent (methyl ethyl ketone / butyl acetate = 8: 1 solution) 90%

<Receptive layer forming composition 3>
Polyethylene wax (Hitech E1000, manufactured by Toho Chemical Industries) 2%
Urethane-modified ethylene-acrylic acid copolymer (Hitech S6254, manufactured by Toho Chemical Industry Co., Ltd.) 8%
Methyl ethyl cellulose (SM15, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1%
90% water

Example 1
On the base material sheet (U2L92W-188, manufactured by Teijin DuPont Films Co., Ltd.), the actinic ray curable resin composition 1 is applied to form a coating film so that the thickness of the coating film becomes 10 μm. Ultraviolet rays were irradiated under the irradiation conditions shown in Table 1 using a UV exposure device (Fusion UV, F600V, LH10 lamp, H bulb, and reflecting mirror were cold type). Next, the above-described composition 1 for forming a receiving layer was applied on the semi-cured coating film so that the coating film thickness was 0.2 μm, and then the coating film thickness was 2.5 μm. Then, the receiving layer forming composition 2 was applied, and further, the receiving layer forming composition 3 was applied so that the thickness of the coating film was 0.5 μm. After forming the coating film of the receiving layer forming composition 3, the second ultraviolet ray was irradiated through the coating layer of the receiving layer forming composition 3 under the irradiation conditions shown in Table 1 using a UV exposure device. An image receiving sheet was obtained by irradiation. The second UV irradiation was performed after 2 hours had passed since the composition for forming the receiving layer was applied. The peak illuminance and the integrated exposure amount were measured using a microcure model MC-2 with a UV illuminance meter microcure data reader manufactured by Fusion UV Systems Japan. The peak illuminance and integrated exposure during UV irradiation can be changed by changing the distance (mm) between the light source and the substrate, and also changing the lamp light source output (%) and the conveyance speed (m / min). Adjusted by.

  An IC component and another sheet (U2L92W-188) are bonded to the base sheet side of the obtained image receiving sheet via a hot melt adhesive (Macroplast QR3460, manufactured by Henkel), and makeup is made using a roll cutter. By cutting, an IC card with an image receiving sheet having a thickness of 790 μm and a card size of 55 mm × 85 mm was produced.

Example 2 and Reference Examples 1-4
An IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the exposure conditions in Example 1 were changed as shown in Table 1.

Example 7
In Example 1, a card with an image receiving sheet was produced in the same manner as in Example 1 except that no IC component was added when producing the IC card.

Example 8
An IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the actinic ray curable resin composition 1 used in Example 1 was changed to the actinic ray curable resin composition 2.

Example 9
An IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the actinic ray curable resin composition 1 used in Example 2 was changed to the actinic ray curable resin composition 2.

Example 10
A card with an image receiving sheet was produced in the same manner as in Example 7 except that the actinic ray curable resin composition 1 used in Example 7 was changed to the actinic ray curable resin composition 2.

Example 11
An IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the actinic ray curable resin composition 1 used in Example 1 was changed to the actinic ray curable resin composition 3.

Example 12
An IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the actinic ray curable resin composition 1 used in Example 2 was changed to the actinic ray curable resin composition 3.

Example 13
A card with an image receiving sheet was produced in the same manner as in Example 7, except that the actinic ray curable resin composition 1 used in Example 7 was changed to the actinic ray curable resin composition 3.

Comparative Example 1
In Example 1, an IC card with an image receiving sheet was produced in the same manner as in Example 1 except that the second UV irradiation was not performed.

Comparative Example 2
In Comparative Example 1, an IC card with an image receiving sheet was produced in the same manner as Comparative Example 1 except that the irradiation conditions of the first ultraviolet irradiation were changed to the irradiation conditions shown in Table 1.

Comparative Example 3
In Comparative Example 2, an IC card was produced in the same manner as in Comparative Example 2 except that no receiving layer was formed.

Comparative Example 4
On a base sheet (U2L92W-188, manufactured by Teijin DuPont Films Co., Ltd.), a coating liquid comprising 10% of a thermoplastic resin (Nipporan N5230, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 90% of a solvent (toluene) is used. After applying so that the thickness becomes 10.0 μm, it is dried, and after applying the above-described composition 1 for forming a receiving layer on the coating film so that the thickness of the coating film becomes 0.2 μm, On top, the receiving layer forming composition 2 is applied so that the thickness of the coating film is 2.5 μm, and further, the receiving layer forming composition 3 is applied so that the thickness of the coating film is 0.5 μm. did.

  An IC component and another sheet (U2L92W-188) are bonded to the base sheet side of the obtained image receiving sheet via a hot melt adhesive (Macroplast QR3460, manufactured by Henkel), and makeup is made using a roll cutter. By cutting, an IC card with an image receiving sheet having a thickness of 790 μm and a card size of 55 mm × 85 mm was produced.

Comparative Example 5
In Comparative Example 4, an image receiving sheet is provided in the same manner as Comparative Example 4 except that a white polypropylene resin (Noblen FL25HA, manufactured by Mitsubishi Yuka Co., Ltd.) is provided on the base sheet so as to have a thickness of 10 μm by the extrusion laminating method. An IC card was produced.

<Evaluation of printing quality>
Next, the ink side of the ink sheet for sublimation type thermal transfer recording is superimposed on the surface of the receiving layer of the obtained IC card, and the output is 0.23 W / dot and the pulse width is 0. A person image with gradation was formed on the image receiving layer by heating under conditions of 3 to 4.5 milliseconds and a dot density of 16 dots / mm. Further, the image receiving layer and the ink side of the melt type thermal transfer recording ink sheet are overlapped, and the output is 0.5 W / dot, the pulse width is 1.0 ms, and the dot density is 16 dots / mm from the ink sheet side using the thermal head. Character information was printed by heating under conditions.

Next, a protective layer transfer sheet for forming a protective layer on the image receiving layer (image-formed side) of the IC card was prepared as follows.
First, a 25 μm thick polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., Lumirror) is used as a support, and on one surface thereof, a release layer coating liquid having the following composition is dried by gravure coating. The film was applied to a thickness of 1.5 μm and dried to form a release layer.
<Release layer coating solution>
Norbornene resin (manufactured by Nippon Synthetic Rubber Co., Ltd., Arton G) 40%
Acrylic polyol resin 10%
(Brand name Thermolac SU-100A, manufactured by Soken Chemical Co., Ltd.)
Solvent (methyl ethyl ketone: toluene = 2: 8) 50%

Next, an actinic ray curable resin coating liquid having the following composition was applied on the formed release layer by gravure coating so that the thickness after drying was 6 μm and dried to form a coating film. .
<Actinic ray curable resin coating solution>
Urethane oligomer 12%
(Product name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Multifunctional oligomer 7.5%
(Product name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 9%
(Product name Parapet GF, manufactured by Kuraray Co., Ltd.)
Photopolymerization initiator 1.5%
(Product name: Irgacure 907, manufactured by Ciba Specialty Chemicals)
Methyl ethyl ketone 60%

The coating film formed as described above was irradiated with ultraviolet rays under the following irradiation conditions using the same UV exposure apparatus as used in Example 1. Measurements of peak illuminance and integrated exposure were performed in the same manner as in Example 1.
-Peak illuminance: 50 mW / cm ²
Integrated exposure amount: 50 mj / cm ²

Next, on the actinic ray curable resin layer formed as described above, an intermediate layer coating solution having the following composition was applied by gravure coating so that the thickness after drying was 0.5 μm, and then 50 ° C. An intermediate layer was formed by aging for 24 hours.
<Intermediate layer coating solution>
Polyvinyl butyral resin 8%
(Product name BX-1, ELEX B series, manufactured by Sekisui Chemical Co., Ltd.)
90% methyl ethyl ketone
Hardener (Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) 2%

Subsequently, on the intermediate layer formed as described above, an adhesive layer coating liquid having the following composition was applied by gravure coating and dried so that the thickness after drying was 1.0 μm. Thus, a protective layer transfer sheet having a layer structure of support / active light curable resin layer / intermediate layer / adhesive layer was obtained.
<Adhesive layer coating solution>
Vinyl chloride-vinyl acetate copolymer 20%
Acrylic resin 10%
Solvent (ethyl acetate: toluene = 2: 5) 70%

The IC card and the protective layer transfer sheet are overlapped so that the adhesive surface of the protective layer transfer sheet obtained as described above faces the image receiving layer (image-formed side) of the IC card. Under the transfer conditions, a protective layer was formed on the front surface of the transfer object.
Thermal head: KGT-217-12MPL20 (manufactured by Kyocera Corporation)
-Heating element average resistance: 3195 (Ω)
・ Print density in the main scanning direction: 300 dpi
-Sub-scanning direction printing density: 300 dpi
Applied power: 0.12 (w / dot)
・ One line cycle: 5 (milliseconds)
-Printing start temperature: 40 (° C)
・ Applied pulse: Using a multi-pulse test printer that can vary the number of divided pulses with a pulse length that equally divides a line period into 256 within a line period, and changing the duty ratio of the divided pulses. The number of pulses per line period was fixed at 210, fixed at 60%, solid printing was performed, and the protective layer was transferred to the entire printing screen.

The print quality of the printed matter thus obtained was visually evaluated according to the following evaluation criteria.
○: Characters are printed without any problem △: Slightly printed characters are faint ×: Characters are not printed

<Evaluation of chemical resistance>
Moreover, after immersing the printed matter (card) in a solution of 50% isopropyl alcohol at a liquid temperature of 25 ° C. for one day, the state of the card surface was visually observed to evaluate chemical resistance. The evaluation criteria were as follows.
○: No change from the state before immersion Δ: 50% or more of the printed image information is faint ×: The printed image information is lost

The evaluation results were as shown in Table 2 below.

The evaluation results were as shown in Table 2 below.

Claims (7)

A method for producing an image receiving sheet comprising at least a base sheet, an actinic ray curable resin layer provided on the substrate sheet, and an image receiving layer provided on the actinic ray curable resin layer. ,
Apply the actinic ray curable resin composition on the base sheet to form a coating film,
By irradiating the coating film with actinic rays, the coating film is cured or semi-cured,
Forming an image receiving layer on the cured or semi-cured coating;
Comprising
Actinic ray irradiation to the coating film is performed at least twice to form an actinic ray curable resin layer,
First and second actinic ray irradiations are respectively performed with an integrated exposure amount of 200 to 500 mJ / cm ² ,
After irradiating the actinic ray curable resin composition with the first actinic ray, the image receiving layer forming composition is applied onto the coating film to form a coating film, and then the image receiving layer forming composition is applied. A method of irradiating a coating film with a second actinic ray through the formed coating film . A method for producing an image receiving sheet comprising at least a base sheet, an actinic ray curable resin layer provided on the substrate sheet, and an image receiving layer provided on the actinic ray curable resin layer. ,
Apply the actinic ray curable resin composition on the base sheet to form a coating film,
By irradiating the coating film with actinic rays, the coating film is cured or semi-cured,
Forming an image receiving layer on the cured or semi-cured coating;
Comprising
Actinic ray irradiation to the coating film is performed at least twice to form an actinic ray curable resin layer,
First and second actinic ray irradiations are respectively performed with an integrated exposure amount of 200 to 500 mJ / cm ² ,
A second irradiation is performed after at least one hour has elapsed after the first irradiation .   The method of Claim 1 or 2 that the actinic ray at the time of the 1st irradiation is an ultraviolet-ray.   The method as described in any one of Claims 1-3 that the actinic ray at the time of the 2nd irradiation is an ultraviolet-ray.   The method according to claim 1, wherein the image receiving layer includes an intermediate layer and a metal compound-containing layer.   The method according to claim 1, wherein the image receiving layer includes an intermediate layer, a metal compound-containing layer, and a top layer.   The method as described in any one of Claims 1-6 which apply | coats the said actinic-light curable resin composition so that the thickness of the said coating film may be 3-20 micrometers.