JPH04338593A - Image recording material - Google Patents

Abstract

PURPOSE:To prevent forgery and alteration, in a recording material for an identification card, by laminating a transparent protective layer having unevenness to the image forming surface of a base material on which an image is formed by a thermal transfer system. CONSTITUTION:A base material 1 is formed by providing an image receiving layer 1b consisting of a binder such as a vinyl chloride resin and additives such as a release agent or the like on one side of a support 1a made of paper. A gradation data-containing image 3 and a character data-containing image 2 are formed on the surface of the image receiving layer 1b of the base material 1 by a sublimation type thermal transfer system. A transparent protective layer 4 having an ueven surface and composed of a coating agent containing an ultraviolet-curable prepolymer is formed on the image receiving layer 1b containing both images 3, 2. The unevenness of the protective layer 4 is formed by adding a solid filler such as a silica gel to a protective layer forming material or by treating the surface of the formed protective layer 4 with corona discharge.

Description

[0001] The present invention relates to an image recording medium, and more particularly to an image recording medium that is free from forgery and alteration, that is, an image recording medium that has excellent tamper resistance. Regarding. [0002] Conventionally, many ID cards have been used as identification cards, driver's licenses, membership cards, etc. An ID card usually has a person's image for confirming the card holder and various written items. Since a person image is usually formed as a gradation image, it can be an image containing gradation information. For example, in the case of an identification card, the various items listed include the person's address,
These include name, date of birth, department, date of validity, etc. In the case of a driver's license, for example, the information includes the person's date of birth, name, license number, license type, etc. Since these written items are written in letters, numbers, symbols, etc., the letters, numbers, symbols, etc. can be used as a text information-containing image. In recent years, ID cards with gradation images formed by a sublimation type thermal transfer method have appeared because beautiful images can be easily formed. This sublimation type thermal transfer method generally consists of an image receiving layer of an image receiving sheet formed by forming an image receiving layer on a support, and an ink layer of an ink sheet having an ink layer containing a sublimable dye on the support. This refers to a method in which a sublimable dye is diffused and transferred to the image-receiving layer by superimposing them and heating imagewise, thereby forming a gradation image such as a human face image in the image-receiving layer. By the way, what is important about ID cards is that forgery or alteration of ID cards must be absolutely prevented. The reason why ID cards should not be forged or altered is so obvious that no explanation is necessary. However, as mentioned above, an ID card consisting of a support and an image-receiving layer on which a gradation image has been formed by a sublimation type thermal transfer method is such that the area on which the gradation image has been formed is cut out, and a gradation image area prepared separately is added to the area where the gradation image has been formed. It can easily be counterfeited or altered by inserting it. [0005] Therefore, in ID cards, it is necessary to prevent the image-receiving layer having a gradation image from being cut off by some method to prevent forgery and alteration of the ID card. In order to protect the gradation image on the ID card and prevent its forgery and alteration, the conventional method is to laminate a transparent sheet on the surface of the ID card (Japanese Patent Application Laid-open No. 1-1-1999).
80391) has been proposed. However, even if a transparent sheet is laminated onto an ID card having a gradation image formed on the image-receiving layer by a sublimation type thermal transfer method, the image-receiving layer itself is made of, for example, a thermoplastic resin sheet. Moreover, since the transparent sheet is also a thermoplastic resin sheet, the image-receiving layer and the transparent sheet can be easily peeled off, and the gradation image area can be cut out after peeling off the transparent sheet. By inserting a forged gradation image area therein and then laminating it again with a transparent sheet, it is easy to forge an ID card. [0007] Therefore, when a simple transparent sheet is laminated
This method cannot completely prevent counterfeiting and alteration. Additionally, a method of forming a hologram layer on an ID card is also said to be effective in preventing ID cards from being tampered with (
(Japanese Patent Application Laid-open No. 2-212193). [0008] In this method, the ID card is characterized by a hologram in which a three-dimensional image is reproduced so that it cannot be tampered with, but in the past, this hologram layer was used as an image-receiving layer to simplify the process. Since the image is formed under the image-receiving layer, there remains a risk that the image formed on the image-receiving layer may be easily tampered with. Due to the nature of ID cards, facial photographs must never be falsified. Furthermore, automobile licenses are issued only by certain public institutions, and must never be freely created or forged by any other than the above-mentioned public institutions. [0009] One of the important issues now is the development of technology that can completely prevent forgery and alteration of various image recording cards such as ID cards. The present invention has been made based on the above circumstances. An object of the present invention is to solve the above-mentioned problems and provide an image recording medium having excellent tamper-proof properties. Means for Solving the Problems The invention according to claim 1 for solving the problems described above includes a base material on which an image is formed by a thermal transfer method, and a base material on which an image is formed on the image forming surface of the base material. An image recording body characterized in that it has a transparent protective layer that is laminated on a substrate and a transparent protective layer that is uneven. The present invention is an image recording body characterized by having a hologram layer laminated on an image forming surface of a base material. FIG. 1 shows an image recording medium according to an embodiment of the present invention, and this image recording medium has a base material 1 comprising a support 1a and an image receiving layer 1b provided on one side thereof. Then, on a predetermined surface of the image-receiving layer 1b, a gradation information-containing image 3 is formed by a sublimation type thermal transfer method, and a text information-containing image 2 is formed by a melting type thermal transfer method or a sublimation type thermal transfer method, and the gradation information-containing image is formed. A transparent protective layer 4 is formed on the image-receiving layer 1b including the layer 3 and the character information-containing image 2, and a writing layer 5 is further provided on the opposite surface of the base material 1. The surface of the transparent protective layer 4 is formed with unevenness 6. FIG. 2 shows an image recording medium according to another embodiment of the present invention, and this image recording medium has a base material 1 having an image receiving layer 1b provided on one side of a support 1a. Then, on a predetermined surface of the image-receiving layer 1b, a gradation information-containing image 3 is formed by a sublimation type thermal transfer method, and a text information-containing image 2 is formed by a melting type thermal transfer method. Further, on the surface of the image receiving layer 1b on which these image layers are formed, a hologram forming layer [hologram layer (relief layer)] is applied via an adhesive layer 6.
/thin film reflective layer] 7 is formed, and this hologram forming layer 7
A transparent protective layer 4a is formed thereon. Note that FIGS. 1 and 2 show an image recording medium according to a preferred embodiment of the present invention, and the present invention is not limited thereto. Below, including the above two embodiments,
The base material, gradation information-containing image, character information-containing image, hologram layer, transparent protective layer, and others will be explained in detail in order. A. Substrate A suitable substrate in the present invention is a substrate on which at least an image containing gradation information by a sublimation type thermal transfer method and an image containing character information by a melting type thermal transfer method or a sublimation type thermal transfer method are formed together when producing an image recording medium. and has a certain mechanical strength such as strength and rigidity to withstand use as a card, for example.
There are no particular restrictions. When used as a card, a base material formed by laminating sheets of the same or different types can also be used in order to maintain its mechanical strength. Furthermore, it is also possible to use a base material in which information common to cards of the same type is printed on the visible layer, and watermarks can also be added as a measure to prevent counterfeiting or alteration of the card itself. It is also possible to use a base material that has undergone special processing to prevent forgery that can be confirmed by physical means. [0015] A general structure of the base material includes a base material in which an image-receiving layer is laminated on a support. In this case, the image-receiving layer may be provided on one or both sides of the support, may be provided on the entire surface of the support, or may be provided only on a desired portion. In addition, as this image-receiving layer, for example, as shown in FIG. 3, when forming an image 3 containing gradation information and an image 2 containing character information, a first Image receiving layer 1 of
c and a second image-receiving layer 1d prepared to be able to adhere well to hot-melt ink may be separately provided on predetermined surfaces of the support 1a. However, in order to simplify the manufacturing process and increase applicability, it is usually preferable to use an image-receiving layer that is prepared so that both images containing gradation information and images containing character information can be formed satisfactorily. In addition, as another aspect of the base material in the present invention, when the support itself is made of a material that can suitably form an image containing gradation information and an image containing character information, the support itself can be used as a base material. It can also be used as a material. In this case, the support serves as an image-receiving layer that receives the sublimable dye. The shape of the substrate used in the present invention is not particularly limited, and may be of various sizes and forms (sheet-like, block-like, etc.). For example, when making cards,
A base material processed into a card size may be used, or the original base material may be cut into a desired card size at any point in the manufacturing process of the image recording medium of the present invention. [0018] The base material may be provided with embossing, a signature, an IC memory, an optical memory, a magnetic recording layer,
Other printing or the like may also be provided. These may be used at any point in the manufacturing process of the image recording medium of the present invention (for example,
It is possible to provide the transparent protective layer after forming the transparent protective layer) or even after manufacturing. In addition, in order to prevent white spots and improve sensitivity, for example, Japanese Patent Application Laid-Open No. 60-236794,
As described in Japanese Patent Application Laid-Open No. 61-258793,
A cushion layer or a heat insulating layer may be provided on the surface of the support. Next, the support and the image-receiving layer will be described in detail. (A.1) Support Supports include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or composite materials made of paper and paper), white vinyl chloride, etc. based resin sheet, white polyethylene terephthalate base film, transparent polyethylene terephthalate base film, polyethylene naphthalate, ABS, AS
Examples include various plastic films or sheets such as PP, PS base films, films or sheets made of various metals, films or sheets made of various ceramics, and the like. [0020] In order to improve the clarity of the image formed in a later step, white pigments such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, calcium carbonate, etc. are added in advance to the support. is preferably added. Furthermore, if the image recording medium is to be used as an ID card such as a car license, the support may be
It is generally composed of a sheet or film made of a composition of the white pigment and a vinyl chloride resin described below. [0021] When the base material is formed as a laminate of a support and an image-receiving layer, the thickness of the support is usually 100 to 1.
000 μm, preferably 100 to 800 μm. The thickness of the support is usually 100 to 1,000 μm, preferably 200 to 800 μm. The support may be provided with embossing, a signature, an IC memory, an optical memory, a magnetic recording layer, other printing, etc., as required. (A.2) Image-receiving layer The image-receiving layer formed on the surface of the support can be formed from a binder and various additives. Further, depending on the case, the image-receiving layer may be formed only from a binder. - Binder As the binder for the image-receiving layer, a commonly known binder for sublimation type heat-sensitive transfer recording can be used as appropriate. As the main binder, various binders can be used, such as vinyl chloride resin, polyester resin, polycarbonate resin, acrylic resin, and various heat-resistant resins. However, if there are practical requirements for the images formed by the present invention (for example, ID cards to be issued are required to have a certain heat resistance),
It is necessary to consider the type or combination of binders to satisfy such requirements. Taking the heat resistance of an image as an example, if heat resistance of 60°C or higher is required, the Tg should be 6, taking into account the bleeding of sublimable dyes.
It is preferred to use a binder whose temperature is above 0°C. [0024] Although the type of binder can be selected arbitrarily,
Vinyl chloride resins are preferred in terms of image storage stability and the like. Polyvinyl chloride alone can be used as a self-supporting image-receiving layer and is very practical. Furthermore, examples of the vinyl chloride resin include polyvinyl chloride resins and vinyl chloride copolymers. Examples of the vinyl chloride copolymer include copolymers of vinyl chloride and other comonomers containing vinyl chloride as a monomer unit in a proportion of 50 mol % or more. Examples of the other comonomers include vinyl acetate, vinyl propionate, vinyl esters of fatty acids such as vinyl acetate and vinyl tallow, acrylic acid,
Acrylic acid or methacrylic acid and its alkyl esters such as methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, maleic acid, maleic acid Examples include maleic acid and its alkyl alkyl esters such as diethyl, dibutyl maleate, and dioctyl maleate, and alkyl vinyl ethers such as methyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, palmityl vinyl ether, and stearyl vinyl ether. Furthermore, the comonomers include ethylene, propylene, acrylonitrile, methacrylonitrile, styrene, chlorostyrene, itaconic acid and its alkyl esters, crotonic acid and its alkyl esters, dichloroethylene, trifluoroethylene, and other halogenated olefins, cyclopentene, etc. Examples include cycloolefins such as, aconitic acid esters, vinyl benzoate, benzoyl vinyl ether, and the like. The vinyl chloride copolymer may be a block copolymer, a graft copolymer, an alternating copolymer, or a random copolymer. Further, in some cases, it may be a copolymer with a material having a peeling function such as a silicon compound. In addition to the vinyl chloride resin, polyester resins can also be suitably used as the image-receiving layer for sublimation type thermal transfer. [0027] Examples of the polyester resin that can be used in the present invention include those disclosed in JP-A-58-188695;
Compounds described in JP-A-62-244696 can be mentioned. Polycarbonate resins can also be used as binders, for example:
Various compounds described in JP-A-62-169694 can be used. -Metal ion-containing compound-If the heat-diffusible dye for forming an image containing gradation information is a compound that forms a chelate with metal ions as described below, the image-receiving layer contains a metal ion-containing compound. By allowing this to occur, it is possible to form an image containing gradation information with good fixability. When the metal ion-containing compound is contained in the image-receiving layer, metal ions constituting the metal ion-containing compound include divalent and polyvalent metals belonging to Groups I to VIII of the periodic table. Among them, Al, Co, Cr
, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, with Ni, Cu, Co, Cr and Zn being particularly preferred. As compounds containing these metal ions, inorganic or organic salts of the metals and complexes of the metals are preferred. Specific examples include Ni2+, Cu2+,
A complex represented by the following general formula containing Co2+, Cr2+ and Zn2+ is preferably used. [M(Q1)k(Q2)m(Q3)n]p
+p(L-) However, in the formula, M represents a metal ion, and Q
1, Q2, and Q3 each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M, and these coordination compounds include, for example, the coordination compounds described in "Chelate Kagaku (5) (Nankodo)". can be selected from position compounds. Particularly preferred are coordination compounds having at least one amino group that coordinates with a metal, and more specific examples include ethylenediamine and its derivatives, glycinamide and its derivatives, picolinamide and its derivatives. It will be done. L is a counteranion capable of forming a complex,
Examples include inorganic compound anions such as Cr, SO4, ClO4, and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives, but particularly preferred are tetraphenylboron anions and their derivatives, and alkylbenzenesulfonic acid anions and their derivatives. be. k represents an integer of 1, 2 or 3, m is 1
, 2 or 0, and n represents 1 or 0, which is determined depending on whether the complex represented by the above general formula has a tetradentate or hexadentate coordination, or Q1 , Q2 , Q3
is determined by the number of ligands in p represents 1, 2 or 3. [0032] This kind of metal ion-containing compounds include:
Examples include those illustrated in US Pat. No. 4,987,049. The amount of the metal ion-containing compound added is preferably 0.5 to 20 g/m2, more preferably 1 to 10 g/m2, relative to the image receiving layer. - Additives - A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), and a pigment may be added to the image-receiving layer. Furthermore, a plasticizer, a hot solvent, etc. may be added as a sensitizer. The release agent can improve the releasability between the sublimation type heat-sensitive transfer ink sheet and the image-receiving layer, which will be described later. Such release agents include silicone oil (including what is called silicone resin); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; Among them, modified silicone polymers are preferred. Examples of modified silicone polymers include polyester-modified silicone resin (or silicone-modified polyester resin), acrylic-modified silicone resin (or silicone-modified acrylic resin), and urethane-modified silicone resin (
Alternatively, silicone-modified urethane resin), cellulose-modified silicone resin (or silicone-modified cellulose resin), alkyd-modified silicone resin (or silicone-modified alkyd resin), epoxy-modified silicone resin (
or silicone-modified epoxy resin). A release agent layer can also be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the above-mentioned release agent in a suitable solvent and applying the solution, followed by drying. Note that it is preferable that a release agent such as silicone is not used at all or added in as small a amount as possible in consideration of adhesiveness with the protective layer. Next, as the antioxidant, antioxidants described in JP-A No. 59-182785, JP-A No. 60-130735, JP-A No. 1-127387, etc., and those that improve image durability in photographs and other image recording materials, are used. Known compounds can be mentioned as improving substances. [0036] The UV absorber and light stabilizer include:
JP-A-59-158287, JP-A No. 63-74686,
No. 63-145089, No. 59-196292, No. 62-229594, No. 63-122596, No. 61
Examples include compounds described in publications such as No. 283595 and JP-A No. 1-204788, and compounds known to improve image durability in photographs and other image recording materials. [0037] Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, etc., and examples of the organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicone resin particles. can be mentioned. These inorganic/organic resin particles vary depending on their specific gravity, but are preferably added in an amount of 0.1 to 70% by weight. Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, acid clay, and the like. [0038] As the plasticizer, phthalate esters (
For example, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), trimellitic acid esters (for example, octyl trimellitate,
trimellitic acid isononyl ester, trimellitic acid isodesol ester, etc.), pyromellitic acid esters such as pyromellitic acid octyl ester, adipate esters (dioctyl adipate, methyl lauryl adipate, di-2-adipate) ethylhexyl, ethyl lauryl adipate, etc.), other oleic acid esters,
Succinic acid esters, maleic acid esters, sebacic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearate, as well as esters such as triphenyl phosphate and tricresyl phosphate. Phosphite esters, phosphorous esters such as triphenyl phosphite, tris tridecyl phosphite, dibutyl hydrogen phosphite, glycol esters such as ethyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, etc. can be mentioned. Incidentally, since excessive addition of plasticizer deteriorates the storage stability of images, the amount of plasticizer added is usually in the range of 0.1 to 30% by weight based on the binder in the image-receiving layer. (A.3) Writing layer A writing layer may be formed on the surface of the support opposite to the surface on which the image-receiving layer is formed. This image recording body can be used as an ID such as a car license.
When used as a card, it is particularly preferable to provide a writing layer. This is because it is convenient to form a writing layer so that various information can be written on the ID card. The description regarding the writing layer in the present invention can be found in Japanese Patent Application Laid-Open No. 1-2011.
The detailed description thereof will be omitted and will be replaced with the explanation regarding the "writing layer" described from line 14 in the upper right column on page 4 to line 2 in the lower right column on page 4 of Publication No. 5155. (A.4) Formation of the image-receiving layer The image-receiving layer in the present invention is prepared by preparing a coating liquid for the image-receiving layer by dispersing or dissolving the components forming the image-receiving layer in a solvent.
It can be manufactured by a coating method in which the image-receiving layer coating liquid is applied to the surface of the support and dried. It can also be produced by a lamination method, etc., in which a mixture containing the components forming the image-receiving layer is melt-extruded and laminated onto the surface of a support. The solvent used in the coating method includes water, alcohol, methyl ethyl ketone, toluene,
Conventionally known solvents such as dioxane and cyclohexanone can be used. [0041] When employing the lamination method, a coextrusion method may also be employed. The image receiving layer may be formed over the entire surface of the support, or may be formed on a part of the surface of the support. The thickness of the image-receiving layer formed on the surface of the support is generally about 2 to 50 μm, preferably about 3 to 20 μm. On the other hand, when the image-receiving layer itself is a support because it is self-supporting, the thickness of the image-receiving layer is 60 to 200 μm, preferably 90 μm.
m to about 150 μm. In addition, in this image-receiving sheet for thermal transfer recording, in order to more effectively prevent fusion with the ink layer of the ink sheet for thermal transfer recording, a release agent (the above-mentioned silicone resin, modified silicone resin, A release layer containing a silicone oil film or a cured product thereof may be further laminated. [0042] The thickness of this peeling layer is usually 0.03 to 2.
It is 0 μm. Further, in the present invention, a cushion layer or a barrier layer may be provided between the support and the image-receiving layer. By providing a cushion layer, it is possible to transfer and record an image corresponding to image information with good reproducibility with less noise. Examples of the material constituting the cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, and epoxy resin. The thickness of the cushion layer is usually 1 to 50 μm, preferably 3 to 30 μm.
It is um. Providing a barrier layer can prevent the dye from diffusing into the support and prevent the dye from bleeding within the support. Examples of the material constituting the barrier layer include hydrophilic binders such as gelatin and casein, and polymers with high Tg. Furthermore, when forming a hologram layer on the surface of the image receiving layer as described later, it is preferable to provide an adhesive layer between the image receiving layer and the hologram layer. B. Image containing gradation information The image containing gradation information referred to here can be formed using a sublimable dye. Many of the images formed by sublimable dyes have monochrome or multicolor tonality. When this image recording medium is an ID card such as a driver's license, the image containing gradation information is often a portrait of a person. However, if this image recording medium is a prepaid card such as a telephone card, a business card, or an advertising flyer,
This gradation information-containing image is not limited to a human figure, but may also be a landscape, a painting, or an abstract pattern. This gradation information-containing image is formed on the image-receiving layer by an image forming method described later using a sublimation type thermal transfer recording ink sheet described later. (B.1) Ink sheet for sublimation type thermal transfer recording The ink sheet for sublimation type thermal transfer recording can be composed of a support and an ink layer containing a sublimable dye formed thereon. (B.1.1) Ink layer containing sublimable dye The above ink layer containing sublimable dye basically contains a sublimable dye and a binder. (B.1.1.1) Sublimable dye As the sublimable dye, conventionally known sublimable dyes can be used. Examples of this sublimable dye include cyan dye,
Examples include magenta dye and yellow dye. Examples of the cyan dye include JP-A-59-78896, JP-A-59-227948, JP-A-60-24966, and JP-A-60.
-53563, 60-130735, 60-1
No. 31292, No. 60-239289, No. 61-19
No. 396, No. 61-22993, No. 61-31292
No. 61-31467, No. 61-35994, No. 61-49893, No. 61-148269, No. 62
-191191, 63-91288, 63-9
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in publications such as No. 1287 and No. 63-290793. [0047] As the magenta dye, JP-A-59-
No. 78896, JP-A-60-30392, JP-A-60
-30394, JP 60-253595, JP 61-262190, JP 63-5992, JP 63-205288, JP 64-159, JP 64-63194 Examples include anthraquinone dyes, azo dyes, azomethine dyes, etc., which are described in various publications such as No. As a yellow pigment, JP-A-59-788
No. 96, JP-A-60-27594, JP-A-60-31
No. 560, JP-A-60-53565, JP-A-61-1
Examples include methine dyes, azo dyes, quinophthalone dyes, and anthrisothiazole dyes described in publications such as No. 2394 and JP-A No. 63-122594. Particularly preferable sublimable dyes are those formed by a coupling reaction between a compound having an open-chain or closed-chain active methylene group and an oxidized product of a p-phenylenediamine derivative or an oxidized product of a p-aminophenol derivative. It is an indoaniline dye obtained by a coupling reaction between the obtained azomethine dye and an oxidized product of a phenol or naphthol derivative, a p-phenylenediamine derivative, or an oxidized product of a p-aminophenol derivative. [0049] If the image to be formed is monochromatic, the sublimable dye contained in the ink layer may be a yellow dye,
It may be either a magenta dye or a cyan dye. Furthermore, depending on the tone of the image to be formed, it may contain two or more of the above three types of dyes or other sublimable dyes. In the present invention, when the image-receiving layer contains a metal ion-containing compound, it is preferable to use a sublimable dye that can react with the metal ion-containing compound to form at least a bidentate chelate. It is preferred to use the sublimable dyes shown. ##STR1## In the formula, X1 is a group in which at least one ring is 5--
Represents a collection of atoms necessary to complete an aromatic carbocycle or heterocycle consisting of seven atoms, and at least one adjacent position of the carbon atom bonded to the azo bond is a nitrogen atom or a chelate. A carbon atom substituted with a group. Further, X2 represents an aromatic heterocycle or aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms, and G represents a chelating group. Specific examples of such dyes include, for example, JP-A-59-78893 and JP-A-59-78893;
-109349 etc. The amount of the sublimable dye used is usually 0.2 to 10 per m2 of support.
g, preferably 0.3 to 3 g. (B.1.1.2) Binder - Binders for the sublimable dye-containing ink layer include cellulose resins such as cellulose adducts and cellulose esters; polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, etc. Polyvinyl acetal resin, polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, styrene resin, poly(meth)
Examples include vinyl resins such as acrylic acid esters, poly(meth)acrylic acid, and (meth)acrylic acid copolymer resins, rubber resins, ionomer resins, olefin resins, and polyester resins. Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resins, which have excellent acid resistance, are preferred. The above-mentioned various binders can be used alone or in combination of two or more. The weight ratio of the binder to the sublimable dye is preferably 1:10 to 10:1, particularly preferably 2:8 to 8:2. (B.1.1.3) Other optional components Furthermore, various additives may be added to the sublimable dye-containing ink layer as long as they do not impede the object of the present invention. The additives include silicone resin, silicone oil (reactive curing type is also possible), silicone modified resin, fluororesin, surfactant, and release compounds such as waxes.
Examples include fillers such as fine metal powder, silica gel, metal oxides, carbon black, and fine resin powder, and curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylics, and epoxies). can. Further, examples of additives include heat-melting substances for accelerating transfer, such as waxes and higher fatty acid esters, which are described in Japanese Patent Application Laid-open No. 106997/1983. (B.1.2) Support The support for the ink sheet for sublimation type thermal transfer recording may be any material as long as it has good dimensional stability and can withstand the heat during recording with a thermal head. Specifically, JP-A-63-19
The film or sheet described in the lower left column, lines 12 to 18 of page 2 of Publication No. 3886 can be used. The thickness of the support is preferably 2 to 10 μm, and the support has a subbing layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support. You can leave it there. Furthermore, an anti-sticking layer may be provided on the back surface of the support (the surface opposite to the sublimable dye-containing ink layer) for the purpose of preventing the head from fusing, sticking, or wrinkling the support. [0057] The thickness of this anti-sticking layer is usually:
It is 0.1 to 1 μm. The shape of the support is not particularly limited, and may be of any shape, such as a wide sheet or film, or a narrow tape or card. (B.2) Manufacture of ink sheet for sublimation type thermal transfer recording The ink sheet for sublimation type thermal transfer recording is produced by dispersing or dissolving the various components that form the sublimable dye-containing ink layer in a solvent. It can be produced by preparing a forming coating solution, coating it on the surface of a support, and drying it. [0058] The above-mentioned binders are used by dissolving one or more of them in a solvent or dispersing them in a latex form. The solvents include water, alcohols (e.g. ethanol, propanol), cellosolves (e.g. methyl cellosolve, ethyl cellosolve), aromatics (e.g. toluene, xylene, chlorobenzene), ketones (e.g. acetone, methyl ethyl ketone), esters. Examples include solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane), chlorinated solvents (eg, chloroform, trichlorethylene), and the like. [0059] For the above-mentioned coating, conventional methods such as a surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method, etc. can be employed. The sublimable dye-containing ink layer may be formed as a layer containing a monochromatic sublimable dye on the entire surface or a part of the surface of the support, or may be formed as a layer containing a sublimable dye of a single color on the entire surface or a part of the surface of the support, or a yellow sublimation ink layer containing a binder and a yellow dye. color pigment-containing ink layer,
A magenta sublimable dye-containing ink layer containing a binder and a magenta dye and a cyan sublimable dye-containing ink layer containing a binder and a cyan dye are applied over the entire surface or one part of the surface of the support in a constant repetition along the plane direction. It may be formed on the surface of the part. The thickness of the sublimable dye-containing ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm. In the present invention, convenience in use can be achieved by forming perforations on the sublimation type thermal transfer recording ink sheet or providing detection marks for detecting the positions of areas with different hues. [0061] The ink sheet for sublimation type thermal transfer recording is not limited to the structure consisting of a support and an ink layer containing a sublimable dye formed on the support, and other layers may be formed on the surface of the ink layer containing a sublimable dye. It's okay if it's done. For example, an overcoat layer may be provided for the purpose of preventing fusion with the image-receiving layer and setting-off (blocking) of the sublimable dye. (B.3) Method for forming an image containing gradation information To form an image containing gradation information, the surface of the sublimable dye-containing ink layer of the ink sheet for sublimation type thermal transfer recording and the surface of the image-receiving layer of the base material are bonded. The sublimable dye-containing ink layer and image-receiving layer are superimposed, and thermal energy is applied imagewise to the ink layer and the image-receiving layer. The sublimable dye in the sublimable dye-containing ink layer vaporizes or sublimates in an amount corresponding to the applied thermal energy, moves to the image-receiving layer side, and is received. As a result, an image containing gradation information is formed on the image receiving layer. [0063] As the heat source for providing the thermal energy,
A thermal head is generally used, but other known devices such as a laser beam, an infrared flash, and a thermal pen can also be used. Alternatively, heating may be performed through a pattern or halftone dot pattern that continuously expresses the shading of an image, such as black, or a colored layer such as black on one side and a negative of the above pattern. Heating may be performed in combination with negative patterns. Thermal energy can be applied from the ink sheet side for sublimation thermal transfer recording, from the substrate side, or from both sides, but if priority is given to effective use of thermal energy, sublimation thermal transfer It is desirable to perform this from the recording ink sheet side. [0065] By the above-mentioned sublimation type thermal transfer recording method, it is possible to record a one-color image on the image-receiving layer of the base material, but according to the method described below, it is also possible to obtain a color photo-like color image consisting of a combination of various colors. can. For example, yellow
By sequentially replacing the magenta, cyan, and, if necessary, black thermal transfer recording ink sheets and performing thermal transfer according to each color, it is also possible to obtain a color photographic color image consisting of a combination of each color. The following method is also effective. That is, instead of using ink sheets for sublimation type thermal transfer recording of each color as described above, an ink sheet for sublimation type thermal transfer recording having areas pre-painted in each color is used. Then, first, the yellow area is used to thermally transfer the yellow color separation image, then the magenta area is used to thermally transfer the magenta color separation image, and then the process is repeated sequentially to create yellow, magenta, cyan, and the necessary A method is adopted in which the image is thermally transferred in order with the black separated color image. C. In an image recording medium containing character information, such as an ID card, in addition to the gradation information-containing image, various characters, figures, symbols, etc. having certain information are recorded as images. Images such as characters, figures, symbols, etc. are usually formed in a single color such as black. Therefore, images of characters, figures, symbols, etc. formed in a single color can be understood as images containing character information. This character information-containing image can be formed on the image-receiving layer using the heat-melting ink sheet described in detail below, or the above-mentioned ink sheet for sublimation type thermal transfer recording. (C.1) Heat-melting ink sheet The heat-melting ink sheet can have a known structure as it is. (C.2) Formation of an image containing character information Similarly to the recording of gradation image containing information, it can be formed by a normal method using a thermal head or the like. D. Transparent Protective Layer In the invention as set forth in claim 1, a transparent protective layer is provided at least on the image-receiving layer having the gradation information-containing image formed by a sublimation type thermal transfer method. The area covered by this transparent protective layer may be only the image-receiving layer having the gradation information-containing image, or may be both the image-receiving layer having the gradation information-containing image and the character information-containing image. . In the first aspect of the invention, the surface of the transparent protective layer is uneven. An image recording medium having such a transparent protective layer as an outer layer has the feature that the irregularities on the surface of the transparent protective layer give it a unique feel to the touch, or that a special pattern such as a tint pattern is formed by the irregularities. Since it is attached, there is no risk of alteration or forgery compared to when the surface is flat. In other words, it is possible to exhibit excellent tampering prevention properties. Further, since the surface is uneven, it is easy to distinguish it from other cards by its texture or appearance, and therefore, it is convenient to be able to easily identify this image recording medium. [0071] In order to make the surface of the transparent protective layer uneven, a solid filler may be added to the transparent protective layer forming materials described below, that is, a heat-melting compound and a thermoplastic resin, prior to forming the transparent protective layer. Alternatively, the surface of the transparent protective layer once formed may be subjected to a surface treatment such as corona discharge, or the transparent protective layer may be transferred to the image-receiving layer using a hot stamp press roller provided with irregularities. [0072] Examples of the solid filler include inorganic fine particles and organic resin particles. These inorganic fine particles include silica gel, calcium carbonate, titanium oxide,
Examples of organic fine particles include acid clay, activated clay, alumina, glass, magnesium carbonate, barium sulfate, mica, and talc. Examples of organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicone resin particles. can be mentioned. Although these inorganic/organic resin particles vary depending on their specific gravity, it is desirable to add them with care not to impair the transparency and strength of the material for forming the transparent protective layer. The transparent protective layer also has the following effects. That is, when it is desired to coat an image or an image recording medium with an ultraviolet curing protective layer in order to improve its protection and durability, if
When a coating agent containing an ultraviolet curable resin is applied directly onto an image-receiving layer containing an image containing gradation information, the gradation caused by the sublimable dye is caused by the action of the ultraviolet curable resin and solvent present in the coating agent. This causes problems such as blurring and discoloration of the image containing tone information, making it impossible to obtain a clear image. On the other hand, when the transparent protective layer is provided as described above, at least the image formed by the sublimable dye is prevented from coming into contact with the coating agent, and as a result, the bleeding and discoloration of the sublimable dye are prevented. The formed image can be protected in its clear state. Also,
In order to prevent deterioration of the sublimable dye (presumably caused by decomposition or reaction with other substances) and discoloration due to ultraviolet irradiation during the formation of the ultraviolet curing protective layer, the transparent protective layer is It is valid. However, by providing the transparent protective layer on the surface of the image-receiving layer having the gradation information-containing image, the gradation information-containing image must not be damaged. Therefore, the properties required of this transparent protective layer include, in addition to the above-mentioned uneven surface shape, transparency, and minimal diffusion movement of the sublimable dye.More preferably, the sublimable dye should be Examples include being able to minimize the interference of ultraviolet rays to the dye, and preventing the coating agent from coming into contact with the sublimable dye when applying the coating agent. (D.1) Structure of transparent protective layer A transparent protective layer that satisfies these requirements is disclosed in Japanese Patent Application Laid-open No. 1838-1983.
The heat-melting compounds described in Publication No. 81, page 9, lower left column, line 9 to page 10, page 10, upper left column, line 15, and page 10, upper left column, line 16 to page 11, lower left column, line 9. It can be formed from an exemplary thermoplastic resin. It is also possible to include an ultraviolet absorber in the transparent protective layer to protect the image containing gradation information from the ultraviolet rays that occur when a coating agent containing an ultraviolet curable prepolymer is irradiated with ultraviolet rays and cured. It is effective for Examples of the ultraviolet absorber include the compounds exemplified in the description of the image-receiving layer. The amount of these compounds in the transparent protective layer varies depending on the type of compound and can be determined experimentally for each compound. The thickness of the transparent protective layer is usually 0.5 to 20.0 μm, preferably 1.0 to 10.0 μm, considering uniform application of the ultraviolet curable resin. (D.2) Transfer sheet for forming a protective layer A transfer sheet for forming a protective layer is preferably used to form a transparent protective layer on a base material on which an image containing gradation information has been formed. This transfer sheet for forming a protective layer can be constructed by laminating a release layer, a transparent protective layer, and an optional adhesive layer on a support in this order. [0079] This transparent protective layer may be formed sequentially on the same plane of the same sheet base material as the heat-melting ink sheet. As the layer structure of the transfer sheet for forming a protective layer, a known structure such as a structure used for a heat-melting ink sheet or a structure used for a transfer sheet for hot stamping can be used. That is, in order to transfer the protective layer efficiently, a release layer can be provided between the protective layer and the support, or an adhesive layer can be provided on the surface of the protective layer. E. Hologram Layer In the second aspect of the invention, the hologram layer is provided on at least a base material having a gradation information-containing image formed by a sublimation thermal transfer method. The region where this hologram layer is formed may be only the image receiving layer having the gradation information containing image, or may be both the image receiving layer having the gradation information containing image and the character information containing image. [0081] As described above, an image recording medium having a hologram layer does not have a hologram layer because the hologram image is reproduced three-dimensionally by daylight, white light such as illumination light, or specific reproduction light such as laser light. Compared to image recording media, it has remarkable specificity and can exhibit particularly excellent tampering prevention properties. The hologram layer can be formed by adhering a hologram sheet onto the image receiving layer. As the hologram sheet, a relief type hologram sheet can be used. The relief type hologram sheet is made by laminating a hologram forming layer and a hologram effect layer in this order on a support film. Specifically, a hologram sheet is a resin layer that is solid at room temperature and has thermoformability, such as a thermoplastic electron beam curable resin layer that is solid at room temperature, on the surface of a support film such as a polyethylene terephthalate film. A resin layer (hologram forming layer) is formed, and a hologram original plate on which a hologram interference pattern is formed in a concavo-convex shape is brought into contact with pressure, the concavo-convex shape is transferred to the surface of the resin layer, hardened, and then The uneven surface has sufficient transparency and high reflectivity at certain angles,
It can also be obtained by forming a thin hologram hardening layer made of a material (for example, an aluminum vapor deposited film) having a different refractive index from that of the hologram forming layer. [0083] A hologram whose image is reproduced using white light such as daylight or illumination light has excellent decorative properties because the hologram image can be observed even under normal conditions. On the other hand, the type in which the image is reproduced using laser light has an excellent ability to detect tampering. In the present invention, the transparent protective layer described in section D above may be laminated on the hologram layer, or the hologram support may also serve as the transparent protective layer. Further, an ultraviolet protective layer described in Section F below may be laminated on this transparent protective layer. In any case, compared to the case where only a hologram layer is provided, even more excellent tampering prevention properties can be exhibited. (E.1) Adhesive, Adhesive Layer The hologram layer is usually laminated on the image-receiving layer via an adhesive layer. The adhesive is not particularly limited, but generally includes heat-melting substances and/or low softening point thermoplastic resins. Moreover, a tackifier can be used in combination with these. The heat-melting substances include vegetable waxes such as carnauba wax, wood wax, auriculie wax, and espar wax; animal waxes such as beeswax, insect wax, shellac wax, and spermaceti wax; paraffin wax, microcrystal wax, and polyethylene wax. , petroleum waxes such as ester waxes and acid waxes; and mineral waxes such as montan wax, ozokerite, and ceresin; and in addition to these waxes, palmitic acid, stearic acid, margaric acid, etc. and higher fatty acids such as behenic acid; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol and eicosanol; cetyl palmitate, myricyl palmitate, cetyl stearate and myricyl stearate; Examples include higher fatty acid esters; amides such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide and amide wax; and higher amines such as stearylamine, behenylamine and palmitylamine. Examples of the thermoplastic resin having a low softening point include ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer, polyamide resins such as nylon and dimer acid, and styrene-vinyl acetate copolymer. Polystyrene resins such as butadiene copolymers, styrene-isoprene copolymers, styrene-ethylene-butylene copolymers, polyester resins, polyolefin resins,
Examples include polyvinyl ether resins, polymethyl methacrylate resins, ionomer resins, cellulose resins, polyurethane resins, acrylic resins, epoxy resins, melamine resins, and vinyl chloride resins. Examples of the tackifier include unmodified or modified rosin tackifiers, water-added rosin tackifiers, maleic acid tackifiers, polymerized rosin tackifiers, rosin phenol tackifiers, etc. Examples include rosin-based tackifiers, terpene-based tackifiers, petroleum resin-based tackifiers, and modified tackifiers thereof. [0088] These tackifiers can be used singly or in combination of two or more. The thickness of the adhesive layer is preferably not very thick, and is usually 0.1 to 2.0 μm. F. Ultraviolet Curing Protective Layer In the image recording material of the present invention, a substantially transparent ultraviolet curing protective layer cured by ultraviolet irradiation is formed on the surface of the protective layer and the surface of the image receiving layer other than the protective layer, Furthermore, it is also effective to make the recorded information and the recording medium durable. The ultraviolet curable protective layer can be formed by applying a coating agent containing an ultraviolet curable resin onto the support and irradiating it with ultraviolet rays. (F.1) Coating agent This coating agent can be formed from a composition whose main components are an ultraviolet curable prepolymer and a polymerization initiator. Examples of the ultraviolet curable prepolymer include prepolymers containing two or more epoxy groups in one molecule. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols,
Examples include polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These prepolymers can be used alone or in combination of two or more. The content of the prepolymer having two or more epoxy groups in one molecule in the coating agent is 70% by weight.
The above is preferable. The polymerization initiator is preferably a cationic polymerization initiator, and specific examples include aromatic onium salts. Examples of aromatic onium salts include salts of Group Va elements of the periodic table, such as phosphonium salts (
salts of group VIa elements such as sulfonium salts (e.g. triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, tris(4-thiomethoxy phenyl), sulfonium and triphenylsulfonium hexisafluoroantimonate), and salts of Group VIIa elements such as iodonium salts (such as diphenyliodonium chloride). The use of such aromatic onium salts as cationic polymerization initiators in the polymerization of epoxy compounds is disclosed in US Pat. No. 4,058,401 and US Pat.
69,055, No. 4,101,513, and No. 4,161,478. Preferred cationic polymerization initiators include sulfonium salts of Group VIa elements. Among them, from the perspective of storage stability of UV curable and UV curable compositions,
Triarylsulfonium hexafluoroantimonate is preferred. The content of the cationic polymerization initiator in the coating agent is preferably 3 to 20% by weight, particularly preferably 5 to 12% by weight. If the content of the cationic polymerization initiator does not exceed 1% by weight of the coating agent, the curing speed may become extremely slow when irradiated with ultraviolet rays, which is not preferable. [0093] The UV-curable resin is not limited to the above-mentioned epoxy-based curable resin, and may include radically polymerizable resins such as monofunctional or polyfunctional acrylate compounds. The coating agent may also contain oils (particularly silicone oil), surfactants such as silicone-alkylene oxide copolymers (for example, L-5410, commercially available from Union Carbide), and aliphatic epoxides containing silicone oil. , FO-171 available from 3M Company and FO-171 available from 3M Company.
430, Me commercially available from Dainippon Ink Co., Ltd.
Fluorocarbon surfactants such as gafac F-141 may also be included. This coating agent further contains, for example, vinyl monomers such as styrene, paramethylstyrene, methacrylic esters, and acrylic esters, cellulose, thermoplastic polyester, phenyl glycidyl ether, silicon-containing monoepoxide, Monoepoxides such as butyl glycidyl ether may be contained within a range that does not impede the effects of the present invention. This coating agent also contains dyes, pigments, thickeners, plasticizers, stabilizers, leveling agents, coupling agents, tackifiers, silicone group-containing activators, and fluorocarbon groups as inactive components. Wetting agents such as surfactants and other various additives, as well as acetone, methyl ethyl ketone, methyl chloride, etc., which hardly react with the cationic polymerization initiator, are used to improve the fluidity of the coating agent during application. A small amount of solvent may be included. (F.2) Coating method and coating conditions In order to apply the coating agent to the surface of the substrate containing the transparent protective layer, the coating agent may be adjusted to an appropriate viscosity by adding a solvent or the like as the case may be. A, double roll coater,
The coating may be applied to the surface of the substrate using a conventional method such as a slit coater, air knife coater, wire bar coater, slide hopper, or spray coating. As a result, the coated layer of the coating agent is applied to the surface of the base material including the transparent protective layer with a thickness of usually 0.1 to 30 μm, preferably 1 to 1 μm.
It is applied to a thickness of 4 μm. After coating, the coated layer of the coating agent is irradiated with ultraviolet rays, and the polymerization reaction or curing reaction of the ultraviolet curable prepolymer in the coating agent proceeds. Here, when we say ultraviolet rays, we mean light in the ultraviolet region, and also include light rays that include light in the ultraviolet region. Therefore, examples of UV irradiation include sunlight rays, low-pressure mercury lamp irradiation, high-pressure mercury lamp irradiation, ultra-high-pressure mercury lamp irradiation, carbon arc irradiation, metal halide lamp irradiation, xenon lamp irradiation, etc. . [0098] The atmosphere when irradiating ultraviolet rays is as follows:
An inert gas atmosphere such as air, nitrogen gas, carbon dioxide gas, etc. is preferable. The irradiation time of ultraviolet rays varies depending on the type of irradiation light source in the ultraviolet region, but is usually 0.5 seconds to
5 minutes, preferably 3 seconds to 2 minutes. Usually, when the irradiation time is short, a large light source with high irradiation intensity is required.
When the irradiation time is long, a light source with low irradiation intensity can be used. However, a light source with a low irradiation intensity requires a long curing action time, which is not advantageous in terms of the manufacturing process. However, in the present invention, by using an ultraviolet generating lamp of 200 W or less and irradiating for 3 seconds to 2 minutes,
A cured film having practically sufficient strength can be formed. In addition, during curing, the curing time can be shortened by heating the coating film of the coating agent during or before and after irradiation with ultraviolet rays. When performing such heating, the heating temperature is preferably 30 to 80°C. Before irradiation with ultraviolet rays, the heating time at the heating temperature may be long or short, but after irradiation with ultraviolet rays, the heating time is preferably 1 to 120 minutes. EXAMPLES Next, examples of the present invention will be described in detail. Note that in the following, "parts" indicate "parts by weight." (Example 1) (1) Manufacturing thickness of card-sized base material: 45
Thickness 1 on both sides of 0μm hard white PVC resin sheet
A coating liquid for an image-receiving layer having the following composition was applied by a wire bar method to a wide white vinyl chloride resin sheet with a thickness of 750 μm obtained by thermally welding a 50 μm hard transparent vinyl chloride resin sheet. By drying and removing the solvent, an image-receiving layer with a thickness of 4.0 μm was formed. Coating liquid for image-receiving layer: Vinyl chloride resin・・・・・・・・・・・・・・・
...9.9 parts [manufactured by Shin-Etsu Chemical Co., Ltd.]
TK-600] Solvent・・・・・・・・・・・・・
・・・・・・・・・・・・90.0 parts (Methyl ethyl ketone/cyclohexanone=8/2) Silicone resin (mold release agent)・・・・・・・・・・・・・・・・・・0
．． 1 part [manufactured by Shin-Etsu Chemical Co., Ltd., X24 830]
0]. Next, a writing layer coating liquid having the following composition was applied to the surface of the support opposite to the image-receiving layer and dried to form a writing layer having a thickness of 40 μm. By cutting the wide image-receiving sheet thus obtained, a card-sized base material measuring 54.0 mm x 85.5 mm was obtained. Coating liquid for writing layer: Colloidal silica・・・・・・・・・・・・・・・・・・・・・
2.5 parts Gelatin・・・・・・・・・・・・・・・
・・・・・・7.0 parts Hardening agent (see chemical formula 2)・
・・・・・・・・・・・・・・・・・・0.5 parts Water・・・・・・・・・・・・・・・・・・・・・・・・
・90.0 copies. embedded image (2) Production of ink sheet for sublimation thermal transfer recording Three types of ink layer forming coatings having the following compositions were applied to the corona discharge treated surface of a 6 μm thick polyethylene terephthalate sheet as a support. Using the wire bar coating method,
Yellow (Y),
Apply it to magenta (M) and cyan (C) separately, then dry it, and apply silicone oil (X-41, 403A) to the back side that has not been corona treated.
, manufactured by Shin-Etsu Silicone Co., Ltd.) with a dropper and spread it over the entire surface, and a backside treatment coating was performed to obtain an ink sheet for thermal transfer recording in three colors of Y, M, and C. Coating liquid for forming yellow ink layer:
Yellow disperse dye・・・・・・・・・・・・・・・
・・・・・・3.0 parts [Mitsui Toatsu Dye Co., Ltd.]
manufactured by MS Yellow] Polyvinyl Brachyl・・・・・・・・・・・・・・・5.0 parts
[Polymerization degree 1700, Tg 85.5°C, acetalization degree 64 mol%, acetyl group 3 mol% or less, manufactured by Sekisui Chemical Co., Ltd., BX-1] Polyester modified silicone...・・・・・・
0.4 parts [manufactured by Shin-Etsu Chemical Co., Ltd., X-24-
8310] Toluene・・・・・・・・・・・・
・・・・・・・・・・・・40.0 parts Methyl ethyl ketone・・・・・・・・・・・・40.
Part 0 Dioxane・・・・・・・・・・・・・・・
・・・・・・・・・10.0 copies. Coating liquid for forming magenta ink layer
Magenta disperse dye・・・・・・・・・・・・・・・
...5.0 parts [Mitsui Toatsu Dye Co., Ltd., MS Magenta] Polyvinyl Brachyl ...5.0 parts
[Polymerization degree 1700, Tg 85.5°C, acetalization degree 64 mol%, acetyl group 3 mol% or less, manufactured by Sekisui Chemical Co., Ltd., BX-1] Polyester modified silicone... ...0
．． 4 parts [Manufactured by Shin-Etsu Chemical Co., Ltd.: Product name X-2
4-8310] Toluene・・・・・・・・・
・・・・・・・・・・・・40.0 parts Methyl ethyl ketone・・・・・・・・・・・・・・・4
0.0 part dioxane・・・・・・・・・・・・
・・・・・・・・・10.0 copies. Coating liquid for forming cyan ink layer:
Cyan disperse dye・・・・・・・・・・・・・・・
...4.0 parts [Nippon Kayaku Co., Ltd., Kayaset Blue 136] Polyvinyl Brachyl
・・・・・・・・・・・・・・・・・・5.0 copies
[Polymerization degree 1700, Tg 85.5°C, acetalization degree 6
4 mol%, 3 mol% or less of acetyl group, manufactured by Sekisui Chemical Co., Ltd., BX-1] Polyester modified silicone 0.4 part [Shin-Etsu Chemical Co., Ltd. Co., Ltd., X-24-8310
] Toluene・・・・・・・・・・・・・・・
・・・・・・40.0 parts Methyl ethyl ketone・・・・・・・・・・・・40.0 parts
Dioxane・・・・・・・・・・・・・・・・・・
...10.0 copies. (3) Production of a sheet having a heat-fusible ink layer and a transparent protective layer A coating liquid for a heat-fusible ink layer is applied to one side of the surface of a polyethylene terephthalate sheet with a thickness of 4.5 μm using a wire bar method. By drying, the thickness is reduced to 1.
A 2 μm thick hot-melt ink layer was formed. Further, a transparent protective layer coating solution having the following composition is applied by a wire bar method to the uncoated portion of the surface of the polyethylene terephthalate sheet on which the heat-melting ink layer has been formed as described above, and then dried. As a result, a transparent protective layer with a thickness of 3.0 μm was formed. That is, as a result, a heat-melting ink layer and a transparent protective layer were separately formed on one side of the polyethylene terephthalate sheet. An anti-sticking layer coating solution having the following composition was applied to the surface of this polyethylene terephthalate sheet opposite to the heat-melting ink layer to form an anti-sticking layer having a thickness of 0.6 μm. Coating liquid for heat-melting ink layer:
Carnauba wax・・・・・・・・・・・・・・・・・・
...1.0 parts ethylene-vinyl acetate copolymer
・・・・・・・・・・・・・・・1.0 part (Mitsui DuPont Chemical Co., Ltd., EV-40Y) Carbon black・・・・・・・・・・・・・・・・・・...6.0
Part Phenol resin・・・・・・・・・・・・・・・
......12.0 parts (manufactured by Arakawa Chemical Co., Ltd., Tamanol 526) Methyl ethyl ketone...
・・・・・・・・・80.0 copies. Coating liquid for transparent protective layer: Polyester resin・・・・・・・・・・・・・・・・・・・・・
・6.5 parts [manufactured by Toyobo Co., Ltd., Byron 200]
Ultraviolet absorber・・・・・・・・・・・・・・・・・・
...3.5 parts (2,4-dihydroxybenzophenone) Methyl ethyl ketone (solvent)...
・・・・・・・・・・・・90.0 copies. Coating agent for anti-sticking layer: Nitrocellulose・・・・・・・・・・・・・・・
...3.0 parts Acrylic silicone resin...
・・・・・・・・・・・・・・・・・・7.0 parts [Cymac US-270, manufactured by Toagosei Co., Ltd.] Methyl ethyl ketone・・・・・・・・・・・・・・・・・・・・90
．． 0 copies. (4) Production of image recording material The image-receiving layer of the base material and the sublimable dye-containing layer of the ink sheet for sublimation type thermal transfer recording are superimposed, and output from the ink sheet side for sublimation type thermal transfer recording using a thermal head. 0.
By heating under the conditions of 23 W/dot, pulse width of 0.3 to 4.5 msec, and dot density of 16 dots/mm, a human face image with gradation was formed on the image receiving layer. [0115] Next, the transparent protective layer is transferred to the image-receiving layer of the base material in a slightly larger size than the human face image so that the transparent protective layer is positioned on the surface of the human face image, and then a hot-melt ink is applied. The layers are stacked, and a thermal head is used for the heat-melting ink layer, with an output of 0.5 W/dot and a pulse width of 1.0.
Character information was transferred by heating under conditions of msec and dot density of 16 dots/mm. Further, the transparent protective layer could be easily transferred onto the image-receiving layer by applying heat at 180° C. for 1 second using a hot stamp press roller with an uneven surface and then peeling off the support. (Example 2) (1) Production of card-sized base material A card-sized base material was produced in the same manner as in Example 1. (2) Production of ink sheet for sublimation type thermal transfer An ink sheet for sublimation type thermal transfer was manufactured in the same manner as in Example 1. (3) Production of heat-melt ink layer A heat-melt ink layer was produced in the same manner as in Example 1. (4) The image-receiving layer of the image forming substrate and the sublimable dye-containing layer of the ink sheet for sublimation type thermal transfer recording are superimposed, and an output of 0.000 is applied from the side of the ink sheet for sublimation type thermal transfer recording using a thermal head.
By heating under the conditions of 23 W/dot, pulse width of 0.3 to 4.5 msec, and dot density of 16 dots/mm, a human face image with gradation was formed on the image receiving layer. Next, the heat-fusible ink layer of the sheet in item (3) above is placed on the image-receiving layer, and the heat-fusible ink layer is heated using a thermal head with an output of 0.5 W/dot and a pulse width of 1.0.
Character information was transferred to the image-receiving layer by heating under conditions of msec and dot density of 16 dots/mm. (5) Creation of hologram transfer sheet As shown in Figure 4, it is made of polyester and has a thickness of 25 μm.
A protective layer 9, a hologram forming layer 10, a reflective thin film layer 11, and an adhesive layer 12 are sequentially formed on one side of the base film 8,
A hologram transfer sheet was created. After forming the resin layer, the hologram forming layer was constructed as a relief hologram. Composition for forming a protective layer (dry film thickness: 3 μm): Acrylic resin...
・・・・・・・・・・・・・・・10 parts Methyl ethyl ketone・・・・・・・・・・・・・・・50
Part Toluene・・・・・・・・・・・・・・・
・・・・・・40 parts Hologram forming layer: Acrylic resin・・・・・・・・・
・・・・・・・・・40 parts Melamine resin...
・・・・・・・・・・・・・・・・・・10 copies
Anon・・・・・・・・・・・・・・・・・・・・・
・50 parts Methyl ethyl ketone・・・・・・・・・
・・・・・・・・・50 copies. Reflective thin film layer: ZnS was formed as a reflective thin film on the relief forming surface by vacuum evaporation to a thickness of 100 angstroms. Adhesive layer (dry film thickness, 2 μm): Vinyl chloride-vinyl acetate resin...
・・・・・・・・・20 parts Polyester resin・
・・・・・・・・・・・・・・・・・・20 parts Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
40 parts Toluene・・・・・・・・・・・・・・・
・・・・・・40 copies. (6) Transfer of hologram forming layer The hologram transfer sheet was placed facing the information-recorded card, and the hologram was transferred onto the entire surface of the card using a hot stamping method. (7) A UV-curable resin layer was further coated on the cards obtained in (1) to (6) above, and then UV-cured and the card surface was processed. Effects of the Invention The image recording medium of the present invention has a transparent protective layer with an uneven surface formed on a base material on which an image is formed by a thermal transfer method, or a hologram layer is formed thereon. Therefore, it not only has excellent durability but also has remarkable specificity compared to the case where these layers are not provided, and therefore can exhibit excellent tampering prevention properties. Moreover, it can be easily distinguished from other cards. Therefore, the image recording medium of the present invention can be used as a particularly reliable ID card.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of an image recording medium showing one embodiment of the present invention.

FIG. 2 is a sectional view of an image recording medium showing another embodiment of the present invention.

FIG. 3 is a cross-sectional view showing an image-receiving sheet used for manufacturing an image recording medium that is an embodiment of the present invention.

FIG. 4 is a sectional view showing a hologram transfer sheet used in one embodiment of the present invention.

[Explanation of symbols]

1 Base material 4 Transparent protective layer 7 Hologram layer

Claims (3)

[Claims] 1. An image recording material comprising a base material on which an image is formed by a thermal transfer method, and a transparent protective layer which is laminated on the image forming surface of the base material and is uneven. 2. An image recording body comprising a base material on which an image is formed by a thermal transfer method, and a hologram layer laminated on the image forming surface of the base material. 3. The image recording body according to claim 2, wherein a transparent protective layer is laminated on the hologram layer.