JPH08324137A - Image recording material and production thereof - Google Patents

Abstract

PURPOSE: To provide an image recording material forming a sharp transparent image and prevented from forgery and alteration by providing a transparent protective layer and a transparent cured protective layer formed by curing a coating agent containing a prepolymer having an epoxy group by the irradiation with ultraviolet rays on an image layer formed by a sublimation type transfer system. CONSTITUTION: An image recording material A suitable for an ID card is obtained by providing an image receiving layer 1b on the single surface of a support 1a. An image layer having a gradation data-containing image 3 formed by a sublimation type transfer system and a character data-containing image 2 formed by a melt transfer system is provided on the surface of an image receiving layer 1b. A transparent protective layer 4 is formed on the gradation data-containing image layer 4 and a cured protective layer 5 is provided on the surface of the base material and a wrinting layer 6 is provided on the opposite surface thereof. The cured protective layer 5 is formed by curing a coating agent containing a prepolymer having two or more epoxy groups in one molecule thereof by the irradiation with ultraviolet rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording body and a method for manufacturing the same. More specifically, the present invention provides a card-sized image recording medium having a clear gradation image and high image durability without using a laminate film and having no risk of forgery and alteration, and a method of manufacturing the same in a manufacturing process. Irradiation with ultraviolet light does not damage the image due to the sublimable dye, does not produce chips as when using a laminated film, and is capable of rapidly producing a card-sized image recording medium having the above-mentioned excellent characteristics. On how you can do it.

[0002]

2. Description of the Related Art Conventionally, many ID cards such as identification cards, driver's licenses and membership cards have been used. The ID card usually has a person image for confirming the card holder and various items to be described.
Since the person image is usually formed as a grayscale image, it can be a gradation information-containing image. Various items are, for example, in the case of identification, for example, the address of the person
The driver's license includes, for example, the date of birth, the name, the license number, the type of license, and the like. These items are written in letters, numbers or symbols.
Numerals or symbols can be used as character information containing images.

There are two conventional methods for forming a gradation information-containing image on an ID card. One is a sublimation type thermal transfer system, and the other is a silver halide photographic system. Whatever method is used to form the gradation information-containing image, what is important in the ID card is that forgery or alteration of the ID card must be absolutely prevented. The reason why the ID card should not be counterfeited is apparently unnecessary to explain.

Conventionally, in order to prevent forgery and alteration of the ID card, a transparent sheet is laminated on the surface of the ID card (this method may be abbreviated as a laminating method), and an ultraviolet curable resin is used. It is effective to form a curable film obtained by coating the surface of an ID card and then irradiating ultraviolet rays to cure the ultraviolet curable resin (this method may be abbreviated as an ultraviolet irradiation method). It is supposed to be.

However, even when a transparent sheet is laminated on an ID card having a gradation information-containing image formed on an image receiving layer by a sublimation type thermal transfer method, the image receiving layer itself is, for example, a thermoplastic resin sheet, and the transparent sheet is also used. Since it is a thermoplastic resin sheet, the image receiving layer and the transparent sheet may easily peel off. Therefore, forgery and alteration cannot be completely prevented by laminating the transparent sheet.

Further, since the gradation information-containing image formed on the image receiving layer by the sublimation type thermal transfer system is formed by the sublimable dye, the gradation information-containing image is heated by heating when laminating the transparent sheet on the ID card. There is a problem that is damaged. That is, the gradation information-containing image formed on the image receiving layer by the sublimation thermal transfer system has no durability against the laminating process.

When laminating an ID card with a transparent sheet, a transparent sheet having a larger area than an ID card is usually used. That is, the gradation information-containing image forming surface of the ID card is covered with a transparent sheet having a larger area than that of the ID card, and then heat treatment is performed, and then the transparent sheet protruding from the ID card is cut. Therefore, in the method of laminating ID cards, there is a problem that chips on the transparent sheet are generated, and a large amount of chips are generated at a site where a large number of ID cards are produced.

When a protective layer is formed by an ultraviolet irradiation method on the surface of an ID card having a gradation information-containing image formed on an image receiving layer by a sublimation type thermal transfer method, the image surface having the gradation information-containing image is cured by ultraviolet curability. When the resin is coated, bleeding occurs in the gradation information containing image formed with the sublimable dye,
There is a problem that the sharpness of an image is impaired. If a person image which is a gradation information-containing image is blurred, an ID card for which personal identification cannot be surely performed will be formed. Therefore, such an ultraviolet irradiation method cannot be adopted for ID card creation. This is a fatal defect method.

On the other hand, regarding the ID card for forming the gradation information containing image formed by the silver salt photographic system, the ID having the gradation information containing image formed by the sublimation type thermal transfer system is used.
Although the various problems as in the case of a card are not inevitable, many steps such as development, fixing, and bleaching are required to form an image containing gradation information, so that it takes a lot of time to create an ID. Therefore, in silver halide photography, I
The method of creating a D card is extremely difficult to employ in a field where a large number of ID cards must be created quickly.

[0010] The present invention has been made based on the above circumstances. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a card-size image recording body which has a clear image containing gradation information and has high image durability without using a laminate film and which is free from the risk of counterfeit alteration. Also, there is no damage to the image due to the sublimable dye even by irradiation with ultraviolet rays during the manufacturing process, no chips like when a laminate film is used, and a card-size image recording body having the above-mentioned excellent characteristics. An object of the present invention is to provide a method that can be manufactured quickly.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and focused mainly on the following points. This point of interest will be described by taking an example of issuing an ID card such as a car license.

First, it was noted that the sublimation type thermal transfer method is far more advantageous in terms of time than the silver salt method in order to smoothly form a color facial photograph image in a short time.
Attention is also paid to the fact that printing and printing ID data such as characters and codes or common data by a fusion-type thermal transfer method or a sublimation-type thermal transfer method can simplify operations and equipment, which is advantageous in many cases. did.

However, in this case, the gradation information-containing image is printed by the sublimation type thermal transfer method.
In particular, an image that does not need to be a gradation information-containing image can be sufficiently printed by a fusion-type thermal transfer method, and it was considered that these methods may be appropriately selected and used according to the case.

However, in the case of an image (color face photograph image or the like) printed by the sublimation type thermal transfer method, the image is protected for the purpose of protecting the image or the image recording medium or preventing the image from being tampered as described above. There is a problem in that an image formed by the sublimable dye is blurred or discolored due to heat at the time of laminating so as to completely adhere to the laminating material.

Therefore, instead of the laminating method, in order to provide protection and durability of the image or the image recording body, an ultraviolet curable resin film conventionally used for silver salt type images is used. We focused on a method of forming a protective film by coating. The formation of the protective film can be easily achieved by applying an ultraviolet-curable resin-containing coating agent on the entire or desired surface of the image recording medium and curing the resin or monomer by ultraviolet irradiation. According to this method, it should be able to be performed more quickly without applying heat.

However, when a protective film made of this UV-curable resin film is provided, the sublimable dye of the sublimation-type thermal transfer image is bleeding by a resin, a monomer or a solvent at the time of applying the coating agent, New problems have been found in that the image is damaged and the sublimable dye alienates the curing of the ultraviolet curable resin.

Therefore, the present inventors have conducted intensive studies to solve this problem. That is, an appropriate protective layer is provided on the image surface formed by the sublimation type thermal transfer method, the coating agent containing the ultraviolet-curable resin is applied through the protective layer, and then the protection made of the ultraviolet-curable resin film is applied. When the film was formed, the image formed by the sublimation-type thermal transfer method had no bleeding or the like, a clear and stable image containing gradation information was formed, and the protection and durability of the image were significantly improved. I found what I could get. In addition, according to this method, an ID card such as a car license is used.
Not only can it be used to produce image recordings of various sizes or forms with excellent protection and durability, but also quickly and easily with simple operations and equipment, and can completely prevent forgery and falsification. It was also confirmed that there were advantages such as generation of cut dust and thermal deformation of the card base, which were one of the major problems in laminating. We have
Based on these ideas and knowledge, the present invention has been completed.

The present invention for solving the above-mentioned problems provides a substrate, an image layer formed on the surface of the substrate with a sublimable dye by a sublimation type thermal transfer method, and a substantially transparent image layer on the image layer. It has a protective layer and a substantially transparent cured protective layer formed on the protective layer by curing a coating agent containing a prepolymer containing two or more epoxy groups in one molecule by ultraviolet irradiation. An image recording material characterized by: a step of forming an image layer on the surface of a substrate with a sublimable dye by a sublimation type thermal transfer method; a step of forming a substantially transparent protective layer on the image layer; An image recording, which comprises a step of forming a substantially transparent cured protective layer formed by curing a coating agent containing a prepolymer having two or more epoxy groups therein by irradiating with ultraviolet rays. body It is a manufacturing method.

The present invention will be described below with reference to the drawings.

FIG. 1 conceptually shows a sectional view of the whole or a part of an example of a preferred embodiment of the image recording medium of the present invention. FIG. 1 is provided for easier understanding of the image recording medium of the present invention and the method of the present invention, and the image recording medium of the present invention is not limited to the embodiment shown in FIG. .

In FIG. 1, the image recording material A is a support 1.
a) having a base material 1 formed by providing an image receiving layer 1b on one surface. Then, on a predetermined surface of the image receiving layer 1b,
Image 3 containing gradation information formed by the sublimation thermal transfer method
And an image layer having a character information-containing image 2 formed by a fusion-type thermal transfer method, a transparent protective layer 4 is formed on the surface of the gradation information-containing image layer 3, and a transparent protective layer is formed. A hardening protective layer 5 is formed over the entire surface of a base material 1 having a gradation information containing image 3 having a layer 4 and a character information containing image 2, and a writing layer 6 is provided on the opposite surface of the base material 1. Has been. The transparent protective layer 4 is the “transparent protective layer” in the present invention, and the curing protective layer 5 is
Is the "substantially transparent curing protective layer" in the present invention.

The substrate, the gradation information containing image, the character information containing image, the transparent protective layer and the cured protective layer will be described in detail in this order, including the example shown in FIG.

A. Substrate As a suitable substrate in the present invention, at the time of producing an image recording body, at least a gradation information containing image by a sublimation type thermal transfer system and a character information containing image by a melting type thermal transfer system or a sublimation type thermal transfer system are both formed. There is no particular limitation as long as it has a certain strength and mechanical strength such as rigidity that can be used as a card. When used as a card, a base material formed by laminating the same or different kinds of sheets can be used in order to maintain the mechanical strength. Furthermore, it is also possible to use a base material on which common information is printed on the same type of card in the visible layer, and to add a watermark as a measure to prevent forgery or alteration of the card itself. of,
It is also possible to use a substrate which has been subjected to a special processing for preventing forgery which can be confirmed by physical means.

In another embodiment of the substrate according to the present invention, the support itself is made of a material capable of suitably forming at least a gradation information containing image, preferably a gradation information containing image and a character information containing image. When formed, the support itself can be used as a substrate. In this case, the support is an image receiving layer that receives the sublimable dye.

When the image receiving layer is provided on the support, it may be provided on one side 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. . The image receiving layer is prepared so as to be able to favorably receive the sublimable dye when forming the gradation information containing image 3 and the character information containing image 2 as exemplified in FIG. The first image receiving layer 1c and the second image receiving layer 1d prepared so that the hot-melt ink can be satisfactorily adhered to each other may be provided separately on a predetermined surface of the support 1a. Good. But usually,
An image receiving layer prepared so that both a gradation information-containing image and a character information-containing image for simplifying the manufacturing process and enhancing applicability can be favorably formed. Further, when forming gradation information or character information, for example, Japanese Patent Application Laid-Open No.
As described in Japanese Patent Publication No. 794 and Japanese Patent Laid-Open No. 61-258793, a cushion layer or a heat insulating material layer may be provided on the surface of the support.

As another embodiment of the base material in the present invention, it is possible to form the base material only with a support that cannot accept a sublimable dye but can adhere a heat-meltable ink well. In this case, in order to form a gradation information-containing image on the base material surface, a gradation information-containing image by a sublimable dye is formed on a transfer body having an image receiving layer by a sublimation thermal transfer method,
Next, the image containing the gradation information recorded on the transfer body is transferred onto the surface of the support together with the image receiving layer of the transfer body.

The shape of the substrate is not particularly limited,
Various sizes and various forms (sheets, blocks, etc.) can be mentioned. For example,
In the case of producing the cards, a substrate having a shape preliminarily processed to the card size may be used, or the substrate substrate may be prepared at any point in the process for producing the image recording material of the present invention. The swatch may be cut to the desired card size.

Further, the substrate may be provided with an emboss, a sign, an IC memory, an optical memory, a magnetic recording layer, other prints, etc., if necessary. At any point in the manufacturing process of the recording medium (for example, after the formation of the transparent protective layer, etc.), it is also possible to provide an emboss, sign, magnetic recording layer, etc. after the manufacturing.

Next, the support and the image receiving layer will be described in detail.

(A.1). Support As the support, various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper), white chloride Made of various plastic films or sheets such as vinyl resin sheets, white polyethylene terephthalate base film, transparent polyethylene terephthalate base film, polyethylene naphthalate base film, etc., films or sheets made of various metals, and various ceramics. Examples thereof include films and sheets.

In the support, white pigments such as titanium white, magnesium carbonate, zinc carbonate, barium sulfate, and the like are added in order to enhance the sharpness of the image formed in the subsequent step.
It is preferable that silica, talc, clay, calcium carbonate and the like are added.

Further, if the image recording medium is an ID card such as an automobile license, the support may be constituted by a sheet or a film comprising a composition of the white pigment and a vinyl chloride resin described below. Is common.

When the substrate is formed as a laminate of a support and an image receiving layer, the thickness of the support is usually from 100 to 1,
000 μm, preferably 100-800 μm. When the substrate is formed only of a support, the thickness of the support is usually 100 to 1,000 μm, preferably 20 to 1,000 μm.
It is 0 to 800 μm.

When the substrate is provided with an emboss, a sign, an IC memory, an optical memory, a magnetic recording layer, other printing, etc., as necessary, the emboss, a sign, the IC memory, It is preferable to provide an optical memory, a magnetic recording layer, other printing, and the like.

(A.2). Image-Receiving Layer When the image-receiving layer is formed on the surface of the support, the image-receiving layer is
It can be formed with a binder and various additives.
In some cases, it may be formed only from the binder. The image-receiving layer in the present invention may form an image by a sublimation dye by a sublimation type thermal transfer system and may form an image by a fusion type thermal transfer system. In such a case, the dyeability of the sublimable dye must be good and the adhesiveness of the hot-melt ink must be good. To obtain an image receiving layer having such special properties, as described below,
It is necessary to appropriately adjust the types of the binder and various additives and the amounts thereof.

The components constituting the image receiving layer will be described in detail below.

(A.2.1). Binder As the binder for the image receiving layer in the invention, a generally known image receiving layer for sublimation type thermal transfer recording can be appropriately used. As the main binder, various binders such as vinyl chloride resin, polyester resin, polycarbonate resin, acrylic resin and various heat resistant resins can be used. However, if there is a practical requirement for the image formed by the present invention (for example, the ID card to be issued is required to have a predetermined heat resistance), the binder is required to satisfy such requirement. It is necessary to consider the type or combination. Taking heat resistance of an image as an example, if heat resistance of 60 ° C. or higher is required, it is preferable to use a binder having Tg of 60 ° C. or higher in consideration of bleeding of a sublimable dye.

The choice of the type of binder is arbitrary,
A vinyl chloride resin is preferred in terms of image storability and the like. Examples of the vinyl chloride resin include polyvinyl chloride resin and vinyl chloride copolymer. Examples of the vinyl chloride copolymer include a copolymer of vinyl chloride containing vinyl chloride as a monomer unit in a proportion of 50 mol% or more and another comonomer.

Examples of the other comonomers include vinyl acetate, vinyl propylene oxide, vinyl esters of fatty acids such as vinyl acetate and vinyl beef tallow, acrylic acid,
Acrylic acid or methacrylic acid such as methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, and 2-ethylhexyl acrylate, and alkyl esters thereof, maleic acid, and maleic acid Examples thereof include maleic acid such as diethyl, dibutyl maleate and dioctyl maleate, and alkylalkyl esters thereof, and alkyl vinyl ethers such as methyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, palmityl vinyl ether, and stearyl vinyl ether. Further, as the comonomer, other halogenated olefins such as ethylene, propylene, acrylonitrile, methacrylonitrile, styrene, chlorostyrene, itaconic acid and its alkyl esters, crotonic acid and its alkyl esters, dichloroethylene and trifluoroethylene, and cyclopentene And the like, such as cycloolefins, aconitic esters, vinyl benzoate, and benzoyl vinyl ether.

The vinyl chloride copolymer may be any of a block copolymer, a graft copolymer, an alternating copolymer, and a random copolymer. In some cases, it may be a copolymer with a compound having a peeling function such as a silicon compound.

In addition to the vinyl chloride resin, a polyester resin can also be suitably used as the image receiving layer for sublimation type thermal transfer. Examples of the polyester resin that can be used in the present invention include compounds described in JP-A-58-188695 and JP-A-62-244696. Further, a polycarbonate resin can also be used as a binder, and for example, various compounds described in JP-A No. 62-169694 can be used.

Next, the heat resistant resin has good heat resistance, is not a resin having an extremely low softening point or glass transition point (Tg), but is compatible with the vinyl chloride resin and is substantially colorless. As long as it is, various known heat resistant resins can be used. The term "heat resistance" as used herein means that the resin itself does not cause coloration such as yellowing when it is stored under heat, and the physical strength is not extremely deteriorated.

The heat-resistant resin has a softening point of 50 to 200.
C., especially Tg of 80 to 150.degree. C. are preferred.

If the softening point is lower than 50 ° C., it is not preferable because the ink sheet and the image receiving layer may be fused when transferring the heat diffusible dye. When the softening point exceeds 200 ° C., the sensitivity of the image receiving layer is lowered, which is not preferable.

Examples of the heat-resistant resin satisfying the above conditions include a phenol resin, a melamine resin, a urea resin, and a ketone resin. Among them, a urea aldehyde resin and a ketone resin are particularly preferable.

The urea aldehyde resin is obtained by condensation of urea and aldehydes (mainly formaldehyde), and the ketone resin is obtained by condensation reaction of ketone and formaldehyde. Various resins are known depending on the starting ketone, and any of them can be used in the present invention.

Examples of the above-mentioned raw material ketone include methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and methylcyclohexanone.

Examples of easily available urea aldehyde resins include Laropearl A81 and Laropearl A101 (manufactured by BASF) and ketone resins include Laropearl K80 (manufactured by BASF).

The binder selected from the above various resins in the present invention is used for the purpose of improving physical properties such as increasing the film strength of the image receiving layer, preventing fusion during transfer of the sublimable dye, and preventing bleeding of the sublimable dye. Curing with an isocyanate-based curing agent, curing with an ultraviolet curable resin or the like may be performed. Further, as a method for improving the physical properties of the image-receiving layer, suitable additives may be added in addition to the curing agent.

(A.2.2). 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. Further, a plasticizer, a hot solvent or the like may be added as a sensitizer.

The release agent can improve the releasability between the sublimation type thermal transfer ink sheet described later and the image receiving layer.

Examples of such a release agent include silicone oils (including those referred to as silicone resins); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphate-based surfactants Agents, among which silicone oil is preferred.

The silicone oil is classified into a type of simply adding (simple addition type) and a type of curing or reacting (curing reaction type).

In the case of the simple addition type, it is preferable to use a modified silicone oil in order to improve the compatibility with the binder.

As the modified silicone oil, polyester modified silicone resin (or silicone modified polyester resin), acrylic modified silicone resin (or
Silicon-modified acrylic resin), urethane-modified silicone resin (or silicon-modified urethane resin), cellulose-modified silicone resin (or silicon-modified cellulose resin), alkyd-modified silicone resin (or silicon-modified alkyd resin), epoxy-modified silicone resin ( Alternatively, a silicon-modified epoxy resin) can be used.

That is, a polyester-modified silicone resin containing a polysiloxane resin in the main chain and copolymerizing polyester in a block shape, and a silicon-modified polyester resin having a dimethylpolysiloxane portion as a side chain bonded to the polyester main chain. Block copolymers, alternating copolymers, graft copolymers, random copolymers, and the like of dimethylpolysiloxane and polyester can also be used as the modified silicone oil or resin.

In particular, in the present invention, in consideration of the transferability of the hot-melt ink, the transferability of the protective layer, and the applicability of the coating liquid containing an ultraviolet curable resin for forming the cured protective layer, the image receiving layer is preferably used. It is desirable to add a release agent having good compatibility with the binder for use. For example, if a vinyl chloride resin is used as a binder, a polyester-modified silicone resin is preferable as a combination.

Typical polyester-modified silicone resins include, for example, a block copolymer of a polyester, which is a copolymer of diol and dibasic acid or a ring-opening polymer of caprolactone, with dimethylpolysiloxane (both dimethylpolysiloxane). (Including copolymers in which the terminal or one end is blocked with the polyester moiety, or conversely, the polyester is blocked with dimethylpolysiloxane.) Copolymers obtained by binding siloxane can be mentioned.

The amount of addition of these simple addition type silicone oils cannot be determined uniformly because they may vary in various ways depending on the type thereof. 0.5 to
It is 50% by weight, preferably 1 to 20% by weight.

As the curing reaction type silicone oil,
Reaction curing type, light curing type, catalyst curing type and the like can be mentioned.

Examples of the reaction-curable silicone oil include those obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil.

As the catalyst-curable or photocurable silicone oil, KS-705F-PS and KS-705 are available.
F-PS-1, KS-770-PL-3 [both catalyst-curable silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.], KS
-720, KS-774-PL-3 [all are photocurable silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.] and the like.

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image receiving layer.

A release agent layer may be provided on a part of the surface of the image receiving layer by dissolving or dispersing the release agent in an appropriate solvent and applying the solution, followed by drying.

Next, as the antioxidant, JP-A-59
-182785, 60-130735, JP-A-1
Examples thereof include antioxidants described in JP-A-127373 and known compounds that improve image durability in photographs and other image recording materials.

The UV absorber and the light stabilizer include:
JP-A-59-158287, JP-A-63-74686,
63-145089, 59-196292, 62-229594, 63-122596, 61.
Compounds described in JP-A-283595, JP-A-1-204788 and the like, and compounds known to improve image durability in photographs and other image recording materials can be mentioned.

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 and the like, and organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. Can be mentioned. These inorganic / organic resin particles differ depending on the specific gravity, but it is preferably added in an amount of 0.1 to 70% by weight.

Representative examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

Examples of the plasticizer include phthalic acid esters (for example, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), trimellitic acid esters (for example, octyl trimellitic acid ester, isononyl trimellitic acid). Ester, trimellitic acid isodesol ester, etc., pyromellitic acid octyl ester and other pyromellitic acid esters, adipate esters (dioctyl adipate, methyllauryl adipate, di-2-ethylhexyl adipate, ethyl adipate) Lauryl etc.), other oleic acid esters, succinic acid esters, maleic acid esters, sebacic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearic acid epoxies, and Acid triphenyl, orthophosphoric acid esters such as tricresyl phosphate, triphenyl phosphite, tris-tridecyl phosphite, dibutyl
Examples include phosphites such as hydrogen phosphite and glycol esters such as ethylphthalylethyl glycolate and butylphthalylbutyl glycolate. Since excessive addition of the plasticizer deteriorates the storability of the image, the addition amount of the plasticizer 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 image receiving layer forming surface. This image recording body is the ID such as a car license
When a card is used, it is particularly preferable to provide a writing layer. By forming the writing layer, it is convenient because various information can be written on the ID card.

The description relating to the writing layer in the present invention will be replaced with the description relating to the “writing layer” described on page 4, upper right column, line 14 to page 4, lower right column, second line of JP-A-1-205155. , And a detailed description thereof will be omitted.

(A.4). Production of Substrate The substrate in the present invention is prepared by dispersing or dissolving the components for forming the image-receiving layer in a solvent to prepare a coating solution for the image-receiving layer. It can be manufactured by a coating method in which a working liquid is applied to the surface of a support and dried.

It is also possible to produce by a laminating method or the like in which a mixture having the components forming the image receiving layer is melt extruded and laminated on the surface of the support.

Examples of the solvent used in the coating method include conventionally known solvents such as water, alcohol, methyl ethyl ketone, toluene, dioxane, and cyclohexanone.

When the above-described laminating method is employed, a co-extrusion method may 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 can be both a support and a substrate since the image receiving layer is self-supporting, the thickness of the image receiving layer is 60 to 200 μm, preferably 9 to 200 μm.
It is about 0 μm to 150 μm.

In this heat-sensitive transfer recording image-receiving sheet, in order to more effectively prevent fusion of the heat-sensitive transfer recording ink sheet with the ink layer, a release agent (the above-mentioned silicone resin, a modifying agent) is formed on the surface of the image-receiving layer. A release layer containing a silicone resin, a silicone oil film or a cured product thereof may be further laminated.

The thickness of the release layer is usually from 0.03 to 2.
0 μm.

Further, the substrate in the present invention may be provided with a cushion layer or a barrier layer between the support and the image receiving layer.

By providing the cushion layer, it is possible to transfer and record an image corresponding to image information with good reproducibility with little noise.

Examples of the material constituting the cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, epoxy resin and the like.

The thickness of the cushion layer is usually 1 to 50 μm.
m, preferably 3 to 30 μm.

The provision of the barrier layer can prevent the dye from diffusing into the support and prevent the dye from bleeding into the support. Examples of the material constituting the barrier layer include a hydrophilic binder such as gelatin and casein, and a polymer having a high Tg.

B. Gradation information containing image The gradation information containing image referred to here is an image formed of a sublimable dye. Many of the images formed by the sublimable dye have a monochromatic or polychromatic gradation. When the image recording body is an ID card such as an automobile license, the gradation information-containing image is often a person image. However, when the image recording medium is a prepaid card such as a telephone card, a business card, or an advertising flyer, the gradation information-containing image is not limited to a human image, but may 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 below using a sublimation type thermal transfer recording ink sheet described below.

(B.1). Sublimation-Type Thermal Transfer Recording Ink Sheet The sublimation-type thermal transfer recording ink sheet can be composed of a support and a sublimable dye-containing ink layer formed thereon.

(B.1.1). Sublimable Dye-Containing Ink Layer The sublimable dye-containing ink layer basically contains a sublimable dye and a binder.

(B.1.1.1). Sublimable Dye Sublimable dyes include cyan dye, magenta dye and yellow dye.

As the cyan dye, there is disclosed in JP-A-59-7.
8896, 59-227948, and 60.
No. 24966, No. 60-53563, and No. 6
Nos. 0-130735, 60-131292, 60-239289, and 61-19396.
No. 61-29293, No. 61-3129.
No. 2, gazette 61-31467, gazette 61-359.
94, 61-49893, 61-14.
No. 8269, No. 62-191191, No. 63.
-912288, 63-91287, and 6
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in JP-A-3-290793.

The magenta dye is described in JP-A-59-1984.
No. 78896, JP-A-60-30392, JP-A-60-30394, JP-A-60-25359
5, JP-A 61-262190, JP-A 6-62
Anthraquinone dyes, azo dyes and azomethine dyes described in JP-A-3-5992, JP-A-63-205288, JP-A-64-159, JP-A-64-63194, etc. And the like.

As the yellow dye, JP-A-59-78 can be used.
896, JP-A-60-27594, JP-A-60-31560, JP-A-60-53565, JP-A-61-12394, JP-A-63-12.
Examples thereof include methine dyes, azo dyes, quinophthalone dyes, and anthryothothiazole dyes described in various publications such as 2594.

Particularly preferred as a sublimable dye is a compound having an open or closed type active methylene group, which is an oxidized p-phenylenediamine derivative or p-phenylenediamine derivative.
Azomethine dyes obtained by a coupling reaction with an oxidized form of an aminophenol derivative and indoaniline obtained by a coupling reaction with an oxidized form of a phenol or naphthol derivative or a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative It is a pigment.

The sublimable dye contained in the sublimable dye-containing ink layer is such that if the image to be formed is a single color,
Any of a yellow dye, a magenta dye, and a cyan dye may be used.

Further, depending on the color tone of the image to be formed, two or more of the above three kinds of dyes or other sublimable dyes may be contained.

The amount of the sublimable dye used is usually 0.1 to ²⁰ g, preferably 0.2 to 5 g per 1 m ^{2 of} the support.
Is.

(B.1.1.2). Binder-As a binder for the sublimable dye-containing ink layer, a cellulose resin such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate or cellulose acetate butyrate. Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, polyester, polyvinyl acetate, polyacrylamide, polyvinyl acetoacetal, styrene resin, styrene copolymer resin, polyacrylic acid ester, polyacrylic acid, acrylic acid copolymer, etc. Vinyl resins, rubber resins, ionomer resins, olefin resins and the like.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resin having excellent acid resistance is preferable.

The various binders may be used alone or in combination of two or more.

The weight ratio between the binder and the sublimable dye is preferably from 1:10 to 10: 1, and particularly preferably from 2: 8 to 8: 2.

(B.1.1.3). Other Optional Components Various additives can be added to the sublimable dye-containing ink layer as long as the object of the present invention is not impaired.

As the additives, silicone resin, silicone oil (reaction hardening type is also acceptable), silicone modified resin, fluororesin, surfactant, peeling compound such as wax, fine metal powder, silica gel, metal oxide. Substances, carbon black, fillers such as resin fine powder, and curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylics, epoxies, etc.)
And so on.

Further, as an additive, a heat-fusible substance for promoting transfer, for example, compounds described in JP-A-59-106997, such as waxes and higher fatty acid esters, can be mentioned.

(B.1.2) Support The support for the ink sheet for sublimation-type thermal transfer recording may be any as long as it has good dimensional stability and can withstand heat during recording with a thermal head. Japanese Patent Laid-Open No. 63-1
No. 93886, page 2, lower left column, lines 12 to 18 can be used.

The thickness of the support is preferably from 2 to 10 μm, and the support has an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the transfer of dye to the support side and dyeing. May be.

Further, an anti-sticking layer may be provided on the back surface of the support (on the side opposite to the sublimable dye-containing ink layer) for the purpose of preventing the head from fusing, sticking and wrinkling to the support. .

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.
For example, a wide sheet or film, a narrow tape or a card, or any other shape.

(B.2). Production of Sublimation-Type Thermal Transfer Recording Ink Sheet The sublimation-type thermal transfer recording ink sheet is prepared by dispersing or dissolving the above-mentioned various components forming a sublimable dye-containing ink layer in a solvent and then sublimating the ink. Prepare a coating liquid for forming a dye-containing ink layer,
It can be manufactured by applying this on the surface of a support and drying.

The binder may be used alone or as a mixture of two or more kinds dissolved in a solvent or dispersed in latex.

Examples of the solvent include water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene), ketones (eg acetone, methyl ethyl ketone). ), Ester solvents (eg ethyl acetate, butyl acetate, etc.), ethers (eg tetrahydrofuran, dioxane),
Chlorine-based solvents (eg chloroform, trichloroethylene) and the like can be mentioned.

For the coating, a conventionally known gravure roll-coating method, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted.

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 contain a binder and a yellow dye. A yellow sublimable dye-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 have a constant repetition along a planar direction. May be formed on the entire surface or a part of the surface of the support.

The thickness of the sublimable dye-containing ink layer thus formed is usually from 0.2 to 10 μm, and preferably from 0.3 to 3 μm.

In the present invention, the sublimation type thermal transfer recording ink sheet may be conveniently used by forming a perforation or providing a detection mark for detecting the position of an area having a different hue. it can.

The ink sheet for sublimation-type thermal transfer recording is not limited to the structure comprising the support and the heat-sensitive layer formed thereon, and other layers are formed on the surface of the sublimable dye-containing ink layer. Is also good.

For example, an overcoat layer may be provided for the purpose of preventing fusion with the image-receiving sheet for thermal transfer recording or set-off (blocking) of the sublimable dye.

(B.3). Method of Forming Image Containing Gradation Information In order to form an image containing gradation information, the sublimable dye-containing ink layer of the sublimation type thermal transfer recording ink sheet and the image receiving surface of the substrate are combined. When superposed, imagewise heat energy is applied to the sublimable dye-containing ink layer and the image receiving layer.

The sublimable dye in the sublimable dye-containing ink layer is vaporized or sublimated by an amount corresponding to the applied heat energy, and is transferred to the image receiving layer side and received.

As a result, an image containing gradation information is formed on the image receiving layer.

The heat source for providing the heat energy includes:
A thermal head is generally used, but other known ones such as a laser beam, an infrared flash, and a hot pen can also be used.

When a thermal head is used as a heat source for applying thermal energy, the applied thermal energy can be changed continuously or in multiple steps by modulating the voltage or pulse width applied to the thermal head.

When laser light is used as a heat source for giving heat energy, the heat energy to be given can be changed by changing the light amount of the laser light or the irradiation area.

In this case, in order to easily absorb the laser light, a laser light absorbing material (for example, carbon black or an infrared absorbing material in the case of a semiconductor laser) is added to the sublimable dye-containing ink layer or the sublimable dye-containing ink. It is good to let it exist near the layer.

When a laser beam is used, the sublimation type thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet may be sufficiently adhered to each other.

If a dot generator having a built-in acousto-optical element is used, heat energy corresponding to the size of a halftone dot can be applied.

When an infrared flash lamp is used as a heat source for supplying heat energy, it is preferable to heat through a colored layer such as black as in the case of using laser light.

Alternatively, the heating may be carried out through a pattern or a halftone dot pattern in which the gradation of the image such as black is continuously expressed, or it corresponds to the negative of the above-mentioned pattern and a colored layer of one surface such as black. You may heat by combining a negative pattern.

The thermal energy may be applied from the sublimation type thermal transfer recording ink sheet side, from the base material side, or from both sides. If priority is given to the effective use of thermal energy, It is desirable to carry out from the sublimation type thermal transfer recording ink sheet side.

A single-color image can be recorded on the image receiving layer of the substrate by the above-described sublimation type thermal transfer recording method. However, according to the following method, a color image of a color photograph composed of a combination of each color can be obtained. it can.

For example, by sequentially replacing the yellow, magenta, cyan and, if necessary, black heat-sensitive transfer recording heat-sensitive sheets, and performing heat transfer in accordance with each color, a color photographic color image composed of a combination of each color is obtained. You can also.

The following method is also effective. That is, instead of using the sublimation type thermal transfer recording ink sheet of each color as described above, the sublimation type thermal transfer recording ink sheet having an area formed by separately coating each color is used.

Then, first, the yellow color separation image is thermally transferred using the yellow area, and then the magenta color separation image is thermally transferred using the magenta area. Thereafter, the yellow, magenta, and cyan colors are sequentially repeated. And, if necessary, a method of thermal transfer in the order of the black color separation image.

C. Character information-containing image (C.1). Hot-melt ink sheet The hot-melt ink sheet is formed by laminating a hot-melt ink layer on a support. In addition, this heat-meltable ink sheet,
You may have another layer in the range which does not impair the characteristic. For example, a release layer may be provided between the heat-fusible ink layer and the support, and an intermediate layer or the like may be laminated between the release layer and the support.
Another layer may be laminated on the hot-melt ink layer, such as providing an ink protective layer on the outermost layer. Further, the release layer and the heat-meltable ink layer may have a multilayer structure as required.

Next, the structure of the hot-melt ink sheet of the present invention will be described in the order of the support, the release layer, and the hot-melt ink layer.

(C.1.1). Support The support in the heat-fusible ink sheet desirably has good heat resistance and high dimensional stability.

The material thereof is, for example, JP-A-63 / 1988.
No. 193886, page 2, lower left column, lines 12 to 18
The films or sheets mentioned in the rows can be used.

The thickness of the support is usually 30 μm or less, preferably in the range of 2 to 30 μm. When the thickness of the support exceeds 30 μm, the thermal conductivity is deteriorated, and the print quality may be deteriorated.

In the hot-melt ink sheet, the structure on the back side of the support is arbitrary, and for example, a backing layer such as a sticking prevention layer may be provided.

(C.1.2). Heat-meltable ink layer The heat-meltable ink layer is composed of a heat-meltable compound, a thermoplastic resin, a colorant and the like.

As the heat-fusible compound, those usually used in the heat-fusible ink layer of this kind of heat-fusible ink sheet can be arbitrarily used. Specifically, for example, polystyrene resin, Low molecular weight thermoplastic resins such as acrylic resins, styrene-acrylic resins, polyester resins, polyurethane resins, and the like, JP-A-63-193886
From the fourth page, upper left column, line 8 to the upper right column, line 12 of the same publication, the exemplified substances can be mentioned. In addition to these, rosin, hydrogenated rosin, polymerized rosin, rosin-modified glycerin, rosin Examples include rosin derivatives such as modified maleic acid resins, rosin modified polyester resins, rosin modified phenolic resins and ester gums, and phenolic resins, terpene resins, ketone resins, cyclopentadiene resins and aromatic hydrocarbon resins. it can.

These heat-meltable compounds generally have a molecular weight of 10,000 or less, especially 5,000 or less,
Those having a melting point or softening point in the range of 50 to 150 ° C are preferred.

The heat fusible compounds may be used alone or in combination of two or more.

As the thermoplastic resin used as a component of the hot-melt ink layer, various types such as those usually used for the hot-melt ink layer of this type of hot-melt ink sheet can be used. Yes, for example,
No. 193886, page 4, upper right column, page 5, upper left column, 18
Exemplary substances can be listed in the row.

As the colorant used as a component of the heat-meltable ink layer, those usually used for the heat-meltable ink layer of this kind of heat-meltable ink sheet can be used without limitation, For example, JP-A-63-1938
Pigments such as inorganic pigments and organic pigments, and dyes such as organic dyes described in JP-A-86-86, page 5, upper right column, lines 3 to 15 can be mentioned.

These various colorants may be used alone or, if necessary, in combination of two or more.

The heat-meltable ink layer may optionally contain other components other than those described above, as long as the object of the present invention is not impaired.

For example, the heat-fusible ink layer may contain a fluorine-based surfactant. The blocking phenomenon of the ink layer can be prevented by containing a fluorine-based surfactant.

In order to improve the sharpness of the transferred character information image, that is, to improve the sharpness of the character boundary, organic fine particles are used.
It is also effective to add inorganic fine particles and an incompatible resin.

The thickness of the hot-melt ink layer is usually
It is 0.6 to 5.0 μm, and particularly preferably 1.0 to 4.0 μm.

This hot-melt ink layer is applied by dispersing or dissolving the forming components in an organic solvent (organic solvent method), or by applying a thermoplastic resin or the like in a softened or molten state by heating (hot melt). The coating may be performed by using a coating method) or the like, but it is preferable that the coating is performed using an emulsion or a solution in which the forming components are dispersed or dissolved in water or an organic solvent.

The total content of the layer forming components in the coating liquid used for coating the hot-melt ink layer is usually 5 to 50.
It is set within the range of% by weight.

The coating method can be carried out using a usual method. Examples of the coating method include a method using a wire bar, a squeeze coating method, and a gravure coating method.

It is necessary that the hot-melt ink layer is provided in at least one layer. For example, the type and content of the colorant, or the mixing ratio of the thermoplastic resin and the hot-melt compound, etc. Two or more different heat-meltable ink layers may be laminated.

(C.1.3) Release Layer The release layer is provided on at least the release layer when heated by a heating mechanism such as a thermal head for image transfer during image formation. At least one of these layers contains a coloring agent. The main purpose is to peel and transfer sufficiently quickly, and a layer in which the attribute of the heat-fusible compound is dominant by containing a heat-fusible compound suitable for achieving this object, particularly It is configured as a layer having excellent peelability.

The release layer may be composed of the above-mentioned heat-meltable compound itself, but it is usually preferable to be composed of the heat-meltable compound and / or a binder resin such as a thermoplastic resin.

As the heat-fusible compound used as a main component of the release layer, various compounds such as known compounds may be appropriately selected and used. From page 4, upper left column, line 8 to page 12, upper right column, line 12 of 193886, the exemplified substances can be used.

The heat-fusible compound used as a main component of the release layer of the heat-fusible ink sheet has a melting point or softening point in the range of 50 to 100 ° C. among the various heat-fusible compounds exemplified above. Certain microcrystalline waxes, paraffin waxes, carnauba waxes and the like are preferred. If the melting point or softening point is too high, sufficient releasability may not be obtained, and in particular, characteristics such as desired releasability in high-speed printing may not be sufficiently exhibited.
On the other hand, if it is too low, it may cause trouble such as peeling in a normal state.

These heat-meltable compounds may be used alone or in combination of two or more.

The binder resin of the release layer or the thermoplastic resin used as a component thereof is not particularly limited, and is used for the release layer of the known heat-melt type transfer recording ink sheet of this type. Various items such as the above may be appropriately selected and used.

Specific examples of the thermoplastic resin include, for example, an ethylene copolymer such as an ethylene-vinyl acetate resin, a polyamide resin, a polyester resin, a polyurethane resin, a polyolefin resin, an acrylic resin, and a cellulose resin. And the like. In addition, for example, vinyl chloride resin, rosin resin,
Resins such as petroleum-based resins and ionomer resins, elastomers such as natural rubber, styrene-butadiene rubber, isoprene rubber and chloroprene rubber, ester gum,
Rosin maleic resin, rosin derivatives such as rosin phenol resin and hydrogenated rosin, and phenol resin,
Terpene resins, cyclopentadiene resins, aromatic resins and the like can also be used depending on the case.

Of these, ethylene copolymers such as an ethylene-vinyl acetate copolymer or an ethylene-vinyl acetate copolymer and a cellulose resin are preferred, and particularly, ethylene-vinyl acetate copolymer and ethylene-vinyl acetate copolymer are preferred. Cellulose resins are preferred.

When these various thermoplastic resins are used, they may be used alone or in combination of two or more.

In the present invention, the thermoplastic resin used as a component of the release layer has a melting point or a softening point of usually 50 among the various thermoplastic resins exemplified above.
Those having a temperature within a range of from 150 to 150 ° C, particularly from 60 to 120 ° C, or those having a temperature within the range by mixing two or more kinds are preferably used.

The release layer may optionally contain a colorant.

When a colorant is contained in the release layer, the content thereof is usually set to 30% by weight or less, preferably 20% by weight or less based on all the components constituting the release layer. Is appropriate.

As the coloring agent, a usual coloring agent can be used, and the same coloring agents as described in the section of “(C.1.2). Hot-melt ink layer” can be used.

In addition to the above-mentioned components, the release layer may optionally further contain other components as long as the object of the present invention is not impaired. Other components include
For example, higher fatty acids, higher alcohols, higher fatty acid esters, amides, higher amines and the like can be mentioned. When used, these may be used alone or in combination of two or more.

The layer thickness of the release layer is usually 0.2 to 4
Suitably, it is in the range of μm, preferably in the range of 0.5 to 2.5 μm.

The release layer may contain, in addition to the above components, a surfactant for controlling the release property.
Examples of typical surfactants used in the present invention include polyoxyethylene chain-containing compounds. Further, inorganic or organic fine particles (metal powder, silica gel, etc.) or oils (linseed oil, mineral oil, etc.) can also be added.

The release layer mainly serves to adjust the adhesive force between the hot-melt ink layer formed thereon and the support, and for example, a back surface of the support (for example, a release layer) by a thermal head or the like. This is a layer for facilitating separation of the layers from the support by heating from the side where the layers are not formed).

That is, the release layer maintains mechanical properties such as film-forming properties and film strength of the hot-melt ink layer on the support, and the hot-melt ink layer is separated from the support immediately after heating. At this time, the hot-melt ink layer is quickly peeled and transferred onto the substrate.

(C.2). Formation of Image Containing Character Information Although the heat-melting transfer method using this heat-meltable ink sheet is not different from the usual heat-sensitive transfer recording method, it is the most typical heat source as a heat source. The case of using a head will be described as an example.

First, the heat fusible ink layer of the heat fusible ink sheet is brought into close contact with the image receiving surface of the base material, and if necessary, a heat pulse is applied from the back surface of the base material by a platen. To locally heat the hot-melt ink layer corresponding to a desired print or transfer pattern.

The heated portion of the heat-fusible ink layer rises in temperature and is quickly softened and transferred to the image receiving surface of the substrate.

The formation of the character information-containing image may be performed prior to the formation of the gradation information-containing image, or after the formation of the gradation information-containing image. Formation may be performed.

D. Transparent protective layer In the image recording medium of the present invention, it is important that the transparent protective layer is provided on at least a gradation information-containing image layer or a gradation information-containing image formed by a sublimation thermal transfer method. is there.

The main purpose of providing this transparent protective layer is as follows. That is, when forming a cured protective layer made of a resin cured product cured by irradiation of ultraviolet rays for improving the protection and durability of an image or an image recording medium, if a coating containing an ultraviolet-curable resin is used.
When a coating agent is applied directly on the image containing gradation information,
Due to the action of the UV-curable resin or solvent present in the coating agent, the gradation information-containing image due to the sublimable dye may be blurred or discolored, and a clear image cannot be obtained. Therefore, in the image recording material of the present invention, the transparent protective layer is provided as described above to avoid contact between at least the image formed by the sublimable dye and the coating agent, and the bleeding of the sublimable dye. It also prevents discoloration and protects the formed image as it is in a clear state.

Further, deterioration of the sublimable dye (presumed to be caused by decomposition or reaction with other substances) or discoloration due to the irradiation of the ultraviolet rays during the formation of the curing protective layer is effectively prevented. Therefore, it is necessary to provide a transparent protective layer.

However, the provision of the transparent protective layer on the surface of the gradation information containing image should not impair the gradation information containing image.

Therefore, the properties required for this transparent protective layer are that it is transparent, that the diffusion movement of the sublimable dye is as small as possible, and that the interference of ultraviolet rays with the sublimable dye at the time of ultraviolet irradiation can be minimized. It is required that the coating agent be prevented from coming into contact with the sublimable dye when the coating agent is applied.

The area covered by this transparent protective layer is
Only the gradation information-containing image layer may be used, or both the gradation information-containing image layer and the character information-containing image layer may be used.

(D.1). Structure of Transparent Protective Layer As a transparent protective layer satisfying such requirements, Japanese Patent Laid-Open Publication No.
No. 3,183,881 from page 9, lower left column, line 9,
It can be formed from the heat-fusible compound described in page 0, upper left column, line 15 and the thermoplastic resin exemplified in page 10, upper left column, line 16 to page 11, lower left column, line 9 of the same publication.

An ultraviolet absorber may be contained in the transparent protective layer, or a gradation information-containing image can be obtained from ultraviolet rays when the ultraviolet-curable prepolymer-containing coating agent is irradiated with ultraviolet rays and cured. It is effective in protecting.

Examples of the ultraviolet absorber include the compounds exemplified in the description of the image receiving layer.

The blending amount of these in the transparent protective layer is
Since it varies depending on the type of compound, it can be experimentally determined 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 in consideration of the uniform coating property of the ultraviolet curable resin.

(D.2). Transfer Layer for Protective Layer Formation In order to form a transparent protective layer on an image containing gradation information, it is preferable to use a transfer sheet for protective layer formation.

This protective layer-forming transfer sheet can be constructed by laminating a peeling layer, a transparent protective layer, and an adhesive layer, if necessary, in this order on a support.

As a transfer sheet of a preferred embodiment for forming a transparent protective layer, a protective layer forming sheet portion obtained by laminating the release layer and the transparent protective layer in this order on a support, and a heat-meltable ink sheet portion. Can be formed by dividing.

In this transfer sheet, an image containing character information can be formed on the image receiving surface of the base material with the heat-meltable ink sheet, and the base layer image-receiving surface is formed by the protective layer forming sheet portion. A transparent protective layer can be simultaneously formed on the image surface containing gradation information formed on the surface.

As the layer structure of the heat-meltable ink sheet portion, the laminated structure described in the above "(C.1) Heat-meltable ink sheet" can be adopted.

E. Curing protective layer In the image recording material of the present invention, a substantially transparent curing protective layer which is cured by irradiation with ultraviolet rays is formed on the entire surface of the substrate having the gradation information-containing image and the character information-containing image. There is.

The curing protective layer can be formed by applying a coating agent containing an ultraviolet curable resin on the above base material and irradiating it with ultraviolet rays.

(E.1). Coating Agent This coating agent can be formed from a composition containing an ultraviolet curable prepolymer and a polymerization initiator as main components.

The UV-curable prepolymer is 1
Prepolymers containing two or more epoxy groups in the molecule can be mentioned. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyl of aromatic polyol. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, epoxidized polybutadienes, and the like. These prepolymers may be used alone or in a mixture of two or more.

The content of the prepolymer having two or more epoxy groups in one molecule in the coating agent was 70% by weight.
It is preferable that this is the case.

The polymerization initiator is preferably a cationic polymerization initiator, and specific examples thereof include aromatic onium salts.

As the aromatic onium salt, V.
A salt of a group a element such as a phosphonium salt (for example, triphenylphenacylphosphonium hexafluorophosphate), a salt of a Group VIa element such as a sulfonium salt (for example, triphenylsulfonium tetrafluoroborate,
Triphenylsulfonium hexafluorophosphate, tris (4-thiomethoxyphenyl) hexafluorophosphate, triphenylsulfonium sulphonium and hexisafluoroantimonate, and salts of Group VIIa elements such as iodonium salts such as diphenyliodonium chloride ).

The use of such an aromatic onium salt as a cationic polymerization initiator in the polymerization of an epoxy compound is disclosed in US Pat. Nos. 4,058,401 and 4,058.
Nos. 69,055, 4,101,513 and 4,161,478.

Preferred cationic polymerization initiators include
Examples thereof include sulfonium salts of Group VIa elements. Among them, triarylsulfonium hexafluoroantimonate is preferred from the viewpoint of ultraviolet curability and storage stability of the ultraviolet curable composition.

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. When the content of the cationic polymerization initiator does not exceed 1% by weight of the coating agent, the curing rate may be extremely slow when irradiated with ultraviolet rays, which is not preferable.

The UV-curable resin is not limited to the above-mentioned epoxy-based curable resin, but may be a radical-polymerizable resin such as a monofunctional or polyfunctional acrylate compound.

Further included in the coating agent are surfactants such as oils (particularly silicone oil), silicone-alkylene oxide copolymers (for example, L-5410 commercially available from Union Carbide Co.), and silicone oil-containing fats. Group epoxides, FO-commercially available from 3M Company
171 and FO-430 commercially available from 3M Company,
Megafa marketed by Dainippon Ink Co., Ltd.
c A fluorocarbon surfactant such as F-141 may be contained.

The coating agent further contains, for example, vinyl monomers such as styrene, paramethylstyrene, methacrylic acid ester, acrylic acid ester and the like, cellulosics, thermoplastic polyester, phenylglycidyl ether, silicon-containing monoepoxide, A monoepoxide such as butyl glycidyl ether may be contained within a range that does not impair the effects of the present invention.

In addition, in this coating agent, as an inert component, for example, fillers such as talc, calcium carbonate, alumina, silica, mica, barium sulfate, magnesium carbonate and glass, dyes, pigments and thickeners. , Plasticizers, stabilizers, leveling agents, coupling agents, tackifiers, wetting improvers such as silicone group-containing activators, fluorocarbon group-containing surfactants, and other various additives, and flow during coating of coating agents For the purpose of improving the properties, a small amount of solvent such as acetone, methyl ethyl ketone, and methyl chloride which hardly reacts with the cationic polymerization initiator may be contained.

(E.2). Coating Method and Coating Conditions The coating agent is coated on the surface of the substrate by coating the coating agent and optionally a coating agent whose viscosity is adjusted by adding a solvent or the like. It can be achieved by coating the surface of the substrate with a usual method such as a roll coater, a slit coater, an air knife coater, a wire bar coater, a slide hopper, and spray coating.

By any of these appropriate coating methods, the coating layer of the above coating agent is usually applied to the surface of the substrate by 0.1
It is applied to a thickness of 〜30 μm, preferably 1-14 μm.

After coating, the coating layer of the coating agent is irradiated with ultraviolet rays, and the polymerization reaction or curing reaction of the UV-curable prepolymer in the coating agent proceeds.

Here, the term "ultraviolet light" means light in the ultraviolet region, and also includes light rays containing light in the ultraviolet region. Therefore, examples of UV irradiation include irradiation with sunlight, irradiation with a low-pressure mercury lamp, irradiation with a high-pressure mercury lamp, irradiation with an ultra-high-pressure mercury lamp, irradiation with a carbon arc lamp, irradiation with a metal halide lamp, irradiation with a xenon lamp, and the like. .

The atmosphere for irradiating with ultraviolet rays is as follows.
An inert gas atmosphere such as air, nitrogen gas or carbon dioxide gas is preferred.

The irradiation time of ultraviolet rays varies depending on the kind of irradiation light source in the ultraviolet region, but is usually 0.
It is 5 seconds to 5 minutes, preferably 3 seconds to 2 minutes. Usually, when the irradiation time is short, a large light source with a large irradiation intensity is required, and when the irradiation time is long, a light source with a small irradiation intensity can be used. However, a light source with low irradiation intensity has a long curing action time, which is not advantageous in the manufacturing process. However, in the present invention, a cured film having practically sufficient strength can be formed by irradiation with an ultraviolet ray generating lamp of 200 W or less for 3 seconds to 2 minutes.

In curing, heating the coating film of the coating agent before or after irradiation with ultraviolet rays can shorten the curing time. When such heating is performed, the heating temperature is preferably 30 to 80 ° C. Before the ultraviolet irradiation, the heating time at the heating temperature may be long or short, but after the ultraviolet irradiation, the heating time is preferably 1 minute to 120 minutes.

[0215]

Next, embodiments of the present invention will be described in detail. In the following, “parts” indicates “parts by weight”.

Example 1 (1) A card-sized image-receiving sheet was manufactured as follows. That is, a wide white vinyl chloride sheet having a thickness of 750 μm obtained by heat-welding a 150 μm thick hard transparent vinyl chloride sheet to both sides of a 450 μm thick hard white vinyl chloride sheet has the following composition. The coating liquid for an image receiving layer was applied by a wire bar method, and the solvent was dried and removed to form an image receiving layer having a thickness of 4.0 μm.

[Composition of coating liquid for image receiving layer] Vinyl chloride [TK-600 manufactured by Shin-Etsu Chemical Co., Ltd.] 9.9 parts Solvent (methyl ethyl ketone / cyclohexanone = 8/2) .0 part Silicone resin (release agent) [X24 8300, manufactured by Shin-Etsu Chemical Co., Ltd.] ... 0.1 part.

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, an image-receiving sheet having a card size of 54.0 mm × 85.5 mm was obtained.

[Composition of coating liquid for writing layer] Colloidal silica: 2.5 parts by weight Gelatin: 7.0 parts by weight Hardener (see Chemical formula 1) 0.5 parts by weight Water: 90 parts by weight

[0221]

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(2) A sublimation type thermal transfer recording ink sheet was manufactured as follows. The surface of the polyethylene terephthalate sheet having a thickness of 6 μm as a support was subjected to corona discharge treatment, and three kinds of coating liquids for forming an ink layer having the following compositions were formed by a wire bar coating method so that the thickness after drying was 1 μm.
m so that m (m) is applied along the longitudinal direction of the polyethylene terephthalate sheet so that yellow (Y), magenta (M), and cyan (C) are applied separately, and then dried and not corona-treated. Apply 1 or 2 drops of silicone oil (X-41,403A, manufactured by Shin-Etsu Silicone Co., Ltd.) on the back surface and spread it on the entire surface. A back surface treatment coating is applied to obtain Y, M, and C three-color thermal transfer recording ink sheets. Obtained.

[Yellow Ink Layer Forming Coating Liquid] Yellow Disperse Dye [MS Yellow, Mitsui Toatsu Dyestuff Co., Ltd.] 3 parts Polyvinyl bratile ... 5 parts [Polymerization degree 1700, Tg 85.5 ° C., acetalization] Degree 64 mol%, acetyl group 3 mol% or less, trade name BX-1: manufactured by Sekisui Chemical Co., Ltd.] polyester modified silicone: 0.4 parts [manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X- 24-8310] Toluene ・ ・ ・ 40 parts Methyl ethyl ketone ・ ・ ・ 40 parts Dioxane ・ ・ ・ 10 parts [Coating liquid for forming a magenta ink layer] Magenta disperse dye [MS Magenta, Mitsui Toatsu dye] ··· 5 parts Polyvinyl bra Tea: 5 parts [Polymerization degree 1700, Tg 85.5 ° C., acetalization degree 64 mol%, acetyl group 3 mol% or less, trade name BX-1: Sekisui Chemical Co., Ltd. Industrial Co., Ltd.] Polyester modified silicone: 0.4 parts [Shin-Etsu Chemical Co., Ltd .: trade name X-24-8310] Toluene: 40 parts Methyl ethyl ketone :: 40 parts Dioxane:・ ・ ・ 10 parts [Coating liquid for forming cyan ink layer] Cyan disperse dye [Kayaset Blue 136, Nippon Kayaku Co., Ltd.] ・ 4 parts Polyvinylbracil ・ ・ ・ 5 parts [Polymerization degree 1700, Tg85.5] ° C, acetalization degree 64 mol%, acetyl group 3 mol% or less, trade name BX-1: Sekisui Chemical Co., Ltd.] Polyester modified silicone: 0.4 parts [Shin-Etsu Chemical Co., Ltd .: Trade name X-24-8310] Toluene ··· 40 parts Methyl ethyl ketone ··· 40 parts Dioxane ··· 10 parts (3) A sheet having a heat-meltable ink layer and a transparent protective layer It was prepared as. That is, the thickness is 4.5 μm
A coating liquid for a hot-melt ink layer was applied on one side of the surface of the polyethylene terephthalate sheet by a wire bar method, and dried to form a hot-melt ink layer having a thickness of 1.2 μm. Further, the uncoated portion on the surface of the sheet on which the heat-meltable ink layer is formed as described above, a coating solution for a transparent protective layer having the following composition is applied by a wire bar method and dried. Thickness 3.0μ
m transparent protective layer was formed.

That is, the heat-fusible ink layer and the transparent protective layer were separately formed on one surface of the polyethylene terephthalate sort. An anti-sticking layer having a thickness of 0.6 μm was formed by applying an anti-sticking layer coating solution having the following composition to the surface of the polyethylene terephthalate sheet opposite to the heat-meltable ink layer.

[Composition of coating liquid for heat-meltable ink layer] Carnauba wax: 1 part Ethylene-vinyl acetate copolymer Combined (Mitsui DuPont Chemical EV 40Y) 1 part Carbon black ・ ・ ・ ・ ・ ・ ・ ・ 6 parts Phenolic resin (Arakawa Chemical Tamanoru 521) ・ ・ ・・ ・ ・ ・ ・ ・ 12 parts Methyl ethyl ketone ・ ・ ・ ・ ・ ・ 80 parts [Composition of coating liquid for transparent protective layer] Polyester resin Byron Co., Ltd. 200) ... 6.5 parts Ultraviolet absorber (2,4-dihydrooxybenzophenone) ... 3.5 parts Methyl ethyl ketone (solvent)・ ・ ・ ・ ・ 90 parts Anti-sticking layer coating agent Nitrocellulose・ ・ ・ ・ ・ ・ ・ ・ 3 parts Acrylic silicone resin ・ ・ ・ ・ ・ ・ 7 parts Methyl ethyl ketone ・・ ・ ・ ・ ・ ・ 90 copies.

(4) Preparation of UV-Curable Resin-Containing Coating Liquid A UV-curable resin-containing coating liquid having the following composition was prepared.

[UV-Curable Resin-Containing Coating Liquid] (Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate (UCL ERL 4299) ... 70 parts Bisphenol A glycidyl ether ... 10 parts 1,4-butanediol glycidyl ether ... 13 parts Triarylsulfonium fluoroantimony ..... ... 7 copies.

(5) An image recording material was manufactured as follows. That is, the image receiving layer on the image receiving sheet and the sublimable dye-containing layer of the ink sheet for sublimation type thermal transfer recording are overlapped, and an output of 0.23 W / dot and a pulse width of 0 from the ink sheet side for sublimation type thermal transfer recording using a thermal head. .3
By heating under the conditions of 4.5 msec and a dot density of 16 dots / mm, a human face image with gradation was formed on the image.

Next, a transparent protective layer is formed on the image receiving layer of the image receiving sheet by the following method so that the transparent protective layer is slightly larger than the human face image so that the surface of the human face image formed on the image receiving layer of the image receiving sheet is positioned. After the transfer, a heat-meltable ink layer is overlaid, and the heat-meltable ink layer is heated with a thermal head under the conditions of an output of 0.5 W / dot, a pulse width of 1.0 msec, and a dot density of 16 dots / mm. , Transcribed text information. Further, the transparent protective layer was easily transferred to the image receiving layer by peeling off the support after applying heat at 120 ° C. for 1.2 seconds using a heat roller.

As described above, the ultraviolet-curable resin-containing coating liquid was applied to the surface of the image receiving layer having the character information image and the human face image so that the coating amount was 10 g / m ^2, and the curing conditions were as follows. The ultraviolet-curable resin-containing coating liquid was cured to form a curing protective layer.

[0231] Curing Conditions optical scanning with a high pressure mercury lamp irradiation with light irradiation source · · · 60 W / cm ² distance · · · 10 cm illumination mode · · 3 cm / min Thus, in Example 1 the image recording member obtained To do.

(6) Evaluation was carried out as follows.

Appearance The aesthetics of the created sample,
We compared the performance of the products.

Anti-counterfeiting property 1) Under the environment of 80 ° C., a state was observed in which the surface protective layer on the image receiving layer was peeled off.

2) Falsification of Writing on Items Described on Image Receiving Layer Durability The surface of each sample is rubbed with a pencil having a hardness of H. The results are shown in Table 1.

(Comparative Examples 1 to 4) For comparison, the sample of Example 1 not coated with the UV-curable resin protective layer is Comparative Example 1, the sample of Example 1 not coated with the transparent protective layer is Comparative Example 2, and both are compared. The sample which was not applied was used as Comparative Example 3.

For the sample of Comparative Example 3, a commercially available so-called pouch film (100 μm manufactured by Japan GBC Co., Ltd.) was used as a simple laminator (LPC1 manufactured by Fuji Plastic Machine Co., Ltd.).
Sample No. 70) which was heat-sealed at 140 ° C. was used as Comparative Example 4.

Performance comparisons of these four types of samples with respect to the same evaluation items as in Example 1 were performed. The results are shown in Table 1.

From the above results, all the comparative examples have a fatal defect as an ID card, while Example 1 of the present invention provides an ID card having an excellent appearance, anti-counterfeiting property and durability. be able to.

[0240]

[Table 1]

(Examples 2 to 5, Comparative Examples 5 to 8) Next, the coating properties of the ultraviolet curable resin when the amount of the release agent added in the image receiving layer in Example 1 was changed as shown in Table 2 were obtained. , 80 ° C
The surface protection layer on the image receiving layer was peeled off under the environment.

For comparison, samples in which the pouch film used in Comparative Example 4 was used as the surface protective layer instead of the transparent protective layer and the ultraviolet curable resin layer of the samples in Examples 2 to 5, respectively, were prepared in Comparative Examples 5 to 8 respectively. And

The evaluation contents in Table 2 are as follows.

XX: Very good XX: Good ◯: Some coating unevenness occurred, though not so much that the commercial value was lost.

[0245]

[Table 2]

(Examples 6 to 9) Next, the transparent protective layer in Example 1 was formed into a two-layer structure as described below, and the ultraviolet absorber was added to
-Hydroxybenzophenone was used, and this was carried out in the same manner as in Example 1 except that this was added to the lower layer (layer on the image receiving layer side) in the amount shown in Table 3, and these were designated as Examples 6 to 9. The images in Examples 6 to 9 and Comparative Examples 3 and 4
The light resistance was compared with that of the image. The weather resistance of the image is
It measured and evaluated as follows.

Weather resistance: 72 in a xenon weather meter
The decrease in the reflection density at the highest density portion of cyan in the dye image after the time exposure was measured with a PDA65 manufactured by Konica Corporation.

Transparent protective layer: Composition of upper layer Polyparabanic acid (Tonen Petrochemical Co., Ltd. XT 4): 9.5 parts Silicon resin powder (Toshiba Silicone Co., Ltd. Tosval 108): 0.5 parts 1.4 dioxane 90 parts upper layer thickness 0.22.0 μm lower layer composition The coating liquid of the same weight ratio as in Example 1 except for the ultraviolet absorber. Lower layer thickness 2.0 μm

[0249]

[Table 3]

[0250]

According to the method of the present invention, (1) a card-sized image recording medium can be rapidly manufactured, and (2)
Since the film is not laminated on the image forming surface, it is not necessary to generate chips of the laminated film when producing the image recording medium, and (3) the transparent protective layer is formed on the surface of the image formed with the sublimable dye. Therefore, even if a coating liquid containing a UV-curable resin is applied and cured by irradiating UV light, the image formed by the sublimable dye is not hindered at all, and therefore has a clear floor that is not damaged in the manufacturing process. (4) Since the cured protective layer formed of an ultraviolet curable resin and the image receiving layer are integrally bonded and formed inseparably, any of the gradation image and the character information image can be formed. Neither forgery nor alteration can be performed, and therefore, a highly reliable image recording body can be manufactured for information based on images, and the obtained image recording body has high image durability.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an image recording body that is an embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating an image receiving sheet as an example in an image recording medium according to an embodiment of the present invention.

[Explanation of symbols]

 A Image recording body 1a Support 1b Image receiving layer 2 Image containing character information 3 Image containing gradation information 4 Transparent protective layer 5 Curing protective layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoki Kawamura 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (2)

[Claims] 1. A substrate, an image layer formed on the surface of the substrate with a sublimable dye by a sublimation thermal transfer method, a substantially transparent protective layer on the image layer, and a protective layer on the protective layer. An image recording body, which is provided with a substantially transparent curing protective layer formed by curing a coating agent containing a prepolymer having two or more epoxy groups in one molecule by ultraviolet irradiation. 2. A step of forming an image layer on the surface of a substrate with a sublimable dye by a sublimation type thermal transfer method, a step of forming a substantially transparent protective layer on the image layer, and an epoxy group in one molecule. A method for producing an image recording material, which comprises the step of forming a substantially transparent cured protective layer by curing a coating agent containing two or more prepolymers on the protective layer by UV irradiation.