JPH09254561A - Image recording material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve writing properties by transferring a protective layer of which the surface becomes uneven after transfer to a surface having a dye image recorded thereon. SOLUTION: A protective layer of which the surface becomes uneven after transfer can be provided on a dye receiving layer having a dye image formed thereon by transferring the protective layer to the dye receiving layer from a protective layer transfer material wherein the protective layer and an adhesive layer are successively laminated on a support. A method for making a surface uneven by interfacial peeling can be achieved by using a support of which the surface has an uneven shape or a support on which a release layer having an uneven shape is laminated. A method for making a surface uneven by cohesive failure can be achieved by a release layer or a protective layer generating cohesive failure. In order to provide sufficient writing properties without exerting adverse effect on an image, it is pref. to set Ra of the surface of the transferred protective layer so that the measured value of Ra based on JIS B0601 is set to 0.02-5.0μm, especially, 0.1-2.0μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a writable image recording body, and more particularly to a suitable method for producing the image recording body.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a hard copy, a recording method by thermal transfer, electrophotography, ink jet or the like has been studied. For example, in the thermal transfer method, a transfer sheet having a heat-meltable ink layer on a support is heated by a thermal head to melt-transfer the ink from the heat-meltable ink layer onto an image-receiving sheet, or a heat diffusion property on the support. An image recording material is prepared by heating a dye-providing material having an ink layer containing a dye with a thermal head to thermally diffuse the heat diffusible dye from the ink layer to the dye receiving material. Among them, the latter uses a dedicated dye receiving material provided with a dye receiving layer containing a resin having a dyeing property to a heat diffusible dye. In such a special paper, the writability on the surface on which an image is formed is not sufficient, and it is the current situation that recording can be performed on the surface only with a specific writing instrument.

[0003] In recent years, inspection reports in which text information and image information coexist (medical donation inspection reports, material analysis reports, etc.), observation records (biopsy records, medical charts, plant / animal observations) Attempts have been made to apply the above recording method to reports, structural records of buildings, etc., but the poor writability on the image recording surface is a major obstacle.

In order to remedy such drawbacks, from the viewpoint of cost and hand, paper closer to plain paper is required. For example, JP-A-1-125282 and 1-
160682, 1-161672, 1-225
No. 591, No. 2-63892, No. 2-122946
No. 3,234,592, No. 4-323086, No. 4-336287, etc., a dye receiving layer was transferred from a dye receiving layer transfer material onto a substrate instead of using a dedicated dye receiving material. Later, recording methods and materials for recording images have been proposed. According to this method, the area other than the transfer portion of the dye receiving layer is closer to that of plain paper, but it is still insufficient in terms of writing on the surface of the dye receiving layer.

[0005]

The present invention has been made based on the above circumstances. That is, the object of the present invention is to
An object of the present invention is to provide an image recording material having excellent writability and a method for producing the image recording material.

[0006]

As a result of earnest studies, the present inventors have found that the above-mentioned problems can be solved by providing a protective layer of some kind on the image recording surface, and have completed the present invention. That is, the object of the present invention is achieved by the following configurations.

(1) In an image recording body in which a dye image is formed by transferring a dye imagewise from a dye-donor material to a dye-receiving material having a dye-receiving layer provided on a substrate in accordance with heat energy, An image recording body, which is obtained by transferring a protective layer on the surface on which a dye image is recorded so that the surface becomes uneven after being transferred.

(2) After transferring the dye receiving layer from the dye receiving layer transfer material onto the substrate, the dye image is transferred onto the dye receiving layer from the dye donating material in an imagewise manner in response to heat energy. In the image recording material on which is formed, a protective layer having a surface that becomes uneven after being transferred is transferred to the surface on which the dye image is recorded.

(3) A dye image comprising a dye capable of coordinating with a metal ion at two or more sites transferred from a dye-donor material, and a metal ion-containing compound capable of chelating with the dye contained in the dye-receiving layer. The image recording material according to (1) or (2), which is a chelate dye image formed imagewise by a reaction.

(4) In an image recording body on which a dye image is formed by transferring a dye capable of coordinating with a metal ion at two or more sites imagewise from a dye-donating material to a dye-receiving layer, 3. The image recording material according to claim 1, wherein a protective layer containing a metal ion-containing compound capable of chelating with a dye is transferred to the surface on which the dye image is recorded to form an image-like chelate dye image. .

(5) The protective layer is transferred by heat (1) to
The image recording material according to any one of (4).

(6) Ra on the surface of the protective layer after transfer
However, the value measured by JIS B0601 is 0.02-5.
The image recording material according to any one of (1) to (5), which has a thickness of 0 μm.

(7) The image recording material according to any one of (1) to (6), wherein the transferred protective layer contains a porous pigment.

(8) Information is recorded on the surface of the image recording body opposite to the surface provided with a protective layer having an uneven surface by a thermal fusion transfer method, an ink jet method or an electrophotographic recording method. It is recorded (1)-(7)
The image recording material according to any one of 1.

(9) When producing the image recording material according to any one of (1) to (8), image data input means, character information input means, and the image of a dye image formed imagewise A method for producing an image recording medium, characterized by having a means for editing data and character information and performing these operations while confirming them on a CRT.

(10) The method for producing an image recording medium according to (9), further comprising means for registering or retrieving respective data.

(11) The method for producing an image recording medium according to (9) or (10), wherein the image data forming device for image-formed dye image has a handwriting inputting device.

The image recording material of the present invention and the method for producing the image recording material will be described in detail below.

The image recording material of the present invention is classified into two types depending on the process for forming a dye image.

<First Aspect> The image recording material of the present aspect is an image formed from a dye-donor material having a dye-receiving layer having a dye-receiving layer on a substrate and an ink layer containing a dye on a support. Thus, the dye can be transferred, and the protective layer can be formed by transferring the protective layer from the protective layer transfer material in which the protective layer is laminated on the support on the dye receiving layer after the transfer.

Hereinafter, these materials will be described in detail.

(Dye-Receiving Material) As the dye-donor material used in the present invention, a commercially available image-receiving material used for transferring a heat-diffusible dye can be used as it is, or it can be newly prepared by a conventionally known technique. You may.

When a new dye receiving material is prepared, it is constructed by laminating a dye receiving layer on a substrate. Examples of such a base material include various papers such as paper, coated paper, synthetic paper (polypropylene, polystyrene, or composite materials obtained by laminating them with paper), vinyl chloride resin, polyethylene terephthalate, polycarbonate, and other resins. Examples thereof include various plastic films or sheets in which a single layer or two or more layers are laminated. In addition, a resin having a small neck-in and a good drawdown property (high-density polyethylene, represented by photographic resin-coated paper) on a surface or both surfaces of the core material paper or the dye receiving layer of the base film to be laminated, A base material obtained by hot-melt extrusion laminating single or two or more kinds of low-density polyethylene, polypropylene, etc. can also be preferably used.

The paper used as the base material is preferably a pulp paper made from natural pulp, synthetic pulp or a mixture thereof, and above all, natural pulp paper containing wood pulp as a main component is preferred. The paper is made using a Fourdrinier paper machine or the like, and for the purpose of improving smoothness, it is preferable to carry out calendering using a machine calender, super calender, thermal calender or the like after paper making. Further, in order to improve smoothness, a base paper coated with a resin layer containing a pigment can be preferably used. More specifically, high-quality paper, art paper, coated paper, single-sided glossy paper, impregnated paper, paperboard and the like can be mentioned. In order to provide smoothness when the laminate layer is provided, the Bekk smoothness of the paper is preferably 50 seconds or more, more preferably 100 seconds or more, and further preferably 200 seconds or more. The thickness of the paper is not particularly limited, but is 30 to 800.
μm is preferable, and 50 to 500 μm is more preferable.

In the above base paper, if necessary, a sizing agent,
Fixing agent, paper strengthening agent, filler, antistatic agent, dye, pigment,
Additives such as optical brighteners, antioxidants, and lubricants may be included.

In the case of a reflection image, in order to improve the sharpness of the image formed, a white pigment,
For example, titanium oxide, zinc oxide, silica, barium sulfate,
Magnesium carbonate, calcium carbonate, talc, clay and the like may be added.

The thickness of the substrate is usually 20 to 1000 μm, preferably 50 to 800 μm, and is appropriately selected from such a range.

The dye receiving layer is composed of a binder resin and an additive which is added if necessary. The binder resin may be a polyester type, a polyvinyl acetal type,
Urethane type, amide type, cellulose type, olefin type,
Vinyl chloride type, acrylic type, styrene type, polycarbonate type, polyvinyl alcohol type, polyvinylpyrrolidone type, polysulfone type, polycaprolactone type, polyacrylonitrile type, urea type, epoxy type, phenoxy type resin, etc. The resins may be used alone or in combination of two or more. The binder resin is contained in the dye-receiving layer-forming composition in an amount of usually 40 to 99.5% by weight, preferably 70 to 97% by weight.

In order to form a chelate dye image on a dye receiving material by using a dye capable of coordinating with a metal ion at two or more sites described below, the dye receiving layer contains a metal ion-containing compound capable of chelating with the dye. To do. As the metal ion-containing compound, inorganic metal salts or complexes, organic metal complexes,
Examples thereof include complexes having an organic compound as a ligand. Specific examples of the compound include those disclosed in JP-A-59-78893 and JP-A-59-78893.
-2398, JP-A-3-197088 and 6-12.
Examples thereof include metal ion-containing compounds described in No. 7156.

When the metal ion-containing compound is added, it is usually in the range of 3 to 60% by weight, preferably 10 to 40% by weight in the dye receiving layer forming composition.

A releasing compound may be added to the dye-receiving layer in order to facilitate separation between the dye-receiving material ink layer and the dye-receiving layer after image formation, which will be described later. Examples of the releasing compound include silicone compounds (polyester modified silicone resin, urethane modified silicone resin, acrylic modified silicone resin, etc.), solid waxes (polyethylene wax, amide wax, etc.), fluorine compounds (Teflon powder, etc.), Examples thereof include surfactants and fillers (titanium oxide, silica, metal oxides, graphite, resin fine powder, etc.). These may be used alone or in combination of two or more.

In the dye receiving layer, in addition to the above-mentioned metal ion-containing compound and releasing compound, if necessary, an antioxidant,
Other additives such as UV absorbers, light stabilizers, fillers (inorganic fine particles, organic resin particles), pigments and antistatic agents may be added. Further, a plasticizer, a heat-fusible substance or the like may be added as a sensitizer.

As the antioxidant, a chroman compound,
Claman-based compounds, phenol-based compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane-based compounds, sulfur-based compounds, phosphorus-based compounds and the like are mentioned, and JP-A-59-182785 and 60-130735,
61-159644, JP-A-1-127387,
"11290 chemical products", Chemical Industry Daily, 862-8
Examples thereof include the compounds described on page 68, and compounds known as those that improve image durability in photographs and other image recording materials.

Examples of the ultraviolet absorber and the light stabilizer include JP-A-59-158287, JP-A-63-74686 and JP-A-6-158686.
Nos. 3-145089, 59-196292 and 62
-229594, 63-122596, 61-
No. 283595, JP-A-1-204788, “112
90 chemical products "(supra), pages 869 to 875, and the like, compounds and optical brighteners are described in JP-A-61-23
No. 7693, No. 63-122596, No. 63-147.
The compounds described in JP-A No. 166, etc., and compounds known to improve the image durability of 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, etc., and organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. And so on. 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 antistatic agent include cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles and the like, and "11290".
Chemical products "(supra), pages 875-876, etc. are also preferably used.

As the plasticizer, phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, oxalic acid esters, epoxidized soybean oil, epoxidized linseed oil, In addition to epoxidized stearic acid, orthophosphoric acid ester, phosphorous acid ester, glycol ester, etc., “112
The compounds described in "Chemical products of 90" (supra), pp. 843-857, etc. are also preferably used.

Examples of the heat-melting substance include alcohols such as terpineol, amides such as acetamide, esters such as benzyl cinnamate, ethers such as diphenyl ether, ketones such as p-methylacetophenone, vanillin and the like. Hydrocarbons such as aldehydes and stilbenes,
Higher fatty acids such as margaric acid, higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, single molecule compounds represented by higher amines such as behenylamine, carnauba wax, beeswax , Waxes such as paraffin wax, ester wax, montan wax, amide wax, etc., ester gum, rosin maleic acid resin, rosin derivative such as rosin phenol resin, phenol resin, ketone resin, diallyl phthalate resin, terpene resin, aliphatic carbonization Examples thereof include hydrogen resins, cyclopentadiene resins, polymer compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol, and the like.

In the present invention, the melting point or softening point of the above-mentioned heat-meltable substance is preferably 10 to 150 ° C.

The addition amount of the above-mentioned additive is preferably selected in the range of 0.1 to 50% by weight in the dye receiving layer forming composition, and the thickness of the image receiving layer is usually 2 to 50 μm, preferably It is selected in the range of 3 to 20 μm. The image-receiving layer may be formed as a single layer, or may have a multi-layer structure having the same composition or a multi-layer structure having two or more different compositions.

In the present invention, an intermediate layer may be provided between the dye receiving layer and the substrate for the purpose of imparting heat insulating properties, cushioning properties and the like. Examples of the resin forming the intermediate layer include polyurethane resin, polyester resin, polybutadiene resin, poly (meth) acrylic acid ester resin, epoxy resin, polyamide resin, rosin-modified phenol resin, terpene phenol resin, ethylene-vinyl acetate copolymer,
Polyolefin resin, cellulose resin, gelatin,
Examples include casein. Further, in order to impart cushioning properties, the intermediate layer may be formed of a layer containing fine bubbles.

When an intermediate layer is provided, it is usually 3 to 50 μm.
m, preferably in the range of 5 to 30 μm. Further, the intermediate layer may be a single layer, or, if necessary, may be provided as a multi-layer structure of two or more layers having the same composition or different compositions to separate the functions.

On the surface opposite to the dye receiving layer, antistatic,
A backing layer for the purpose of preventing plural sheets from serving, providing slipperiness, preventing adhesion with other dye receiving layers, preventing curling, or enabling recording by methods such as thermal melt transfer recording method, inkjet recording method and electrophotographic recording method. May be provided. For the purpose of antistatic, it is preferable to add the antistatic agent described in the section of the dye receiving layer additive. To prevent multiple sheets from serving, add slipperiness, and prevent adhesion to other dye receiving layers,
It is preferable to add an antistatic agent and / or a filler or a pigment described in the section of the dye receiving layer additive. To prevent curling, it is preferable to use a heat-resistant resin with a small thermal deformation, or a resin cured by heat or ionizing radiation after forming the backing layer. As the heat-resistant resin, cellulosic resins such as methyl cellulose and nitrocellulose, polystyrene, styrene resins such as styrene-acrylonitrile copolymer, acrylic resins such as polymethyl methacrylate and polyacrylic acid, and polyester resins such as polyethylene terephthalate. Resin, polycarbonate, polyarylate, polyacetal, polysulfone, polyether sulfone, polyether nitrile, polyether ether ketone, modified polyphenylene oxide, polyoxybenzylene, polyimide, polyetherimide,
Polyamideimide, polyphenylene sulfide, polyparabanic acid resin, etc. can be mentioned.

The backing layer provided for the purpose of enabling recording by a method such as a heat-melt transfer recording method, an ink jet recording method and an electrophotographic recording method is not particularly limited as long as it is a recording layer suitable for these conventionally known recording methods. Can be used without.

Specifically, the recording layer suitable for melt transfer can be formed by a binder resin and various additives as required. Examples of the binder resin include polyvinyl butyral, polyvinyl acetoacetal, polyvinyl alcohol, and other polyvinyl alcohol derivatives; starch, corn starch, casein, gelatin, and other natural products and derivatives thereof; methylcellulose, hydroxypropylcellulose, and other cellulosic resins; water-soluble polyamides. , Water-soluble resins such as polyacrylic acid; synthetic resins such as vinyl chloride resins, butadiene resins, acrylic resins, polyolefin resins, polyurethane resins, epoxy resins and the like. The synthetic resin may be either a resin dissolved in an organic solvent or a resin dispersed in water such as a latex or emulsion, depending on the application.

Various additives may be added to the recording layer in the melt transfer for the purpose of improving the affinity with the ink to be transferred and the color tone of the recording layer. In order to improve the oleophobicity of the ink, it is preferable to add a porous pigment. Examples of the porous pigment include natural or synthetic zeolite, kaolin, calcined kaolin, talc, rouxite, diatomaceous earth, silica,
Examples thereof include synthetic silica, clay, calcium carbonate, magnesium hydroxide, magnesium carbonate, magnesium silicate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler and aluminum hydroxide. These porous pigments may be used alone or in combination of two or more, and usually 5 to 95 relative to the total amount of the recording layer forming composition.
It is preferable to add 10% by weight, more preferably 10 to 80% by weight. In addition, pigment dispersants, thickeners, fluidity improvers, defoamers, foam suppressors, mold release agents, foaming agents, penetrants, colored pigments, colored dyes, optical brighteners, ultraviolet absorbers, oxidation agents. Various additives such as an inhibitor, an antiseptic, an antifungal agent, an antistatic agent, and a thermal solvent can be added as needed at appropriate times. The thickness of the melt transfer recording layer is usually 0.5 to 20 μm, preferably 1 to 10 μm.
It is selected in the range of. Further, the recording layer may be formed as a single layer, or may have a multilayer structure having the same composition or a multilayer structure having two or more different compositions.

The recording layer in the ink jet recording method can be used without particular limitation as long as it can sufficiently receive ink, and the recording layer suitable for the ink jet system is composed of a composition mainly containing ultrafine inorganic pigments. It is preferable to improve the absorbability of the ink. The primary particle diameter of the ultrafine inorganic pigment used in this case is 100 nm or less, preferably 50 nm or less.
The smaller the particle size, the more uniform the surface coating, which is preferable. These ultrafine-particle inorganic pigments are usually used by dispersing them in a solvent in a colloidal state while maintaining the primary particle size.

Examples of the above-mentioned ultrafine inorganic pigments include silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate thereof, pseudo-boehmite, etc.), surface-treated cation. Colloidal silica, aluminum silicate, magnesium silicate, magnesium carbonate, titanium dioxide, zinc oxide and the like. Among them, it is more preferable that the primary particles are porous, but the coating liquid is adjusted even if it is non-porous. Sometimes agglomerates, and further agglomerates during coating drying,
It is preferable that a porous film is formed as the ink receiving layer. The ultrafine particle inorganic pigments may be used alone or in combination of two or more kinds.

Further, as the inorganic pigment that can be used in combination with the ultrafine particle inorganic pigment, conventionally known inorganic pigments can be used as long as the object of the present invention is not impaired.
For example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, aluminum silicate, diatomaceous earth, calcium silicate, synthetic amorphous silica,
Examples thereof include aluminum hydroxide, lithopone, zeolite, hydrohaloysite, magnesium hydroxide, synthetic mica and the like. Among these inorganic pigments, porous inorganic pigments are preferable, and examples thereof include porous synthetic amorphous silica, porous calcium carbonate, porous alumina, and the like, and porous synthetic amorphous silica having a large pore volume is particularly preferable.

Further, instead of or in combination with the inorganic fine particles, styrene resin particles, acrylic resin particles, polyethylene, microcapsules, urea resin, melamine resin,
Organic pigments such as fluorine resin particles may be used. The above-mentioned ultrafine particle inorganic pigment, inorganic pigment and organic pigment are usually contained in the composition for forming a receiving layer in an amount of 30 to 80% by weight, preferably 40.
It is preferably about 70% by weight.

In forming the ink jet recording layer, it is preferable to add a binder resin in addition to the above-mentioned ultrafine particle inorganic pigment, inorganic pigment and organic pigment in order to impart strength to the ink receiving layer. Examples of the binder resin include polyvinyl alcohol, vinyl acetate, oxidized starch, etherified starch, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; casein, gelatin, soybean protein, silyl modified polyvinyl alcohol; maleic anhydride resin, styrene-butadiene resin. , Conjugated methacrylate copolymer latex such as methyl methacrylate-butadiene copolymer, acrylic polymer latex such as polymer or copolymer of acrylic acid ester and methacrylic acid ester; vinyl type such as ethylene vinyl acetate copolymer Polymer latex; or functional group-modified polymer latex with a functional group-containing monomer such as carboxyl group of these various polymers; water-based binder such as thermosetting synthetic resin system of melamine resin, urea resin, etc .; Acrylate,
Examples thereof include synthetic resin binders such as polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal resin, and alkyd resin. The above-mentioned resins may be used alone or 2
One or more kinds may be used in combination, and the amount used is in the receiving layer forming composition,
It is usually 10 to 70% by weight, preferably 20 to 50% by weight.

Further, the ink jet recording layer may contain a pigment dispersant, depending on the substrate, as long as the object of the present invention is not impaired.
Thickeners, flow improvers, defoamers, foam suppressors, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, optical brighteners, ultraviolet absorbers, antioxidants, preservatives, anti-prevention agents. Other additives such as a by-product, a water resistant agent, a wet paper strength enhancer, a dry paper strength enhancer, and an antistatic agent may be added. These various additives can be added usually in the range of 0 to 10% by weight in the composition for forming the receiving layer.

In the present invention, the method of coating the surface of the base material may be a coating method or an impregnation method depending on the type of the base material, but the thickness of the ink jet recording layer is usually 0.5 to 30 g / gram basis weight.
It can be appropriately selected and used in the range of m ² , preferably 1.0 to 20 g / m ² . On the other hand, as a recording layer suitable for electrophotography, the temperature applied during the toner image fixing step,
Although it varies depending on the pressure and time, the recording layer for melt thermal transfer of the above-mentioned thermal transfer recording method or the recording layer for inkjet recording method can be selected and used as appropriate.

When the above-mentioned backing layers are provided, it is preferable that the thickness of each is usually selected in the range of 0.01 to 20 μm, and it may be a single layer, or if necessary, the composition or the like is the same or not. It may be provided as a multi-layer structure of two or more different layers to separate the functions.

The dye-receptive material has a coating method in which the components for forming the dye-receptive layer are dispersed or dissolved in a solvent to prepare a coating solution, which is applied and dried on the surface to be laminated, and a component for forming the dye-receptive layer. Hot-melt extrusion lamination method in which the mixture is melt extruded and laminated on the surface to be laminated, transfer method in which the above layer is formed on a peelable sheet and then laminated by heating and / or pressing on the surface to be laminated, etc. Can be formed by.

As the solvent used in the above coating method, water, alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), aromatics (toluene, xylene, chlorobenzene, etc.), ketones ( Acetone, methyl ethyl ketone, cyclohexanone, etc., ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, dioxane, etc.), chlorine solvents (chloroform, trichloroethylene, etc.), amide solvents (dimethylformamide, N-methyl) Pyrrolidone etc.), dimethyl sulfoxide and the like.

For coating, conventionally known gravure roll coating methods, extrusion coating methods, wire bar coating methods, roll coating methods and the like can be employed. Even when other layers are provided, they can be formed by the same method as that for the dye receiving layer.

When the adhesive strength between the layers to be laminated is insufficient (for example, when the difference in the wetting angle (contact angle) between the resins to be laminated is large, particularly 5 deg or more), the layer to be laminated is provided. Before, it is preferable to place a treatment on the surface to be laminated, as the method of this surface treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, Known resin surface modification techniques such as low-temperature plasma treatment and grafting treatment can be applied as they are. Specifically, you can refer to the methods described in "Basics and Applications of Polymer Surfaces (below)" Kagaku Dojin, Chapter 2 and / or "Handbook of New Polymer Materials" Maruzen, Chapter 8, etc. It is also possible to use two or more species together.

(Dye-donor material) As the dye-donor material used in the present invention, a commercially available material used for thermal diffusion dye transfer can be used as it is, or it can be newly prepared by a conventionally known technique. May be.

When a new dye-providing material is prepared, it is constituted by laminating an ink layer containing a dye on a support.

This support has good dimensional stability,
Anything can be used as long as it can withstand the heat of recording with a thermal head, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone, polyvinyl alcohol cellophane,
A heat resistant plastic film such as polystyrene can be used, and the thickness of the support is 2.0 to 10.0 μm.
m is preferred.

As the dye used in the thermal diffusion dye transfer, the conventionally used cyan dye, magenta dye and yellow dye can be used as they are. As the cyan dye, conventionally known naphthoquinone type, anthraquinone type and azomethine dyes can be used. System, indoaniline type dyes, etc .; magenta dyes, anthraquinone type, azo type, azomethine type dyes, etc .; and yellow dyes, methine type, azo type, quinophthalone type, anthryothiazole type dyes, etc.

Further, as a dye used when a chelated dye image is formed on an image recording medium by using a dye which is capable of coordinating with a metal ion at the bidentate or more, for example, JP-A-59-78893. No. 59-109349, JP-A-4-73191, 4-82784, 4-82.
785, 4-89289, 4-158809
No. 4, No. 4-164690, No. 5-16545, No. 5
The dye etc. which are described in -177958 etc. can be used. These dyes capable of coordinating with a metal ion at two or more sites may be used alone or in combination of two or more.

The heat diffusible dye is usually contained in the ink layer forming composition in an amount of usually 5 to 70% by weight, preferably 10 to 50% by weight.

In addition to the above dyes, a binder resin is added to the ink layer to retain the dyes. Examples of the binder resin include cellulose resins (ethyl cellulose, nitrocellulose, etc.), polyvinyl acetal resins (polyvinyl formal). , Polyvinyl acetoacetal, polyvinyl butyral, etc.), acrylic resins (polymethyl methacrylate, etc.), styrene resins (styrene-acrylonitrile copolymer, etc.), etc., and these may be used alone. Also, two or more kinds can be used in combination.

The binder resin is used in the ink layer forming composition.
Usually, the range is 30 to 95% by weight, preferably 50 to 90% by weight.

Further, various additives can be appropriately added to the ink layer. Examples of the additive include a releasing compound, a filler, a curing agent capable of reacting with a binder component (for example, a radiation active compound such as isocyanates, acryls, and epoxies), an antistatic agent, and a heat-melting substance. The additives that can be added to the image-receiving layer can be appropriately selected and used as needed.

The thickness of the ink layer is usually 0.2 to 5 μm,
It is preferably selected in the range of 0.5 to 2 μm and may be formed as a single layer.
It may be a multilayer structure having more than two layers.

The dye-providing material is not limited to a two-layer structure composed of a support and an ink layer, and other layers may be formed. For example, an overcoat layer may be provided on the surface of the ink layer for the purpose of preventing fusion with the heat-sensitive transfer recording image receiving material and settling (blocking) of the dye.

Further, for the purpose of improving the adhesiveness to the ink layer on the support, and preventing the transfer and dyeing of the dye to the support side,
It may have an undercoat layer.

Further, a backing layer may be provided on the back surface of the support (on the side opposite to the ink layer) for the purpose of running stability, heat resistance, antistatic and the like.

The thickness of the overcoat layer, the undercoat layer and the backing layer is usually 0.1 to 1 μm.

The dye-providing material is prepared by dispersing or dissolving the components for forming the ink layer in a solvent to prepare a coating liquid, and coating and drying the coating liquid on the surface to be laminated, or by coating the layer on a peelable sheet. After the formation, it can be formed by a transfer method or the like in which only the layer is transferred by heating and / or pressing on the surface to be laminated.

As the solvent used in the above coating method, water, alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), aromatics (toluene, xylene, chlorobenzene, etc.), ketones ( Acetone, methyl ethyl ketone, cyclohexanone, etc., ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, dioxane, etc.), chlorine solvents (chloroform, trichloroethylene, etc.), amide solvents (dimethylformamide, N-methyl) Pyrrolidone etc.), dimethyl sulfoxide and the like.

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

The above-mentioned layer may be formed on the entire surface of the surface to be laminated, or may be formed on a part of the surface, if necessary. Further, other layers can be provided in the same manner.

(Protective Layer Transfer Material) A protective layer having a surface which becomes uneven after transfer is formed by forming a dye image from a protective layer transfer material in which a protective layer and an adhesive layer are laminated in this order on a support. It can be provided by transferring a protective layer on the dye-receiving layer thus formed, and various methods can be adopted to make the surface uneven when the protective layer is transferred.

Specifically, any method can be used as long as the object of the present invention can be achieved, such as a method of peeling the interface to make the surface uneven, and a method of causing cohesive failure to make the surface uneven. May be adopted. More specifically, as a method of peeling the interface so that the surface becomes uneven, a structure in which a support having an uneven surface is used, or a release layer which will be described later and is laminated on the support has an uneven shape is used. Due to
The method of causing cohesive failure to make the surface uneven can be achieved by a constitution such as cohesive failure of the release layer or the protective layer.

However, whichever method is used, in order to have sufficient writability without adversely affecting the viewing of the image, Ra of the transferred protective layer surface is determined by JIS.
The value measured by B0601 is preferably in the range of 0.02 to 5.0 μm, more preferably 0.1 to 2.0 μm.

The protective layer transfer material whose surface becomes uneven after transfer will be described in detail below.

The support for the protective layer transfer material is not particularly limited as long as it is a material excellent in dimensional stability, and for example, a support used for a dye-donor material can be appropriately selected and used.

In order to make the surface of the support itself uneven, it can be formed by forming a film of a kneaded product in which a filler is mixed at the time of melt kneading of the resin, and the above-mentioned protective layer laminating surface of the support. The surface can be made uneven by applying a surface treatment such as sandblasting. The thickness of the support is usually 3 to
It is 50 μm, preferably 6 to 30 μm.

The peeling layer is provided as necessary in order to peel the support from the protective layer, and the component forming the peeling layer is a layer containing a compound capable of ensuring peelability from the protective layer. If it is composed of, it can be used without particular limitation.

Compounds capable of ensuring such releasability include solid compounds such as silicone compounds, fluorine compounds, polyethylene wax, amide wax, Teflon powder, fluorine-based and phosphoric ester-based surfactants,
Examples of the filler include metal fine powder, silica gel, metal oxide, carbon black, and resin fine powder.
It is preferably composed of a layer containing a silicone-based compound and / or a fluorine-based compound. Silicone type and / or
Alternatively, the fluorine-based compound refers to a resin itself that is solid at room temperature, an oil-like compound, a wax-like compound, or the like.

Examples of the silicone oil (including wax) include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil and methyl hydrogen silicone oil; olefin modified silicone oil, polyether modified silicone oil, epoxy modified silicone. Oil, epoxy / polyether modified silicone oil, alcohol modified silicone oil, fluorine modified silicone oil, amino modified silicone oil, phenol modified silicone oil,
Radical-reactive silicone oil such as mercapto-modified silicone oil, carboxy-modified silicone oil, higher fatty acid-modified silicone oil, carnauba-modified silicone oil, amide-modified silicone oil, (meth) acryl-modified silicone oil; end reaction of silicone diol or silicone diamine Silicone oil; organic modified silicone oil modified with a halogen group, an alkoxy group, an ester group, an amide group, an imide group and the like can be mentioned.

As the silicone resin, polysiloxane such as dimethylpolysiloxane, methylhydrogenpolysiloxane and methylphenylpolysiloxane, polyester-modified silicone in which the resin and the silicone component are block, alternating, random or graft copolymerized. Resin (or silicone modified polyester resin), acrylic modified silicone resin (or silicone modified acrylic resin), urethane modified silicone resin (or silicone modified urethane resin), epoxy modified silicone resin (or silicone modified epoxy resin), cellulose modified silicone resin ( Or silicone modified cellulose), alkyd modified silicone resin (or silicone modified alkyd resin), polyimide modified silicone resin (or silicone modified polyimide resin) ) Modified silicone resin (or silicone-modified resin or the like) and the like.

Examples of fluorine compounds include polytetrafluoroethylene, tetrafluoroethylene copolymers (alkyl vinyl ether, ethylene, etc.), polyvinylidene fluoride, fluoroalkyl methacrylate, fluorine resins such as fluororubber, and perfluoropolyether oil. , Low molecular weight fluorine compounds such as fluoroalcohol, fluorocarboxylic acid, perfluoroalkylcarboxylic acid salt, perfluoroalkyl quaternary ammonium salt, perfluoroalkylbetaine, perfluoroalkylethylene oxide (adduct), perfluoroalkyl oligomer, etc. Can be mentioned.

In the present invention, one kind or a mixture of two or more kinds of these compounds can be used. Further, the amount of these compounds added is usually preferably 2% by weight or more, more preferably 5% by weight or more, in the release layer forming composition.

The various oils and / or resins described above may be crosslinked or cured by radiation, heat, moisture, a catalyst, a crosslinking agent or the like by utilizing the reaction active points thereof. , A radiation-active monomer such as acrylics, and a crosslinking agent such as isocyanate can be used.

The release layer may contain a binder resin in addition to the compound capable of ensuring releasability as long as the purpose is not impaired. Further, the surface of the release layer can be made uneven by adding a filler or a pigment in addition to the above-mentioned compound or binder resin capable of ensuring releasability. The thickness of the release layer is usually 0.01 to 5 μm, preferably 0.05 to 2 μm.

The protective layer laminated on the above-mentioned support or peeling layer is composed of a binder resin and various additives which are added as required.
Polyvinyl acetal resins such as polyvinyl alcohol and polyvinyl butyral; cellulose derivatives such as nitrocellulose and methyl cellulose; acrylic resins such as polymethylmethacrylate; styrene resins such as styrene-acrylonitol; vinyl chloride resins such as polyvinyl chloride; bisphenol Z. Examples include polycarbonates such as type polycarbonates, polyester resins, and the like, which are formed by curing an active energy ray-curable or thermosetting compound such as an epoxy group- or acryl group-containing compound after coating the protective layer. The protective layer may be appropriately selected and used.

Further, it is preferable that a filler or a pigment is added to the protective layer in order to impart writability.

Examples of such fillers include inorganic fine particles and organic resin particles, and examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay and alumina. Examples of particles include fluorine resin, guanamine resin, acrylic resin, and silicone resin particles, and examples of pigments include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, and activated clay. , Acid clay and the like.

In order to improve the oil absorbency of the ink, it is preferable to add a porous pigment in order to provide the writing property for ink such as a ballpoint pen. Examples of the porous pigment include natural or synthetic zeolite, kaolin, Calcined Kaolin, Talc, Rouseki, diatomaceous earth, silica, synthetic silica, clay, calcium carbonate, magnesium hydroxide, magnesium carbonate, magnesium silicate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler,
Aluminum hydroxide etc. are mentioned.

These porous pigments may be used alone or in combination of two or more, and usually 5 to 95% by weight, more preferably 10 to 80% by weight in the protective layer forming composition. It is preferable to add.

The image-protecting material of the present invention, in the sense of improving the durability of the image, contains an ultraviolet absorber, a light stabilizer and an antioxidant which are added to the above-mentioned dye receiving layer in the protective layer to be transferred. And the like, and when the dye-donor material contains a dye capable of coordinating with a metal ion at two or more sites, a metal ion-containing compound capable of chelating with the dye is appropriately selected and included. May be.

The thickness of the protective layer is usually 0.2 to 10 μm, preferably 0.5 to 7 μm.

Further, the protective layer transfer material is preferably provided with an adhesive layer on the protective layer in order to secure the adhesiveness with the dye receiving layer when the material is transferred to the dye receiving material. It itself has adhesiveness at room temperature, including those that develop adhesiveness by applying pressure, or those that develop adhesiveness by applying heat, such as a resin with a low softening point, an adhesion promoter, and the like, It is formed by mixing a heat-meltable substance and / or a thermoplastic substance. Alternatively, the adhesive composition may be laminated on the surface of a resin layer made of a heat-meltable substance and / or a thermoplastic substance. Alternatively, the adhesive substance may be contained in a microcapsule by a known method in a resin layer made of a heat-fusible substance and / or a thermoplastic substance to form the adhesive layer.

Resins having a low softening point used for the adhesive layer include polyolefin resins (polyethylene, polypropylene, etc.), ethylene copolymers (ethylene-vinyl acetate, ethylene-ethyl acrylate, etc.), polyamide resins (nylon, dimer). Acid, etc.), styrene copolymer (styrene-butadiene, styrene-isoprene, styrene-ethylene-butylene, etc.), vinyl chloride resin (vinyl chloride-vinyl acetate copolymer, etc.), polyvinyl ether resin, acrylic resin, Examples thereof include ionomer resins, cellulosic resins, polyurethane resins and epoxy resins.

Examples of the adhesion-imparting agent include rosin,
Examples include unmodified or modified products of hydrogenated rosin, rosin maleic acid, polymerized rosin and rosin phenol, terpenes, petroleum resins and modified products thereof.

As the heat-fusible substance that can be contained in the adhesive layer, a substance added to the dye-receiving layer can be appropriately selected and used, and further, the dye-donor material is bidentate or more and coordinates with a metal ion. In the case of containing a possible dye, a metal ion-containing compound capable of chelating with the dye may be appropriately selected and contained.

The thickness of the adhesive layer is usually 0.1 to 10 μm, preferably 0.2 to 5 μm.

When the dye receiving layer does not contain a metal ion-containing compound, the metal ion-containing compound is contained as an essential component in the adhesive layer and / or the protective layer to which the protective layer transfer material is transferred. The content of the metal ion-containing compound in this case is usually 5 to 70% by weight in the layer forming composition,
It is preferably 10 to 50% by weight.

(Image Recording Material) The image recording material of the present invention is formed by using the above-mentioned dye receiving material, dye donating material and protective layer transfer material, and the forming method thereof will be described in detail below.

First, the ink layer surface of the dye-donor material and the dye-receiving layer surface of the dye-receiving material are faced to each other, imagewise heat energy is applied, and the dye is thermally diffused from the ink layer to form a dye on the dye-receiving layer. Form an image. Then, the dye receiving layer on which the dye image is formed and the adhesive layer of the protective layer transfer material are faced to each other, and the protective layer is transferred onto the dye receiving layer to form an image recording material.

When the dye contained in the ink layer contains a dye capable of coordinating with a metal ion at two or more sites and the dye receiving layer contains a metal ion-containing compound capable of chelating with the dye, an image-like appearance is obtained. Apply heat energy to the ink layer,
A dye capable of coordinating with a metal ion at the locus or higher is thermally diffused to the dye receiving layer and reacted with a metal ion-containing compound capable of chelating with the dye contained in the dye receiving layer to form a chelate dye image. In this case, if the chelation reaction is insufficient, it is preferable to complete the chelation reaction at the time of transferring the protective layer.

When the dye-receptive layer does not contain a chelateable metal ion-containing compound, the protective layer and / or the adhesive layer of the protective layer transfer material contains a dye-chelatable metal ion-containing compound. At the same time as the transfer of the protective layer, the chelate dye image is formed by the reaction of the dye and the chelateable metal ion-containing compound.

A thermal head is generally used as the heat source for applying the thermal energy in the above-mentioned manner, but other known sources such as a current-carrying head, a laser beam, an infrared flash, and a heating pen can be used. When a thermal head or an energizing head is used as a heat source that gives heat energy, the heat energy can be changed continuously or in multiple steps by modulating the applied voltage or pulse width.

When laser light is used as a heat source for giving heat energy, an optical system such as a lens can be used to adjust the heat energy by changing the light amount or irradiation area of the laser light. If a dot generator with a built-in acousto-optic device is used, it is possible to give heat energy according to the size of the halftone dot.

When an infrared flash lamp is used as a heat source for providing heat energy, it is preferable to heat through a colored layer such as black as in the case of using laser light. Further, heating may be performed through a pattern such as black that continuously expresses the shade of an image or a halftone dot pattern, or a negative pattern corresponding to the negative of the above-mentioned pattern and a colored layer such as black on one surface. You may heat by combining.

As the method for transferring the protective layer onto the dye receiving layer, it is possible to use a method such as pressure transfer or heating / pressure transfer depending on the type of the adhesive layer.

In the case of pressure transfer, a pressure stamp, a pressure roll or the like can be used without particular limitation as long as a pressure sufficient for transfer is applied. Further, in the case of heating / pressurizing transfer, not to mention a heat roll, a hot stamp, etc., a thermal head or the like used at the time of image formation of melt transfer or thermal diffusible dye transfer can also be suitably used.

The heating temperature when a heat roll is used in this transfer is usually 60 to 200 ° C., preferably 80.
The temperature is in the range of up to 180 ° C, and the transport speed is usually 0.1 to 1.
00 mm / sec, preferably 0.5 to 50 mm / sec. When using a hot stamp, the heating temperature is usually 60 to 200 ° C., preferably 80 to 150 ° C., and the pressure is usually 0.05 to 10 kg / cm ² ,
Preferably 0.5 to 5 kg / cm ² , and the heating time is
It is usually 0.1 to 30 seconds, preferably 0.5 to 10 seconds.

When information is recorded on the surface opposite to the surface provided with a protective layer having an uneven surface by any one of the thermal fusion transfer recording method, ink jet recording method and electrophotographic recording method. Can be recorded using a known means.

<Second Embodiment> In the image recording material of the present embodiment, the dye receiving layer is transferred onto various substrates, and the dye is transferred from the dye-donor element having the ink layer containing the dye on the support. It is formed by transferring a protective layer from a protective layer transfer material in which a protective layer is laminated on a support, onto the dye receiving layer on which a transfer image is formed.

In the first embodiment, it is necessary to use a dye-receiving layer provided in advance at least on the dye-transferred portion. In contrast, in the present embodiment, plain paper or a plain paper excellent in writability for a ballpoint pen or the like is used in advance. Since synthetic paper or the like can be used, it is possible to form an image recording body that emphasizes writability in a portion other than the image area.

In the formation of the image recording material, the steps after providing the dye receiving layer on the substrate are the same as those in the first embodiment, and therefore, the substrate, the dye receiving layer transfer material, and the dye receiving layer on the substrate. Only material transfer is detailed below.

The base material used in this embodiment is not only known resin films and sheets, but also various kinds of paper, coated paper, synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper). A base material excellent in writability represented by papers can be mentioned.

The image receiving layer transfer material is characterized in that at least a dye receiving layer and an adhesive layer are sequentially laminated on a support.

The support is not particularly limited as long as it is a material excellent in dimensional stability, and for example, the support used in the dye-donor material of the first aspect can be selected and used at any time. The thickness of the support is usually selected from the range of 2 to 500 μm, preferably 4.5 to 100 μm.

For the dye-receiving layer, a material for forming the receiving layer used in the dye-receiving material of the first embodiment can be selected and used at a suitable time, and the thickness of the receiving layer depends on the cutting condition of the edge portion when transferred. From the above relationship, it is usually in the range of 1 to 10 μm, preferably 2 to 5 μm.

For the adhesive layer, a material for forming the adhesive layer used in the protective layer transfer material of the first aspect can be appropriately selected and used, and the thickness of the adhesive layer depends on the cutting condition of the edge portion at the time of transfer. From the above relationship, it is usually 0.1 to 10 μm, preferably 0.2 to 5 μm.

In the present invention, a peeling layer may be provided between the support and the receiving layer in order to improve the peeling between the receiving layer and the supporting. For such a peeling layer, a material forming the peeling layer used in the protective layer transfer material of the first aspect can be appropriately selected and used, and the thickness of the peeling layer is usually 0.01 to
It is preferably 5 μm, and more preferably 0.05 to 2 μm.

The image-receiving layer transfer material may be provided with a layer other than the above-mentioned layers, and between the image-receiving layer and the adhesive layer in order to secure the concealing property of the base material during dye image formation. A hiding layer may be provided.

As the concealing layer, for example, a layer containing white fine particles and / or a thin film layer made of a metal can ensure the concealing property.

As the white fine particles, both inorganic fine particles and organic fine particles can be used. Examples of the inorganic fine particles include silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, metal oxides such as aluminum borate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, and nitriding. Examples thereof include metal salts such as boron, kaolin, clay, talc, zinc white, lead white, syclite, quartz, diatomaceous earth, perlite, bentonite, mica, and synthetic mica.The organic fine particles include melamine resin, guanamine resin, styrene. -Acrylic copolymer resin, silicone resin, fluorine resin k particles, hollow resin particles thereof, and the like. The average particle size of the white fine particles is usually 0.01 to 10 μm, preferably 0.0
It is 2-5 micrometers.

The white fine particles are preferably selected in the range of usually 1 to 90% by weight, particularly 5 to 80% by weight in the hiding layer forming composition.

Further, the concealing layer contains a binder resin in addition to the above-mentioned white fine particles. As the binder resin, the resin used in the dye receiving layer of the dye receiving material of the first aspect and the adhesion of the protective layer transfer material are adhered. The resin used for the layer can be appropriately selected and used. The thickness of the hiding layer is usually 0.1 to 20 μm, preferably 0.3 to 10 μm.
It is.

When more concealing property is required, it is preferable to form the concealing layer with a thin film layer made of a metal. For example, various fine metal powders can be dispersed in a binder resin. However, in order to transfer the dye receiving layer to an arbitrary position on the substrate, it is preferable to form the hiding layer with a thin film of only metal.

As a method for forming a thin film layer made of a metal, a metal deposition thin film can be provided as a metal deposition thin film by a known method such as a vacuum deposition method, an ion plating method and a sputtering method. The metals used are aluminum, zinc, antimony, indium, selenium, tin, tantalum, chromium, lead,
It can be formed by using one kind or a combination of two or more kinds of metals such as gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, manganese, tungsten and palladium. This metal thin film layer is usually 0.005-2.
It is 0 μm, preferably 0.02 to 5.0 μm.

When the concealing layer is formed of a metal thin film layer, it is preferable that the dye receiving layer contains white fine particles and / or a concealing layer formed of a layer containing the white fine particles is used together. It is preferable because color tone and sharpness can be secured.

To form an image recording material, first, a dye receiving layer is transferred from a dye receiving layer transfer material onto a substrate. As the method for transferring, the method used for transferring the protective layer in the first aspect can be selected and used at appropriate times. Further, subsequent image-like dye image formation, transfer of the protective layer having an uneven surface, and recording of information on the surface opposite to the surface of the protective layer having an uneven surface, if necessary, are carried out in the same manner as in the first embodiment. It can be carried out.

Here, an example of the image recording medium producing system will be described with reference to the drawings.

FIG. 1 shows the system configuration. The system consists of a film scanner (with OCR reader), a pan-con (image editing device), a magneto-optical disk unit, a sublimation type thermal transfer printer, and a laser (electrophotographic) printer.

(Image Data Input) A positive film in which full-color image data output from a medical diagnostic apparatus and patient ID information written in alphanumeric characters are written is used to read the image data with a scanner and at the same time to obtain the ID information with OCR. Recognize and search the reception computer with this information as a search key, and from the reception computer the patient's name, sex,
It receives detailed information such as the date of birth and records it in the magneto-optical disk unit together with the image data.

(Recording of Image) When recording image data in the magneto-optical disk unit, it is possible to efficiently refer to the image data by constructing a database.

The database is stored in the Pancon and manages individual images inside the magneto-optical disk and a plurality of magneto-optical disks. As the database, in addition to patient information such as patient name, patient sex, and patient birth date, information regarding images such as imaging date and imaging site may be registered.

(Structure of Database) FIG. 6 shows the relationship between the database and the image data of the magneto-optical disk. The database may be a relational high-performance type or a simple type, but an example of the simple type will be described.

The database is composed of a record of images, and in each record, incidental information of the image and point information indicating the image position are recorded. The supplementary information of the image is as described above, and the point information is the MOD ID number and MOD.
It consists of the number in.

When searching by patient ID number, the corresponding record having the specified patient ID number is selected, and the MOD
The image is specified by the ID number and the image number.

(Editing of Image) In the image editing section of Pancon, one page of editing is divided into a sublimation type thermal transfer image editing area and a laser printer editing area.
You can edit by specifying the area.

At the time of editing, first, a template to be used is read from a template whose layout has been determined. In the sublimation type thermal transfer image editing area, it is possible to import and edit from the image database. In the laser printer editing area, any character can be selected and input to edit a sentence or figure. Patient information can be referred to and selected from the information of the receiving computer through the network.

(Save of Edited Image) The edited data can be saved in the edited image file of the magneto-optical disk.

(Hard copy) FIG. 2 shows the structure of a laser printer, and FIG. 3 shows the structure of a sublimation type thermal transfer printer.

Reference numeral 13 denotes a dye-providing material supply roll, 10 denotes the same winding roll, 12 denotes a dye-providing material, 11 denotes a thermal head (300 DPI), and 14 denotes a dye-receiving material.

FIG. 4 shows a sectional view of the dye receiving material. The adhesive layer 19 and the image receiving layer 18 are laminated on the base material 20.

FIG. 5 shows a plan view of the dye-donor element. PE
Yellow 15, magenta 16, cyan 1 on T base
The ink layer is applied in the order of 7 and the heat resistant layer is applied on the back surface.

First, the dye receiving material is printed by a laser printer. Then, the image receiving layer surface and the ink surface of the dye-providing material are superposed, heat corresponding to the image is applied from the back surface of the ink layer by the thermal head, and the heat diffusing dye is thermally diffused to the image receiving layer according to the amount of heat, and the image is transferred. An image recording material having writability can be prepared by transferring the protective layer of the present invention after forming the image recording medium.

In this case, the surface to be printed by the laser printer is the surface opposite to the image receiving layer of the dye receiving material and / or
Alternatively, it may be on the image-receiving layer surface, or may be printed by a laser printer after forming a dye image by a sublimation type thermal transfer printer.

When a dye-receptive layer transfer material is used, plain paper is used in place of the dye-receptive material, except that the dye-receptive layer is transferred before the heat-diffusible dye transfer. An image recording material having writability can be prepared by the method of. In this case, the protective layer may be provided on the entire surface of the plain paper or may be provided only on the dye receiving layer transfer portion.

[0151]

EXAMPLES The image recording material of the present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following examples, "parts" means "parts by weight as active ingredients" unless otherwise specified.

Example 1 (Preparation of protective layer transfer material) Semi-transparent biaxially stretched transparent polyethylene terephthalate (PE) having a thickness of 25 μm and roughened
T) One side of a film (manufactured by Diafoil Hoechst: E150) is subjected to corona discharge treatment, and a release layer forming coating solution, a protective layer forming coating solution and an adhesive layer forming coating solution having the following composition are applied to the treated surface by a wire. By sequentially coating and drying by bar coating, the thickness is 0.1 μm and 1.0 μm, respectively.
m, a protective layer transfer material having a protective layer of 2.0 μm and an adhesive layer was prepared.

Release layer forming coating liquid modified silicone resin 5 parts (Dainichi Seika Kogyo: Dialomer SP712) Methyl ethyl ketone 95 parts Protective layer forming coating liquid polyvinyl acetal resin 8 parts (Sekisui Chemical Co., Ltd .: S-REC KW-1) ) Synthetic silica 0.4 parts (Fuji Silysia Chemical: Sylysia 250N) Calcium carbonate 1.5 parts (Nitto Flour Processing Co .: NS # 3000) Surfactant 0.1 parts (BASF: FT248) Distilled water 90 parts Adhesive Layer Forming Coating Liquid Vinyl Chloride Resin 20 Parts (Union Carbide: VYHH) Methyl Ethyl Ketone 80 Parts (Preparation of Image Recorder) Next, separately, a sublimation printer (Mitsubishi Electric: Mitsubishi Full Color Printer S3600-30)
Shape) is used to heat and pressurize (140 ° C., 2 ° C.) a hot stamp having an area of 10 cm × 10 cm on a full-color image created by using a dedicated ink sheet and an image receiving sheet.
(kg / cm ² , 5 seconds) to transfer the protective layer to prepare an image recording material.

The degree of surface irregularity on the image recording surface side of the image recording body prepared as described above and various writability were evaluated according to the following criteria. The results are shown in Table 1.

<< Surface Asperity Degree (Ra) >> Using a shape measuring instrument (Mitutoyo: Surftest 501), JIS
The center line average value Ra defined by B0601 is set to a driving speed of 0.05 mm / sec, a cutoff value (λc) of 0.08 m.
It was measured under the condition of m.

<< Writability and Durability >> Black ballpoint pen (manufactured by Pilot: BP-2), black oil-based felt-tip pen (manufactured by ZEBRA: Macky Extra Fine), black water-based pen (manufactured by Mitsubishi Pencil:
Rib L-50), HB pencil (made by Tombow Pencil: Mono), writing on an area of 5 mm × 5 mm, and then, as a durability test, the image recording body was fixed to a flat metal sheet with a double-sided tape. Absorbent cotton (made by Dynic: Sofpat)
Is applied, a load of 500 g / cm ² is applied, a moving distance of 150 mm is reciprocated 10 times at a speed of 100 mm / sec, and the density immediately after writing and the density after the durability test are measured with a densitometer (manufactured by X-rite). : V of X-rite 310TR)
It was measured at the isual concentration.

Example 2 (Preparation of Transfer Material for Protective Layer) As a transfer material for the protective layer, one side of a biaxially stretched white PET film (manufactured by Diafoil Hoechst: W410) having a thickness of 38 μm was subjected to corona discharge treatment, and the treated surface was treated. A release layer forming coating solution, a protective layer forming coating solution, and an adhesive layer forming coating solution having the following compositions were sequentially applied by wire bar coating and dried to obtain thicknesses of 0.3 μm, 2.0 μm, and 0. A protective layer transfer material having a release layer of 5 μm, a protective layer, and an adhesive layer was prepared.

Release Layer Forming Coating Liquid Nitrocellulose 6 parts (Asahi Kasei Kogyo: CELNOVA BTH1 / 2) Modified silicone resin 1 part (Dainichi Seika Kogyo: Dialomer SP-712) Silicone resin particles 1 part (Shin-Etsu Chemical Co., Ltd.) Manufactured : Tospearl 108) Methyl ethyl ketone 92 parts Protective layer forming coating liquid polymethyl methacrylate 24 parts (Mitsubishi Rayon: Dyanal BR-83) Zinc oxide 20 parts (Sumitomo Cement: ultrafine zinc oxide ZnO-100) Kaolin 5 parts ( Tsuchiya Kaolin Industry: ASP-170) Light stabilizer / antioxidant 1 part (Ciba Geigy: Irganox B225) Methyl ethyl ketone 50 parts Adhesive layer forming coating solution Hydroxypropyl cellulose 2 parts (Shin-Etsu Chemical: Shin-Etsu HPC) EF-G) Acrylic resin 8 parts (Toa Gosei Kagaku) Industrial: Arontuck HVC-5200) Distilled water 90 parts (Preparation of image recording material) Next, a 10 cm image is formed on a full-color image separately prepared by using a dedicated ink sheet and image receiving sheet of a sublimation printer (described above). Heat and pressure treatment with a hot stamp having an area of × 10 cm (120 ° C, 3 kg / c
m ² for 10 seconds) to transfer the protective layer to prepare an image recording material.

The degree of surface irregularity on the image recording surface side of the image recording body prepared as described above and various writability were evaluated according to the same criteria as in Example 1, and the results are shown in Table 1.

Example 3 (Preparation of Dye-Donating Material) Biaxially Stretched Transparent PET Film with Easy-to-Adhere Layer having a Thickness of 6 μm (Dia foil Hoechst: K
203E / 6F), the surface opposite to the easy-adhesion layer is subjected to corona discharge treatment, and then the surface is coated with a methyl ethyl ketone solution of a modified silicone resin having a solid content of 5% by weight (previously: Dialomer SP712) and dried to obtain a thickness. 0.5 μm
Was provided with a backing layer.

Separately, an ink layer-forming coating liquid having the following composition was prepared, and the dye-donor material having an ink layer having a thickness of 1.0 μm was prepared by coating the PET film on the easy-adhesion layer side and drying.

Yellow ink layer forming coating solution Polyvinyl acetal resin 5 parts (Sekisui Chemical Co., Ltd .: S-REC KS-5Z) Modified silicone resin 0.2 parts (Dainichi Seika Chemical Co., Ltd .: Dialomer SP2105) Thermal diffusible dye (D -1) 2.8 parts Methyl ethyl ketone 2.8 parts Magenta ink layer forming coating liquid Same composition as the yellow ink layer except that the heat diffusing dye was changed to D-2.

Cyan ink layer forming coating liquid Same composition as the yellow ink layer except that the heat diffusing dye was changed to D-3.

[0164]

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(Preparation of Dye Receiving Material) First, on both sides of plain paper (Konica U-Bix Paper for PPC), on one side of white PET pet film (manufactured by Diafoil Hoechst: W900J) which was subjected to both sides easy contact processing. 2. A polyester resin (Vylon 200, manufactured by Toyobo) and an isocyanate compound (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) were mixed and mixed at a ratio of 4/1 to give a methyl ethyl ketone solution having a solid content of 10%, which was then dried to a thickness of 3. The material provided with a 0 μm adhesive layer was heated and pressure-treated with a heat roll to be laminated to prepare a base material.

Then, a coating solution for forming a lower layer of a dye-receiving layer and a coating solution for forming an upper layer of the dye-receiving layer having the following compositions were successively applied on one surface of the substrate by wire bar coating and dried to obtain respective thicknesses. 3.0 μm, 0.5 μm
A dye receiving material having a dye receiving layer lower layer and a dye receiving layer upper layer was prepared.

Dye receptive layer lower layer forming coating solution Polyvinyl acetal resin 6 parts (Sekisui Chemical Co., Ltd .: S-REC BX-1) Metal ion-containing compound (MS-1) 4 parts Methyl ethyl ketone 90 parts

[0168]

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Dye Receptor Layer Upper Layer Coating Liquid Polyvinyl chloride 6 parts (Shin-Etsu Chemical Co., Ltd .: Shin-Etsu PVC TK300) Vinyl chloride resin 3.5 parts (BASF: Laroflex MP25) Modified silicone resin 0.5 parts ( Shin-Etsu Chemical Co., Ltd .: X-24-8300) Methyl ethyl ketone 90 parts (Preparation of image recording material) Sublimation printer (supra) using the dye-donor and dye-receptive materials prepared in this way.
After forming a full-color image with, a heating / pressurizing process (120 ° C., 3 kg / cm) with a hot stamp having an area of 10 cm × 10 cm using the protective layer transfer material used in Example 2 was performed.
^Then , the protective layer was transferred to produce an image recording material.

The degree of surface irregularity on the image recording surface side of the image recording body prepared as described above and various writability were evaluated according to the same criteria as in Example 1, and the results are shown in Table 1.

Example 4 (Preparation of Dye Receiving Layer Transfer Material) Transparent PE having a thickness of 24 μm
On one side of a T film (manufactured by Diafoil Hoechst: T100), a release layer forming coating solution, a dye receiving layer forming coating solution, a pigment layer forming coating solution, and a vapor deposition anchor layer forming coating solution having the following composition were applied. By sequentially coating and drying by coating, thickness of 0.1 μm, 1.5 μm,
A 0.5 μm and 0.2 μm release layer, a dye receiving layer, a pigment layer, and a vapor deposition anchor layer were formed.

Release Layer Forming Coating Liquid Modified Polyimide Resin 2.5 parts (Sumitomo Bakelite: Sumirezin Excel CRC7010) Dioxane 5 parts Dye Receptor Layer Forming Coating Liquid Polyvinyl Butyral 5 parts (Sekisui Chemical Co., Ltd .: S-REC BX-1) ) Titanium oxide dispersion 4 parts (MHI white # 148) p-benzyl biphenyl 0.5 part Modified silicone resin 0.5 part (Mikuni dye: X-24-8300) Methyl ethyl ketone 45 parts Toluene 45 parts Pigment layer Forming coating liquid Acrylic resin 6.5 parts (Mitsubishi Rayon: Dyanal BR-87) Ethylene-vinyl acetate copolymer 1.3 parts (Nippon Gosei Kagaku: Soarex R-DH) Rosin ester 3.7 parts (Harima Kasei: Harrier Star DS-90) Titanium oxide dispersion 38.5 parts (previously: MHI ho Ito # 148) 50 parts of methyl ethyl ketone deposition anchor layer forming coating liquid 20 parts of the acrylic resin (supra: the trade name: DIANAL BR-83) Ethyl acetate 80 parts The above deposition anchor layer, thickness 400 by a metal deposition method
After forming the aluminum metal thin film layer of Å, prepare an adhesive layer forming coating solution of the following composition, apply and dry by wire bar coating to form an adhesive layer with a thickness of 1.5 μm, thereby forming a concealing layer. A dye-receiving layer transfer material having the same was prepared.

Adhesive layer forming coating solution Ethylene-vinyl acetate copolymer 3 parts (Evaflex EV410 manufactured by Mitsui DuPont Polychemical) Toluene 97 parts (Preparation of dye receiving material) Dye receiving layer transfer prepared as described above The material is heat-pressurized (140 ° C, 3 kg / c) on one side of plain paper (described above) copied by electrophotography with a hot stamp having an area of 10 cm × 10 cm.
m ² for 5 seconds) to transfer the dye receiving layer to prepare a dye receiving material.

(Preparation of protective layer transfer material)
One side of a semi-transparent biaxially stretched transparent PET film (manufactured by Diafoil Hoechst: E150) having a roughened surface of μm was subjected to corona discharge treatment, and the treated surface was coated with a release layer forming coating solution and a protective layer forming coating solution. The coating solution and the adhesive layer forming coating solution are sequentially applied and dried by wire bar coating to obtain thicknesses of 0.1 μm, 0.8 μm and 0.2 μm, respectively.
A protective layer transfer material having the protective layer and the adhesive layer in Example 1 was prepared.

Release Layer Forming Coating Liquid Same as the above-mentioned image receiving layer transfer material.

Protective Layer Forming Coating Liquid Calcium Carbonate 3 parts (Shiraishi Chemical Co., Ltd .: Brilliant 15) Colloidal silica 1 part (Nissan Chemical Co., Ltd .: Snowtex YL) Polyvinyl alcohol 15.9 parts (Kuraray: PVA124) Polyacrylic acid 0.5 part Distilled water 80 parts Adhesive layer forming coating liquid Same as the protective layer transfer material of Example 1.

(Preparation of image recording material) Next, the above-mentioned dye receiving material in which a dye receiving layer is provided on a part of plain paper, and Example 3
Using the dye-donor material prepared in step 1 above, a sublimation printer (described above) was used to prepare a full-color image on the part provided with the dye-receiving layer, and then the above-mentioned protective layer transfer material was used to provide the dye-receiving layer. Heat and pressure treatment (140 ° C, 2 kg / cm) with hot stamp of 10 cm x 10 cm area
^The protective layer was transferred for ² and 5 seconds) to prepare an image recording material.

The degree of surface irregularity on the image recording surface side of the image recording body prepared as described above and various writability were evaluated according to the same criteria as in Example 1, and the results are shown in Table 1.

Comparative Example 1 Using a sublimation printer (Mitsubishi Electric: Mitsubishi full color printer S3600-30 type), a dedicated color ink sheet and an image receiving sheet were used to prepare a full color image-free image recording material without a protective layer. .

The degree of surface irregularity on the image recording surface side of this image recording body and various writability were evaluated according to the same criteria as in Example 1, and the results are shown in Table 1.

Comparative Example 2 In the protective layer transfer material described in Example 2, the release layer, the protective layer and the adhesive layer were provided in the same thickness as in Example 2 except that the silicone resin particles in the release layer forming composition were removed. To prepare a protective layer transfer material.

Next, using this protective layer transfer material, a 10 cm × 10 cm image was formed on a full-color image formed using a dedicated ink sheet and image receiving sheet for a sublimation printer (described above).
Heat and pressure treatment with a hot stamp of area cm (120
The protective layer was transferred by applying a temperature of 3 ° C / cm ² for 10 seconds to prepare an image recording material.

The degree of surface irregularity on the image recording surface side of the image recording body prepared in this manner and various writability are evaluated in Example 1.
Evaluation was made on the same basis as in Table 1 and the results are shown in Table 1.

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[Table 1]

From the results shown in Table 1, it can be seen that the image recording material according to the present invention is excellent in writability by various writing instruments and has good durability after writing.

[0186]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an image recording material such as a medical chart for medical use in which character information and image information are mixed, and the recording material has excellent writability.

[Brief description of drawings]

FIG. 1 is an example of a system configuration diagram of an image recording body of the present invention.

FIG. 2 is a structural diagram of a laser printer.

FIG. 3 is a structural diagram of a sublimation thermal transfer printer.

FIG. 4 is a cross-sectional view of a dye receiving material.

FIG. 5 is a structural plan view of a dye-donor element.

FIG. 6 is a diagram showing a relation between a database and image data of a magneto-optical disk.

[Explanation of symbols]

 10 Dye donating material winding roll 11 Thermal head 12 Dye donating material 13 Dye donating material supply roll 14 Dye receiving material 15 Yellow ink layer 16 Magenta ink layer 17 Cyan ink layer 18 Image receiving layer 19 Adhesive layer 20 Substrate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location // B41J 2/325 B41M 5/26 101H B41J 3/20 117A (72) Inventor Tetsuya Iwata Tokyo 1st Sakura-cho, Hino City Konica Stock Association In-house

Claims (11)

[Claims] 1. An image recording body on which a dye image is formed by transferring a dye imagewise from a dye-donor material to a dye-receiving material having a dye-receiving layer on a substrate in accordance with heat energy. An image recording body, which is obtained by transferring a protective layer on the surface on which a dye image has been recorded, the protective layer having an uneven surface after being transferred. 2. A dye image is formed by transferring a dye-receiving layer from a dye-receiving layer transfer material onto a substrate and then imagewise transferring the dye from the dye-donor material to the dye-receiving layer in accordance with heat energy. An image recording body, wherein the formed image recording body has a protective layer transferred onto the surface on which the dye image has been recorded, the protective layer having an uneven surface after transfer. 3. A reaction of a dye image, which is transferred from a dye-donor element, and is capable of coordinating with a metal ion at two or more sites, and a compound containing a metal ion capable of chelating with the dye contained in the dye-receiving layer. 3. The image recording material according to claim 1, which is a chelate dye image formed imagewise by 4. An image recording body on which a dye image is formed by transferring a dye capable of coordinating with a metal ion at two or more sites imagewise from a dye-donating material to a dye-receiving layer, wherein the dye image is formed. The image recording material according to claim 1 or 2, wherein a protective layer containing a metal ion-containing compound capable of chelating with is transferred to the surface on which the dye image is recorded to form an image-like chelate dye image. 5. The image recording material according to any one of claims 1 to 4, wherein the protective layer is transferred by heat. 6. The Ra of the surface of the protective layer after transfer is
The value measured by JIS B0601 is 0.02-5.0μ
The image recording body according to any one of claims 1 to 5, wherein m is m. 7. The image recording body according to claim 1, wherein the transferred protective layer contains a porous pigment. 8. An image recording body records information on a surface opposite to a surface provided with a protective layer having an uneven surface by a recording method such as thermal fusion transfer, ink jet or electrophotographic recording method. The image recording body according to any one of claims 1 to 7, wherein the image recording body is a printed image. 9. An image data inputting means, a character information inputting means and a character information inputting means for a dye image formed imagewise when the image recording material according to claim 1 is produced. A method of creating an image recording medium, characterized by having a means for editing information and performing these operations while confirming them on a CRT. 10. The method for producing an image recording body according to claim 9, further comprising means for registering or retrieving respective data. 11. The method for producing an image recording body according to claim 9, wherein the image recording body producing method has a handwriting inputting means as an image data inputting means for the dye image formed imagewise. .