JPH04332690A - Image receiving sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To provide the title image receiving sheet forming an image generating no blur and excellent in preservability and also excellent in environmental aptitude at the time of manufacturing. CONSTITUTION:An image receiving sheet for thermal transfer recording has an image receiving layer containing a metal ion-containing compound forming a chelate upon the reaction with a heat-diffusible dye and a binder resin formed by an aqueous coating method.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-receiving sheet for thermal transfer recording, and more particularly to an image-receiving sheet for thermal transfer recording that is free from image bleeding, has excellent image storage stability, and has excellent environmental suitability during production.

0002

[Prior Art and Problems to be Solved by the Invention] In thermal transfer recording using the thermal diffusion transfer method, the dye used in the thermal transfer recording material is important. That is, it has the drawback of poor light resistance and fixing properties. Therefore, in order to improve these drawbacks, JP-A-59-78893, JP-A-59-109394, and JP-A-60-2398 disclose using thermally diffusible dyes that can be chelated, and using thermal transfer technology. An image forming method is disclosed in which an image is formed on a recording image-receiving sheet using a chelated dye.

However, although these image forming methods are excellent methods for improving heat resistance and fixing properties, in the production of image-receiving sheets for thermal transfer recording used in these methods, heat treatment that does not involve a chelation reaction is required. Similar to binder resins applied to diffusible dyes, coating liquids containing organic solvents that completely dissolve binder resins (eg, polyester resins, vinyl chloride resins, etc.) have been used.

In order to produce an image-receiving sheet for thermal transfer recording, when a coating solution containing an organic solvent is coated on a support, the vapor of the organic solvent spreads over the workpiece as the coating solution dries. Not only does it have a negative impact on the health of workers, but
There is also a risk of ignition and explosion. Therefore, there is an urgent need to improve the working environment, such as installing exhaust ducts in the workplace or creating an explosion-proof structure. Furthermore, prevention of image bleeding and image storage stability were sometimes insufficient.

The present invention has been made to improve the above situation. The purpose of the present invention is to eliminate image blurring,
An object of the present invention is to provide an image-receiving sheet for thermal transfer recording which has excellent image storage stability and excellent environmental suitability during production.

[0006]

[Means for Solving the Problems] To achieve the above object, the present invention is directed to a water-based coating solution containing a binder resin and a metal ion-containing compound that reacts with a heat-diffusible dye to form a chelate. This is an image-receiving sheet for thermal transfer recording, characterized by having an image-receiving layer on a support. (1) Image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording of the present invention can usually be composed of a support and an image-receiving layer formed thereon.

-Support- The support for the image-receiving sheet for thermal transfer recording of the present invention is as follows:
There are no particular limitations, and various materials, layer configurations, and sizes can be appropriately selected and used depending on the purpose of use. Examples of the support include paper, coated paper,
and various papers such as synthetic paper (polypropylene, polystyrene, or composite materials made by gluing them together with paper), vinyl chloride resin sheets, ABS resin sheets, polyethylene terephthalate base films, polybutylene terephthalate base films, polyethylene naphthalate base films. A single layer of film, polyarylate base film, polycarbonate base film, polyetheretherketone base film, polysulfone base film, polyethersulfone base film, polyetherimide base film, polyimide base film, etc., or a laminate of two or more layers thereof. Examples include various plastic films or sheets made of various metals, films or sheets made of various ceramics, or composite materials laminated by appropriately combining the above-mentioned materials. .

[0008] The support is preferably highly transparent when transparency is required, such as for use in transmissive documents such as OHP, stickers attached to glass, and the like. In the case of reflective images, white pigments such as titanium white, magnesium carbonate, zinc oxide, barium sulfate,
Preferably, silica, talc, clay, calcium carbonate, etc. are added. The thickness of the support is usually 20 to 100
The thickness is 0 μm, preferably 20 to 800 μm, and is appropriately selected from within this range.

-Image-receiving layer- The image-receiving layer is formed from an aqueous coating liquid containing a binder for the image-receiving layer, a metal ion-containing compound, and various additives used as necessary. 1. Binder for the image-receiving layer The binder for the image-receiving layer is one that has dyeability for heat-diffusible dyes and also has good solubility or dispersibility in water since it is used in the preparation of the water-based coating solution described below. is preferred.

Examples of binders for the image-receiving layer include polyvinyl chloride resins, copolymer resins of vinyl chloride and other monomers (such as isobutyl vinyl ether, vinyl propionate, etc.), polyester resins, poly(meth)acrylic acid, and polyvinyl chloride resins. (Meth)acrylic ester, polyvinylpyrrolidone, polyvinyl acetal resin, polyvinyl alcohol, polycarbonate, cellulose triacetate, polystyrene, copolymer of styrene and other monomers (e.g. acrylic ester, acrylonitrile, ethylene chloride, etc.), ethylene Copolymers of and other monomers (e.g. vinyl acetate, acrylic esters, etc.), vinyltoluene acrylate resins, polyurethane resins, polyamide resins, urea resins, epoxy resins, phenoxy resins, polycaprolactone resins, polyacrylonitrile resins, methyl cellulose, etc. Examples include cellulose resins, gelatin, starch, casein, and modified products thereof.

Among the above-mentioned resins, preferred for the purpose of the present invention are polyvinyl chloride resins, copolymers of vinyl chloride and other monomers, polyvinyl acetal resins, copolymers of styrene and other monomers, polyester resin,
It is an epoxy resin. These resins can be used alone or in combination of two or more. The above various resins may be newly synthesized and used, or commercially available products may also be used.

[0012] In forming the image-receiving layer, the various resins mentioned above utilize their reactive active sites (if there are no reactive active sites, they are added to the resin), and are treated with radiation, heat, catalysts, etc. It may be crosslinked or cured. In that case, radiation active monomers such as epoxy and acrylic, and crosslinking agents such as isocyanates can be used.They may be added directly to the coating solution, but like isocyanates, they react with water. In such a case, it is preferable to microcapsule the product and use it.

2. Metal ions constituting the metal ion-containing compound contained in the metal ion-containing compound image-receiving layer include divalent and polyvalent metals belonging to Groups I to VIII of the periodic table, among which Al, Co , C
r, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti
and Zn are preferred, with Ni, Cu, Co, Cr and Zn being particularly preferred. As compounds containing these metal ions, inorganic or organic salts of the metals and complexes of the metals are preferred. Specific examples include Ni, Cu,
Inorganic metal salts such as Co, Cr, and Zn halides, hydroxides, cyanides, sulfides, sulfates, nitrates, perchlorates, thiocyanates, acetic acid, oxalic acid, citric acid, higher fatty acids, etc. Organometallic salts of Ni2+, Cu2+
A complex represented by the following general formula containing , Co2+, Cr2+ and Zn2+ is preferably used.

[M(Q1) k(Q2) m(Q3)n]p
+p(L-) However, in the formula, M represents a metal ion, and Q
1, Q2, and Q3 each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M, and these coordination compounds include, for example, the coordination compounds described in "Chelate Kagaku (5) (Nankodo)". can be selected from position compounds. Particularly preferred are coordination compounds having at least one amino group that coordinates with a metal, and more specific examples include ethylenediamine and its derivatives, glycinamide and its derivatives, picolinamide and its derivatives. It will be done.

L is a counteranion capable of forming a complex,
Examples include inorganic compound anions such as Cr, SO4, ClO4, and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives, but particularly preferred are tetraphenylboron anions and their derivatives, and alkylbenzenesulfonic acid anions and their derivatives. be.

k represents an integer of 1, 2 or 3, m is 1
, 2 or 0, and n represents 1 or 0, which is determined depending on whether the complex represented by the above general formula has a tetradentate or hexadentate coordination, or Q1 , Q2 , Q3
is determined by the number of ligands in p represents 1, 2 or 3. Examples of this type of metal ion-containing compound include those exemplified in US Pat. No. 4,987,049. The amount of the metal ion-containing compound added is preferably 0.5 to 20 g/m2, more preferably 1 to 15 g/m2, based on the image receiving layer.

3. Additives The image-receiving layer may contain release agents, surfactants,
Additives such as antioxidants, UV absorbers, light stabilizers, fillers (inorganic fine particles, organic resin particles), and pigments may be added. Furthermore, a plasticizer, a heat-melting substance, etc. may be added as a sensitizer. The release agent is used to improve the releasability between the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording, and in the case of the present invention, it is preferably contained in the outermost layer.

Such release agents include silicone oil (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; Among them, silicone oil is preferred. There are two types of silicone oil: a type in which it is simply added (simple addition type) and a type in which it is cured or reacted (curing reaction type).

In the case of a simple addition type, modified silicone oil (for example, polyester modified silicone oil, urethane modified silicone oil, acrylic modified silicone oil, alcohol modified silicone oil, amide modified silicone oil) is added to improve the compatibility with the resin. It is preferable to use silicone oil, etc.).

[0020] The amount of these simple addition type silicone oils cannot be uniformly determined as it may vary depending on the type of silicone oil, but generally speaking, it is usually The amount is 0.1 to 50% by weight, preferably 0.5 to 20% by weight. Examples of the curing reaction type silicone oil include a reaction curing type (for example, a reaction curing of an amino-modified silicone oil and an epoxy-modified silicone oil), a photo-curing type, a catalyst-curing type, and the like.

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the resin for the image-receiving layer. In addition,
A release agent layer can also be provided by dissolving or dispersing the above-mentioned release agent in a suitable solvent and coating it on a part of the surface of the image-receiving layer, followed by drying. The above-mentioned surfactant is used to improve the coating properties of the image-receiving layer forming coating solution on the support, and any conventionally used anionic, cationic, nonionic or amphoteric surfactant may be used. be able to.

[0022] Next, as the above-mentioned antioxidant,
-182785, 60-130735, JP-A-1-1
Antioxidants such as those described in No. 27387, and compounds known to improve image durability in photographs and other image recording materials can be mentioned. Examples of the UV absorber and light stabilizer include JP-A No. 59-158287, No. 63-74686, No. 63-145089, No. 59-1.
96292, 62-229594, 63-12259
6, No. 61-283595, and JP-A-1-204788, as well as compounds known to improve image durability in photographs and other image recording materials.

[0023] Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, etc., and examples of the organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicone resin particles. can be mentioned. These inorganic/organic resin particles vary depending on their specific gravity, but are preferably added in an amount of 0 to 30% by weight.

Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay. The plasticizers include phthalate esters, trimellitate esters, adipate esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearate, etc. Examples include polymer plasticizers such as esters, orthophosphoric esters, phosphorous esters, glycol esters, and polyvinyl acetate and polyols.

The heat-melting substances include alcohols such as terpineol, menthol, 1,4-cyclohexanediol, and phenol, amides such as acetamide and benzamide, esters such as coumarin and benzyl cinnamate, diphenyl ether, and crown. Ethers such as ether, ketones such as camphor and p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, and palmitic acid. Monomolecular compounds represented by higher fatty acid esters such as cetyl, higher fatty acid amides such as stearic acid amide, higher amines such as behenylamine, waxes such as carnauba wax, beeswax, paraffin wax, ester wax, montan wax, and amide wax. , ester gum, rosin derivatives such as rosin maleic acid resin, rosin phenolic resin, phenolic resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene resin, aliphatic hydrocarbon resin, cyclopentadiene resin, polyolefin resin, polyethylene glycol , and polymer compounds typified by polyolefin oxides such as polypropylene glycol.

[0026] In the present invention, it is preferable that the above-mentioned heat-melting substance has a melting point or softening point of 10 to 150°C. In the present invention, the total amount of additives added is preferably selected in the range of 0.1 to 30% by weight based on the resin for the image-receiving layer. Note that the thickness of the image-receiving layer is usually 3
It is appropriate to select the thickness in the range of 30 μm to 30 μm, preferably 5 to 20 μm.

Further, the image receiving layer may be a single layer,
Alternatively, if necessary, it may be provided as a multilayer structure of two or more layers having the same or different compositions. moreover,
An intermediate layer (subbing layer) may be provided between the image-receiving layer and the support for the purpose of imparting properties such as heat insulation, barrier properties, cushioning properties, and adhesive properties. Further, an overcoat layer may be laminated on the surface of the image-receiving layer for the purpose of preventing fusion between the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording. When providing the above intermediate layer or overcoat layer, the thickness of each layer is usually 0.1 to 20 μm.
It is preferable to select within the range of .

(2) Manufacture of image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording of the present invention is prepared by dispersing or dissolving the components forming the image-receiving layer in water or an aqueous solution to prepare an aqueous coating liquid. It can be manufactured by a coating method in which a water-based coating liquid is applied to the surface of the support and dried. When preparing an aqueous coating solution, it is desirable to dissolve or disperse the resin in water depending on the solubility or dispersibility of the binder resin for the image-receiving layer in water. In some cases, alcoholic solvents, acetone, dioxane, etc. that are miscible with water may be used in combination at a ratio of 20% by weight or less based on 100% by weight of water. That is, in order to prepare this water-based coating solution, the binder must be made of a water-soluble resin that dissolves well in water (for example, water-soluble polyvinyl acetal resin, water-soluble polyester, polyvinyl alcohol, starch, casein, gelatin, polyacrylic acid). etc.), dissolve it in water or an aqueous solution, or if the binder is an emulsion resin formed by solution polymerization using water as a solvent (e.g. polyvinyl chloride resin, styrene-butadiene copolymer, etc.), By suspending it in water or an aqueous solution together with an appropriate surfactant, or by using a dispersant as a binder, a dispersion resin (such as an epoxy resin, a combination of vinyl chloride and other monomers) that can be dispersed in water can be used. polymers, etc.), it is processed using a dispersant using a known dispersing machine such as an attritor, a ball mill, etc.
It is desirable to disperse it in water or an aqueous solution using a sand grinder or the like.

[0029] These coating liquids can be used in combination as appropriate, and emulsion resins and dispersion resins can be used as commercially available suspensions (for example, vinyl chloride latex, styrene-butadiene latex, ethylene-butadiene latex). vinyl acetate latex, water-dispersed polymer polyester, etc.)
It may also be used in the form of a liquid or a dispersion. The aqueous coating liquid is applied onto the support using a known coating method, such as an extrusion coating method, a wire bar coating method, a roll coating method, or the like. Drying after application may be forced drying or natural drying.

[0030] As described above, when an aqueous coating liquid is used to form the image-receiving layer, the environmental suitability during the production of an image-receiving sheet for thermal transfer recording is significantly improved compared to when a conventional organic solvent is used. What should be further noted is that when a water-based coating liquid is used, the image formed on the image-receiving layer is less likely to bleed after printing and during storage, and the storage stability of the image is also improved. 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.

(3) Ink sheet for thermal transfer recording The ink sheet for thermal transfer recording can basically consist of a support and an ink layer formed thereon. -Ink layer- The ink layer contains a heat-diffusible dye and a binder as essential components. 1. Heat-diffusible dye The heat-diffusible dye used in the present invention is a magenta dye, a yellow dye, or a cyan dye that can form at least a bidentate chelate, and is preferably a dye represented by Chemical Formula 1.

[0032]

[Chemical formula 1]

[0033] In the formula, at least one ring of X1 is 5-
Represents a collection of atoms necessary to complete an aromatic carbocycle or heterocycle consisting of seven atoms, and at least one adjacent position of the carbon atom bonded to the azo bond is a nitrogen atom or a chelate. A carbon atom substituted with a group. Further, X2 represents an aromatic heterocycle or aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms, and G represents a chelating group.

Specific examples of such dyes include, for example, those disclosed in Japanese Patent Application Laid-open Nos. 59-78893 and 59-10934.
Publication No. 9, Specification of Japanese Patent Application No. 2-213303, Japanese Patent Application No. 213303
The compounds described in Japanese Patent Application No. 2-214719 and Japanese Patent Application No. 2-103742 can be exemplified as suitable dyes in the present invention. The amount of the heat-diffusible dye used is usually 0.1 to 20 g, preferably 0.2 to 5 g per m 2 of the support.

2. Binder Binders for the ink layer include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and cellulose acetate butyrate; polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone,
polyester, polyvinyl acetate, polyacrylamide,
Examples include vinyl resins such as polyvinyl acetoacetal, styrene resins, styrene copolymer resins, polyacrylic esters, polyacrylic acids, and acrylic acid copolymers, rubber resins, ionomer resins, and olefin resins.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resins, which have excellent acid resistance, are preferred. The above-mentioned various binders can be used alone or in combination of two or more. The weight ratio of the binder to the heat-diffusible dye is preferably 1:10 to 10:1, particularly preferably 2:8 to 8:2.

3. Other Optional Components Furthermore, various additives may be added to the ink layer as long as they do not impede the object of the present invention. Additives include fillers such as fine metal powder, silica gel, metal oxides, carbon black, and fine resin powder, mold release agents such as silicone resin and fluororesin, and hardening agents that can react with binder components (such as isocyanates). and radiation active compounds such as acrylics and epoxies). Further, examples of additives include heat-melting substances for accelerating transfer, such as waxes and higher fatty acid esters, which are described in Japanese Patent Application Laid-open No. 106997/1983.

-Support- Any support for the ink sheet for thermal transfer recording may be used as long as it has good dimensional stability and can withstand the heat during recording with a thermal head, but condenser paper, glassine paper, etc. Heat resistant plastic films such as tissue paper, polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polysulfone, polyvinyl alcohol, cellophane, polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm, and the support has a subbing layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support. You can leave it there. Furthermore, a backing layer may be provided on the back surface of the support (the side opposite to the ink layer) for purposes such as running stability, heat resistance, and antistatic properties. The thickness of this backing layer is usually 0.1 to 1 μm. The shape of the support is not particularly limited, and may be of any shape, such as a wide sheet or film, or a narrow tape or card.

(4) Production of ink sheet for thermal transfer recording The ink sheet for thermal transfer recording is prepared by dispersing or dissolving the various components forming the ink layer in a solvent to prepare a coating liquid for forming the ink layer. It can be manufactured by coating this on the surface of a support and drying it. Note that one or more of the binders are used by dissolving them in a solvent or dispersing them in a latex form.

Examples of the solvent include water, alcohols (eg, ethanol, propanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), and aromatics (eg, methyl cellosolve, ethyl cellosolve).
(e.g., toluene, xylene, chlorobenzene), ketones (e.g., acetone, methyl ethyl ketone), ester solvents (e.g., ethyl acetate, butyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane), chlorinated solvents (e.g., chloroform, trichloroethylene)
etc.

[0042] For the above-mentioned coating, conventional methods such as a surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method, etc. can be employed. The ink layer may be formed as a layer containing a monochromatic heat-diffusible dye on the entire surface or a part of the surface of the support, or a yellow ink layer containing a binder and a yellow dye, or a layer containing a binder and a yellow dye. Even if a magenta ink layer containing a binder and a magenta dye and a cyan ink layer containing a binder and a cyan dye are formed on the entire surface or a part of the surface of the support in a constant repetition along the planar direction, good.

The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm.
It is μm. In the present invention, convenience in use can be achieved by forming perforations on the ink sheet for thermal transfer recording, or providing detection marks for detecting the positions of areas with different hues. Note that the ink sheet for thermal transfer recording is not limited to the structure consisting of a support and a heat-sensitive layer formed thereon, and other layers may be formed on the surface of the ink layer. for example,
An overcoat layer may be provided for the purpose of preventing set-off (blocking) of the heat-diffusible dye.

(5) Image formation (thermal transfer recording) To form an image, the ink layer of the ink sheet for thermal transfer recording and the image receiving layer of the image receiving sheet for thermal transfer recording of the present invention are superimposed, and the ink layer and Apply thermal energy imagewise to the interface of the image-receiving layer. In this way, the heat-diffusible dye in the ink layer is vaporized or sublimated in an amount corresponding to the applied thermal energy, and transferred to and received by the image-receiving layer. As a result, an image is formed on the image receiving layer.

At this time, since the thermodiffusible dye is a dye that can be chelated, it reacts with the metal ion-containing compound contained in the image-receiving layer to form a chelate, and as a result, the fixation of the dye in the image-receiving layer is improved. do. A thermal head is generally used as a heat source for providing the thermal energy, but other known sources such as a laser beam, an infrared flash, and a thermal 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 stages by modulating the voltage or pulse width applied to the thermal head. When a laser beam is used as a heat source for providing thermal energy, the amount of thermal energy provided can be changed by changing the amount of laser light or the irradiation area. In this case, in order to facilitate the absorption of laser light, a laser light absorbing material (for example, in the case of a semiconductor laser, carbon black, an infrared absorbing substance, etc.) may be present in the ink layer or near the ink layer.

When using a laser beam, it is preferable to bring the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording into close contact with each other. If a dot generator with a built-in acousto-optic element is used, thermal energy can be applied depending on the size of the halftone dot. When using an infrared flash lamp as a heat source that provides thermal energy,
As in the case of using laser light, heating is preferably performed through a colored layer such as black. Alternatively, heating may be performed through a pattern or halftone dot pattern that continuously expresses the shading of an image, such as black, or a colored layer such as black and a negative pattern corresponding to the negative of the above pattern. Heating may be performed in combination.

Thermal energy may be applied from the ink sheet side for thermal transfer recording, from the image receiving sheet side for thermal transfer recording, or from both sides, but priority is given to effective use of thermal energy. If so, it is desirable to do so from the ink sheet side for thermal transfer recording. By the above thermal transfer recording, a one-color image can be recorded on the image-receiving layer of the image-receiving sheet for thermal transfer recording, but according to the method described below, it is also possible to obtain a color photographic color image consisting of a combination of various colors.

For example, by sequentially replacing yellow, magenta, cyan, and, if necessary, black heat-sensitive transfer recording sheets and performing thermal transfer according to each color, a color photo-like color image consisting of a combination of each color is obtained. You can also do that. In addition, the following method is also effective. That is, instead of using ink sheets for heat-sensitive transfer recording of each color as described above, an ink sheet for heat-sensitive transfer recording is used that has areas pre-painted in each color.

[0050] First, the yellow area is used to thermally transfer the yellow color separation image, and then the magenta area is used to thermally transfer the magenta color separation image. , cyan, and if necessary, black color images are thermally transferred in this order. Although it is possible to obtain a color photographic-like color image with this method as well, this method has the further advantage that there is no need to replace the heat-sensitive sheet for heat-sensitive transfer recording as described above.

Furthermore, after forming an image by the method described above, heat treatment may be performed by the method described above for the purpose of improving the image storage stability. For example, over the entire image forming surface,
The heat treatment may be performed using a thermal head using a portion of the ink sheet for thermal transfer recording where the ink layer is not provided, or a new heat treatment using a heat roll or the like may be performed. Furthermore, when a near-infrared absorber is contained, the image forming surface may be exposed using an infrared flash lamp. In either case, the heating means does not matter, but since the purpose is to further diffuse the dye into the image-receiving layer, it is effective and preferable to heat from the support side of the image-receiving layer.

[0052]

【Example】

(Example 1) - Ink sheet for thermal transfer recording - A coating for forming an ink layer having the following composition was applied to the corona discharge treated surface of a 6 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] as a support. Apply the liquid to the wire bar
The coating method was applied to a thickness of 1 μm after drying, and at the same time, a silicone resin [SP-2 manufactured by Dainichiseika Co., Ltd.
An ink sheet for thermal transfer recording was obtained by applying one or two drops of a nitrocellulose solution containing 105] with a dropper and spreading it over the entire surface, and performing a back treatment coat.

[0053] Coating liquid for forming ink layer: Heat-diffusible dye...................................................................
・・Part 3 Chemical 2 Nitrocellulose・・・・・・・・・・・・・・・
...3 parts [Cellnova BTHI/2, manufactured by Asahi Kasei Industries, Ltd.] Methyl ethyl ketone ...
・・・・・・・・・・・・44 parts Dioxane...
・・・・・・・・・・・・・・・・・・40 copies
Cyclohexanone・・・・・・・・・・・・・・・・・・
...10 copies.

[0054]

[Chemical 2]

- Manufacture of image-receiving sheet for thermal transfer recording - A white polyethylene terephthalate film with a thickness of 125 μm [manufactured by Diafoil Co., Ltd., W400 #12] was used as a support.
A coating solution for forming an image-receiving layer having the following composition was dispersed on the surface treated with corona discharge in [5] using a sand grinder, applied by a coating method, dried, and then heat-treated at 100°C for 1 hour to form white polyethylene terephthalate. An image-receiving sheet for thermal transfer recording was obtained by forming an image-receiving layer with a thickness of 10 μm on the tallate film.

Coating liquid for forming image-receiving layer: Vinyl chloride resin latex...
27.5 parts [Nippon Zeon Co., Ltd., G-351]
Metal ion-containing compounds・・・・・・・・・・・・・・・
...20.0 parts [[Ni(NH2 COCH2
NH2) 2+ [(C6 H5)4 B]2-
] Polyester modified silicone resin...
......2.5 parts [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Water ......
・・・・・・・・・・・・・・・・・・45.0 parts Ethanol・・・・・・・・・・・・・・・・・・・・・・
...5.0 copies.

-Image Formation- First, the ink sheet for thermal transfer recording and the image receiving sheet for thermal transfer recording are superimposed so that the surface of the ink layer of the former is in contact with the surface of the image receiving layer of the latter. An image was formed by applying a thermal head to the ink sheet for thermal transfer recording from the support side under the following conditions. Linear density of main scanning and sub-scanning: 8 dots/mm Recording power
: 0.6W/dot Heating time of thermal head: 20msec (applied energy - approx. 11.0msec)
2 × 10-3 J) to 2 msec (applied energy - approx. 1
．． The heating time was adjusted stepwise between 12 x 10-3).

Next, the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording were peeled off, and the image was transferred onto the image-receiving sheet for thermal transfer recording. After the image was recorded, the transfer density on the surface of the image-receiving layer, the heat resistance, light resistance, fixing property, and bleeding prevention property of the image were evaluated according to the following criteria. The results are shown in Table 1.

Transfer density: Reflection density OD value was measured using an optical densitometer. ◎・・・・・・OD value is 2.5 or more 〇・・・・・・OD value is 2.0 to 2.5△・・・・・・
OD value is 1.7 to 2.0×・・・OD value is 1.7
below.

Heat resistance (heat-resistant image stability): The image-receiving sheet for thermal transfer recording on which an image has been recorded is kept at 77°C and relative humidity 80%.
The samples were kept in this environment for 72 hours, and the presence or absence of bleed-out of the dye and discoloration or fading of the dye was determined visually and evaluated by measuring with a spectrophotometer and an optical densitometer. ◎...No discoloration or fading of the pigment was observed. ○... Slight discoloration or fading of the pigment is observed. Δ: Discoloration or fading of the pigment is observed. ×: Significant discoloration or fading of pigment.

Lightfastness (lightfast image storage stability): After exposing an image-receiving sheet for thermal transfer recording on which an image has been recorded for 72 hours using a xenon weathermeter, the image is visually observed, and also The determination was made by measuring with an optical densitometer. ◎...No discoloration or fading of the pigment was observed. ○... Slight discoloration or fading of the pigment is observed. Δ: Discoloration or fading of the pigment is observed. ×: Significant discoloration or fading of pigment.

Dye fixability: The image-receiving sheet for thermal transfer recording on which an image has been recorded is placed face to face with the image-receiving sheet for thermal transfer recording on which the image of the present invention is not recorded, and a load of 40 g/cm2 is applied. After being left at 60 DEG C. for 48 hours, judgment was made based on the transfer density of the dye transferred to an image-receiving sheet for thermal transfer recording on which no image was recorded. ◎・・・Transferred dye is not observed at all. ○...The transferred dye density is less than 0.10. △・・・Transferred dye density is 0.10 or more, 0.15
It is as follows. ×...The transferred dye density is 0.15 or more.

Prevention of dye bleeding: After the image-receiving sheet for thermal transfer recording on which an image was recorded was left at 50° C. for one month, the degree of dye bleeding was visually judged. 〇...Breaking is almost not observed. ×... Bleeding is observed. (Example 2) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, an image was transferred to the image-receiving layer, and evaluation was conducted. I did it. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Polyvinyl acetoacetal resin・・・・・・・・・・・・・・・
11.0 parts [KW-1, manufactured by Sekisui Chemical Co., Ltd.]
Metal ion-containing compounds・・・・・・・・・・・・・・・
...8.0 parts [[Ni(C2 H5 NHC
H2 CH2 NH2 )]2+[(C6 H5 )4
B]2-] Polyester modified silicone resin...
・・・・・・・・・・・・1.0 copy [Shin-Etsu Silico
X-24-8300 manufactured by N Co., Ltd.] Water...
・・・・・・・・・・・・・・・・・・80.0
Department.

(Example 3) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for image-receiving layer formation: Epoxy resin・・・・・・・・・・・・・・・・・・・・・
10.8 parts [Manufactured by Toto Kasei Co., Ltd., Epoto YD-
017] Metal ion-containing compound...
・・・・・・・・・8.0 parts [[Ni(NH2
COCH2 NH2 )]2+[(C6 H5 )4
B]2-] Polyester modified silicone resin...
......1.0 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Dispersant...
・・・・・・・・・・・・・・・・・・・・・0.2 part Water・・・・・・・・・・・・・・・・・・・・・
...80.0 copies.

(Example 4) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Water-dispersed polymer polyester・・・・・・・・・・・・・・・
11.0 parts [Toyobo Co., Ltd., Byronal MD1
220] Metal ion-containing compound...
・・・・・・・・・8.0 parts [[Ni(C2H
5 NHCH2 CH2 NH2 )]2+[(C6
H5)4 B]2-] Polyester modified silicone
Resin・・・・・・・・・・・・1.0 parts [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Water.
・・・・・・・・・・・・・・・・・・・・・・・・
-70.0 parts Ethylene glycol mono-n-butyl ether...10.0 parts.

(Example 5) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Vinyl chloride-isobutyl vinyl ether copolymer...
10.8 parts [vinyl chloride content: 81.0%, Tg
: 61°C, degree of polymerization: 740] Metal ion-containing compound・・・・・・・・・・・・・・・8.0 parts
[[Ni(NH2 COCH2 NH2)]2+[(
C6 H5)4 B]2-]Polyester modified silicone resin・・・・・・・・・・・・1.0 part
[Manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300]
Dispersant・・・・・・・・・・・・・・・・・・
・・・・・・0.2 parts Water・・・・・・・・・・・・・
......70.0 parts Ethylene glycol mono-n-butyl ether...1
0.0 part.

(Example 6) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Vinyl chloride-benzyl methacrylate copolymer...
10.0 parts [vinyl chloride content: 83.7%, Tg
: 51°C, degree of polymerization: 520] Metal ion-containing compound・・・・・・・・・・・・・・・8.0 parts
[[Ni(C2 H5 NHCH2 CH2 NH2
)]2+[(C6H5)4B]2-]Polyester modified silicone resin・・・・・・・・・・・・・・・
・1.0 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-
8300] Dispersant・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.2 part Water・・・・・・・
・・・・・・・・・・・・・・・・・・70.0 parts Ethylene glycol mono-n-methyl ether...
...10.0 copies.

(Example 7) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for image-receiving layer formation: Vinyl chloride-mono-2-ethylhexyl maleate copolymer.
10.8 parts [vinyl chloride content: 85.1%, Tg
:75°C, degree of polymerization: 500] Metal ion-containing compound・・・・・・・・・・・・・・・8.0 parts
[[Ni(C2 H5 NHCH2 CH2 NH2
)]2+[(C6H5)4B]2-]Polyester modified silicone resin・・・・・・・・・・・・・・・
・1.0 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-
8300] Dispersant・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.2 part Water・・・・・・・
・・・・・・・・・・・・・・・・・・70.0 parts Ethylene glycol mono-n-methyl ether...
...10.0 copies.

(Example 8) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Vinyl chloride latex・・・・・・・・・・・・・・・・・・
25.0 parts [Nippon Zeon Co., Ltd., G-351]
Metal ion-containing compounds・・・・・・・・・・・・・・・
...20.0 parts [[Ni(C2 H5 NHC
H2 CH2 NH2 )]2+[(C6 H5 )4
B]2-] Polyester modified silicone resin...
・・・・・・・・・・・・2.5 parts [Shin-Etsu Silico
Manufactured by Kon Co., Ltd., X-24-8300] Silicone resin fine powder 2.5
Part [Tospar 104, manufactured by Toshiba Silicone Co., Ltd.]
water······················
・・・・・・45.0 parts Ethanol・・・・・・
・・・・・・・・・・・・・・・・・・5.0 copies.

(Example 9) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Vinyl chloride latex・・・・・・・・・・・・・・・・・・
20.0 parts [Nippon Zeon Co., Ltd., G-351]
Metal ion-containing compounds・・・・・・・・・・・・・・・
...20.0 parts [[Ni(C2 H5 NHC
H2 CH2 NH2 )]2+[(C6 H5 )4
B]2-] Polyester modified silicone resin...
・・・・・・・・・・・・2.5 parts [Shin-Etsu Silico
X-24-8300 manufactured by N Co., Ltd.] Ultraviolet absorber/
・・・・・・・・・・・・・・・・・・・・・7.5
[Manufactured by BASF, Uvinal N-35] Water/
・・・・・・・・・・・・・・・・・・・・・・・・
・45.0 parts ethanol・・・・・・・・・・・・
・・・・・・・・・・・・5.0 copies.

(Example 10) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Vinyl chloride latex・・・・・・・・・・・・・・・・・・
10.0 parts [Nippon Zeon Co., Ltd., G-576]
Polyvinylacetoacetal resin・・・・・・・・・
...10.0 parts [Sekisui Chemical Co., Ltd., KW
-1] Metal ion-containing compound...
・・・・・・・・・20.0 parts [[Ni(C2 H5
NHCH2 CH2 NH2 )]2+[(C6 H
5)4 B]2-] Polyester modified silicone resin 2.5 parts [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Silicone Resin fine powder・・・・・・・・・・・・・・・・・・
・2.5 parts [Tospar 104, manufactured by Toshiba Silicone Co., Ltd.] Ultraviolet absorber・・・・・・・・・・・・・・・
・・・・・・・・・・・・5.0 parts [Manufactured by BASF, Uvinal N-35] Water・・・・・・・・・・・・
・・・・・・・・・・・・・・・45.0 parts ethanol
Ru・・・・・・・・・・・・・・・・・・・・・
5.0 copies.

(Comparative Example 1) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for image-receiving layer formation: Epoxy resin・・・・・・・・・・・・・・・・・・・・・
11.0 parts [Manufactured by Toto Kasei Co., Ltd., Epoto YD-
017] Metal ion-containing compound...
・・・・・・・・・8.0 parts [[Ni(NH2
COCH2 NH2 )]2+[(C6 H5 )4
B]2-] Polyester modified silicone resin...
・・・・・・・・・・・・1.0 parts [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone・・・・・・・・・・・・・・・・70.0 parts cyclohexanone・・・・・・・・・・・・・・・
...10.0 copies.

(Comparative Example 2) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and an image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for image-receiving layer formation: Vinyl chloride-mono-2-ethylhexyl maleate copolymer.
・5.5 parts [vinyl chloride content: 85.1%, Tg
: 75°C, degree of polymerization: 500] Metal ion-containing compound 4.0 parts
[[Ni(C2 H5 NHCH2 CH2 NH2
)]2+[(C6H5)4B]2-]Polyester modified silicone resin・・・・・・・・・・・・・・・
・0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-
8300] Methyl ethyl ketone...
・・・・・・・・・・・・80.0 parts Cyclohexanone・・・・・・・・・・・・・・・・10.0 parts.

(Comparative Example 3) An image-receiving sheet for thermal transfer recording was produced in the same manner as in Example 1, except that the coating liquid for forming the image-receiving layer was changed to the following composition, and the image was transferred to the image-receiving layer. , conducted an evaluation. The results are shown in Table 1. Coating liquid for forming image-receiving layer: Polyvinyl chloride resin・・・・・・・・・・・・・・・・・・
・4.0 parts [manufactured by Shin-Etsu Chemical Co., Ltd., TK600]
Compounds containing metal ions・・・・・・・・・・・・
...4.0 parts [[Ni(C2 H5 NH
CH2 CH2 NH2 )]2+[(C6 H5 )
4 B] 2-] Polyester modified silicone resin
・・・・・・・・・・・・・0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Phthalic acid dialkyl ester・・・・・・・・・・・・・・・...1.
5 parts [Daihachi Chemical Co., Ltd., DOP] Methyl ethyl ketone・・・・・・・・・・・・・・・
...80.0 parts cyclohexanone...
・・・・・・・・・・・・・・・10.0 copies.

[0075]

[Table 1]

[0076]

[Effects of the Invention] The image receiving sheet for thermal transfer recording of the present invention has the following properties:
It has no image smearing, has excellent image storage stability, and has excellent environmental suitability during manufacturing.

Claims (3)

[Claims] 1. A heat-sensitive transfer device comprising, on a support, an image-receiving layer formed of an aqueous coating solution containing a binder resin and a metal ion-containing compound that reacts with a heat-diffusible dye to form a chelate. Image receiving sheet for recording. 2. The image-receiving sheet for thermal transfer recording according to claim 1, wherein the binder resin is at least one selected from water-soluble resins, emulsion resins, and dispersion resins. 3. The binder resin is selected from polyvinyl chloride, a copolymer of vinyl chloride and other monomers, a polyvinyl acetal resin, a copolymer of styrene and other monomers, a polyester resin, and an epoxy resin. The image-receiving sheet for thermal transfer recording according to claim 1, which contains at least one selected one.