JPH11170711A - Sublimative thermal recording medium and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image having a good fixing property and preservative stability. SOLUTION: The sublimative recording medium is to form an image by superimposing a color element donative material with an ink layer containing heat diffusive color element and a color element receptor material with a color element receptor layer on a carrier. and permitting the color element to thermally diffuse in the color element receptor material by heat, wherein an oxazoline compound is contained in either the color element donative material or the color receptor material, and a reactive compound which reacts with an oxazoline compound is contained in material having no oxazoline compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimable heat-sensitive recording medium (hereinafter, also referred to as a heat-sensitive transfer recording material) and an image forming method (hereinafter, also referred to as a heat-sensitive transfer recording method). The present invention relates to a thermal transfer recording material capable of forming an image and a thermal transfer recording method.

[0002]

2. Description of the Related Art In recent years, with the development of the information industry, demand for color hard copies such as electrophotography has been increased, and images with rich gradations have been demanded. Various methods using ink jet, electrophotography, silver halide photography, thermal transfer and the like have been proposed as methods for obtaining them. As a thermal transfer method, there is a fusion transfer method in which the heat-meltable ink layer on the dye-donor material is melted by a thermal head and transferred to an image receiving sheet, and the dye on the dye-donor material is thermally diffused by the heat of the thermal head, There is a sublimation type thermal transfer recording system in which the dye is transferred to a dye receiving material. Among them, the sublimation type thermal transfer recording method has attracted particular attention as a method that can obtain an image with a simple and easy-to-use image because the dye amount can be changed for each pixel. The present invention relates to a sublimation type thermal transfer recording material.

In the thermal transfer recording of the sublimation type thermal transfer system, the dye contained in the dye donating material is transferred to the dye receiving material by the heat of the thermal head to form an image.
However, since the dye is thermally diffused to form an image, there is a problem in durability and storability of the image.

For example, JP-A-59-78893, JP-A-4-62092, JP-A-4-65294, and JP-A-4-731
Nos. 91, 4-82784, 4-82785, 4-82787, and the like describe metal ions contained in a dye-receiving layer (hereinafter, also simply referred to as a receiving layer) using a chelatable dye. JP-A-59-101395 discloses a technique for fixing a dye by adsorbing the dye transferred to the receiving layer to an adsorbent contained in the receiving layer. 614, 521,
JP-A Nos. 59-59495, 59-64393, 60-260381, 60-110494, and 6
0-260391, JP-A-8-318683, 8
Japanese Patent Application Laid-Open No. 1-18839 discloses a technique in which a dye having a reactive functional group is transferred and fixed with a resin or a compound having a reactive group in a receiving layer.
No. 1, No. 1-228601, No. 1-229755,
No. 1-229756, No. 3-83885, No. 3-8
Nos. 3687, 3-83688 and 3-83689
Nos. 3-92385, 3-92386, 3-
Japanese Patent Application Laid-Open No. 6-64343 discloses a technique for fixing a dye to a mordant contained in a receptor layer by reacting the dye with the dye using a dye having a phenolic hydroxyl group. Many methods, such as a method of fixing by a Diels-Alder reaction using a dienophile contained in a layer, are disclosed.

However, any of these methods has a disadvantage that the image is blurred due to insufficient fixing, or a defect that the hue changes with time due to a difference in the hue between the dye before fixing and the dye after fixing, or However, there is a problem such as a change in hue due to a change in environment, and it is still insufficient to obtain an image with gradation having good storability.

[0006]

SUMMARY OF THE INVENTION Accordingly, in view of the above circumstances, an object of the present invention is to provide a sublimable heat-sensitive recording medium which has good fixability and gives an image having excellent storage stability. An object of the present invention is to provide an image forming method which is excellent in storage stability by using this recording medium.

[0007]

The above objects of the present invention have been attained by the following constitutions.

[0008] 1. A dye-donating material having an ink layer containing a heat-diffusible dye and a dye-receiving material having a dye-receiving layer are overlaid on a support, and the dye is thermally diffused into the dye-receiving material by heat to form an image. A dye-donating material or a dye-receiving material containing an oxazoline compound, and a material not containing the oxazoline compound containing a reactive compound that reacts with the oxazoline compound. Sublimation thermosensitive recording medium.

[0009] 2. 2. The sublimable heat-sensitive recording medium according to 1, wherein when the oxazoline compound according to 1 is contained in a dye-providing material, the oxazoline compound has an absorption maximum in a visible region.

[0010] 3. 2. The sublimable thermosensitive recording medium according to 1, wherein when the oxazoline compound according to 1 is contained in the dye-receiving material, the oxazoline compound has substantially no absorption in the visible region.

4. 2. The sublimable thermosensitive recording medium according to 1, wherein the reactive compound according to 1 is a compound having acidic hydrogen.

5. A dye-donating material having an ink layer containing a heat-diffusible dye and a dye-receiving material having a dye-receiving layer are overlaid on a support, and the dye is thermally diffused into the dye-receiving material by heat to form an image. In an image forming method, a dye-donating material or a dye-receiving material contains an oxazoline compound, and a dye-donating material or a dye-receiving material containing no oxazoline compound contains a reactive compound that reacts with the oxazoline compound. An image forming method comprising superposing a dye-providing material and the dye-receiving material, and transferring the dye to the dye-receiving material by heat to form an image.

That is, the present inventor has conducted intensive studies and as a result,
A sublimation thermosensitive recording medium in which a dye-donating material provided with an ink layer containing a heat-diffusible dye on a support and an image receiving sheet are superimposed, and the dye is thermally diffused to the dye-receiving material by heat to form an image. An oxazoline compound is contained in either the dye-donor material or the dye-receiving material, and a reactive compound that reacts with the oxazoline compound is contained in a material not containing the oxazoline compound, and is contained in the dye-donor material. It has been found that the oxazoline compound or the reactive substance reacts with the reactive compound or the oxazoline compound in the receptor layer by thermal diffusion to form an excellent image without bleeding or retransfer. The above object is achieved by the following constitutions.

A dye-donor material provided with an ink layer containing a heat-diffusible dye on a support and a dye-receiving material are superimposed,
In a sublimable thermosensitive recording medium in which an image is formed by thermally diffusing the dye into a dye-receiving material, an oxazoline compound is contained in either the dye-donating material or the dye-receiving material, and a sheet containing no oxazoline compound is used. To provide a thermosensitive recording medium characterized by containing a reactive compound that reacts with the oxazoline compound. When the oxazoline compound is contained in the dye-providing material, the oxazoline compound has an absorption maximum in the visible region. Preferably, when the oxazoline compound is contained in the dye receiving material, it is preferable that the dye receiving material has substantially no absorption in the visible region. Further, the reactive compound is preferably a compound having acidic hydrogen.

Further, a dye-providing material provided with an ink layer containing a heat-diffusible dye and a dye-receiving material provided with a dye-receiving layer are superimposed on a support, and the dye is thermally diffused into the dye-receiving material by heat. An image forming method for forming an image by
An oxazoline compound is contained in a dye-donating material or a dye-receiving material, and a reactive compound that reacts with the oxazoline compound is contained in a dye-donating material or a dye-receiving material that does not contain the oxazoline compound. An object of the present invention is to provide an image forming method characterized in that an image is formed by superimposing a receiving material and transferring the dye to the dye receiving material by heat.

Hereinafter, the configuration of the present invention will be specifically described.

The oxazoline compound contained in the ink layer refers to a compound represented by the following general formula (1).

Formula (1) Dye- (L) _m -X wherein Dye represents a dye residue, L represents a divalent linking group, and X represents an oxazolyl group. M is 0 or 1
Represents the natural number of. The dye residue represented by Dye may be any known dye. Examples include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, methine dyes, quinophthalone dyes, fluoran dyes, triphenylmethane dyes, xanthene dyes, and cyanine dyes.

Examples of the divalent linking group represented by L include an alkylene group (eg, a methylene group, an ethylene group, a propylene group, a butylene group, etc.) and an arylene group (eg, an o-phenylene group, a p-phenylene group, etc.) A divalent heterocyclic group (eg, pyrrolidyl group, morpholyl group, piperazyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, pyridyl group, thiazolyl group, benzothiazolyl group, imidazolidine-2,4-dioneyl group, etc.), Examples include an ether group, a thioether group, an imino group (for example, an imino group, a methylimino group, an ethylimino group, and the like), an ester group or an oxycarbonyl group, a carbonyl group, an amide group, a sulfamide group, a ureido group, and the like. Further, a linking group in which a plurality of these groups are combined may be used.

The oxazolyl group represented by X is substituted,
Or an unsubstituted 1,2-oxazolyl group or a substituted or unsubstituted 1,3-oxazolyl group. Preferably, it refers to a substituted or unsubstituted 1,3-oxazolyl group.

Examples of the substituent which may be present include an alkyl group (methyl group, ethyl group, propyl group, butyl group, octyl group, etc.) and an alkylene group (ethylene group, propylene group,
Butenyl), aralkyl (benzyl, phenylethyl, etc.), aryl (phenyl, chlorophenyl, tolyl, etc.), halogen (fluorine, chlorine, bromine, etc.), cyano, sulfonyl Groups (methylsulfonyl group, phenylsulfonyl group, etc.), alkoxy groups (methoxy group, ethoxy group, phenoxy group, etc.), and the like, preferably an alkyl group, an aralkyl group, and an aryl group.

The following are specific examples of the oxazoline compound (compound represented by the general formula (1)) when contained in the ink layer used in the present invention, but the present invention is particularly limited by these. is not.

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Next, the reactive compound contained in the ink layer means a compound represented by the following general formula (2).

Formula (2) Dye- (L) _m -Y wherein Dye represents a dye residue, L represents a divalent linking group, and Y represents a group having an acidic hydrogen. M represents a natural number of 0 or 1. In the general formula (2), Dye
And a natural number of 0 or 1 represented by m represents a dye represented by Dye in the case of an oxazoline compound contained in the ink layer. A residue, a divalent linking group represented by L and m
Is synonymous with a natural number of 0 or 1 respectively.

The group having an acidic hydrogen represented by Y specifically refers to a carboxyl group, a hydroxy group, a hydroxyphenyl group, a mercapto group, a sulfo group, and a sulfine group.

Specific examples of the reactive compound (compound represented by the general formula (2)) when contained in the ink layer used in the present invention are shown below, but the present invention is particularly limited by these. Not something.

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Next, the reactive compound contained in the receptor layer means a compound in which a group having at least one acidic hydrogen is substituted for a part of an organic compound having no absorption for visible light. And known low molecular weight and high molecular weight compounds can be used. The substituent having an acidic hydrogen refers to a carboxyl group, a hydroxy group, a hydroxyphenyl group, a mercapto group, a sulfo group, and a sulfine group.

Hereinafter, specific examples of the reactive compound contained in the receptor layer used in the present invention are shown, but the present invention is not particularly limited by these.

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Next, the oxazoline compound contained in the receptor layer refers to a compound in which one or more oxazolyl groups are substituted for a part of an organic compound that does not absorb visible light.

The oxazoline compound may be any generally known oxazolyl compound, and may be a monomer or a polymer having a repeating unit.

Examples of the polymer include polystyrene,
Acrylic, a polymer obtained by copolymerizing a monomer having an oxazoline group with a polyvinyl monomer such as a vinyl chloride type, or a polymer obtained by copolymerizing a monomer having a carboxylic acid and then deriving an oxazoline group,
Alternatively, a polymer in which an oxazole group is derived from a terminal carboxylic acid such as polyester can be used.

Hereinafter, specific examples of the oxazoline compound when contained in the receptor layer used in the present invention are shown, but the present invention is not particularly limited by these.

[0061]

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The oxazoline compound used in the present invention can be easily synthesized. Hereinafter, specific synthesis examples of the oxazoline compound used in the present invention will be described.

Synthesis Example 1 << Synthesis of Exemplified Compound D-120 >> Reaction Scheme

[0065]

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Compound (Exemplified Compound D-220) 0.43
g was dissolved in 30 ml of toluene, 0.1 g of 2-aminoethanol was added, and the mixture was refluxed for 3 hours. After concentrating the reaction solution with an evaporator, column purification was performed, and 0.25 g of the target oxazoline compound (D-120) was obtained.
Obtained.

Other oxazoline compounds can be easily synthesized, for example, by reacting the corresponding carboxylic acid with an aminoethanol in the same manner as described above.

Hereinafter, the dye receiving material of the present invention and an image forming method using the same will be described in detail.

(Dye-Receiving Material) A dye-receiving material used in combination with a dye-providing material having a dye-containing ink layer on a support is basically a support having a receiving layer on a support. If the receiving layer itself has self-supporting properties, the support may be omitted.

The support used for the dye receiving material having the receiving layer laminated thereon includes various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper); Vinyl-based, ABS
System, polyethylene terephthalate system, polyethylene naphthalate system, polyimide system, polyetherimide system, polyarylene system, polycarbonate system, polyetherketone system, polysulfone system, polyethersulfone system, etc. in a single layer or two or more layers Various laminated resin films or sheets, films or sheets formed of various ceramics, and the like can be used.

A specific example of the support is described in JP-A-59-8 / 1984.
No. 5972, No. 60-245593, No. 61-172
No. 795, No. 61-197282, No. 62-8739
No. 0, No. 62-158095, No. 62-198497
Nos. 62-278087 and 63-315293
No. 64-44481, JP-A-1-188392.
Nos. 1-280586, 2-16051, 2
No.-25392, No.2-1110457, No.2-223
No. 484, No. 2-225086, No. 2-263689
No. 3-49990, No. 3-51187, No. 3-
And a support described in No. 76687 and the like.

Further, JP-B-60-30930, JP-A-61-112693, JP-A-62-148293, and JP-A-6-148293.
2-152793, 63-1595, 63-2
Nos. 31984, 64-44481, 64-475
No. 36, JP-A-1-168493 and 2-92592
Supports having a porous structure, such as those described in Japanese Patent Application Laid-Open Publication No. H11-216, can also be suitably used.

Also, resins having a small neck-in and good drawdown properties, for example, polyolefin resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, polybutene, polypentene, polystyrene, and ethylene-vinyl acetate copolymer; Polyester resin such as polyethylene terephthalate, ionomer resin, nylon, polyurethane, etc.
A core resin typified by photographic resin-coated paper or a resin coated with a receiving layer on the base film or on both sides thereof can also be suitably used. These are disclosed in JP-A 1-263081 and 2-1.
Nos. 06397 and 2-305688, U.S. Pat.
It can be produced by the methods described in JP-A Nos. 74,224 and 4,999,335.

In the case where transparency is required, such as a transparent original such as an OHP or a mask material, or a seal attached to glass or the like, the support preferably does not impair the required transparency. In the case of a reflection image, a white pigment such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, or calcium carbonate is added to enhance the sharpness of the formed image. Is preferred.

The thickness of the support is usually 10 to 1000 μm,
It is preferably from 25 to 800 μm, and is appropriately selected from such a range.

The receiving layer is composed of a binder resin and optional additives.

As the binder resin, a known resin conventionally used for a receptor layer of an image receiving sheet for thermal transfer recording can be used. For example, polyester resin, polyvinyl acetal resin, urethane resin, amide resin, cellulose resin, olefin resin, vinyl chloride resin, acrylic resin, styrene resin, polycarbonate resin, polyvinyl alcohol resin, polyvinylpyrrolidone Resins, polysulfone, polycaprolactone resins, polyacrylonitrile resins, urea resins, epoxy resins, phenoxy resins, and the like. These resins can be used alone or in combination of two or more. Can be done.

Further, in order to accelerate the reaction, a resin obtained by blending, copolymerizing, or graft-polymerizing butadiene, methyl acrylate, or the like having a low glass transition point with the above resin can also be used.

The binder resin is preferably used in an amount of usually 20 to 99% by weight, more preferably 50 to 95% by weight, in the composition for forming a receptor layer.

In order to further improve the sensitivity, image storability, handleability, etc., the receiving layer may be provided with a release material, a plasticizer, a heat-meltable compound, an antioxidant, a Feller,
An antistatic agent or the like may be added. As a release material,
(Modified) silicone oil or (modified) silicone resin,
Solid waxes such as polyethylene wax, amide wax and Teflon powder, fluorine-based and phosphate-based surfactants, and Feller such as silica and titanium oxide.

As the heat-fusible compound, a compound which is solid at normal temperature and becomes liquid when heated is used. Specifically, alcohols such as terbinetol, menthol, 1,4-cyclohexanediol, and phenol; amides such as acetamide and benzamide; esters such as coumarin and benzyl cinnamate; ethers such as diphenyl ether; camphor; Ketones such as methyl acetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as stearic acid, eicosanol,
Monomolecular compounds represented by higher alcohols such as stearyl alcohol, higher fatty acid esters such as cetyl parimidate, higher fatty acid amides such as stearamide, higher amines such as behenylamine, beeswax, carnauba wax, paraffin wax , Microcrystalline wax, ester wax, montan wax,
Waxes such as amide wax, ester gum, rosin maleic acid resin, rosin derivatives such as rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene hydrocarbon resin, cyclopentadiene resin, polyolefin resin, Examples thereof include high molecular compounds represented by polyolefin oxides such as polycaprolactam resins, polyethylene glycol and polypropylene glycol.

In the present invention, the melting point and the softening point of the above-mentioned heat-meltable compound are preferably 10 to 150 ° C.

Examples of the antioxidant include chroman compounds, Claman compounds, phenol derivatives, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like. Specifically, JP-A-59-182785, 6
No. 0-182785, No. 60-130735, No. 61
-159644, JP-A-1-127287, and "11.
290 Chemical Products "Chemical Daily, Inc., pp. 862-868, and known compounds used for improving durability in photographs and other image recording materials.

Further, examples of the Feller include inorganic fine particles and organic resin particles. Examples of the inorganic particles include silica gel, calcium carbonate, titanium oxide, zinc oxide, barium sulfate, talc, clay, kaolin, acid clay, activated clay, and alumina. Examples of the organic fine particles include fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles.

Examples of the antistatic agent include cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, conductive fine particles, and the like. , Pp. 875-876, etc. can also be suitably used.

In the present invention, the total amount of the additives is usually preferably selected in the range of 0.1 to 30% by weight in the composition for forming a receptor layer.

The thickness of the receiving layer is usually selected in the range of 1 to 30 μm, preferably 3 to 20 μm.
The receiving layer may be a single layer or, if necessary, may be provided as two or more layers having different compositions.

The dye receiving material is not limited to a two-layer structure comprising a support and a receiving layer, and other layers may be formed. For example, for the purpose of improving properties such as heat insulating property, barrier property, cushioning property and adhesiveness between the receiving layer and the support, an intermediate layer (undercoat layer) and a dye-providing material described later are provided on the surface of the receiving layer. For the purpose of preventing fusing etc. of the overcoat layer, antistatic on the surface opposite to the receiving layer, preventing multiple sheets from feeding, adding slipperiness, preventing adhesion with other receiving layers, preventing curl, adding writeability, etc. A backing layer may be provided for the purpose.

When the intermediate layer, the overcoat layer and the backing layer are provided, the thickness of each of the layers is set to 0.1.
It is preferable to select the thickness in the range of from 01 to 30 μm, and these layers may be provided as a single layer or as another layer structure of two or more layers having different compositions.

The dye-receiving material is prepared by dispersing or dissolving the above-mentioned components for forming a receiving layer in a solvent to prepare a coating solution, and coating and drying the surface to be laminated, or the above-mentioned layer on a peelable sheet. Can be formed by a transfer method or the like in which only the receptor layer is transferred by applying heat and / or pressure on the surface to be laminated.

Solvents used in the above coating method include water, alcohols (eg, methanol, ethanol, isopropanol), cellosolves (eg, methylcellosolve, ethylcellosolve), aromatics (eg, benzene, toluene, xylene), and the like. Ketones (acetone, methyl ethyl ketone, etc.),
Esters (ethyl acetate, propyl acetate, dimethyl carbonate, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), chlorinated solvents (chloroform,
Dichloromethane, etc., amide solvents (N, N-dimethylformamide, N-methylpyrrolidone, etc.), dimethyl sulfoxide and the like can be used. For the coating, conventionally known wire bar coating, extrusion coating, gravure coating, roll coating, or the like can be used.

Each of the above-mentioned layers may be formed on the entire surface of the surface to be laminated, or may be formed on a part of the surface as required. Other layers can be provided in the same manner.

In the present invention, when the adhesive strength between the layers to be laminated is insufficient, before providing the layers to be laminated,
Corona discharge, flame discharge, ozone treatment,
UV treatment, radiation treatment, surface roughening treatment, chemical treatment,
Known treatment methods such as low plasma treatment and graft treatment may be applied.

(Dye Donor Material) The dye donor material used in combination with the dye receiving material of the present invention basically has an ink layer containing a heat diffusible dye on a support.

As this support, a support used for the dye receiving material can be appropriately selected and used in accordance with an image forming method described later. The thickness of the support is usually 2 to 500.
μm, preferably 4 to 100 μm, and is appropriately selected from such a range.

Specific examples of the dye contained in the ink layer include the following compounds. A heat diffusible dye used in a known image forming method may be used in combination, if necessary. Such dyes include conventionally known naphthoquinone dyes, anthraquinone dyes, azomethine dyes, indophenol dyes, indoaniline dyes, azo dyes, azomethine dyes, styryl dyes,
Examples include methine dyes, quinophthalone dyes, anthrisothiazole dyes, and cyanine dyes.

The amount of the heat-diffusing dye added is preferably from 1 to 80% by weight, more preferably from 30 to 70% by weight, in the ink layer forming composition.

The ink layer preferably contains a resin component as a binder in order to secure film formability and storage stability of the dye. Examples of this resin include cellulose ester resins (ethyl cellulose, acetyl cellulose, cellulose ether, cellulose addition compounds, etc.), polyvinyl alcohol, polyvinyl acetal resins (polyvinyl formal, polyvinyl butyral, etc.), polyester resins, urethane resins, olefin resins. , Vinyl chloride resin, styrene-acrylic resin (poly (meth) methacrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, polystyrene, poly (styrene-vinyl acetate) copolymer, polyacrylonitrile, or ), Polycarbonate resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, rubber resins, polycaprolactone resins, epoxy resins, phenoxy resins Gelatin, etc. can be mentioned casein, may be used those resins alone, or two or more in combination. These resins are usually contained in the ink layer in an amount of 20 to 99% by weight, preferably 3% by weight.
Used at 0-90% by weight.

In the ink layer, in addition to the above components, other additives such as a release agent, an oxygen quencher, a plasticizer, a heat solvent, and an antioxidant, which are added to the receptor layer, may be used as long as they do not inhibit image formation. May be added.

These additives are used in the ink layer forming product in an amount of 0 to
50% by weight is preferred, more preferably 0 to 30% by weight
It is.

The thickness of the ink layer is usually 0.05 to 20 μm.
And preferably 0.1 to 10 μm. Further, the ink layer may be a single layer, or may be provided as a two or more layered structure having different compositions as required.

The dye-donating material is not limited to a two-layer structure comprising a support and an ink layer, and other layers may be formed.

The support is also provided with the purpose of improving the adhesion to the ink layer and preventing the transfer and dyeing of the dye to the support, as disclosed in JP-A-59-124890 and JP-A-60-23299.
No. 6, No. 61-261090, No. 62-128792
No. 62-196184, No. 63-45089,
Nos. 63-135288 and 63-134281, and may have an undercoat layer. Further, on the back side of the support, for the purpose of transportability, heat resistance, antistatic, and the like, JP-A-60-82387, JP-A-60-94390
No., No. 60-115486, No. 60-184883
No. 60-219094, No. 61-279595
No. 62-251192 and No. 62-284784
Nos. 63-212587 and 63-214483
No., No. 64-1586, No. 64-11887, No. 6
4-1188, JP-A-1-214475 and 2-
A backing layer as described in 239973 or the like may be provided.

The thickness of the overcoat layer, the undercoat layer and the backing layer is usually 0.1 to 1 μm, and the thickness of the oxygen barrier layer is usually 1 to 50 μm.

The dye-providing material can be formed by a coating method, a transfer method, or the like, similarly to the dye-receiving material. Other layers can be formed in the same manner.

(Image Forming Method) To form an image, the ink layer surface of the dye-providing material and the receiving layer surface of the dye-receiving material face each other, and thermal energy is applied imagewise to the interface between the ink layer and the receiving layer. The dye in the ink layer thermally diffuses by an amount corresponding to the applied thermal energy, moves to the receiving layer side, is received by the receiving layer, and an image is formed.

As a heat source for applying heat energy, a thermal head is generally used, but an energizing head, a laser beam, an infrared flash, a hot pen or the like may be used.

When a thermal head or a current-carrying head is used as the heat source, the applied heat energy can be changed continuously or in multiple steps by changing the applied voltage or pulse width.

When a laser beam is used as a heat source, an optical system such as a lens can be used to change the amount of laser beam and the irradiation area, thereby changing the applied heat energy. If a dot generator having an acousto-optic element is used, heat energy can be given according to the size of a halftone dot.

The heat energy may be applied from the dye-donor material side, from the dye-receiving material side, or from both sides. However, if priority is given to the effective use of heat energy, the dye-donor material may be applied. It is preferable to carry out from the side, and it is more preferable to carry out the treatment with sufficient contact.

As described above, a single color image can be formed on the receiving layer of the dye receiving material by the image forming method. For example, a plurality of dye donating materials such as yellow, magenta, cyan, and black are sequentially replaced to obtain each color. By forming a corresponding image, a color image of a color tone composed of a combination of each color can be obtained.

[0112]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Dye-donating materials and dye-receiving materials of the present invention and comparative examples having different structures were produced as follows.

<< Preparation of Ink Liquid for Dye Donor Material >> Polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd .: Esrec KS-1) 20 g Dye (D-101) 10 g Methyl ethyl ketone 100 ml Cyclohexanone 20 ml << Preparation of Dye Donor Material >> The above ink liquid With a thickness of 4.5μ
m on a polyethylene terephthalate base on which an undercoat layer has been applied, the amount of coating after drying with a wire bar is 2.
The coating was dried at 3 g / m ² and dried to prepare a dye-providing material 101 having a heat-sensitive transfer layer formed on a polyethylene phthalate film. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) is provided on the back surface of the polyethylene terephthalate base as a sticking preventing layer.

Dye-donating materials 102 to 112 and 201 to 201 shown in Tables 1 and 2 were prepared in the same manner as the dye-donating material 101 except that the dye (D-101) was replaced with the dyes shown in Tables 1 and 2.
212 was produced.

<Preparation of Dye-Receiving Material> A coating solution having the following composition was dried on a support having polyethylene laminated on both sides of a paper (containing a white pigment (TiO ₂ ) and a bluing agent in one polyethylene layer). Coating and drying were performed so that the amount of subsequent coating would be 7.2 g, and a dye-receiving material 101 was produced. Further, in the dye receiving material 101, the compound (R-101) is shown in Table 1,
Dye-receiving materials 102 to 112 and 201 to 212 having the same composition except that they were changed as shown in FIG.

Compound (R-101) 3.0 g Polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical Co., Ltd.) 6.0 g Polyester modified silicone 0.3 g << Thermal transfer recording method >> The dye-donor material and the dye-receiving material were used. The image was recorded with a thermal printer by placing the thermal head on the back side of the dye-providing material, and an image having excellent gradation was obtained on the dye-receiving material.

After recording, the maximum density of the image, the sensitivity of the recording material and the image storability were evaluated according to the following.

Evaluation of Maximum Density: The maximum reflection density of an image (a portion where the application time was the maximum usually) was measured using a microdensitometer (manufactured by Konica: Sakura Densitometer PDM-5).

Evaluation of image bleeding: The obtained image was subjected to 70 ° C.
And left in the oven for 1 week. As a result, the bleeding of the obtained image was set to 5 for good and 1 for bad.
Relative evaluation was performed at each stage.

The results are shown in Tables 1 and 2.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

Embedded image

As is clear from Tables 1 and 2, the heat-sensitive transfer recording material using the dye of the present invention has a high maximum density, is excellent in sensitivity, and shows good fixability.

[0126]

According to the present invention, it is an object of the present invention to provide a sublimable thermosensitive recording medium having good fixability and excellent storage stability. Another object of the present invention is to provide a storage stability using this recording medium. Thus, an excellent image forming method can be provided.

Claims (5)

[Claims] 1. A dye-donating material provided with an ink layer containing a heat-diffusible dye on a support and a dye-receiving material provided with a dye-receiving layer are superimposed, and the dye is thermally diffused into the dye-receiving material by heat. In a sublimable heat-sensitive recording medium that forms an image by forming an oxazoline compound in a dye-donating material or a dye-receiving material, a reactive compound that reacts with the oxazoline compound is contained in a material not containing the oxazoline compound. A sublimable thermosensitive recording medium characterized by being contained. 2. The sublimable thermosensitive recording medium according to claim 1, wherein when the oxazoline compound according to claim 1 is contained in a dye-providing material, the oxazoline compound has an absorption maximum in a visible region. . 3. The sublimation according to claim 1, wherein when the oxazoline compound according to claim 1 is contained in the dye receiving material, the oxazoline compound has substantially no absorption in the visible region. Thermosensitive recording medium. 4. The sublimable thermosensitive recording medium according to claim 1, wherein the reactive compound according to claim 1 is a compound having acidic hydrogen. 5. A dye-donating material provided with an ink layer containing a heat-diffusible dye on a support and a dye-receiving material provided with a dye-receiving layer, and the dye is thermally diffused into the dye-receiving material by heat. In an image forming method of forming an image by forming an oxazoline compound in a dye-donating material or a dye-receiving material, a reactive compound that reacts with the oxazoline compound in a dye-donating material or a dye-receiving material containing no oxazoline compound is used. An image forming method, wherein the dye-donating material and the dye-receiving material are superposed on each other, and the dye is transferred to the dye-receiving material by heat to form an image.