JPH04241994A - Thermal transfer recording method - Google Patents

Abstract

PURPOSE:To obtain an image having excellent image stability in high density and a favorable hue on color reproduction by combining a specific heat diffusive pigment and a compound supplying metallic ions having high reactivity. CONSTITUTION:An image-receiving material is superposed on an ink layer containing a heat diffusive pigment in formula I, and heated in response to image information, and an image is formed onto an image-receiving material in the presence of a compound in formula II supplying metallic ions. In formula I, X and Y represent a group, which can be chelated. R and R' represent a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a cyano group, an acylamino group, an alkyl thio group, an aryl thio group, a sulfonyl amino group, an ureide group, a carbamoyl group, a sulfamoyl group, an alkoxy carbonyl group, anaryloxy carbonyl group, a sulfonyl group, an acyl group, and an amino group respectively. (m) and (n) represent the integer of 0-3, Y a hydroxyl group or -N(R')2 and R' a hydrogen atom or the alkyl group.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a thermal transfer recording method using a thermal transfer recording material, and more specifically, it is possible to obtain images with excellent gradation, light fastness, and stability, high density, and excellent color reproducibility. The present invention relates to a thermal transfer recording method that enables efficient recording using a thermal transfer recording material.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, color recording techniques such as an inkjet method, an electrophotographic method, and a thermal transfer method have been studied as a method for obtaining a color hard copy. This has advantages such as ease of operation and maintenance, miniaturization and cost reduction of the device, and low running cost.

In this heat-sensitive transfer method, a transfer sheet (also called a heat-sensitive transfer recording material) having a heat-melt ink layer on a support is heated by a heat-sensitive head, and ink is transferred from the heat-melt ink layer to the transfer sheet. (also called an image-receiving material), and a transfer sheet having an ink layer containing a heat-diffusible dye (sublimable dye) on a support is heated by a thermal head, and the ink layer transfers the heat-diffusible color from the ink layer. There are two types: a thermal diffusion transfer method (sublimation transfer method) that transfers the dye to the transfer sheet, but the thermal diffusion transfer method changes the amount of dye transferred according to changes in the thermal energy of the thermal head. This is advantageous for full-color recording because the gradation of the image can be controlled.

By the way, in thermal transfer recording using the thermal diffusion transfer method, the dye used in the thermal transfer recording material is important, and with conventional ones, the stability of the image obtained, that is, the light resistance and fixing properties are not good. It has the following drawbacks.

[0005] Therefore, in order to improve these points, Japanese Patent Application Laid-Open Nos. 59-78893, 59-109394, and 6
No. 0-2398 discloses an image forming method in which a heat-diffusible cyan dye that can be chelated is used to form an image on an image-receiving material using the chelated dye.

However, although these image forming methods are excellent methods for improving light fastness and fixing properties, the cyan dyes disclosed in these publications have low transfer properties, making it difficult to produce images of sufficient density. However, it has the problem that it has unnecessary absorption in terms of absorption characteristics, which is unfavorable in terms of color reproduction.

[0007] Also, JP-A-61-57651 and JP-A-63
Publication No. 308072 discloses image formation using an indoaniline dye in a system in which no metal source is present, but although these methods are favorable in terms of color reproduction, fixing and transferability are insufficient. There is a problem that it is not.

The present invention has been made based on the above circumstances.

Based on the above-mentioned viewpoint, the present inventors have conducted various studies on dyes for heat-sensitive transfer materials, and have found that by combining a specific heat-diffusible dye with a compound that supplies highly reactive metal ions, high-reactivity can be achieved. Image stability (fixability) with density
It was discovered that an image with excellent color reproduction and excellent color reproduction can be obtained, and based on this, the present invention was completed.

An object of the present invention is to provide a thermal transfer recording method with improved image density, fixability and hue.

[0011]

[Means for Solving the Problems] To achieve the above object, the present invention provides a heat-sensitive transfer recording material having an ink layer containing a heat-diffusible dye represented by the following general formula [I] on a support. An image-receiving material is superimposed on the ink layer, and the heat-sensitive transfer recording material is heated according to image information in the presence of a compound (hereinafter referred to as metal source) that supplies metal ions represented by the following general formula [II]. The present invention is a thermal transfer recording method characterized by forming an image on an image-receiving material.

0012

[Chemical formula 1]

[

##STR1## In the formula, X and Z each represent a chelatable group.

R and R' each represent a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group,
Cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group,
Represents an amino group. m and n each represent an integer of 0 to 3.

[0015] R and Z may be combined to form a ring,
When m is 2 or more, R may combine with each other to form a ring. Further, R' and X may be combined to form a ring, and n
is 2 or more, R' may be bonded to each other to form a ring.

Y represents a hydroxyl group or -N(R1)2. [However, R1 represents a hydrogen atom or an alkyl group which may have a substituent, and two R1's may be the same or different]. R' and Y may be combined to form a ring.

[M(Q1)k(Q2)m(Q3
)n]p+p(L-)[II][wherein,
M represents a metal ion. Q1, Q2, Q3 are each M
represents a coordination compound capable of forming a coordination bond with the metal ion represented by L is a counter anion capable of forming a complex.

k represents 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0, which means that the complex represented by the above general formula [II] has a tetradentate coordination. or hexadentate configuration, or Q1 , Q2 , Q
3 is determined by the number of ligands. p represents 1, 2 or 3. ] The present invention will be explained in detail below. The dye represented by general formula [I] will be explained in more detail. The X and Z each represent a chelatable group.

The chelatable group may be, for example, a group bonded through an oxygen atom, a sulfur atom or a nitrogen atom.

[0020] Examples of the group bonded through an oxygen atom include a hydroxy group, an alkoxy group, an aryloxy group, and an acyloxy group.

Groups bonded via a sulfur atom include mercapto groups, alkylthio groups, and arylthio groups.

Examples of the group bonded through a nitrogen atom include an amino group, an acylamino group, an alkylamino group, an arylamino group, a ureido group, and a urethane group.

R and R' are hydrogen atoms, halogen atoms (for example, chlorine atoms, fluorine atoms, etc.), alkyl groups (for example, methyl groups, ethyl groups, isopropyl groups, n
-butyl group, etc.), cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.), aryl group (e.g., phenyl group, etc.), alkenyl group (e.g., 2-propenyl group, etc.), aralkyl group (e.g., benzyl group, 2-phenethyl group, etc.) etc.), alkoxy groups (e.g. methoxy, ethoxy, isopropoxy, n-butoxy, etc.), aryloxy groups (e.g. phenoxy, etc.), cyano groups, acylamino groups (e.g. acetylamino, propionylamino, etc.) , alkylthio groups (e.g., methylthio group, ethylthio group, n-butylthio group, etc.), arylthio groups (e.g., phenylthio group, etc.), sulfonylamino groups (e.g., methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido groups (e.g., 3- Methylureido group, 3
, 3-dimethylureido group, 1,3-dimethylureido group, etc.), carbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.)
, sulfamoyl group (e.g. ethylsulfamoyl group,
dimethylsulfamoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group) etc.), acyl groups (e.g. acetyl group, propanoyl group,
butyroyl group, etc.), amino group (e.g. methylamino group,
(ethylamino group, dimethylamino group, etc.).

These groups may be further substituted,
Examples of substituents include alkyl groups (e.g. methyl group, ethyl group, trifluoromethyl group, etc.), aryl groups (e.g. phenyl group), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), amino groups (e.g. methylamino group, ethyl group, etc.). amino group, etc.), acylamino group (e.g., acetyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group), cyano group, nitro group, halogen atom (e.g., chlorine atom, fluorine atom, etc.) ) etc.

[0025] Each of the groups represented by R and R' (including substituents if they have a substituent) preferably has 15 or less carbon atoms (particularly preferably 10 or less). Preferred specific examples of R and R' include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group, a ureido group,
Examples include a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an amino group.

[0026] The above m and n each represent an integer of 0 to 3.

R and Z may be combined to form a ring, and m
is 2 or more, R may combine with each other to form a ring.

R' and X may be combined to form a ring, or when n is 2 or more, R's may be combined with each other to form a ring.

Next, Y is a hydroxyl group or -N(R1)2
represents. However, R1 represents a hydrogen atom or an alkyl group which may have a substituent, and two R1's may be the same or different.

[0030] Examples of the substituent bonded to the alkyl group include a hydroxyl group, an alkoxy group, and an amino group.

Examples of R1 include a methyl group, an ethyl group, an n-butyl group, a 2-hydroxyethyl group, a 2-methanesulfonamidoethyl group, and particularly preferably a dialkylamino group having 8 or less carbon atoms (for example, diethylamino, etc.).

Note that R' and Y may be combined to form a ring.

[0033] The compound represented by the general formula [I], that is, the heat-diffusible dye (cyan dye) according to the present invention, includes, for example, a phenol derivative represented by the following general formula [III] and a compound represented by the general formula [IV]. It can be produced according to a known synthetic method such as an oxidative coupling reaction with a p-phenylenediamine derivative or a p-aminophenol derivative represented by:

[0034]

[Case 2]

(However, R in the general formula [III]
and Z have the same meaning as defined in general formula [I]. Q represents a group, such as a hydrogen atom or a chlorine atom, which is separated by a coupling reaction with general formula [IV]. )

003
6]

[Chemical formula 3]

(However, R' in general formula [IV],
X and Y have the same meanings as defined in general formula [I]. ) This coupling reaction is preferably carried out under basic conditions, and the reaction medium may be an organic solvent, an aqueous organic solvent, or an aqueous solution.

Further, the oxidizing agent may be any organic or inorganic material as long as it has a potential capable of oxidizing p-phenylenediamine derivatives or p-aminophenol derivatives, such as silver halide, hydrogen peroxide, and dioxide. Inorganic oxidizing agents such as manganese, potassium persulfate, and oxygen, and various organic oxidizing agents such as N-bromosuccinimide and chloramine T can be used.

It is also possible to synthesize by electrode reaction by selecting appropriate current, voltage, supporting electrolyte, solvent, electrode, etc.

Next, representative examples of the compounds represented by the general formula [I] are shown in FIG. 1 (exemplary compounds 1 to 4), FIG. 2 (exemplified compounds 5 to 8), and FIG. 3 (exemplified compounds 9 to 12). , Figure 4 (Exemplary Compounds 13 to 16), Figure 5 (Exemplary Compounds 17 to 20),
Figure 6 (Exemplary Compounds 21 to 24), Figure 7 (Exemplary Compound 25
~28), Figure 8 (Exemplified Compounds 29-32), Figure 9 (Exemplified Compounds 33-36), and Figure 10 (Exemplified Compounds 37-4
0), but the present invention is not limited thereto.

The thermal transfer recording material used in the present invention is:
Basically, a layer containing a heat-diffusible dye represented by the general formula [I] and a binder (hereinafter referred to as an ink layer) is provided on a support.

In the thermal transfer recording material of the present invention, an ink (paint for forming an ink layer) is prepared by dissolving at least one of the heat-diffusible dyes in a solvent together with a binder or dispersing it in the form of fine particles. It can be manufactured by forming an ink layer by coating and drying on a support, or by forming an ink layer by a printing method such as a gravure method.

The content of the dye in the ink layer is preferably 0.1 to 20 g per 1 m 2 of the support.

[0044] The thickness of the ink layer is 0.1 in terms of dry film thickness.
~5 μm is preferred.

[0045] As the binder, cellulose type,
Water-soluble polymers such as polyacrylic acid, polyvinyl alcohol, and polyvinylpyrrolidone, acrylic resin,
Mention may be made of polymers soluble in water or organic solvents such as methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, polyvinyl acetal, ethyl cellulose, nitrocellulose.

When a polymer soluble in an organic solvent is used as the binder, one or more of these polymers may be used not only dissolved in the organic solvent, but also in the form of a latex dispersion.

[0047] The amount of binder used is 1 m2 of the support.
0.1 g to 50 g per serving is preferable. As the solvent for preparing the ink of the ink layer, water, alcohols (e.g. ethanol, propanol), cellosolves (
(e.g. methyl cellosolve), esters (e.g. ethyl acetate), aromatics (e.g. toluene, xylene, chlorobenzene), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone), ethers (e.g. tetrahydrofuran, dioxane), chlorinated solvents. (For example, chloroform, trichlorethylene), etc.

[0048] The support has good dimensional stability,
Any material can be used as long as it can withstand the heat during recording with a thermal head, but thin paper such as condenser paper or glassine paper, or heat-resistant plastic film such as polyethylene terephthalate, polyethylene terenaphthalate, polyamide, or polycarbonate may also be used. Can be done.

The thickness of the support is preferably 2 to 30 μm,
Further, the support may have an undercoat layer for the purpose of improving adhesion to the binder and preventing transfer and dyeing of the dye to the support. Further, the back surface of the support (the side opposite to the ink layer) may have an anti-sticking layer for the purpose of preventing the head from sticking to the support.

The heat-sensitive transfer material used in the present invention may have a heat-fusible layer containing a heat-fusible compound as described in JP-A-59-106997 on the ink layer. .

[0051] As this heat-melting compound, 65 to 13
Colorless or white compounds having a melting point of 0°C are preferably used, such as waxes such as carbanal wax, beeswax, and candeli wax, higher fatty acids such as stearic acid and behenic acid, alcohols such as xylitol, acetamide, benzamide, etc. Examples include amides of , ureas such as phenyl urea and diethyl urea.

[0052] These heat-fusible layers may contain polymers such as polyvinylpyrrolidone, polyvinyl butyral, saturated polyester, etc., in order to improve dye retention.

Furthermore, when the thermal transfer recording material is applied to full-color image recording, as shown in FIG.
Three layers, a cyan ink layer 2 containing a heat-diffusible cyan dye, a magenta ink layer 3 containing a heat-diffusible magenta dye, and a yellow ink layer 4 containing a heat-diffusible yellow dye, are sequentially repeated on a support 1. It is preferable that the surface be coated with

[0054] Yellow, magenta,
In addition to each cyan layer, an ink layer containing a black image-forming substance may be further coated, and a total of four layers may be repeatedly coated in sequence.

After the ink layer of the heat-sensitive transfer recording material thus obtained and the image-receiving material are superimposed, heat is applied from the back side of the support of the heat-sensitive transfer recording material in accordance with the image information, thereby forming a thermal image. A dye corresponding to the image can be diffused and fixed onto the image-receiving material to form an image there.

The important point in the thermal transfer recording method of the present invention is that in the above step, heat is applied in accordance with image information in the presence of a compound (metal source) that supplies metal ions represented by the general formula [II]. is applied to the thermal transfer recording material,
An image is formed on an image-receiving material using a chelate dye obtained by reacting the heat-diffusible dye in the ink layer with the metal source.

The metal ions constituting the metal source include divalent and polyvalent metals belonging to groups I to VIII of the periodic table, among which Al, Co, and 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 these metal sources, inorganic or organic salts of the metals and complexes of the metals are preferable.

[0059] To give specific examples, Ni2+, Cu2+,
A complex represented by the following general formula containing Co2+, Cr2+ and Zn2+ can be preferably used.

[M(Q1)k(Q2)m(Q3)n]p
+p(L-) However, in the above formula, M represents a metal ion, and Q1, Q2, and Q3 each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M.

These coordination compounds can be selected from, for example, the coordination compounds described in "Chelate Kagaku (5)" (Nankodo). Particularly preferred are ethylenediamine and its derivatives, glycinamide and its derivatives, and picolinamide and its derivatives.

L is a counter anion capable of forming a complex,
Examples include anions of inorganic compounds such as Cr, So4, and C2O4, and anions of organic compounds such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives, and particularly preferred are tetraphenylboron anions and derivatives thereof.

k represents 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0, which means that the complex represented by the above general formula is tetradentate or hexadentate. It is determined by the coordination, or by the number of ligands of Q1, Q2, and Q3. p represents 1, 2 or 3.

The metal source may be present in the image receiving material in advance, or may be present in the heat-fusible layer provided on the surface of the ink layer.

The amount of the metal source added is preferably 0.2 to 20 g/m2, more preferably 1 to 10 g/m2, based on the image receiving material or the heat-fusible layer.

To explain the thermal transfer recording method of the present invention with reference to the drawings, in FIG. The dye in the ink layer 9 of the recording material 10 is diffused and transferred to the image receiving material 7 by heat from the heating resistor of the thermal head 11, for example, and reacts with the metal source in the image receiving layer 6 to form a chelate dye. .

Further, in FIG. 13, when the metal source is present in the heat-fusible layer 14 provided on the surface of the ink layer 13, the support 15, the ink layer 13, and the heat-fusible layer 1
The dye in the ink layer 13 of the thermal transfer recording material 16 consisting of, for example, the heating resistor 1 of the thermal head 17
Diffused into the thermofusible layer 14 by the heat from 8, where it reacts with the metal source to form a chelate dye,
A portion 14a of the heat-fusible layer containing this chelate dye undergoes cohesive failure or interfacial peeling and transfers to the image-receiving material 19 side.

The image-receiving material used in the present invention generally uses paper, a plastic film, or a paper-plastic film composite as a support, and an image-receiving layer formed thereon by polyester resin, polyvinyl chloride resin, vinyl chloride, or the like. (for example, vinyl acetate), polyvinyl butyral, polyvinylpyrrolidone, polyvinyl carbonate, etc., to form a layer of one or more types of polymers. Further, the support itself may be used as an image-receiving material.

According to the thermal transfer recording method of the present invention, since the dye used in the thermal transfer recording material is thermally diffusible and has good chelation reactivity, images with high density and excellent image stability can be obtained. In addition, it is possible to obtain an image with a preferable hue in terms of color reproduction.

[0070]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Example 1) <Preparation of ink layer> A homogeneous solution ink containing a heat-diffusible dye used in the present invention was obtained from a mixture having the following composition.

Exemplary compound 1 (shown in FIG. 1)
10g nitrocellulose resin
20g methyl ethyl ketone
400cc <Preparation of thermal transfer recording material> The above ink was applied onto a polyethylene terephthalate film (support) 1 with a thickness of 4.5 μm using a wire bar so that the coating amount after drying was 1.0 g/m2.
An ink layer was formed by coating and drying to produce a thermal transfer material-1 according to the present invention.

[0073] On the back side of the polyethylene terephthalate film, a nitrocellulose layer containing a silicone-modified urethane resin (SP-2105, manufactured by Dainichiseika Kaisha, Ltd.) is provided as a sticking prevention layer.

<Preparation of image-receiving material> A paper support made of paper laminated with polyethylene on both sides, and a polyethylene layer on one side [an appropriate amount of white pigment (TiO2) bluing agent and the following metal source (applied amount: 5 g/m2)] An image-receiving material was prepared by coating vinyl chloride resin as an image-receiving layer on the image-receiving layer in an amount of 10 g/m 2 .

[0075] This image-receiving layer is coated with 0.00% silicone oil.
Contains 15g/m2.

[0076] Metal source: [Ni(NH2 CO
CH2 CH2 NHC3 H7)3 ]2+2[Ph
4 B)] <Thermal transfer image recording method> The obtained thermal transfer recording material 1 and the above-mentioned image receiving material are stacked so that the ink layer surface of the thermal transfer recording material and the image receiving layer surface of the image receiving material face each other, and the thermal head is exposed to the image receiving material. Image recording was performed by applying the material to the back side of the thermal transfer recording material.

Maximum reflection density (Dmax) of the obtained image
), The chelation reactivity of the dye, the hue of the image, and the fixability of the image were evaluated using the following methods, and the results are shown in Table 1.

Line density of main scanning and sub-scanning: 8 dots/mm
Recording power: 0.6 W/dot Heating time of thermal head: Heating time was varied in stages from 20 msec (applied energy: approx. 11.2 x 10-3 J) to 2 msec (applied energy: approx. 1.12 x 10-3 J). It was adjusted.

Maximum reflection density (Dmax): Measured using an optical densitometer (Model PCA-65 manufactured by Konica Corporation).

[0080] Light resistance
: The residual rate (%) of the dye after irradiation with a xenon fade meter for 3 days was examined.

Evaluation of hue: The obtained image was visually evaluated. 〇...Good as a cyan dye △...Poor as a cyan dye Evaluation of fixing properties: Transfer of the obtained image by coating the surface of the image-receiving layer and a 5 μm thick nitrocellulose layer on a 180 μm thick polyethylene terephthalate film. Overlap the coated side of the sheet and heat at 140℃ for 1
After heating for a minute, the degree of transfer of the dye from the image-receiving layer to the surface of the nitrocellulose layer was visually evaluated, and it was determined that the less retransfer, the better the fixability.

〇...Retransfer is not observed.

Δ: Slight retransfer is observed.

x: Re-transfer is significant.

(Examples 2 to 8) The dyes shown in Table 1 (
Corresponds to the dye numbers in Figures 1-10. Thermal transfer recording materials 2 to 8 and image-receiving material were prepared in the same manner as in Example 1, except that the following materials were used, and images were formed in the same manner. The results are shown in Table 1.

(Comparative Examples 1 and 2) The following two comparative dyes A and B were used in place of Exemplified Compound 1 in Example 1, and if the amount of solvent used was the same as in Example 1, the dissolution of the dye was insufficient. A thermal transfer recording material and an image-receiving material were prepared under the same conditions as in Example 1, except that the amount of methyl ethyl ketone used was doubled because of its low properties, and images were formed in the same manner.

The results are shown in Table 1.

Comparative dye A:

[0089]

[C4]

Comparative dye B:

[0091]

[C5]

(Comparative Example 3) Same as in Example 1, except that the amount of methyl ethyl ketone used was doubled as in Comparative Examples 1 and 2, and no metal source was added to the image receiving layer. A thermal transfer recording material and an image receiving material were prepared, and images were formed. The results are shown in Table 1.

[0093]

[Table 1]

From Table 1, it was found that the samples of the examples of the present invention were able to obtain cyan images with higher density and better absorption characteristics and image storage properties (light fastness and fixing properties) than the samples of the comparative examples. Recognize.

Comparative Example 3 also shows that the presence of the metal source improves the density and fixing properties.

(Example 9) As shown in FIG. 11, a yellow dye image-forming ink layer was formed on the support used in Example 1,
A magenta image-forming ink layer and a cyan image-forming ink layer were sequentially coated to prepare a thermal transfer recording material.

Note that the cyan ink layer has the same structure as the ink layer of Example 1, and the structures of the yellow ink layer and the magenta ink layer are as shown below.

<Yellow ink layer> Yellow dye: The following structure. Amount applied = 0.6g/m2.

Binder: Polyvinyl butyral. Amount applied = 0.9g/m2.

[0100]

[C6]

<Magenta Ink Layer> Magenta dye: The following structure. Amount applied = 0.6g/m2.

Binder: Nitrocellulose. Amount =
0.9g/m2.

[0103]

[C7]

A full color image was created using the above thermal transfer recording material using a video printer (manufactured by Nikon, CP-3000D).

As a result, a full color image showing good color reproducibility was obtained.

[0106] Furthermore, the image storage stability (lightfastness) of the obtained image was good.

Note that the same image-receiving material as that used in Example 1 was used as the image-receiving material.

That is, by the thermal transfer recording method of the present invention, a full-color image with good gradation, good color reproducibility, and excellent image stability could be obtained.

(Example 10) As an intermediate layer on the thermal transfer recording material of Example 9, 5 g of a ball mill dispersion of p-toluamide, 7 g of polyvinylpyrrolidone, and 3 g of gelatin,
100 cc of an aqueous solution containing 0.3 g of the following hardener was applied so that the amount of p-toluamide applied was 0.5 g/m2.

[0110] Furthermore, on the intermediate layer, as a heat-fusible layer, the following ultraviolet inhibitor (applied amount: 0.1 g/m2), the following antioxidant (applied amount: 0.1 g/m2), and ethylene-vinyl acetate copolymer were added. (Content of vinyl acetate 20% by weight, amount attached 0
．． 2g/m2) containing carvanawa wax (applied amount: 0.2g)
/m2) and the metal source used in Example 1 (applied amount: 5 g/m2) by hot melt coating,
A thermal transfer recording material was obtained.

Hardener:

[0112]

[Chemical formula 8]

[0113] Ultraviolet absorber:

[0114]

[Chemical formula 9]

[0115] Antioxidant:

[0116]

[Chemical formula 10]

[0117] Using the heat-sensitive transfer recording material, a full-color image was recorded using a video printer in the same manner as in Example 9. Note that plain white paper was used as the image-receiving material. As a result, the obtained image had good color reproducibility and stability.

That is, by the method of the present invention, Example 1
If the heat-sensitive transfer recording material having the structure shown in No. 0 is used, excellent full-color recording can be obtained even on plain paper.

[0119]

According to the thermal transfer recording method of the present invention, since the cyan dye according to the present invention is heat diffusible and has good chelate reactivity, highly reactive metal ions are used when forming an image. By combining it with a compound that supplies the above, it is possible to efficiently form an image with a high density, excellent image stability (fixing properties), and a hue favorable for color reproduction.

[Brief explanation of the drawing]

FIG. 1 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 2 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 3 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 4 is a cross-sectional view showing an example of a thermal transfer recording material.

FIG. 5 is a sectional view showing an example of a thermal transfer recording material.

FIG. 6 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 7 is a diagram illustrating a structural formula of a dye according to the present invention.

FIG. 8 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 9 is a diagram illustrating a structural formula of a dye according to the present invention.

FIG. 10 is a diagram illustrating the structural formula of a dye according to the present invention.

FIG. 11 is a cross-sectional view showing an example of a thermal transfer recording material.

FIG. 12 is an explanatory diagram showing the principle of the thermal transfer recording method of the present invention.

FIG. 13 is an explanatory diagram showing the principle of the thermal transfer recording method of the present invention.

[Explanation of symbols]

1 Support, 7 Image receiving material 8 Support 9 Ink layer 10 Thermal transfer recording material 11 Image receiving material 13 Ink layer 15 Support 19 Image receiving material

Claims (1)

[Claims] 1. An image-receiving material is placed on the ink layer of a heat-sensitive transfer recording material having an ink layer containing a heat-diffusible dye represented by the following formula [I] on a support, and the heat-sensitive transfer recording material is coated with image information. 1. A thermal transfer recording method comprising forming an image on an image-receiving material in the presence of a compound that supplies metal ions represented by the following general formula [II] by heating according to the following formula [II]. [In the formula, X and Z each represent a chelatable group. R and R' are each a halogen atom,
Alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, aryloxy group, cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl basis,
Represents an aryloxycarbonyl group, a sulfonyl group, an acyl group, and an amino group. m and n each represent an integer of 0 to 3. R and Z may be combined to form a ring, or when m is 2 or more, R may be combined with each other to form a ring. Further, R' and X may be combined to form a ring, and n is 2
In the above case, R' may combine with each other to form a ring. Y represents a hydroxyl group or -N(R1)2. (however,
R1 represents a hydrogen atom or an alkyl group which may have a substituent, and two R1's may be the same or different. ). R' and Y may be combined to form a ring. [M(Q1)k((Q2)m(Q3)
n]p+p(L-) [II] [Wherein, M represents a metal ion. Q1, Q2, Q3
each represents a coordination compound capable of forming a coordination bond with the metal ion represented by M. L is a counter anion capable of forming a complex. k represents 1, 2 or 3, m represents 1, 2 or 0
and n represents 1 or 0, which is determined depending on whether the complex represented by the general formula [II] has a tetradentate or hexadentate coordination, or whether Q1, Q2, Q3 Determined by the number of ligands. p represents 1, 2 or 3. ]