JPH08319432A - Thermal transfer recording material, method for recording therewith and pigment for image formation - Google Patents

Abstract

PURPOSE: To obtain a thermal transfer recording material excellent in thermal diffusion, chelate reactivity and a hue and capable of giving highly dense and highly stable cyan and magenta images by using a specified azo dye in thermal transfer recording. CONSTITUTION: The azo pigment is represented by the formula (wherein R<1> is a 1-6C alkyl group, an alkenyl group or an aromatic ring; R<2> to R<4> are each H or a monovalent substituent; R<3> and R<4> may be combined with each other to form a ring; and Z is an aromatic ring group necessary for the formation of the pigment). The dye donating material is obtained fro example by forming a transfer layer made of an ink containing the azo pigment on a support, and the ink may be a mixture of at least two azo dyes. The dye content of the transfer layer is desirably 0.05-10g per m<2> of the support. The thickness of the transfer layer is desirably 0.1-10μm in terms of the thickness of a dry film. In the preparation of the ink, a binder (e.g. acrylic resin) and an organic solvent (e.g. alcohol) may be used. As the support, a capacitor paper, a heat-resistant plastic film or the like can be used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an azo dye suitable for use in thermal transfer recording, a chelate dye comprising the azo dye and a metal ion, a dye-donating material using the azo dye, the dye-donating material and the dye-donating material. The present invention relates to a thermal transfer recording material comprising a dye image receiving material containing a metal ion capable of reacting with an azo dye, and a thermal transfer recording method using the azo dye.

[0002]

BACKGROUND OF THE INVENTION Conventionally, it has been studied to record a color image by an ink jet system, an electrophotographic system, a thermal transfer system, a silver halide color photosensitive material system or the like.

Of these, the thermal transfer system has advantages such as easy operation and maintenance, downsizing of the apparatus, cost reduction, and low running cost.

In the heat-sensitive transfer recording system, the dye used in the heat-sensitive transfer material is important, and conventionally known dyes have a drawback that image stability, particularly fixability and light resistance are poor. .

As a technique for improving these points, Japanese Unexamined Patent Publication No. 59-59
-78893, 59-109394 and 60-2398 each disclose a chelating dye that is chelated on an image receiving material using a heat diffusible dye (hereinafter referred to as a post chelate dye) capable of chelating. An image forming method for forming an image is disclosed. However, the post-chelate dyes disclosed in the above publications have a large structural restriction because they form a tridentate chelate with a metal, and have a large structural limitation such as color tone, chelate reactivity, molar extinction coefficient of dye and dye in the ink sheet. Since all the problems such as storage stability and suitability for ink formation (solubility) cannot be satisfied, further improvement has been desired.

[0006]

OBJECTS OF THE INVENTION It is, therefore, a first object of the present invention to provide an azo dye having high sensitivity, good color tone and good storability and a dye-donor element using the azo dye.

A second object of the present invention is to provide a chelate dye having good storage stability.

A third object of the present invention is to provide a heat-sensitive transfer recording material having high sensitivity, good color tone and good storability.

A fourth object of the present invention is to provide a thermal transfer recording method capable of efficiently obtaining an image having high density and good image stability.

[0010]

The above object can be achieved by the following structures. (1) An azo dye represented by the following general formula (1).

[0011]

[Chemical 4] [In the formula, R ¹ represents an alkyl group, an alkenyl group or an aromatic ring group having 1 to 6 carbon atoms, and these alkyl group, alkenyl group and aromatic ring group may have a substituent. R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ³ and R ⁴ may be linked to each other to form a ring. Z represents an aromatic ring group necessary for forming a dye. (2) A chelate dye represented by the following general formula (2).

[0012]

Embedded image [In the formula, Dye represents an azo dye represented by the following general formula (1a).

[0013]

[Chemical 6] In formula (1a), R ¹ represents an alkyl group, an alkenyl group or an aromatic ring group having 1 to 6 carbon atoms, and these alkyl group, alkenyl group and aromatic ring group may have a substituent. Good. R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ³ and R ⁴ may be linked to each other to form a ring. Z represents an aromatic ring group necessary for forming a dye.

[0014] M represents a metal ion, Y ^- represents an organic anion.

X represents an integer of 1 to 3, and p represents 1 or 2. (3) A dye-donor material having a transfer layer containing the azo dye described in (1) above. (4) A thermal transfer recording material comprising a dye-donor material having a transfer layer containing the azo dye described in (1) above and a dye-image-receiving material having an image-receiving layer containing a metal ion donor. (5) A dye image-receiving material having a transfer layer containing the azo dye described in (1) above is overlaid with a dye image-receiving material, and the dye image-providing material is heated in accordance with image information, and the dye image-receiving material is exposed in accordance with image information. The above-mentioned azo dye is transferred, the azo dye is reacted with a metal ion-containing compound before or after the transfer, and an image is formed by a chelate dye formed by the reaction.

The present invention will be described in detail below.

First, the azo dye represented by the following general formula (1) (hereinafter referred to as the azo dye of the present invention) will be described.

[0018]

[Chemical 7] [In the formula, R ¹ represents an alkyl group, an alkenyl group or an aromatic ring group having 1 to 6 carbon atoms, and these alkyl group, alkenyl group and aromatic ring group may have a substituent. R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ³ and R ⁴ may be linked to each other to form a ring. Z represents an aromatic ring group necessary for forming a dye. In the general formula (1), examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group and an isopropyl group, and the alkenyl group is Examples include propenyl group and butenyl group. The aromatic ring of the aromatic ring group represented by R ¹ may be either a homocyclic ring or a heterocyclic ring. Examples of these aromatic ring groups include a phenyl group,
Examples thereof include a thienyl group, a pyrazolyl group and an imidazolyl group.

These alkyl group, alkenyl group and aromatic ring group may have a substituent, and examples of the substituent include a halogen atom (eg chlorine atom, fluorine atom), nitro group and cyano group. , Alkyl group, alkenyl group, alkoxy group, alkyl sulfonamide group, aryl sulfonamide group, anilino group, acylamino group, alkylureido group, arylureido group, alkoxycarbonyl group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, sulfo group Group, carboxy group,
Examples thereof include an aryl group and a heterocyclic group.

The monovalent substituent represented by R ² , R ³ and R ⁴ includes, for example, a halogen atom (eg, chlorine atom, fluorine atom), nitro group, cyano group, alkyl group, alkenyl group, alkoxy. Group, alkylsulfonamide group, arylsulfonamide group, anilino group, acylamino group, alkylureido group, arylureido group, alkoxycarbonyl group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, aryl group, Heterocyclic groups are mentioned.

When R ³ and R ⁴ are linked to each other to form a ring, the ring formed by R ³ and R ⁴ linked to each other is
Examples thereof include a benzene ring, a naphthalene ring, a pyrrolidine ring, a pyridine ring and a piperidine ring. Further, these rings may have a substituent, and as the substituent, the above-mentioned substituents can be mentioned.

As the aromatic ring group necessary for forming the dye represented by Z, a phenyl group, a pyridyl group, a pyrimidine group, a pyrazine group, a pyridazine group and the like are preferable, and a phenyl group and a pyridyl group are more preferable. Further, these aromatic rings may be condensed with other rings as long as they have aromaticity. In addition, these aromatic rings and rings in which another ring is condensed to the aromatic ring may have a substituent.

When the phenyl group is a phenyl group having a substituent, examples of the phenyl group having a substituent include 4-hydroxyphenyl group, 4-methylaminophenyl group and 4-N-ethylaminophenyl group. Four
-N, N-dimethylaminophenyl group, 4-N, N-diethylaminophenyl group, 4-N, N-diethylamino-2-methylphenyl group, 4-methoxyphenyl group, 4
-Anilinophenyl group, 4-acetamidophenyl group,
2-4-dinitrophenyl group, 2-cyano-2-nitrophenyl group, 2,4,5-tricyanophenyl group, 2-
Examples thereof include a methylsulfonyl-4-nitrophenyl group and a 2,6-dicyano-4-nitrophenyl group.
The pyridyl group having a substituent is, for example, 3
-(2-Methyl-6-N, N-diethylamino) pyridyl group, 2- (3-methyl-6-N, N-diethylamino) pyridyl group, 3- (6-N, N-dimethylamino)
Pyridyl group, 2- (5-hydroxy) pyridyl group, 2-
Examples thereof include a (5-methoxy) pyridyl group, a 3- (6-methoxy) pyridyl group, a 3- (6-hydroxy-2-methyl) pyridyl group, and a 2- (3-methyl-5-diethylamino) pyridyl group. .

The dyes represented by the general formulas (1) and (2) are dyes exhibiting a cyan to magenta color.

Specific examples of the azo dye of the present invention are shown below.

[0026]

Embedded image

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13] The chelate dye represented by the general formula (2) of the present invention (hereinafter,
It is called the chelate dye of the present invention. ) Can be obtained by reacting the azo dye of the present invention with a metal ion donor.

Examples of the metal ion donor (metal ion-containing compound) used in the present invention include inorganic or organic metal salts and metal complex compounds, and among them, metal salts and complex compounds of organic acids are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table, among which Al, Co, Cr, Cu, Fe, Mg, and M.
n, Mo, Ni, Sn, Ti and Zn are preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable. Specific examples of the metal ion-containing compound include Ni ²⁺ , Cu ²⁺ ,
Examples thereof include salts of an aliphatic acid such as acetic acid and stearic acid having Cr ²⁺ , Co ²⁺ and Zn ^2+, and an aromatic carboxylic acid such as benzoic acid and salicylic acid.

Further, the complex compound represented by the following general formula (M) can be particularly preferably used as the metal ion donor.

[0034]

Embedded image In the above general formula (M), M represents a metal ion, and preferable metal ions are Ni ²⁺ , Cu ²⁺ and C.
r ²⁺ , Co ²⁺ and Zn ²⁺ .

Q ¹ , Q ² and Q ³ each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M, and these may be the same as or different from each other.

Examples of these coordination compounds include, for example:
It can be selected from the coordination compounds described in “Chelate Science (5)” (Nankodo).

[0037] Y ^- is represents an organic anion, specifically,
For example, a tetraphenylboron anion and an alkylbenzene sulfonate anion can be mentioned.

L, m and n each independently represent an integer of 0 to 3. These values are determined by whether the complex represented by the above general formula is tetradentate or hexadentate, or by the number of ligands of Q ¹ , Q ² and Q ³ . To be done.
p represents 1 or 2.

As the metal ion donor used in the present invention, among the complex compounds represented by the general formula (M), the following general formula (M-1) [in the general formula (M), 1, m, n
In the case of = 0] is more preferable.

[0040]

[Chemical 15] [In the formula, M ²⁺ represents a divalent transition metal ion. Y represents a coordination compound represented by the following general formula (M-2) capable of forming a complex with a divalent metal ion. ]

[0041]

Embedded image [In the formula, Z ₁ represents a hydrogen atom, an alkyl group, an aryl group, an aryloxycarbonyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom. R and R'represent an alkyl group or an aryl group, which may be the same or different, and R and Z ₁ or R'and Z ₁ may combine to form a ring. However, when Z ₁ is a hydrogen atom, neither R nor R ′ is a methyl group. Next, the dye-donor material, the dye-image receiving material and the thermal transfer recording method of the present invention will be described.

The dye-donor element of the present invention can be obtained, for example, by forming a transfer layer on a support using an ink containing the azo dye of the present invention. Two or more kinds of the azo dyes of the present invention may be used in combination in the ink, and other heat-sensitive transfer dyes may be used in combination with the azo dyes of the present invention.

The content of the dye in the transfer layer depends on the amount of Support 1
It is preferably 0.05 to 10 g per m ² .

For the transfer layer, the ink for forming a heat-sensitive transfer layer is prepared by, for example, dispersing the dye in the form of fine particles in a solvent, or dissolving or dispersing the dye together with a binder in the solvent. Can be formed by coating on a support and drying. If necessary, organic or inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an antifoaming agent, an antioxidant, a viscosity adjusting agent and the like can be added to the ink.

The dry thickness of the transfer layer is preferably 0.1 to 10 μm.

As the binder used for preparing the ink, acrylic resin, methacrylic resin, polystyrene,
Solvent-soluble polymers such as polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, ethyl cellulose are preferred. These binders can be used alone or in combination of two or more.
Further, these binders may be used not only in the form of being dissolved in an organic solvent but also in the form of latex dispersion.

The amount of the binder used is 0 per 1 m ² of the support.
1 to 20 g is preferable.

The organic solvent used for preparing the ink is
For example, alcohols (eg, ethanol, propanol), cellosolves (eg, methylcellosolve),
Examples thereof include aromatics (eg toluene, xylene), esters (eg ethyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, dioxane) and the like.

The support is not particularly limited as long as it has good dimensional stability and can withstand the force and heat received from the thermal head during recording, but thin paper such as condenser paper and glassine paper, polyethylene terephthalate, polyamide,
A heat resistant plastic film such as polycarbonate is preferable. The thickness of the support is preferably 2 to 30 μm,
Further, the support may be provided with an undercoat layer for the purpose of improving the adhesiveness to the ink layer and preventing dyeing and transfer of the dye to the support side. Further, the back surface of the support (the side opposite to the heat-sensitive transfer layer) may have a slipping layer for the purpose of preventing the thermal head from sticking to the support.

The heat-sensitive transfer recording material of the present invention can be a heat-sensitive transfer recording material capable of full-color image recording.
In this case, a cyan thermal transfer layer containing a heat-diffusing cyan dye capable of forming a cyan image and a heat-diffusing magenta dye capable of forming a magenta image are contained at separate positions on one side of the support. Magenta thermal transfer layer,
Three layers of a yellow heat-sensitive transfer layer containing a heat diffusible yellow dye capable of forming a yellow image, or these three layers further contain a heat diffusible dye capable of forming a black image. Add thermal transfer layer 4
Two layers are formed in a frame sequence.

In the present invention, as the dye image-receiving material, paper, a plastic film, a paper-plastic film composite or the like is generally used as a support, on which a polyester resin, polyvinyl chloride resin, a dye image-receiving layer, What is formed by forming a polymer layer composed of one or more kinds of a copolymer resin of vinyl chloride and another monomer (for example, vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate and the like is used. In these dye image-receiving materials, if necessary, an antioxidant, a release agent, etc. may be contained in the image-receiving layer, a protective layer may be provided on the image-receiving layer, and a support and an image-receiving layer may be provided. Intermediate layers may be provided between the layers for the purpose of adhesion, heat insulation or cushioning. Further, the back surface of the support (the side opposite to the image receiving layer) may be provided with an antistatic layer and a back layer containing inorganic or organic non-sublimable fine particles for the purpose of preventing blocking. Further, an image receiving layer may be provided on both sides of the support.

To form an image using the dye-donor element and dye-image receptor material of the present invention, the dye-donor element and the dye-image receptor element are in contact with the transfer layer of the dye-donor element and the image-receiving layer of the dye-image receptor element. As described above, the dye may be transferred to the image-receiving material by applying heat according to image information from the back surface of the dye-donating material with a thermal head or the like. At that time, the dye of the present invention is reacted with a metal ion donor (metal ion-containing compound) to form the chelate dye of the present invention.

The metal ion-containing compound that reacts with the dye may be present, for example, in the image receiving layer of the dye image receiving material, or in another layer provided separately from the image receiving layer.

The metal ion-containing compound is usually 0.5 to 20.
It is preferably used in the amount of g / m ^2, and more preferably used in an amount of 1 to 15 g / m ^2.

According to the above thermal transfer recording method, it is possible to efficiently obtain an image having high density and high image stability.

The thermal transfer recording method of the present invention can be used for forming an image on plain paper, for example.

In this case, on the transfer layer of the dye-donor element,
For example, a heat-melting layer containing a heat-melting compound as described in JP-A-59-106997 is further formed. As the heat-meltable compound, a colorless or white compound that melts at a temperature of 65 to 150 ° C. is preferably used,
Examples of these compounds include waxes such as carnauba wax, beeswax, and candelin wax.
Further, these heat-fusible layers can contain polymers such as polyvinylpyrrolidone, polyvinyl butyral, polyester and vinyl acetate.

When the dye-donor element having the heat-fusible layer is used, the dye is transferred to the heat-fusible layer by heating.
An image is formed on plain paper or the like.

In the above case, the metal ion donor is preferably added to the heat fusible layer.

As a heating method for forming an image, a thermal head is generally used, but as the heating method, other heating methods, for example, electric heating or heating using a laser can be used. .

FIGS. 1 and 2 are explanatory views for explaining the heat-sensitive transfer recording method of the present invention. In FIGS.
1 is a support, 2 is an image receiving layer containing a metal ion-containing compound, 3 is a dye image receiving material, 4 is a support, 5 is a transfer layer containing the azo dye of the present invention, 6 is a dye-donor material, and 7 is thermal. A head, 8 is a heating resistor provided in the thermal head 7, 9 is a heat-fusible layer containing a metal ion-containing compound,
10 is a dye-donor element.

FIG. 1 illustrates a method of forming an image on a dye image-receiving material having an image-receiving layer. In FIG. 1, the dye-donor material 6 is a support 4 and a book formed on the support 4. It comprises a transfer layer 5 containing the azo dye of the invention. The dye image receiving material 3 is composed of the support 1 and the image receiving layer 2 formed on the support 1. When the dye-donor material 6 is overlaid on the dye-image-receiving material 3, the thermal head 7 is brought into contact with the dye-donor material 6, and the heating resistor 8 provided on the thermal head 7 is energized to heat the dye-donor material 6, The azo dye of the present invention in the transfer layer 5 is diffuse-transferred to the image receiving layer 2 as shown by an arrow to form a chelate dye. An image is formed on the image receiving layer 2 by scanning the dye-donor material 6 with the thermal head 7 and energizing the heating resistor 8 imagewise.

FIG. 2 illustrates a method of forming an image on a dye image receiving material having no image receiving layer such as plain paper. In FIG. 2, the dye providing material 10 is a support 4 and a support 4. It is composed of a transfer layer 5 containing the azo dye of the present invention formed thereon and a heat-fusible layer 9 formed thereon. Overlaying the dye-donor material 10 on the dye-image-receiving material 3,
Contact the thermal head 7 on the dye-donor material 10,
Energize the heating resistor 8 provided in the thermal head 7,
When the dye-donor material 6 is heated, the azo dye of the present invention in the transfer layer 5 is diffusion-transferred to the heat-meltable layer 9 to form a chelate dye, and the melted heat-meltable layer 9 forms a support as shown by an arrow. Move to 3. An image is formed on the dye image receiving material 3 by scanning the dye donating material 10 with the thermal head 7 and energizing the heating resistor 8 imagewise.

[0064]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto. Example 1 << Synthesis of Azo Dye (D-1) >>

[0065]

[Chemical 17]

(I) 7.32 g of the compound Q is dissolved in 80 ml of acetic acid, and a solution of 3.31 g of sodium nitrite in 30 ml of concentrated sulfuric acid is added dropwise, and the mixture is stirred at 10 ° C. for 30 minutes. (Ii) Compound (10.00 g) is dissolved in acetic acid (30 ml), and the solution obtained in (i) above is added while cooling with ice and stirred for 15 minutes. After stirring at room temperature for 90 minutes, add ice 100
It was poured into 300 ml of water containing g, and the precipitate was collected by filtration and recrystallized from ethanol to obtain 14.25 g of azo dye D-
Got 1.

Example 2 << Synthesis of chelate dye (E-1) >> Azo dye D-1 8.
00 g is dissolved in 30 ml of acetone, 9.74 g of the following metal ion-containing compound is added, and the solvent is distilled off. The residue was subjected to silica gel chromatography to obtain 8.10 g of chelate dye E-1.

[0068]

Embedded image

Example 3 << Preparation of ink >> By mixing, an ink having the following ink liquid composition was obtained. <Ink liquid composition> Thermal diffusible dye D-1 3.5 g Polyvinyl butyral resin (BL-1, manufactured by Sekisui Chemical Co., Ltd.) 6.5 g Methyl ethyl ketone 200 ml The dye had good solubility.

<< Preparation of Dye-donating Material >> A polyethylene terephthalate film having a thickness of 4.5 μm was coated and dried with a wire bar so that the coating amount after drying was 0.8 g / m ² , and polyethylene was used. A dye-donor element having a transfer layer formed on a terephthalate film was prepared.
A nitrocellulose layer containing a silicone-modified urethane resin (SP-2105, manufactured by Dainichiseika) was formed as a sticking prevention layer on the back surface of the polyethylene terephthalate film.

<< Preparation of Dye Image Receiving Material >> An ester-modified silicone is applied by coating on a paper support having polyethylene laminated on both sides (the polyethylene layer on one side contains a white pigment (TiO ₂ ) and a bluing agent). (Attached amount 0.1 g /
m ² ), the following metal ion-containing compound (applied amount 3.5 g /
m ² ), a polyvinyl chloride resin (coating amount: 5 g / m ² ) was formed to obtain a dye image-receiving material.

[0072]

[Chemical 19]

<Thermal Transfer Recording Method> The dye-donor material and the dye-image receiving material obtained as described above were superposed, a thermal head was applied from the back side of the thermal transfer recording material, and image recording was carried out under the following recording conditions. An image with excellent tonality was obtained. (Recording conditions) Recording density for main scanning and sub-scanning: 8 dots / mm Recording power: 0.6 W / dot Heating time: Set heating time stepwise from 20 msec to 0.2 msec Maximum density and light resistance of the obtained image The properties and color tone were evaluated as follows. Further, the raw storability of the dye-providing material was evaluated by the following. The results obtained are shown in Table 1.

<Evaluation of maximum density> Optical density measuring instrument X-ri
te 310 TR (manufactured by X-Rite), heating time is 20ms
The maximum reflection density in the part designated as ec was measured.

<Evaluation of Light Resistance> The obtained image was irradiated with a xenon fade meter for 72 hours, the maximum reflection density after irradiation was determined D, and the residual ratio of the dye was determined according to the following to evaluate the light resistance.

Residual rate (%) of dye = (D / D ₀ ) × 100 (D ₀ is the maximum reflection density before irradiation.)

<Evaluation of Raw Preservability of Dye-Providing Material> The prepared dye-providing material was stored in an environment of 55 ° C. and 80% relative humidity, and the maximum reflection density was measured in the same manner as the evaluation of the maximum density. In addition, the precipitation of the dye was evaluated according to the following evaluation criteria. [Evaluation Criteria] ⊙: No precipitation ○: Slight precipitation ×: Precipitation

<Color tone> The obtained image was visually observed and the color tone was evaluated according to the following evaluation criteria. [Evaluation criteria] ○: No turbidity △: Slightly turbidity

Examples 4 to 9 The heat diffusible dye D-1 was replaced with the heat diffusible dyes D-2, D-12,
Six types of dye-donor elements were prepared in the same manner as in Example 3 except that D-24, D-25, D-29, and D-34 were used.
Image recording was performed under the same conditions. An image with excellent gradation was obtained using any of the dye-donor elements.

Further, with respect to the obtained dye-providing material, the maximum density, light resistance, color tone and raw storability of the dye-providing material were evaluated in the same manner as in Example 3. The results obtained are shown in Table 1.

Comparative Examples 1 and 2 Two kinds of dye-donor materials were prepared in the same manner as in Example 3 except that the following comparative dyes A and B were used instead of the heat diffusible dye D-1.
Image recording was performed under the same conditions.

About the obtained dye-donor element, Example 3
In the same manner as above, the maximum density, light resistance, color tone, and raw storability of the dye-donor element were evaluated. The results obtained are shown in Table 1.

[0083]

Embedded image

[0084]

[Table 1] As is clear from Table 1, according to the thermal transfer recording method of the present invention, an image having high density and excellent light resistance was obtained.

Example 10 A yellow image was formed on a 4.5 μm thick polyethylene terephthalate film having a nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichiseika) as a sticking prevention layer on the back surface. Transfer layer containing dye Y-1 (coating amount 0.5 g / m ² ), transfer layer containing magenta image forming dye M-1 (coating amount 0.5 g / m ² ), cyan image forming dye according to the present invention D-1 (Amount of 0.5g /
m ² ) -containing transfer layers were sequentially applied to prepare a dye-donor element having 3 kinds of transfer layers at separate positions. The same binder as in Example 3 was used for each transfer layer.

Next, using the above-mentioned thermal transfer recording material and the dye image-receiving material described in Example 1, a full-color image was prepared with a full-color printer CP3000D manufactured by Nikon Co., Ltd., and the image stability was excellent at high density. A full color image was obtained.

[0087]

[Chemical 21]

Example 11 On three transfer layers of the dye-donor element described in Example 10, p
100 ml of an aqueous solution containing 5 g of a ball mill dispersion of toluamide, 7 g of polyvinylpyrrolidone, 3 g of gelatin and 0.3 g of a hardener H-1 was added to p-toluamide.
It was coated so as to have a concentration of 0.5 g / m ² to form an intermediate layer. Then, on the intermediate layer, the metal ion-containing compound described in Example 3 (coating amount: 1.0 g / m ² ), UV inhibitor UV-1 (coating amount: 0.1 g / m ² ), antioxidant AO-1. (Attached amount 0.1 g /
m ² ) and an ethylene-vinyl acetate copolymer (vinyl acetate content 20%, coating amount 0.2 g / m ² ) containing carnauba wax (coating amount 2.0 g / m ² ) in a hot-melt coating. To obtain a dye-donor element.

Using this heat-sensitive transfer recording material and white plain paper (dye image receiving material), a full color image was prepared in the same manner as in Example 10. As a result, a full color image having a high density and excellent image fixability was obtained. It was

[0090]

[Chemical formula 22]

[0091]

The azo dye of the present invention is excellent in thermal diffusivity and chelate reactivity, is excellent in color tone, and can give stable cyan and magenta images at high concentration. The dye-donor element has high sensitivity, excellent biostability, and is capable of efficiently forming a stable cyan and magenta image at high density with excellent color tone.

[Brief description of drawings]

FIG. 1 is an explanatory diagram illustrating an example of a thermal transfer recording method of the present invention.

FIG. 2 is an explanatory diagram illustrating another example of the thermal transfer recording method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Support 2 ... Image receiving layer 3 ... Dye image receiving material 4 ... Support 5 ... Transfer layer 6 ... Dye donating material 7 ... Thermal head 8 ... Heating resistance Body 9 ... Heat-fusible layer 10 ... Dye donating material

Claims (5)

[Claims] 1. An azo dye represented by the following general formula (1). Embedded image [In the formula, R ¹ represents an alkyl group, an alkenyl group or an aromatic ring group having 1 to 6 carbon atoms, and these alkyl group, alkenyl group and aromatic ring group may have a substituent. R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ³ and R ⁴ may be linked to each other to form a ring. Z represents an aromatic ring group necessary for forming a dye. ] 2. A chelate dye represented by the following general formula (2). Embedded image [In the formula, Dye represents an azo dye represented by the following general formula (1a). Embedded image In formula (1a), R ¹ represents an alkyl group, an alkenyl group or an aromatic ring group having 1 to 6 carbon atoms, and these alkyl group, alkenyl group and aromatic ring group may have a substituent. Good. R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ³ and R ⁴ may be linked to each other to form a ring. Z represents an aromatic ring group necessary for forming a dye. M represents a metal ion, and Y ⁻ represents an organic anion. x represents an integer of 1 to 3, and p represents 1 or 2. ] 3. A dye-donor element comprising a transfer layer containing the azo dye according to claim 1. 4. A thermal transfer recording material comprising a dye-donor material having a transfer layer containing the azo dye according to claim 1 and a dye-image-receiving material having an image-receiving layer containing a metal ion donor. 5. A dye-donor material having a transfer layer containing the azo dye according to claim 1 is overlaid with a dye-image-receiving material, and the dye-donor material is heated in accordance with image information to form image information on the dye-image receiving material. A thermal transfer recording method comprising transferring the azo dye accordingly, reacting the azo dye with a metal ion-containing compound before or after the transfer, and forming an image with a chelate dye formed by the reaction.