JP3005821B2 - Thermal transfer recording material and thermal transfer recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording material and a heat-sensitive transfer recording method, and more particularly, to an image recording material for obtaining a yellow image having high density and good image stability, and the heat-sensitive transfer recording material. The present invention relates to an image recording method capable of efficiently recording a yellow image by using the method.

[0002]

BACKGROUND OF THE INVENTION A thermal transfer recording method is easy to operate and maintain, and can be downsized and reduced in cost.
Further, it is useful as a method for obtaining a color hard copy because of its advantages such as low running cost.

However, in the thermal transfer recording of the thermal transfer system, the dye used in the thermal transfer material is important, and the conventional one has a disadvantage that the stability of the obtained image, particularly the fixability and the light resistance, are poor. are doing.

[0004] In order to improve this point, Japanese Patent Laid-Open Publication No.
No. 3, No. 59-109349, No. 60-2398, and the like, disclose an image forming method for forming an image on an image receiving material using a chelatable dye by using a chelatable heat diffusible dye. ing.

Although these image forming methods are excellent methods for improving fixability and light fastness, the dyes disclosed in these known patents are capable of chelating used in thermal transfer recording materials. They do not always satisfy the following performance required for dyes (hereinafter referred to as post-chelating dyes).

1) To provide a chelate dye image of good color tone by chelate formation. 2) The post-chelating dye has good thermal diffusivity. 3) The post-chelating dye does not move to the back of the ink sheet or the like during storage of the ink sheet. 4) The post-dye has good solvent solubility (suitability for ink formation). 5) The reactivity of the post-chelating dye (reactivity with the metal ion supplying compound) is good. 6) The stability (fixing property, light resistance) of the chelate dye image is excellent.

[0007] Accordingly, further improvements have been desired for the above-mentioned properties of post-chelating dyes.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermal transfer recording using a post-chelating dye capable of giving a good color tone as yellow by chelation. An object of the present invention is to provide a material and a thermal transfer recording method using the recording material.

It is another object of the present invention that the ink suitability, the thermal diffusivity and the chelate reactivity are good, an image having a high density and good storability can be obtained, and the storability of the ink sheet is good. It is an object of the present invention to provide a thermal transfer recording material using a post-chelating dye and a thermal transfer recording method using the recording material.

[0010]

The above object of the present invention has been attained by the following constitutions. That is, (a) a heat-sensitive transfer recording material having a heat-sensitive transfer layer containing at least a dye represented by the following general formula (1) on a support.

[0011]

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Where R₁₁And R₁₂Is a hydrogen atom,
Represents an alkyl group or an aryl group; ₁₃Is a cyano group, ace
Chill group, -CONHR₁₅Or -COOR₁₅(R₁₅Is a hydrogen atom,
Represents an alkyl group or an aryl group). R₁₄Is hydrogen field
N, a halogen atom or a monovalent substituent, n₁Is 0
Represents an integer of 3. X₁Is -O-, -S-, -N = or -N (R
₁₆)-(R₁₆Represents a hydrogen atom or an alkyl group)
Then Z₁Is X₁Together form a 5- to 6-membered aromatic heterocycle
Represents the group of atoms required for

[0013] The image receiving material is superimposed on a heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the general formula (1) described in (b) or (a) on a support. A heat-sensitive transfer recording method in which an image is formed by heating and forming a chelate dye formed by a reaction between the dye and a metal ion supply compound (hereinafter, referred to as a metal source).

(C) A heat-sensitive transfer recording material having a heat-sensitive transfer layer containing at least a dye represented by the following general formula (2) on a support.

[0015]

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In the formula, R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₂ and R ₂₃ each represent a hydrogen atom, a halogen atom or a monovalent substituent. n ₂ represents an integer of 0 to 3. X ₂ is -O -, - S -, - N = or -N (R ₂₄₎ - (R
₂₄ represents a hydrogen atom or an alkyl group). Z ₂ is X ₂
Represents an atomic group necessary for forming a 5- to 6-membered aromatic heterocycle together with the above.

The image receiving material is superimposed on a heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the general formula (2) described in (d) and (c) on a support. A thermal transfer recording method in which an image is formed by heating and forming a chelate dye formed by a reaction between the dye and a metal ion supply compound.

(E) A heat-sensitive transfer recording material having a heat-sensitive transfer layer containing at least a dye represented by the following general formula (3) on a support.

[0019]

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In the formula, Z ₃ represents a group of atoms necessary for forming a 5- to 6-membered aromatic heterocyclic ring together with 2 carbon atoms and X ₃ , and Z ₄ represents an aromatic carbon ring together with 2 carbon atoms. Represents an atom group forming a ring. R ₃₁ and R ₃₂ each represent a hydrogen atom or 1
N ₃ and n ₄ each represent an integer of 1 to 5; m represents an integer of 0 or 1; X ₃ is -O -, - S -, - N = or -N (R) - represents the (R represents a hydrogen atom or an alkyl group).

The image receiving material is superimposed on a heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the general formula (3) described in (f) and (e) on a support. A thermal transfer recording method in which an image is formed by heating and forming a chelate dye formed by a reaction between the dye and a metal ion supply compound.

The general formulas (1), (2) and (3) of the present invention
The dye represented by (hereinafter referred to as the dye of the present invention) will be described in detail. In the general formula (1), R ₁₁ and R ₁₂
The alkyl group represented by is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms. Specifically, methyl, ethyl,
Examples include propyl, i-propyl, butyl, i-butyl, t-butyl, hexyl, and 2-ethylhexyl groups. Examples of the aryl group represented by R ₁₁ and R ₁₂ include a phenyl group and a naphthyl group, and a phenyl group is preferable.

As the alkyl group and the aryl group represented by R ₁₅ and R ₁₆ , the same groups as those described for R ₁₁ and R ₁₂ can be exemplified.

The monovalent substituent represented by R ₁₄ includes alkyl, aryl, alkoxy, arylthio, alkylthio, amino, acyl, acylamino, carbamoyl,
Alkylsulfonyl, arylsulfonyl, alkylsulfonylamino, arylsulfonylamino, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylamino, aryloxycarbonylamino,
Examples include ureido, hydroxyl, cyano, and nitro groups.

Specific examples of the 5- to 6-membered aromatic heterocycle formed by Z ₁ and X ₁ include pyridine, pyrimidine, triazine, pyrazine, pyridazine, pyrrole, furan, thiophene, pyrazole, imidazole, triazole and oxazole. , Thiazole, and the like. The ring may have a substituent, and examples of the substituent include the same as the monovalent substituent represented by R ₁₄ .

The dye represented by the general formula (1) used in the present invention can be obtained, for example, by subjecting a compound represented by the following general formula (1a) to a diazo compound according to the method described in Chemical Reviews, Vol. 75, 241 (1975). And can be produced by a known coupling reaction with a compound represented by the following general formula (1b).

[0027]

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Typical specific examples of the dye represented by formula (1) of the present invention are shown below.

[0029]

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[0030]

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[0031]

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In the general formula (2), the alkyl group represented by R ₂₁ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 8 carbon atoms. Specifically, methyl, ethyl, propyl, i
Examples include -propyl, butyl, i-butyl, t-butyl, hexyl, and 2-ethylhexyl. R
_The aryl group represented by ₂₁ includes a phenyl group, a naphthyl group and the like, and is preferably a phenyl group.

As the alkyl group represented by R ₂₄ , R ₂₁
The same ones as mentioned above can be mentioned.

The monovalent substituent represented by R ₂₂ and R ₂₃ includes alkyl, aryl, alkoxy, arylthio,
Alkylthio, amino, acyl, acylamino, carbamoyl, alkylsulfonyl, arylsulfonyl, alkylsulfonylamino, arylsulfonylamino,
Examples include alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylamino, aryloxycarbonylamino, ureido, hydroxyl, cyano, and nitro groups.

Examples of the 5- to 6-membered aromatic heterocyclic ring in which Z _{2 and} X ₂ are pyridine, pyrimidine, triazine, pyrazine, pyridazine, pyrrole, furan, thiophene, pyrazole, imidazole, triazole,
Rings such as oxazole and thiazole can be mentioned. The ring may have a substituent, and examples of the substituent include the same as the monovalent substituent represented by R ₂₄ . The dye represented by the general formula (2) used in the present invention also includes a compound represented by the following general formula (2a).
The compound can be diazotized according to the method described in Chemical Reviews, Vol 75, 241 (1975), and can be produced by a coupling reaction with a compound represented by the following general formula (2b).

[0036]

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Representative examples of the dye represented by formula (2) of the present invention are shown below.

[0038]

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[0039]

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[0040]

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[0041]

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[0042] In general formula (3), as the aromatic heterocyclic 5-6 membered Z ₃ forms together with the two carbon atoms and X _3, for example pyridine, pyrimidine, pyrrole, thiophene, furan, pyrazole, triazole , Thiazole, oxazole and the like. Preferred are pyridine, pyrazole and triazole rings.
X ₃ is -O -, - S -, - N = or -N (R) - represents a, among others -N =, - N (R) - are preferred. R represents a hydrogen atom or an alkyl group. As the alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 carbon atom
Represents a straight-chain or branched alkyl group of from 4 to 4, particularly preferably a methyl group.

The aromatic carbocyclic ring formed by Z ₄ with two carbon atoms is a 6- or 10-membered aromatic carbocyclic ring, preferably a benzene ring.

Examples of the monovalent group represented by R ₃₁ and R ₃₂ include a halogen atom (eg, chlorine, bromine, fluorine, etc.), an alkyl group (eg, a linear or branched alkyl having 1 to 12 carbon atoms), Aryl group (for example, phenyl), alkoxy group (for example, linear or branched alkoxy having 1 to 12 carbon atoms), aryloxy group (for example, phenyloxy), amino group (for example, alkylamino, dialkylamino and the like), arylamino Group (for example, phenylamino), acylamino group (for example, linear or branched alkylcarbonylamino or phenylcarbonylamino having 1 to 12 carbon atoms), sulfonyl group (for example, linear or branched having 1 to 12 carbon atoms) Alkylsulfonyl, phenylsulfonyl, etc.), alkoxycarbonyl group (e.g.
12 straight-chain or branched alkyloxycarbonyl), aryloxycarbonyl group (for example, phenyloxycarbonyl), carbamoyl group (for example, straight-chain or branched alkylaminocarbonyl having 1 to 12 carbon atoms, dialkylaminocarbonyl, aryl Aminocarbonyl), a urethane group (for example, a linear or branched alkyloxycarbonylamino having 1 to 12 carbon atoms), a cyano group, and a nitro group. The alkyl group or the aryl group may further have a substituent, and examples of the substituent include the monovalent groups. Preferred examples of R ₃₁ include a hydrogen atom, a halogen atom, an alkyl group (an alkyl group having 1 to 8 carbon atoms), and an alkoxy group (an alkyloxy group having 1 to 8 carbon atoms). R ₃₂ is preferably a hydrogen atom, an alkyl group (an alkyl group having 1 to 8 carbon atoms), an alkoxy group (an alkyloxy group having 1 to 8 carbon atoms),
Phenyl group, alkoxycarbonyl group (C 1 -C 1
And a carbamoyl group (alkylaminocarbonyl group having 1 to 8 carbon atoms, phenylaminocarbonyl group) and a cyano group.
n ₃ and n ₄ represent an integer of 1 to 5, preferably 1 or 2.

Representative examples of the dye represented by formula (3) of the present invention are shown below.

[0046]

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[0047]

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The heat-sensitive transfer recording material of the present invention comprises a heat-sensitive transfer layer containing the dye of the present invention provided on a support. The content of the dye in the heat-sensitive transfer layer is per 1 m ² of the support.
0.05 to 10 g is preferred.

The thermal transfer layer is formed by dissolving one or more of the dyes of the present invention together with a binder in a solvent or by dispersing them in the form of fine particles in the solvent. It can be formed by preparing, applying the ink on a support, and drying it appropriately. The thickness of the thermal transfer layer is 0.1 to 10 μm in dry film thickness
Is preferred.

The binder is preferably a solvent-soluble polymer such as acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, and ethyl cellulose. These binders may be used in the form of a latex dispersion, as well as one or two or more of them dissolved in an organic solvent. The amount of the binder, the support 1 m ² per
0.1-20 g is preferred. Examples of the organic solvent include alcohols (eg, ethanol, propanol), cellosolves (eg, methyl cellosolve), aromatics (eg, toluene, xylene), esters (eg, acetate), ketones (eg, acetone, methyl ethyl ketone), Ethers (eg, tetrahydrofuran, dioxane) and the like can be mentioned.

The support has good dimensional stability,
Any material that can withstand the heating of the thermal head during recording may be used, but thin paper such as condenser paper or glassine paper, or a heat-resistant plastic film such as polyethylene terephthalate, polyamide, or polycarbonate is preferably used. The thickness of the support is preferably 2 to 30 μm,
Further, the support preferably has an undercoat layer made of a polymer selected for the purpose of improving the adhesiveness to a binder and preventing transfer and dyeing of the dye to the support. Further, a slipping layer may be provided on the back surface of the support (the side opposite to the thermal transfer layer) for the purpose of preventing the head from sticking to the support.

The heat-sensitive transfer recording material of the present invention is described in JP-A-59-106997 on the heat-sensitive transfer layer for the purpose of using an image-receiving material described later which is not particularly provided with an image-receiving layer such as plain paper. May have a heat-fusible layer containing such a heat-fusible compound. As this heat-fusible compound,
A colorless or white compound that melts at a temperature of 65 to 150 ° C. is preferably used, and examples thereof include waxes such as carnauba wax, beeswax, and candeline wax. In addition, these heat-meltable layers may contain polymers such as polyvinylpyrrolidone, polyvinylbutyral, polyester, and vinyl acetate.

In order to apply the heat-sensitive transfer recording material of the present invention to a heat-sensitive transfer recording material capable of performing full-color image recording, a yellow heat-sensitive transfer layer containing a yellow dye according to the present invention,
A total of three layers, a magenta thermal transfer layer containing a thermal diffusible dye capable of forming a magenta image and a cyan thermal transfer layer containing a thermal diffusible dye capable of forming a cyan image, are formed on the same surface on a support. It is preferable to repeatedly apply the coating on the top. Further, if necessary, a total of four heat-sensitive transfer layers containing a black image-forming substance may be successively and repeatedly applied on the same surface.

In the thermal transfer recording method of the present invention, after the thermal transfer layer of the thermal transfer recording material and the image receiving material are overlapped, heat corresponding to the image information is applied to the thermal transfer recording material, and An image is formed on the image receiving material by the chelate dye formed by the reaction with the dye of the present invention. In this case, in the present invention, the dye represented by the general formula (1), (2) or (3) is used as the dye, so that a yellow image having high density, high image stability, and favorable color reproduction can be efficiently produced. Can be obtained. The metal source may be present in the image receiving material, or may be present in the heat-meltable layer provided on the heat-sensitive transfer layer.

The above-described thermal transfer recording method will be described with reference to the drawings. In FIG. 1, when a metal source is present in the image receiving layer of the image receiving material 3 comprising the support 1 and the image receiving layer 2, the support 4 and the thermal transfer The dye in the thermal transfer layer of the thermal transfer material 6 composed of the layer 5 is diffused and transferred to the image receiving material 3 by, for example, heat from the heating resistor 8 of the thermal head 7 and reacts with the metal source in the image receiving layer 2 to chelate. A dye image is formed.

In FIG. 2, when a metal source is present in the heat-meltable layer 9 provided on the heat-sensitive transfer layer 5,
The dye in the thermal transfer layer 5 of the thermal transfer recording material 10 composed of the support 4, the thermal transfer layer 5 and the thermal fusible layer 9 is heated by the heat from the heating resistor 8 of the thermal head 7, for example. , And reacts with the metal source to form a chelate dye. The heat-meltable layer containing the chelate dye transfers to the image receiving material 3 by cohesive failure or interfacial peeling to form an image.

Examples of the metal source include inorganic or organic salts and metal complexes of metal ions. Among them, salts and complexes of organic acids are preferable. As the metal, I to V of the periodic table
Monovalent and polyvalent metals belonging to Group III include
Among them, Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable. Specific examples of metal sources include Ni ²⁺ , Cu ²⁺ , C
Examples thereof include salts of r ²⁺ , Co ²⁺ and Zn ²⁺ with aliphatic salts such as acetic acid and stearic acid, and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid.

Further, a complex represented by the following general formula can be particularly preferably used.

[M (Q₁)_l(Q_Two)_m(Q_Three)_n]^{P +}(Y^-)_P  However, in the above formula, M is a metal ion, preferably N
i²⁺, Cu²⁺, Cr²⁺, Co²⁺, Zn²⁺Represents Q₁, Q_Two, Q_ThreeIs
Coordination compounds capable of coordinating with metal ions each represented by M
Represents an object and may be the same or different from each other.
These coordination compounds include, for example, chelate science
(5) Select from the coordination compounds described in (Nankodo)
can do. Y represents an organic anion group;
Include tetraphenylboron anion and alkylbenzenes
And sulfonic acid anions. l is 1, 2 or 3
Represents an integer, m represents 1, 2 or 0, and n represents 1 or 0
In these, the complex represented by the above general formula has a tetradentate coordination.
Or 6-dentate configuration, or Q₁,
Q_Two, Q_ThreeIs determined by the number of ligands. p is 1 or
2 is represented.

The amount of addition of the metal source is usually preferably 0.5 to 20 g / m ² , based on the amount of the image-receiving material or the heat-fusible layer.
~15g / m ² is more preferable.

The image receiving material used in the present invention is generally made of paper, a plastic film, or a paper-plastic film composite as a support, and a polyester resin, a polyvinyl chloride resin, and vinyl chloride as an image receiving layer thereon. Copolymer resins with other monomers (eg, vinyl acetate, etc.), polyvinyl butyral, polyvinyl pyrrolidone,
One or two or more polymer layers such as polycarbonate are formed. Further, the support itself may be used as an image receiving material.

[0062]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (Preparation of ink) The following raw materials were mixed to obtain an ink in a uniform solution containing the heat-diffusing dye according to the present invention.

[0064] thermally diffusible dye Y ₁ -1 (exemplified compound) 5g Polyvinyl butyral resin (BL-1, manufactured by Sekisui Chemical Co.) and 5g methyl ethyl ketone 200 ml (creation of heat-sensitive transfer recording material) The ink thickness 4.5μ
m-sensitive polyethylene terephthalate base, a heat-sensitive transfer recording material having a heat-sensitive transfer layer formed on a polyethylene phthalate base by applying and drying such that the coated amount after drying is 0.8 g / m ² using a wire bar. It was created. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) is provided as a sticking prevention layer on the back surface of the polyethylene terephthalate base.

(Preparation of Image-Receiving Material) On a support in which polyethylene is laminated on both sides of paper (a polyethylene layer on one side contains a white pigment (TiO ₂ ) and a bluing agent)
Polyvinyl chloride resin containing an ester-modified silicone and the following metal source as an image receiving layer (with weight 3.5 g / m ^2), the amount of biasing is applied so as to ^{0.15g / m 2, 5g / m} 2 , respectively,
An image receiving material was obtained. Metal source: [Ni ²⁺ (NH ₂ CH ₂ CONH ₂ ) ₃ ] 2 [(C ₆ H ₅ ) ₄ B] (Thermal transfer recording method) The thermal transfer recording material (hereinafter also referred to as an ink sheet) and an image receiving material When the image was recorded under the following recording conditions by applying a thermal head from the back of the thermal transfer recording material, a yellow image having excellent gradation was obtained.

(Recording conditions) Recording density of main scanning and sub-scanning: 8 dots / mm Recording power: 0.6 W / dot Heating time: Heating time is adjusted stepwise between 20 msec and 0.2 msec. The performance (maximum density, chelation reactivity, fixability, light resistance) and ink sheet storage stability were evaluated by the following methods. The results are shown in Table 1. <Evaluation of Maximum Density> The maximum reflection density of the image (usually, the portion where the application time was the maximum) was measured by X-rite310TR.

<Chelation Reactivity> ：: Almost fully formed chelate dye image Δ: Insufficient formation of chelate dye ×: Formation of chelate dye of only some dyes <Evaluation of fixability> Image reception of obtained image Layer surface and thickness 18
5 μm thick on 0 μm polyethylene terephthalate film
The coated surface of the sheet coated with a μm nitrocellulose layer was overlapped, heated at 140 ° C. for 2 minutes, and the degree of transfer of the dye from the image receiving layer to the nitrocellulose layer was visually evaluated. The less the dye retransfer, the better the fixability. ：: No retransfer was observed. Δ: Retransfer was slightly observed. X: Retransfer was remarkable. <Evaluation of light fastness>
Time light irradiation, the density before irradiation is D ₀ , the density after irradiation is D
The light fastness was evaluated using (D / D ₀ ) × 100 (%) as the residual ratio of the dye.

<Evaluation of Ink Sheet Storage Property> The ink surface of the ink sheet and the back surface (sticking prevention layer surface) of the ink sheet were overlapped and left at 55 ° C. for 3 days to check the state of dye transfer to the sticking prevention layer surface. The ink sheet was visually observed to evaluate the storage stability of the ink sheet.

[0069] ○: △-off is hardly recognized: × smearing is observed: setoff is intense (creation of the recording material -2～10) dye Y ₁ -1 in the recording material -1, Y ₁ - _{4, Y 1 -6, Y 1} -8, Y 1 -11, Y 1 -1
_{5, Y 1 -18, Y 1} -20, Y 1 -25, except that instead of Y ₁ -27 create a nine recording material -2～10 in the same manner as in Recording material -1, similar conditions , And a yellow image having excellent gradation was obtained.

These images and ink sheets were evaluated in the same manner as the recording material-1. The results are shown in Table 1.

(Preparation of Comparative Recording Materials-1 and 2) Two types of comparative recording materials were prepared in the same manner as recording material-1, except that dyes were replaced with comparative dyes A and B.
Image recording was performed under the same recording conditions. The obtained image and ink sheet were evaluated in the same manner as in recording material-1. The results are shown in Table 1.

[0072]

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[0073] Table 1 recording material color element Dmax chelate - DOO fixability lightfastness recording material No.-reactive save of the present invention _{1 Y 1 -1 1.76 ○ ○ 83} ○ 〃 2 Y ₁ -4 1.98 ○ ○ 91 ○ 〃 _{3 Y 1 -6 1.78 ○ ○ 82} ○ 〃 _{4 Y 1 -8 1.93 ○ ○ 87} ○ 〃 _{5 Y 1 -11 1.75 ○ ○ 85} ○ 〃 _{6 Y 1 -15 1.86 ○ ○ 82} ○ 〃 7 Y ₁ - 18 1.84 ○ ○ 85 ○ 〃 _{8 Y 1 -20 1.86 ○ ○ 85} ○ 〃 _{9 Y 1 -25 1.99 ○ ○ 87} ○ 〃 _{10 Y 1 -27 1.91 ○ ○ 87} ○ Comparative -1 A 1.43 △ × 74 × 〃 - 2B 1.41 △ △ 75 △ As can be seen from Table 1, the heat-sensitive transfer recording material of the present invention has excellent chelation reactivity, high-density image fixability,
A yellow image having excellent light fastness can be obtained, and the storage stability of the ink sheet is also good.

Example 2 The dye Y 1-1 of the recording material-1 in Example _{1 was} replaced with Y _{2-
1, Y 2 -4, Y 2} -5, Y 2 -7, Y 2 -10, Y 2 -13, Y 2 -1
5, Y ₂ -17, was replaced by Y ₂ -19 and Y ₂ -28 has created a recording material -11～20 in the same manner as in Example 1. When an image was recorded under the same conditions as in Example 1, a yellow image having excellent gradation was obtained in each case.

Table 2 shows the results of the same evaluations as in Example 1 for these images and ink sheets. Incidentally, the same recording materials-11 and 12 as the comparative recording materials-1 and 2 in Example 1 were used.

Table 2 Recording Materials Color Element Dmax Chelate Fixing Lightfastness Recording Material No. Reactivity Preservation of the Present Invention 11 Y ₂ −1 1.81 ○ 85 〃 12 Y ₂ -4 1.99 ○ 92 ○ 〃 _{13 Y 2 -5 1.77 ○ ○ 90} ○ 〃 _{14 Y 2 -7 1.92 ○ ○ 91} ○ 〃 _{15 Y 2 -10 1.78 ○ ○ 84} ○ 〃 _{16 Y 2 -13 1.85 ○ ○ 81} ○ 〃 17 Y ₂ - 15 1.95 ○ ○ 83 ○ 〃 18 Y ₂ -17 1.90 ○ ○ 84 ○ 〃 19 Y ₂ -19 1.91 ○ ○ 88 ○ 〃 20 Y ₂ -28 1.93 ○ ○ 86 ○ Compare -11 A 1.43 △ × 74 × 〃 − 12B 1.41 △ △ 75 △ It can be seen from Table 2 that the thermal transfer recording material of the present invention is excellent in chelation reactivity, and can obtain a yellow image with high density and excellent image fixability and light resistance. Moreover, it is understood that the preservability of the ink sheet is good.

[0077] The dye Y ₁ -1 recording material 1 in Example 3 Example 1 Y ₃ -
_{1, Y 3 -2, Y 3} -4, Y 3 -8, Y 3 -9, Y 3 -15 and Y ₃
Recording materials-21 to 27 were prepared in exactly the same manner as in Example 1 except that -18 was used. When an image was recorded under the same conditions as in Example 1, a yellow image having excellent gradation was obtained in each case.

(Preparation of Comparative Recording Materials-21, 22, and 23) Three types of comparative recording materials were prepared in the same manner as recording material-21, except that the dyes in recording material-21 were changed to comparative dyes C, D, and E. And image recording was performed under the same recording conditions. The same evaluation as that of the recording material-21 was performed on the obtained image and ink sheet. The results are shown in Table 3.

[0079]

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[0080] Table 3 recording material color element Dmax chelate - DOO fixability lightfastness recording material No.-reactive save of the present invention _{21 Y 3 -1 1.88 ○ ○ 85} ○ 〃 22 Y ₃ -2 1.75 ○ ○ 88 ○ 〃 _{23 Y 3 -4 1.90 ○ ○ 93} ○ 〃 _{24 Y 3 -8 1.73 ○ ○ 90} ○ 〃 _{25 Y 3 -9 1.83 ○ ○ 83} ○ 〃 _{26 Y 3 -15 1.79 ○ ○ 85} ○ 〃 27 Y ₃ - 18 1.73 ○ ○ 88 ○ Comparison -21 C 1.65 △ △ 72 △ 〃 -22 D 1.50 △ △ 73 △ 〃 -23 E 1.42 × × 65 × Also from Table 3, the thermal transfer recording material of the present invention is excellent. I understand.

Example 4 On the polyethylene terephthalate film used as a support in Example 1, a cyan image forming dye C-1 (weight
0.4 g / m ²⁾ thermal transfer layer containing a heat-sensitive transfer layer containing a magenta image-forming dye M-1 (the biasing amount 0.5 g / m ^2), the yellow of the present invention the dye Y ₁ -1 (with weight 0.5 g / creating the recording material -31 sequentially coating thermal transfer layer containing a m ^2). The binder of each heat-sensitive transfer layer was the same as that of Example 1 (the amount applied was 0.4 g / m ^{2 for} each layer).

[0082] In addition, the yellow of the recording material -31 dye Y ₁ -1
The Y ₂ recording material -32 in the same manner as in Recording material -31 except that instead of -1, further recording material -31 yellow dye Y ₁ -
1 was replaced by Y ₃ -1, and the cyan image forming dye C-1 was replaced by C
Recording material-33 was prepared in the same manner as recording material-31, except that -2 was used.

Next, a full-color image was prepared using the recording materials 31, 32, 33 and the same image-receiving material as in Example 1 using a full-color printer CP3000D manufactured by Nikon Corporation. Was obtained. Also, the stability of these images (fixing property, light fastness)
Was good.

[0084]

Embedded image

Example 5 An aqueous solution containing 5 g of a ball mill dispersion of p-toluamide, 7 g of polyvinylpyrrolidone, 3 g of gelatin, and 0.3 g of a hardening agent H-1 was formed on the recording material 31 of Example 4 as an intermediate layer.
l was applied so that the amount of p-tolu-amide was 0.5 g / m ² .

Further, on the intermediate layer, as a heat-fusible layer, the metal source shown in Example 1 (coating amount: 1.0 g / m ² ), UV inhibitor UV-1 (coating amount: 0.1 g / m ² ), antioxidant Agent AO-1
(With weight 0.1 g / m ²⁾ and ethylene - vinyl acetate copolymer (20% content of vinyl acetate, with the amount of 0.2 g / m ²⁾ Carnauba wax (with weight 2.0 g / m ²⁾ containing a hot-melt coating The recording material -41 was obtained.

In the same manner, a recording material-42 was obtained from recording material-32, and a recording material-43 was obtained from recording material-33.

Using these recording materials-41, 42 and 43 and the image-receiving material, full-color image recording was performed by a full-color printer in the same manner as in Example 4. The image receiving material was white plain paper. All of the obtained full-color images were good in color reproducibility, gradation, and image stability. Further, the preservability of each recording material was also good.

[0089]

Embedded image

[0090]

According to the present invention, a heat-sensitive transfer recording material having a high density and a high stability can be obtained by using a dye excellent in thermal diffusivity and chelate reactivity and having good storage stability. And a thermal transfer recording method capable of recording efficiently using the thermal transfer recording method.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are explanatory views showing an example of the thermal transfer recording method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Support, 2 ... Image receiving layer, 3 ... Image receiving material,
4 Support, 5 Thermal transfer layer, 6 Thermal transfer recording material, 7 Thermal head, 8 Heat generating resistor, 9 Thermal fusible layer, 10 ..Thermal transfer recording materials

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-94974 (JP, A) JP-A-4-89290 (JP, A) JP-A-4-82783 (JP, A) 89289 (JP, A) JP-A-4-97894 (JP, A) JP-A-3-256794 (JP, A) JP-A-59-78893 (JP, A) JP-A-60-2398 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38-5/40 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. The method of claim 1, wherein at least the following general formula (1)
A heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the formula: Embedded image [Wherein, R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₃ represents a cyano group, an acetyl group,-
Represents CONHR ₁₅ or —COOR ₁₅ (R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group). R ₁₄ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n ₁ represents an integer of 0 to 3. X ₁ is -O -, - S -, - N = or _{-N (R 16) - (R} 16
Represents represents) a hydrogen atom or an alkyl group, Z ₁ represents an atomic group necessary for forming an aromatic heterocyclic 5-6 membered together with X _1. ] 2. An image receiving material is superimposed on a thermal transfer recording material having a thermal transfer layer containing a dye represented by the general formula (1) according to claim 1 on a support, and heated in accordance with image information. An image is formed by a chelate dye formed by a reaction between the dye and a metal ion supply compound. 3. On a support, at least the following general formula (2)
A heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the formula: Embedded image [Wherein, R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₂ and R ₂₃ each represent a hydrogen atom, a halogen atom or a monovalent substituent. n ₂ represents an integer of 0 to 3. X ₂
Is -O -, - S -, - N = or -N (R ₂₄₎ - represents a (R ₂₄ represents a hydrogen atom or an alkyl group). Z ₂ is 5 with X ₂
It represents an atomic group necessary for forming a 6-membered aromatic heterocyclic ring. ] 4. An image-receiving material is superimposed on a heat-sensitive transfer recording material having a heat-sensitive transfer layer containing the dye represented by the general formula (2) according to claim 3 on a support, and heated in accordance with image information. An image is formed by a chelate dye formed by a reaction between the dye and a metal ion supplying compound. 5. On a support, at least the following general formula (3)
A heat-sensitive transfer recording material having a heat-sensitive transfer layer containing a dye represented by the formula: Embedded image [In the formula, Z ₃ represents an atom group necessary for forming a 5- to 6-membered aromatic heterocyclic ring together with 2 carbon atoms and X ₃ , and Z ₄ represents an aromatic carbon ring together with 2 carbon atoms. Represents a group of atoms to be formed. R ₃₁ and R ₃₂ each represent a hydrogen atom or a monovalent group, n ₃ and n ₄ each represent an integer of 1 to 5, and m represents an integer of 0 or 1. X ₃ is -O-, -S-, -N = or -N (R)-
(R represents a hydrogen atom or an alkyl group). ] 6. An image receiving material is superimposed on a thermal transfer recording material having a thermal transfer layer containing a dye represented by the general formula (3) according to claim 3 on a support, and heated in accordance with image information. An image is formed by a chelate dye formed by a reaction between the dye and a metal ion supplying compound.