JPH10264541A - Heat-sensitive transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a high density image having a high molar absorbance coefficient and a high sensitivity by a method wherein a layer containing at least one kind among coloring matters represented by specified formulae is provided on a support. SOLUTION: On the support, a layer containing a coloring matter represented by a formula I (henceforth expressed as an ink layer) is provided. In the formula I, Q represents a non-metal atom, which is necessary for forming an imidazole-, a pyrroloazole- and pyrazoloazole-ring, in combination with a carbon atom and A reoresents a formula II, in which R1 , R2 , R3 , R4 and R5 represent respectively hydrogen atom or non-valent-substituent, B1 and B2 represent respectively five-membered or six-membered aromatic cyclic residue or heterocyclic residue, (m) represents an integer of 0, 1 or 2 and (n) represents an integer of 1 or 2. An ink liquid is prepared by melting these coloring matters in solvent or dispersing in fine particles in resolvent such as alcohols or the like together with a binder made of a dissolvent-soluble polymer, applied on a support and dried by forming an ink layer. Thus, an image, which has a preferable color tone and an enough density and an excellent storage stability to light and heat, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material (hereinafter also referred to as a recording material) using an imidazoazole, pyrroloazole or pyrazoloazole methine dye having excellent color tone, high concentration and good stability. ).

[0002]

2. Description of the Related Art Thermal transfer recording has advantages such as easy operation and maintenance, reduction in size and cost of the apparatus, and low running cost.

In the thermal transfer recording of the thermal transfer system, a recording material capable of forming an image with high sensitivity and high density in order to form a color image is required, and various thermal transfer recording materials have been proposed. Japanese Patent Publication No. 4-44918 discloses a recording material using a merocyanine methine dye. The image obtained from this recording material has a good color tone, but has a problem in storage stability against heat and light,
Further, the recording material itself has a problem in storage stability over time.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal transfer recording material which solves the above-mentioned problems and needs of the prior art. That is, the first object of the present invention is to
An object of the present invention is to provide a heat-sensitive transfer recording material having a high molar extinction coefficient and a high sensitivity, and thus capable of forming a high-density image.
A second object is to provide a thermal transfer recording material capable of obtaining an image having excellent stability to heat and light, and a thermal transfer recording material having excellent storage stability.
A third object of the present invention is to provide a thermal transfer recording material capable of obtaining an image having a preferable color tone for color reproduction using a dye having a sharp spectral absorption, a small secondary absorption and a high molar extinction coefficient.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies and as a result, the object of the present invention is to provide a thermal transfer recording comprising at least one dye represented by the following general formula (1) on a support. The inventors have found out what can be achieved by the materials and completed the present invention.

[0006]

Embedded image

In the formula, Q represents a nonmetal atom necessary for forming an imidazoazole, pyrroloazole or pyrazoloazole ring together with a carbon atom, and A represents

[0008]

Embedded image

[0009] R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a monovalent substituent, and B ₁ and B ₂ each represent a 5- or 6-membered aromatic ring residue or heterocyclic ring. Represents a residue. m represents an integer of 0, 1 or 2, and n represents an integer of 1 or 2.

Hereinafter, the present invention will be described in more detail.

First, the dye represented by the general formula (1), which is a feature of the present invention, will be described.

In the general formula (1), the imidazoazole, pyrroloazole or pyrazoloazole ring formed from Q and a carbon atom may further have a substituent, and may have another carbon ring (such as a benzene ring or a cyclohexane ring). ) Or a heterocyclic ring (pyridine ring, pyrimidine ring, etc.) to form a condensed ring.

The substituent on the ring includes an alkyl group (methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, t-butyl, etc.), a halogenoalkyl group (chloromethyl, trifluoromethyl, etc.), a cycloalkyl group (Cyclopentyl, cyclohexyl, etc.), aralkyl groups (benzyl, 2-phenethyl, etc.), aryl groups (phenyl, naphthyl, p-tolyl, p-chlorophenyl, etc.),
Heterocyclic group (pyridyl, imidazolyl, thiazolyl, oxazolyl, benzimidazolyl, furyl, thienyl, etc.), acyl group (acetyl, propanoyl, butyroyl, etc.), arylcarbonyl group (benzoyl, etc.), alkylamino group (methylamino, ethylamino, Dimethylamino, diethylamino, morpholino, etc.), arylamino group (methylphenylamino), imide group (phthalimide, etc.), nitro group, cyano group, acylamino group (acetylamino, propionylamino, etc.), arylcarbonylamino group (benzoylamino, etc.) ), Alkoxy groups (methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, butylthio, etc.), arylthio groups (phenylthio, etc.) Sulfonylamino group (methanesulfonylamino, benzenesulfonylamino, etc.), ureido group (3-methylureide, 3,3-dimethylureide, etc.), sulfamoylamino group (dimethylsulfamoylamino, etc.), carbamoyl group (methylcarbamoyl , Ethylcarbamoyl, dimethylcarbamoyl, etc.),
Sulfamoyl group (ethylsulfamoyl, dimethylsulfamoyl, etc.), hydroxyl group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), alkylsulfonyl group (methanesulfonyl,
Butanesulfonyl), an arylsulfonyl group (eg, phenylsulfonyl), a halogen atom (eg, fluorine, chlorine, bromine), a sulfo group, a carboxyl group, a formyl group, and the like. These groups may be further substituted.

When there are a plurality of substituents, the respective substituents may be the same or different, and the substituents may be bonded to each other to form a ring.

More preferably, the substituent on the ring is a halogen atom, an alkyl group, a halogenoalkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, an arylcarbonyl group, an alkylamino group, an arylamino group. Group, cyano group, acylamino group, arylcarbonylamino group, alkoxy group, aryloxy group,
A carbamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. More preferably, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkyl group, an alkylamino group, an alkoxy group and a heterocyclic group, an acyl group having 2 to 11 carbon atoms, an acylamino group, a carbamoyl group and an alkoxycarbonyl group Group, carbon number 5
16 cycloalkyl groups, aryl groups having 6 to 17 carbon atoms, arylamino groups and aryloxy groups, 7 carbon atoms
To 17 aralkyl groups, arylcarbonyl groups and arylcarbonylamino groups.

The imidazoazole ring formed from Q and a carbon atom in the general formula (1) has the following general formula (1-1) or (1)
-2), the pyrroloazole ring is represented by the following general formula (1-3) or (1-4), and the pyrazoloazole ring is represented by the following general formula (1-
Those represented by 5) are preferred.

[0017]

Embedded image

[0018] wherein each Z _a, Z _b and Z _c, -N = or -C (R ₈₎ = represents each R _6, R ₇ and R ₈ are hydrogen atom or a monovalent substituent Represents

The monovalent substituent represented by R ₆ , R ₇ and R ₈ has the same meaning as the above-mentioned substituent on the imidazoazole, pyrroloazole or pyrazoloazole ring, and is more preferably a halogen atom. , Cyano group, alkyl group, halogenoalkyl group, cycloalkyl group, acyl group, acylamino group, alkoxycarbonyl group, aralkyl group, aryl group, heterocyclic group, arylcarbonyl group, arylcarbonylamino group, alkylamino group, arylamino Group, nitro group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ureido group, and carbamoyl group.

More preferably, a halogen atom, a cyano group,
An alkyl group having 1 to 10 carbon atoms, a halogenoalkyl group, an alkylamino group, an alkoxy group, and a heterocyclic group;
Acyl group, acylamino group, carbamoyl group and alkoxycarbonyl group, cycloalkyl group having 5 to 16 carbon atoms, aryl group having 6 to 17 carbon atoms, arylamino group and aryloxy group, aralkyl having 7 to 17 carbon atoms Group, arylcarbonyl group and arylcarbonylamino group.

The imidazoazole ring represented by the general formula (1-1) is more preferably a ring represented by the following general formula (2-1) or (2-2). The imidazoazole ring represented by the following general formula (2-3) or (2-4) is more preferable.

[0022]

Embedded image

[0023] In the formula, R _6, R ₇ and R ₈ are each synonymous with R _6, R ₇ and R ₈ in the general formula (1-1) and (1-2).

The pyrroloazole ring represented by the above general formula (1-3) is more preferably a ring represented by the following general formula (2-5) or (2-6). The pyrroloazole ring represented by the following general formula (2-7) or (2)
-8) is more preferable.

[0025]

Embedded image

In the formula, R ₆ , R ₇ and R ₈ have the same meanings as R ₆ , R ₇ and R _{8 in the} formula (1-3), respectively.

The pyrazoloazole ring represented by the above general formula (1-5) has the following general formula (2-9) or (2-10)
Are more preferable.

[0028]

Embedded image

In the formula, R ₆ and R ₈ have the same meanings as R ₆ and R _{8 in} formula (1-5), respectively.

Among the imidazoazole, pyrroloazole or pyrazoloazole rings formed from Q and carbon atoms in the general formula (1), a pyrazolotriazole ring represented by the general formula (2-9) is particularly preferred. .

A represents

[0032]

Embedded image

In the formula, the monovalent substituent represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ has the same meaning as the above substituent on the imidazoazole, pyrroloazole or pyrazoloazole ring, Those groups may be further substituted.

More preferably, a halogen atom, a cyano group,
Alkyl group, halogenoalkyl group, cycloalkyl group,
An aralkyl group, an aryl group, and a heterocyclic group. More preferred are a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms and a halogenoalkyl group, and a cycloalkyl group having 5 to 16 carbon atoms.

M is an integer of 0 to 2, preferably 0
Or 1, more preferably 0. n is 1 or 2
And preferably 1.

B ₁ and B ₂ each represent a 5- to 6-membered aromatic or heterocyclic ring, and may further have a substituent or a condensed ring on the ring.

Specific examples of the ring include benzene, 3H-
Pyrrole, oxazole, imidazole, thiazole,
3H-pyrrolidine, oxazolidine, imidazolidine,
Each ring includes thiazolidine, 3H-indole, benzoxazole, benzimidazole, benzothiazole, quinoline, pyridine and the like. These rings may further form a ring with another carbon ring (benzene ring, cyclohexane, etc.) or a heterocyclic ring (pyridine ring, pyrimidine ring, etc.).

The substituent on the ring has the same meaning as the substituent on the imidazoazole, pyrroloazole or pyrazoloazole ring, and these groups may be further substituted. Preferably an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an arylcarbonyl group, an alkylamino group, an arylamino group,
A nitro group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a ureido group, a carbamoyl group, and a halogen atom. When there are a plurality of substituents, each substituent may be the same or different, and the substituents may be bonded to each other to form a ring.

Of the dyes represented by the general formula (1), pyrazolotriazole dyes represented by the following general formulas (3-1) or (3-2) are particularly preferred.

[0040]

Embedded image

In the formula, R ₁ , R ₄ , R ₅ , R ₆ , R ₈ , B ₁ and B ₂ are the same as the above-mentioned R ₁ , R ₄ , R ₅ , R ₆ , R ₈ , B ₁
And B ₂ .

Hereinafter, specific examples of the dye represented by the general formula (1) (referred to as the dye of the present invention) are shown, but the present invention is not limited thereto.

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

These dyes can be synthesized by a known synthesis method. Hereinafter, typical synthesis examples will be described. In the synthesis scheme,
Ac ₂ O is acetic anhydride, MeOH is methanol, cHCl
Concentrated hydrochloric acid, PTS ^- represents p- toluenesulfonate anion.

Synthesis Example 1 (Synthesis of Illustrative Dye D-1)

[0053]

Embedded image

30 g of p-methoxyacetophenone (a)
Was dissolved in 400 ml of methanol, and 30.42 g of bromine was added dropwise over 1 hour while maintaining the internal temperature at 45 ° C. The mixture was stirred for 1 hour as it was, allowed to cool to room temperature, and the solvent was distilled off under reduced pressure. 30 ml of methanol was added to the residue to dissolve it, and the solution was dropped into water. The resulting crystals were collected by filtration and identified as compound (b) by NMR. Yield 22.4 g (42% yield).

[0071] 7.1 g of thiocarbohydrazide was suspended in 50 ml of ethanol, and 17.3 g of compound (b) was added.
The mixture was heated and stirred at 40 ° C. for 1 hour. The solvent was evaporated under reduced pressure, the residue was added water, was added portionwise sodium bicarbonate thereto until the pH of the solution is 8. The resulting viscous substance was removed, the aqueous solution was refrigerated, and the resulting crystals were collected by filtration. NM
From R, it was confirmed as compound (c). 7.5 g (yield 6)
0%).

4.2 g of compound (c) was added to acetonitrile 1
The suspension was suspended in 0 ml, trifluoroacetic anhydride was added, and the mixture was heated and refluxed for 1 hour. The resulting crystals were collected by filtration and confirmed as a compound (d) by NMR. Yield 4 g (72% yield).

3.74 g of compound (d) was added to 17 m of acetic anhydride.
and heated and refluxed for 1 hour. After cooling to room temperature,
The solvent was distilled off under reduced pressure, 25 ml of methanol and 3 ml of concentrated hydrochloric acid.
Was added, and the mixture was stirred at room temperature for 1 hour. After neutralization by adding sodium bicarbonate, the mixture was extracted with ethyl acetate, and the solvent was distilled off to obtain crude crystals. The crude crystals were purified by column chromatography to obtain a compound (e). It was identified as the target substance from NMR. Yield 1.2 g (36% yield).

1 g of the compound (e) was dissolved in 20 ml of toluene, and 1.16 g of the compound (f) and 0.37 of piperidine were dissolved.
g, and the mixture was heated and refluxed for 5 hours. The solvent is distilled off under reduced pressure,
Recrystallization from acetonitrile gave Exemplified Dye D-1.
It was confirmed as the target substance by NMR. Yield 0.68 g (yield 3
5%).

The UV-visible absorption spectrum of an acetone solution of this dye has an extremely sharp spectral absorption,
Secondary absorption was low.

Synthesis Example 2 (Synthesis of Exemplified Dye D-8)

[0061]

Embedded image

Compound (g) (50 g) was dissolved in toluene (400 ml).
And m-methylbenzoic acid chloride (h) was dissolved in 38.
6 g was added, and the mixture was heated and refluxed for 2 hours. After cooling to room temperature, 800 ml of water was added, and the aqueous phase was neutralized with potassium carbonate. The toluene layer was taken out, the solvent was distilled off under reduced pressure, 150 ml of acetonitrile was added to the residue, and the resulting crystals were collected by filtration. NMR confirmed that it was compound (i). Yield 32.7 g (58% yield).

Compound (i) (9.94 g) was dissolved in toluene 100
Then, 4.6 g of phosphorus oxychloride was added, and the mixture was heated and refluxed for 1 hour. Distill off the toluene and add methanol 50m
After the addition of 1 l, the mixture was poured into a 10% aqueous potassium hydrogen carbonate solution, and the resulting crystals were collected by filtration. NMR confirmed that it was compound (j). Yield 4.83 g (Yield 5
1%).

3.45 g of the compound (j) was dissolved in 20 ml of water, 5 ml of acetic acid was added, and the mixture was heated and refluxed for 1 hour. Neutralized with sodium hydroxide and the resulting crystals were collected by filtration. NMR
It was confirmed that it was Compound (k). Yield 1.5g
(Yield 57%).

Compound (k) 1.4 g, compound (l) 3.
34 g and 1.76 g of triethylamine in acetone 50
Then, the mixture was dissolved in ml and heated and refluxed for 1 hour. After distilling off the solvent,
The residue was purified by column chromatography. NM
It was confirmed from R that it was Exemplified dye D-8. Yield 0.
32 g (11% yield).

The ultraviolet-visible absorption spectrum of this dye solution in acetone was sharp with almost no secondary absorption in the visible light region.

Synthesis Example 3 (Synthesis of Illustrative Dye D-12)

[0068]

Embedded image

Compound (m) is the same as compound (k) in Synthesis Example 2.
It was synthesized by the same method as described above. 1.5 g of compound (m) and 1.1 g of p-dimethylaminocinnamaldehyde (n)
Was dissolved in 15 ml of toluene, and triethylamine 1.7 was dissolved.
6 g was added and the mixture was heated and refluxed for 1 hour. After evaporating the solvent, the residue was purified by column chromatography. NMR confirmed that this was Exemplified Dye D-12. Yield 1.3
g (56% yield).

The ultraviolet-visible absorption spectrum of a methanol solution of this dye was sharp with almost no secondary absorption in the visible light region.

Synthesis Example 4 (Synthesis of Exemplified Dye D-28)

[0072]

Embedded image

Compound (o) was synthesized in the same manner as for compound (k) in Synthesis Example 2 above. Compound (o) 3.
56 g and 7.5 g of the compound (p) were dissolved in 100 ml of toluene, and 2.22 g of triethylamine was added, followed by heating and reflux for 1 hour. After the solvent was concentrated under reduced pressure to about 1/3 under reduced pressure, it was left in a refrigerator overnight. The resulting crystals were collected by filtration and recrystallized from acetonitrile. NMR confirmed that this was Exemplified Dye D-28. 4.70 g (64% yield).

The ultraviolet-visible absorption spectrum of the acetone solution of this dye was extremely sharp with almost no secondary absorption in the visible light region.

Synthesis Example 5 (Synthesis of Exemplified Dye D-33)

[0076]

Embedded image

Compound (q) was synthesized in the same manner as for compound (e) described on page 21 of JP-A-4-35967. 3 g of the compound (q) and 3.6 g of the compound (r) were dissolved in toluene, and 1.57 g of piperidine was added.
Refluxed. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography. Recrystallized from acetonitrile. From NMR, it was confirmed to be the exemplified dye D-33. Yield 1.13 g (18% yield).

The ultraviolet-visible absorption spectrum of a methanol solution of this dye was sharp with almost no secondary absorption in the visible light region.

Synthesis Example 6 (Synthesis of Illustrative Dye D-37)

[0080]

Embedded image

Compound (s) was synthesized in the same manner as compound (b) described on page 28 of JP-A-4-359968. 4.2 g of the compound (s) and 3.7 g of the compound (t) were dissolved in toluene, and 1.78 g of piperidine was added, followed by heating and reflux for 2 hours. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and recrystallized from methanol. From NMR, it was confirmed to be the exemplified dye D-37. Yield 1.58 g (21% yield).

The UV-visible absorption spectrum of this dye in acetonitrile solution was sharp with almost no secondary absorption in the visible light region.

Synthesis Example 7 (Synthesis of Exemplified Dye D-45)

[0084]

Embedded image

Compound (u) was synthesized in the same manner as for compound (q). 3.8 g of compound (u), compound (t)
3.9 g was dissolved in toluene, 3.5 g of piperidine was added, and the mixture was heated and refluxed for 3 hours. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and then recrystallized from acetonitrile. NMR confirmed that this was Exemplified Dye D-45. 3.25 g (45% yield).

The UV-visible absorption spectrum of this dye in methyl ethyl ketone was sharp with almost no secondary absorption in the visible light region.

The case where the dye of the present invention is used as a thermal transfer recording material will be described. A dye-containing layer according to the present invention is provided on a support to form a dye-containing layer (hereinafter, referred to as an ink layer). The dyes may be used alone or in combination of two or more. Further, a dye other than the present invention, for example, an azomethine dye, an azo dye, an anthraquinone dye, or the like may be used in combination as long as the effects of the present invention are not impaired.

The content of the dye according to the present invention in the ink layer is preferably 0.05 to 10 g per 1 m ² of the support.

The ink layer is prepared by dissolving a dye together with a binder in a solvent or dispersing the dye in a fine particle form in a solvent to prepare an ink liquid for forming an ink layer. It is formed by adding fine particles, a dispersant, an antistatic agent, an antifoaming agent, an antioxidant, a viscosity adjusting agent, and the like, coating the mixture on a support, and appropriately drying the mixture. The thickness of the ink layer is preferably from 0.1 to 10 μm as a dry film thickness.

The binder is preferably a solvent-soluble polymer such as an acrylic resin, a 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 used is preferably 0.1 to ²⁰ g per 1 m ² of the support.

The organic solvent used for the ink liquid includes
Alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), aromatics (toluene, xylene, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), Ethers (such as tetrahydrofuran and dioxane);

The support is not particularly limited as long as it has good dimensional stability and can withstand the heating of the thermal head or the like during recording. However, thin paper such as condenser paper and glassine paper can be used.
A heat-resistant plastic film such as polyethylene terephthalate, polyamide, and polycarbonate is preferably used.

The thickness of the support is preferably from 2 to 30 μm. The support has an undercoat layer for the purpose of improving the adhesiveness with a binder and preventing the transfer and dyeing of the dye to the support. May be. Further, a slipping layer may be provided on the back surface of the support (the side opposite to the ink layer) for the purpose of preventing the thermal head from sticking to the support. If necessary, a heat-meltable layer may be provided on the ink layer.

To apply the recording material to thermal transfer recording capable of recording a full-color image, a cyan thermal transfer layer containing a cyan dye, a magenta thermal transfer layer containing a magenta dye, and a yellow thermal transfer layer containing a yellow dye 3
Preferably, the seeds are each applied in a face-to-face fashion. or,
If necessary, four types including a heat-sensitive transfer layer containing a black image-forming substance may be further provided.

The image receiving material for forming an image with the dye according to the present invention is generally paper, plastic film, or paper-
A plastic film composite is used as a support, on which an image receiving layer is formed of a polyester resin, a polyvinyl chloride resin, a copolymer resin of vinyl chloride and another monomer (such as vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate or the like. It is formed by forming a polymer layer composed of a kind or two or more kinds.

The image receiving material may contain an antioxidant, a releasing agent, a metal ion-containing compound and the like in the image receiving layer as needed, or a protective layer may be provided on the image receiving layer. Furthermore,
An intermediate layer may be provided between the support and the image receiving layer for the purpose of adhesion, heat insulation, or a cushion effect.

On the back surface (the side opposite to the image receiving layer) of the support, an antistatic layer and a back layer containing inorganic or organic non-sublimable fine particles for the purpose of preventing blocking may be provided. Further, an image receiving layer may be provided on both surfaces of the support. Further, the support itself can be used as the image receiving material.

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

Heating by a thermal head is generally used for the thermal transfer recording method. However, electric heating or heating using a laser may be used. The application of heat by a thermal head or the like may be performed from the ink layer side or the back side of the recording material or from the back side of the image receiving material without any particular limitation. In this case, the recording material is preferably from the back side.

[0100]

EXAMPLES The present invention will be described in more 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) Inks having a uniform solution containing a dye according to the present invention were obtained by mixing raw materials having the following compositions. The solubility of each dye was good, and the suitability for ink formation was also good.

Ink liquid composition dye (see Table 1) 1.2 g polyvinyl acetal resin (KY-24: manufactured by Denki Kagaku Kogyo) 2.3 g methyl ethyl ketone 53 g toluene 22 g silicon-modified urethane resin (SP-2105: manufactured by Dainichi Seika) 0.8 g (Preparation of recording material) The above ink was applied onto a 6 μm-thick polyethylene terephthalate (PET) base using a wire bar so that the applied amount after drying was 2.0 g / m ² , followed by drying. A thermal transfer recording material having an ink layer on a PET base was prepared. Drying was performed for 15 minutes in a 70 ° C. oven after preliminary drying with a drier.

On the back surface of the PET base, a silicon-modified urethane resin (SP) was used as a sticking prevention layer.
-2105: above).

(Preparation of Image Receiving Material) Synthetic paper having a thickness of 150 μm (product name: Yupo FPG-150: manufactured by Oji Yuka)
An ester-modified silicon (X-24-) was formed thereon as an image receiving layer.
8300: polyvinyl butyral resin (S-LEC BX-1) containing Shin-Etsu Chemical Co., Ltd., weight 0.3 g / m ² )
(Manufactured by Sekisui Chemical Co., Ltd.) was applied and dried to a coating weight of 6 g / m ² to obtain an image receiving material. Drying was carried out in a 100 ° C. oven for 15 minutes after temporary drying with a drier.

(Thermal Transfer Recording Method) The recording material was superimposed on the image receiving material, and a thermal head was applied from the back side of the recording material to perform image recording under the following recording conditions to obtain a dye image.

(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 and 0.2 msec. The heat-sensitive transfer images according to the present invention and comparative heat-sensitive transfer images were obtained in the same manner as described above, except that the dye according to Comparative Example 1 was changed to Comparative Dye A (Samples 1 to 16).

The color tone, maximum density, storage stability (light fastness and heat resistance) of the obtained image and storage stability of the recording material were evaluated by the following methods. Table 1 shows the evaluation results.

<< Color Tone >> The quality of the color tone was classified into three grades of a color tone that is practically preferable (）), a color tone that is practically no problem (△), and a bad color tone (x), and evaluated visually.

<< Maximum Density >> The maximum reflection density of an image (usually, the portion where the application time is the maximum) was measured by X-write 310TR.

<< Light Resistance >> The dye image was irradiated with light using a xenon fade meter for 72 hours, and the density before light irradiation was defined as D ₀ , and the density after light irradiation was defined as D _{1, which} was determined as (D ₁ / D ₀ ) × 100. It was evaluated by the residual dye rate (%).

<< Heat Resistance >> A dye image was formed at 77 ° C. and 10% RH.
The solution was stored for 7 days under the following conditions. The density before storage was D ₀ , and the density after storage was D ₂ , (D ₂ / D ₀ ) × 100.
The evaluation was based on the residual dye ratio (%) determined in the above.

(Storage Stability of Recording Material) The prepared recording material was allowed to stand at 60 ° C. for 100 hours, and the image-receiving material was rubbed against the ink layer after storage.
A three-stage evaluation was made in which a slight transition was indicated by 、 and a considerable transition was indicated by ×.

[0113]

[Table 1]

[0114]

Embedded image

As is clear from Table 1, the dye image formed from the thermal transfer recording material of the present invention has a preferable color tone, has a sufficient maximum density, and has excellent storage stability against light and heat. That is, the recording material of the present invention is a thermal transfer recording material having excellent storage stability.

Example 2 On the PET base used as the support in Example 1, the following yellow image forming dye Y-1 (0.5 g /
m ² ), the magenta image forming dye (D-1) according to the present invention (coating amount 0.5 g / m ² ), and the cyan image forming dye C-1 (coating amount 0.5 g / m ² ). 5g /
The recording material was prepared by applying an ink layer containing m ² ) in a surface-sequential manner. The binder used in each ink layer was the same as that used in Example 1.

Thereafter, the image receiving material and the recording material used in Example 1 were laminated, and a full-color printer CP30 manufactured by Nikon was used.
A full-color image was recorded by 00D, and a full-color image excellent in color reproducibility was obtained.

[0118]

Embedded image

[0119]

According to the present invention, there can be provided a heat-sensitive transfer recording material which forms an image having excellent storage stability against color tone, light and heat, and also has excellent storage stability of the recording material itself.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Mari Mari Honda, 1st Sakuramachi, Hino-shi, Tokyo In-house (72) Inventor Akira Onishi 1st Sakuramachi, Hino-shi, Tokyo In-house Konica Incorporated

Claims (4)

[Claims] 1. A heat-sensitive transfer recording material comprising a support containing at least one dye represented by the following general formula (1). Embedded image [In the formula, Q represents a group of nonmetallic atoms necessary for forming an imidazoazole, pyrroloazole or pyrazoloazole ring together with a carbon atom, and A represents Represents R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a monovalent substituent, and B ₁ and B ₂ each represent a 5- or 6-membered aromatic ring residue or heterocyclic ring. Represents a residue. m is 0, 1
Or n represents an integer of 2, and n represents an integer of 1 or 2. ] 2. An imidazoazole, pyrroloazole or pyrazoloazole ring formed by Q and a carbon atom in the general formula (1) is represented by the following general formulas (1-1), (1-2),
The heat-sensitive transfer recording material according to claim 1, which is represented by (1-3), (1-4) or (1-5). Embedded image Wherein each Z _a, Z _b and Z _c, -N = or -C
(R ₈ ) =, and R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a monovalent substituent. ] 3. An imidazoazole, pyrroloazole or pyrazoloazole ring formed by Q and a carbon atom in the general formula (1) is represented by the following general formulas (2-1), (2-2),
(2-3), (2-4), (2-5), (2-6),
(2-7), (2-8), (2-9) or (2-10)
The heat-sensitive transfer recording material according to claim 1, which is represented by the following formula. Embedded image Wherein R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a monovalent substituent. ] 4. A heat-sensitive transfer recording material comprising a support containing at least one dye represented by the following general formula (3-1) or (3-2). Embedded image [Wherein R ₁ , R ₄ , R ₅ , R ₆ and R ₈ each represent a hydrogen atom or a monovalent substituent, and B ₁ and B ₂ each represent a 5- or 6-membered aromatic ring residue. Represents a group or a heterocyclic residue. ]