JPH0570704A - Imidazole azomethine dye and thermal transfer dye-donating material containing the same - Google Patents

Abstract

PURPOSE:To prevent an imidazole azomethine dye useful for image formation of as a filter from fading or discoloring in a short time period. CONSTITUTION:An imidazole azomethine dye represented by the formula and a thermal transfer dye-donating material containing the same. In the formula, R<1> to R<4> each is hydrogen or a group of nonmetallic atoms, R<5> and R<6> each is hydrogen, an alkyl, an aryl, or a heterocyclic group, and A and B each is hydrogen or a nonmetallic substituent, provided that B is not phenyl.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an imidazole azomethine dye having excellent absorption characteristics and high light and heat fastness.
And a thermal transfer dye-donor element containing the same.

[0002]

2. Description of the Related Art Azomethine dyes, especially azomethine dyes having a p-dialkylaminophenyl group bonded to the nitrogen atom of an imine, are oxidative coupling reactions of active methylenes and phenols with N, N-dialkyl-p-phenylenediamines. Is widely used as an image-forming dye in a silver halide color photographic light-sensitive material that uses a subtractive method by mixing three colors of yellow, magenta, and cyan because it has a wide variety of color tones such as yellow, red, magenta, blue, and cyan. Has been done. A blue or cyan dye is formed from phenols, naphthols, 2,4-diphenylimidazoles, etc., and 5-pyrazolones, acylacetonitriles, 1H-pyrazolo [1,5
-A] benzimidazoles, 1H-pyrazolo [5,1
-C] -1,2,4-triazoles, 1H-pyrazolo [2,3-b] -1,2,4-triazoles and the like form magenta or blue dyes, and acylacetanilides and diacylmethanes A yellow dye is formed from malondianilides. Such dyes are described in JP-A-60-186567 and 63-14528.
1 and 63-113077. In recent years, new color image forming methods such as color electrophotography, ink jet method, and thermal transfer method have been proposed. On the other hand, along with the development of electronic imaging, there is a demand for filters for solid-state image pickup tubes and color liquid crystal televisions. As a result, azomethine dyes have been applied and studied not only for color photography but also in various systems or products. The imidazole azomethine dye has a sharp absorption waveform and small unwanted absorption on the short wave side.
It has an ideal absorption property as a dye for image formation and a dye for filters.
No. 1, JP-A-1-110565, JP-A-2-28264,
No. 2-53865, No. 2-53866, No. 2-66
No. 8, No. 2-155693, No. 2-181747.

[0003]

However, the fastness of these known imidazole azomethine dyes is not sufficient. Therefore, for example, when these dyes are used as an image forming dye, there is a drawback that the image is discolored or discolored in a short period of time. Further, when these dyes are used as a filter dye, there is a drawback that the durability is insufficient. As described above, development of an imidazole azomethine dye having high fastness has been strongly desired. In order to solve the above problems, the present inventor has conducted earnest research on the relationship between the structure of an imidazole azomethine dye and light fastness. As a result, they have found that an imidazole azomethine dye having a specific structure which has not been known so far has high light fastness. It was also found that when this dye was used as a dye for thermal transfer, it showed excellent transferability, sharp absorption and high light fastness, and that an excellent thermal transfer dye-donating material was obtained. Further, they have found that when an imidazole azomethine dye and other dyes are mixed to prepare a thermal transfer dye-donor material, an image having ideal absorption characteristics as an image-forming dye is provided and the stability of the image over time is also improved. It was In addition, mixed use is
It has also been found to improve the stability over time of thermal transfer dye-donor elements. The present inventors have completed the present invention based on the above findings.

The object of the present invention is to provide a completely new imidazole azomethine dye which has hitherto been unknown. Another object of the invention is to have a sharp absorption,
An object is to provide an imidazole azomethine dye having high fastness to heat, light, moisture, air and chemicals. Another object of the present invention is to provide an imidazole azomethine dye that is easy to synthesize and easily available. Another object of the present invention is to provide a thermal transfer dye-donor element that provides an image with improved fastness. Another object of the invention is to provide a thermal transfer dye-donor element that provides an image with improved stability over time. Another object of the invention is to provide a thermal transfer dye-donor element with improved stability over time.

[0005]

The above objects of the present invention have been achieved by an imidazole azomethine dye represented by the following general formula (I).

[0006]

[Chemical 3]

In the formula (I), R ¹ , R ² , R ³ and R ⁴
Each independently represent a hydrogen atom or a non-metal atomic group. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. A and B
Are each independently a hydrogen atom or a non-metal substituent. However, B is not a substituted or unsubstituted phenyl group. R ¹ and R ² , and / or R ² and R ⁵ , and / or R ⁵ and R ⁶ , and / or R ⁶ and R ³ , and / or R ³ and R ⁴ are bonded to each other to form a ring structure. It may be formed.

Among them, the imidazole azomethine dye in which A is an aryl group or a heterocyclic group more preferably achieved the above object.

Further, the above-mentioned object of the present invention is a thermal transfer dye-donating material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer is an imidazole azomethine dye represented by the following general formula (I). Was achieved by a thermal transfer dye-donor element characterized by containing at least one of

[0010]

[Chemical 4]

In the formula (I), R ¹ , R ² , R ³ and R ⁴
Each independently represent a hydrogen atom or a non-metal atomic group. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. A and B
Are each independently a hydrogen atom or a non-metal substituent. However, B is not a substituted or unsubstituted phenyl group. R ¹ and R ² , and / or R ² and R ⁵ , and / or R ⁵ and R ⁶ , and / or R ⁶ and R ³ , and / or R ³ and R ⁴ are bonded to each other to form a ring structure. It may be formed.

Among them, the above-mentioned object is more preferably achieved by the thermal transfer dye-donating material containing an imidazole azomethine dye in which A is an aryl group or a heterocyclic group.

Furthermore, when the imidazole azomethine dye of the present invention is used in the thermal transfer dye-donor material, it is preferable to use it in combination with other dyes, rather than using only a single dye, in terms of color reproduction. , The maximum concentration is high,
It has been found that the thermal transfer dye-donor element and the formed image have excellent stability over time, and the above object has been achieved particularly preferably.

The general formula (I) will be described in detail below.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a nonmetallic atomic group, and the nonmetallic atomic group is an alkyl group (preferably having 1 to 3 carbon atoms).
0, for example, methyl, ethyl, propyl, butyl), an alkoxy group (preferably having 1 to 30 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy),
Halogen atom (eg bromine, fluorine, chlorine), acylamino group [preferably alkylcarbonylamino group having 1 to 30 carbon atoms (eg formylamino, acetylamino,
Propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (preferably carbon). Number 2
To 30, for example, methoxycarbonyl, ethoxycarbonyl), cyano group, sulfonylamino group (preferably having 1 to 30 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), carbamoyl group [preferably having 2 carbon atoms]. ~ 30 alkylcarbamoyl groups (eg methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxy) Carbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl Phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl), preferably an arylcarbamoyl group having 7 to 30 carbon atoms ( For example, phenylcarbamoyl, p-toluylcarbamoyl, m-methoxyphenylcarbamoyl, 4,5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), preferably 4 carbon atoms
To 30 heterylcarbamoyl groups (eg 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methylphenyl)) 1, 3, 4
-Thiadiazolylcarbamoyl)], a sulfamoyl group (preferably having a carbon number of 0 to 30, such as methylsulfamoyl, dimethylsulfamoyl), an aminocarbonylamino group (preferably having a carbon number of 1 to 30, such as methylaminocarbonylamino, Dimethylaminocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino), hydroxy group, carboxylic acid group (including salts thereof), sulfonic acid group (including salt thereof) ) And amino groups (including anilino groups and quaternary amino groups, for example, amino, dimethylamino, diethylamino).

Preferred among R ² , R ³ and R ⁴ is a hydrogen atom. Preferred among R ¹ are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom (fluorine, chlorine, bromine),
An acylamino group having 1 to 30 carbon atoms, a sulfonylamino group having 1 to 30 carbon atoms, an aminocarbonylamino group having 1 to 30 carbon atoms, and an alkoxycarbonylamino group having 2 to 30 carbon atoms. Of these, R ¹ is most preferably an acylamino group.

R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 30, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-
Methoxyethyl, 3-methoxypropyl, ethoxyethyl, 2-phenylethyl, 2-cyanoethyl, cyanomethyl, 2-chloroethyl, 3-bromopropyl, 2-methoxycarbonylethyl, 3-ethoxycarbonylpropyl, 2- (N-methylamino) Carbonyl) ethyl, 3
-(N, N-dimethylaminocarbonyl) propyl, 2
-Acetylaminoethyl, 3- (ethylcarbonylamino) propyl, 2-acetyloxyethyl, allyl, homoallyl, prenyl, n-dodecyl), an aryl group (preferably having 6 to 30 carbon atoms such as phenyl, p-tolyl, p). -Methoxyphenyl, 2,4-dichlorophenyl, p-nitrophenyl, 2,4-dicyanophenyl,
2-naphthyl) or a heterocyclic group (including those having a substituent. Preferably, it has 3 to 30 carbon atoms, for example, the following chemical formula 5
Represents a group).

[0018]

[Chemical 5]

Preferred among R ⁵ and R ⁶ are optionally substituted alkyl groups having 1 to 30 carbon atoms (eg, methyl, ethyl, propyl, 2-cyanoethyl, 2-acetyloxyethyl, 2-ethoxycarbonyl). Ethyl, 2-
Methoxyethyl, allyl). The ring which R ⁵ and R ⁶ may combine to form, for example,
And the ring which R ² and R ⁵ and / or R ³ and R ⁶ may combine to form, for example, a group shown in the following chemical formula 7 Can be mentioned.

[0020]

[Chemical 6]

[0021]

[Chemical 7]

A represents a hydrogen atom or a non-metal substituent. More specifically, A is a hydrogen atom, aryl group, heterocyclic group, alkyl group, cyano group, carboxyl group, acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, alkoxycarbonylamino group, aryl. Oxycarbonylamino group, sulfonylamino group, aminocarbonylamino group,
It represents a sulfamoylamino group, an amino group (including anilino group), an alkoxy group, an aryloxy group, a silyloxy group, a heteryloxy group, an alkylthio group, an arylthio group, a heterylthio group and the like. Specific examples of A include a hydrogen atom and an aryl group (preferably having 6 to 3 carbon atoms).
0, for example phenyl, m-acetylaminophenyl, o
-Acetylaminophenyl, p-methoxyphenyl),
Alkyl group (preferably having 1 to 30 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, n-octyl, n-dodecyl), cyano group, carboxyl group, acyl group (preferably having 1 to 30 carbon atoms, for example, Acetyl,
Pivaloyl, benzoyl, furoyl, 2-pyridyl),
Carbamoyl group (preferably having 1 to 30 carbon atoms such as methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl), alkoxycarbonyl group (preferably having 1 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl). , An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, for example, phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), an acylamino group [preferably an alkylcarbonyl having 1 to 30 carbon atoms. An amino group (eg, formylamino, acetylamino, propionylamino, cyanoacetylamino),
Preferably an arylcarbonylamino group having 7 to 30 carbon atoms (for example, benzoylamino, p-toluylamino,
Pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a C4-30 hetarylcarbonylamino group (for example, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], an alkoxycarbonylamino group (preferably Represents 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p- Methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino, o-chlorophenoxycarbonylamino), a sulfonylamino group (preferably having a carbon number of 1 to 1).
30, for example, methanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), an aminocarbonylamino group (preferably having 1 to 30 carbon atoms, such as methylaminocarbonylamino, ethylaminocarbonylamino, anilinocarbonylamino, dimethylaminocarbonylamino). , A sulfamoylamino group (preferably having a carbon number of 1 to 30, such as methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), an amino group (including an anilino group, preferably having a carbon number of 0 to 30, such as amino , Methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, anilino), alkoxy groups (preferably having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, n-butoxy, Tokishietokishi, n- dodecyloxy), an aryloxy group (preferably 6-3 carbon atoms
0, for example, phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), a silyloxy group (preferably having 3 to 30 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, cesyldimethylsilyloxy, phenyldimethyl). Silyloxy), heteryloxy groups (preferably having 3 to 3 carbon atoms)
0, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), an alkylthio group (preferably having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-butylthio, t-
Butylthio), arylthio groups (preferably having 6 to 6 carbon atoms)
30, for example, phenylthio), a heterylthio group (preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2-
(1,3-benzoxazolyl) thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1-
(3-N-octadecylcarbamoyl) phenyl-1,
2,3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having 3 to 30 carbon atoms, for example, a group represented by the following chemical formula 8, a group represented by the following chemical formula 9, a group represented by the following chemical formula 10, In addition to the group represented by the following chemical formula 11 and the group represented by the following chemical formula 12, further examples include pyrrolyl, thiazolyl, imidazolyl, isoxazolyl, isothiazolyl, pyrazolyl, furazyl, pyrimidyl, indolyl) and the like.

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical formula 12]

In the groups shown in Chemical formulas 8 to 12, R ¹¹ represents a hydrogen atom or a nonmetallic atomic group, and n represents an integer of 1 to 4. Specific examples of R ¹¹ include those mentioned for R ¹ in formula (I).

Of these, A is preferably an aryl group or a heterocyclic group. These aryl groups and heterocyclic groups are
It may be substituted with a substituent or may be unsubstituted. When it is substituted, it is preferably substituted with an electron-withdrawing group having a Hammett's substituent constant sigma para (σ _p ) value of +0.2 or more.

Among the heterocyclic groups, those represented by the following chemical formula 13 are advantageous in that they can be synthesized by a synthetic method different from the usual synthetic method of imidazoles.

[0031]

[Chemical 13]

In the chemical formula 13, R ¹¹ and R ¹¹ 'represent a substituent. R ¹¹ is preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group. R ¹¹ ′ is preferably a substituent having a Hammett's substituent constant sigma para (σ _p ) value of +0.2 or less.

R ¹¹ and R ¹¹ ′ will be described in more detail. R ¹¹ ′ is preferably a substituent having a Hammett's substituent constant σ _p of +0.2 or less, and more specifically, a hydrogen atom, a fluorine atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group. , Heterocyclic oxy groups, alkylthio groups, acylamino groups, sulfonamide groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, ureido groups, sulfamoylamino groups, anilino groups, azolyl groups, hydroxyl groups and the like.

More specifically, it is a hydrogen atom, a fluorine atom or an alkyl group (for example, a straight chain or branched chain alkyl having 1 to 35 carbon atoms, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl. More specifically, for example. , Methyl, ethyl, isopropyl, t-butyl, decyl, 4-phenylbutyl, vinyl, ethynyl, allyl, cyclohexyl, cyclohexenyl), an aryl group (for example, phenyl, naphthyl, 4-t-butylphenyl, 4-). Hydroxyphenyl, 4-methylaminophenyl, 2-dimethylaminophenyl, 2-methoxyphenyl, 2,4,6-trimethylphenyl, 4-tetradecanamidophenyl, 4-methoxyphenyl, 2,
6-dimethoxyphenyl), a heterocyclic group (eg 2-furyl, 2-thienyl, 3-furyl, N-methyl-2-pyrrolyl), an alkoxy group (eg methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy,
2-methanesulfonylethoxy, isopropoxy), an aryloxy group (for example, phenoxy, 2-naphthoxy,
2-methylphenoxy, 2-methoxyphenoxy, 4-
t-butylphenoxy), a heterocyclic oxy group (for example, 1
-Phenyltetrazole-5-oxy, tetrahydropyranyloxy), an alkylthio group (e.g. methylthio,
Octylthio, tetradecylthio, phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), acylamino groups (eg acetamide, benzamide, tetradecanamide,
2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxybenzenesulfonyl) phenoxy} decanamide), sulfone Amide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-
Methoxy-5-t-butylbenzenesulfonamide),
An alkoxycarbonylamino group (eg methoxycarbonylamino, tetradecyloxycarbonylamino),
An aryloxycarbonylamino group (for example, phenoxycarbonylamino), a ureido group (for example, phenylureido, methylureido, N, N-dibutylureido),
Sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), anilino group (for example, phenylamino,
2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5
-{2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), azolyl group (eg imidazolyl, pyrazolyl, 3-chloropyrazole-1)
-Yl, triazolyl), and a hydroxyl group.

R ¹¹ ′ is preferably a substituent having a Hammett's substituent constant σ _{p in} the range of −0.4 to +0.1, more preferably a hydrogen atom in which σ _p is a group within the above range. , An alkyl group, an aryl group, an alkoxy group, an aryloxy group or an acylamino group.

R ¹¹ preferably represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group. Specific examples thereof include an alkyl group (eg, methyl, ethyl, iso-propyl, t-butyl, dodecyl, methoxyethyl) and an aryl group (eg, R ¹¹ ′).
In addition to the groups shown in, 4-chlorophenyl, 2,4-dichlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, 4-trifluoromethylphenyl, pentafluorophenyl, 3-bromophenyl , 3-nitrophenyl, 4-methoxycarbonylphenyl, 4-benzenesulfonylphenyl, 3
-Benzoylphenyl, 3-methanesulfonylphenyl), a heterocyclic group (for example, the group represented by R ¹¹ ′,
2-pyridinyl, 4-pyridinyl, 4-methoxycarbonylpyridin-2-yl, 1,3-diazin-2-yl, 1,3,5-triazin-2-yl), an alkoxy group (eg, at R ¹¹ ′) In addition to the groups shown, 1-ethoxycarbonylmethoxy, trifluoromethoxy, 2,2,2
-Trifluoroethoxy, 1-benzenesulfonylmethoxy), an aryloxy group (for example, the group represented by R ¹¹ ', 4-ethoxycarbonylphenoxy, 3,5-
Dichlorophenoxy, tetrafluorophenoxy, 4-
Benzenesulfonylphenoxy) may be mentioned. More preferably, R ¹¹ is an alkyl group or an aryl group, and particularly preferably an aryl group.

B represents a hydrogen atom or a non-metal substituent. However, B is not a substituted or unsubstituted phenyl group.
Specific examples of B include R ¹ , R ² , R ³ , R ⁴ and A.
The above mentioned can be mentioned. B is preferably an alkyl group (preferably having 1 to 30 carbon atoms, for example,
Methyl, ethyl, isopropyl, trifluoromethyl,
t-butyl), oxycarbonyl group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenoxycarbonyl), aminocarbonyl group (preferably having 1 to 3 carbon atoms).
0, for example, methylaminocarbonyl, ethylaminocarbonyl, anilinocarbonyl), an acylamino group (preferably having a carbon number of 1 to 30, such as acetylamino, pivaloylamino, benzoylamino), an oxycarbonylamino group (preferably having a carbon number of 2). 30, for example, methoxycarbonylamino, ethoxycarbonylamino, t
-Butoxycarbonylamino, phenoxycarbonylamino), aminocarbonylamino group (preferably having 1 to 30 carbon atoms, for example, aminocarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, dimethylaminocarbonylamino, anilinocarbonylamino), Sulfonyl group (preferably having 1 to 3 carbon atoms
0, for example, methanesulfonyl, benzenesulfonyl), an acyl group (preferably having 1 to 30 carbon atoms, for example,
Acetyl, pivaloyl, benzoyl), a heterocyclic group (preferably having 3 to 30 carbon atoms, examples of which include those mentioned in A), and a cyano group. Among these,
B is more preferably an alkyl group, an acylamino group, an oxycarbonylamino group, an aminocarbonylamino group, an acyl group or a sulfonyl group. Of these, an alkyl group (having 1 to 30 carbon atoms) is most preferable.

When the dye of the present invention is used for thermal transfer, the substituent is preferably selected so that the molecular weight of the dye is 700 or less. More preferably, the molecular weight is 6
00 or less is selected.

Here, the Hammett's substituent constant used in the present specification will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L. et al. P. Hammett
This is a rule of thumb advocated by, which is widely accepted today. Substituent constants obtained by the Hammett's law include σ _p values and σ _m values, and these values can be found in many general textbooks.
A. Dean, “Lange's Handbook”
of Chemistry ", 12th Edition, 1979 (McGraw-Hill) and" Chemical Areas "special edition, 1
No. 22, pp. 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value found in the above-mentioned book. It goes without saying that, even if the value is unknown in the literature, it also includes a substituent that may be included in the range when measured based on Hammett's rule. In the future, the σ _p value and the σ _m value will have this meaning.

The dye of the present invention may have an atomic group having an effect of suppressing fading in the dye molecule. It is particularly preferable when high image fastness is required. An atomic group having an effect of suppressing fading is R ¹ of a dye,
It may be bonded to any position of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , A and B. As the atomic group having an effect of suppressing fading, all those described in JP-A-3-205189 can be used. Specific examples of the atomic group having an effect of suppressing fading are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

Specific examples of the dye compound of the present invention are shown below, but the present invention is not limited thereto.
In the following specific examples, Ph represents a phenyl group and tB
u is t-butyl group, Et is ethyl group, iPr is i-
Propyl group and nPr represent n-propyl group. [Compound example]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

[0054]

[Chemical formula 26]

[0055]

[Chemical 27]

Some of the dyes of the present invention have too sharp absorption when used alone, which is disadvantageous in color reproduction of a color image. Therefore, it is preferable for color reproduction that one of the dyes of the present invention is mixed with another dye having a different absorption maximum wavelength. The two kinds of dyes mixed and used as described above may have different absorption maximum wavelengths from each other. Therefore, if the absorption maximum wavelengths are different from each other, the general formula (I) of the present invention is used.
It is also possible to use a mixture of two kinds of dyes included in
More specifically, in the case of the dye of the present invention having an absorption maximum wavelength of about 650 nm, the absorption gap of the magenta dye becomes large, and reproduction of highly pure blue becomes disadvantageous. On the other hand, in the case of the dye of the present invention having an absorption maximum wavelength of about 620 nm, there is little absorption on the longer wavelength side than 650 nm, and the amount of cyan dye used must be increased in order to reproduce black,
The high ε (molar absorption coefficient), which is an advantage of the dye of the present invention, cannot be utilized. Further, there is a drawback that the dependency of irradiation light on the gray balance of an image becomes large. In the present invention, that the absorption maximum wavelengths are different from each other means that the absorption maximum wavelengths of the two kinds of dyes are separated by 5 nm or more. And the difference between the maximum absorption wavelengths of the two dyes is 10 to 5
A combination of dyes that is 0 nm is preferred to achieve the purpose. When the dye of the present invention is used alone in a thermal transfer dye-donor material, the storability of the thermal transfer dye-donor material (precipitation of dye crystals) or the storability of an image formed on the thermal transfer dye-image receiving material (bleeding with time) ) Had some problems. Therefore, it is preferable to use one kind of the dye of the invention and at least one other dye having a different structure in order to solve the above problems. The two kinds of dyes mixed and used for the purpose of improving the storage stability may be those having different structures. Therefore, two kinds of dyes included in the general formula (I) of the present invention can be mixed and used as long as they have different structures. When the dye of the present invention and another dye are mixed and used, the use ratio may be any ratio. When two kinds of dyes having different absorption maximum wavelengths are mixed and used for the purpose of improving color reproduction of a color image, the absorption characteristics obtained by mixing are the blocking dyes required for so-called image forming dyes. It suffices to select a dye mixing ratio that is as close as possible to the absorption characteristics. On the other hand, when two kinds of dyes having different structures are mixed and used for the purpose of improving the storability of a color image with time, the mixture ratio of the two kinds of dyes has the lowest melting point or two kinds of dyes. A mixing ratio that maximizes the solubility of the dye in a solvent (eg, ethyl acetate, methyl ethyl ketone, etc.) may be selected. The most suitable mixing ratio is usually 1: 3 by weight, for the purpose of improving color reproduction or storability.
It is often in the range of 3: 1 to 3: 1. Therefore, the mixing ratio of the dyes is preferably in the range of 1: 3 to 3: 1 by weight.
Even when three or more kinds of dyes are mixed, the preferable mixing ratio can be selected in the same manner as in the case of mixing the above two kinds. As the dye used in combination with the dye of the present invention, those represented by the following general formulas (II) and (III) are preferable.

[0057]

[Chemical 28]

In the formulas (II) and (III), R ¹² represents a hydrogen atom or a non-metal atomic group. Specific examples thereof include those described for R ¹ in the general formula (I). R
¹ , R ² , R ³ and R ⁴ are R ¹ , R ² and R ^{1 in the} general formula (I),
It has the same meaning as that represented by R ³ and R ⁴ . Specific examples,
The preferred examples are also the same. R ¹³ and R ¹⁴ represent a hydrogen atom or a non-metal atomic group. Specific examples thereof include those described for R ¹ in the general formula (I). R ¹³
And R ¹⁴ may combine with each other to form a ring structure. Specific examples thereof include those that form a benzene ring,
The thing which forms a nitrogen-containing heterocycle can be mentioned.
X represents -OH or -NR ⁵ R ^6. R ⁵ , R
⁶ has the same meaning as that represented by R ⁵ and R ^{6 in} formula (I). The specific example and the preferable example are also the same.

Further, as another preferable dye to be mixed with the dye of the present invention, a dye represented by the following general formula (IV) can be mentioned.

[0060]

[Chemical 29]

In the formula (IV), R ¹⁵ and R ¹⁶ represent a hydrogen atom or a non-metal substituent. Specific examples thereof include those described for A in the general formula (I). R ¹⁵ ,
R ¹⁶ is preferably an aryl group or a heteroaromatic ring group.
R ¹ , R ² , R ³ and R ⁴ are each R ¹ of the general formula (I),
It has the same meaning as that represented by R ² , R ³ and R ⁴ . The specific example and the preferable example are also the same. X is -OH or -N
Represents R ⁵ R ⁶ . R ^5, R ⁶ are, R ⁵ of formula (I),
It has the same meaning as that represented by R ⁶ . The specific example and the preferable example are also the same.

Further, as the dye used in combination with the dye of the present invention, those represented by the following general formula (V) are preferable.

[0063]

[Chemical 30]

In the formula (V), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are
Represents a hydrogen atom or a non-metal substituent. Specific examples thereof include those described for A in the general formula (I). R ¹⁹ and R ²⁰ may be bonded to each other to form a ring structure. Among those in which R ¹⁹ and R ²⁰ form a ring structure, those forming a naphthalene ring are preferable. At that time, R ¹⁷ is preferably —CO—NHR ²¹ . R ²¹ represents an alkyl group, an aryl group, or a heterocyclic group. R ¹⁹ and R
Other preferred ones in which ²⁰ forms a ring structure are —R ¹⁹ —R
²⁰ - is _{^{-NHCO- (CR 22 R 23) n}} - is of.
n is an integer of 1 to 3. At that time, R ¹⁷ is —NH—C.
OR ²¹ is preferred. R ²¹ has the same meaning as described above.
When R ²⁰ is a hydrogen atom, R ¹⁸ is a hydrogen atom and R ¹⁷ , R
It is preferable that both ¹⁹ are —NH—CO—R ²¹ . R ²¹ has the same meaning as described above. When R ²⁰ is a chlorine atom, R
¹⁸ is a hydrogen atom, R ¹⁹ is an alkyl group, and R ¹⁷ is —NH—
CO-R ²¹ is preferred. R ²¹ has the same meaning as described above. R ¹ , R ² , R ³ and R ⁴ are R of the general formula (I).
^{It has the} same meaning as that represented by ¹ , R ² , R ³ and R ⁴ . Specific examples thereof include those described in the general formula (I). R ² , R ³ and R ⁴ are preferably hydrogen atoms. R ¹ is
A hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, an arylcarbonylamino group and an aminocarbonylamino group are preferable. X
Represents -OH or -NR ⁵ R ^6. R ⁵ and R ⁶ are
It has the same meaning as R ⁵ and R ^{6 in} formula (I). Specific examples of R ⁵ and R ⁶ include those described in the general formula (I). The preferable example is also the same as that of the general formula (I).

Other dyes preferable as the dye to be used by mixing with the dye of the present invention are those represented by the following general formula (VI).

[0066]

[Chemical 31]

In the formula (VI), R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R
²⁸ and R ^{29 each} represent a hydrogen atom or a nonmetallic atomic group.
D, E represents -OH or -NR ³⁰ R ^31. R ³⁰ , R
³¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Specific examples of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ include those mentioned for R ¹ in the general formula (I). Preferred ones of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are
It is a hydrogen atom. R ²⁴ and R ²⁵ are each independently a hydrogen atom, an alkoxy group, a cyano group, an aminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
An acyl group is preferred. D, E are both, -NR ³⁰ R ³¹ are preferred.

Other dyes preferable as the dye to be used by mixing with the dye of the present invention are those represented by the following general formula (VII).

[0069]

[Chemical 32]

In the formula (VII), R ¹ , R ² , R ³ , R ⁴ and R
⁵ , R ⁶ are R ¹ , R ² , R ³ , R ⁴ of the general formula (I),
It is synonymous with R ⁵ and R ⁶ . R ³² represents a hydrogen atom or a non-metal substituent. R ³³ , R ³⁴ , R ³⁵ and R ³⁶ represent a hydrogen atom or a non-metal atomic group. F and G each independently represent a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an aminocarbonyl group.
Specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include those described in the general formula (I). Of these, hydrogen atoms are preferable for R ² , R ³ and R ⁴ .
R ⁵ and R ⁶ are preferably alkyl groups. R ¹ is preferably a hydrogen atom or an alkyl group. Specific examples of R ³² include those mentioned for R ¹ in the general formula (I) (however, a halogen atom is excluded). Among them, preferred are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
It is a cyano group. Among them, a hydrogen atom is particularly preferable.
Specific examples of R ³³ , R ³⁴ , R ³⁵ and R ³⁶ include R of the general formula (I).
^The ones mentioned in ¹ can be mentioned. R ³³ , R ³⁴ , R
^{Both 35} and R ³⁶ are preferably hydrogen atoms. Both F and G are preferably a cyano group.

Preferred specific examples of other dyes used in combination with the dye of the present invention are shown below, but the present invention is not limited thereto.

[0072]

[Chemical 33]

[0073]

[Chemical 34]

[0074]

[Chemical 35]

[0075]

[Chemical 36]

The dye of the present invention is synthesized by oxidatively coupling the following coupler a and the following developing agent b.

[0077]

[Chemical 37]

In the above formula, X is a hydrogen atom or a leaving group which is eliminated during the coupling reaction. Of course, coupler a may be its tautomer. Alternatively, the dye of the present invention is synthesized by dehydration condensation of the coupler a and the following compound c. In this case, X is a hydrogen atom.

[0079]

[Chemical 38]

The dye of the present invention is synthesized by condensing the coupler a with the compound d.

Next, an example of synthesizing the dye of the present invention will be shown to explain the synthesizing method. The coupler a is an amidine compound and α-
It can be easily synthesized by a method of synthesizing imidazoles which reacts with a halocarbonyl compound. Further, those having the heterocyclic group represented by the above chemical formula 13 as a substituent can be easily synthesized from aminopyrazoles by the synthetic method described later. (Synthesis Example 1) Synthesis of Compound 1

[0082]

[Chemical Formula 39]

(Step 1) 6.58 g (0.05 mol) of 5-amino-4-chloro-3-methylpyrazole (Compound A) was dissolved in 40 cc of 1,2-dichloroethane,
To this, 8.95 g (0.05 mol) of α-bromopinacolone and 6.05 g (0.05 mol) of γ-collidine were added, and the mixture was heated under reflux for 10 minutes. Crystals precipitated when the reaction solution was cooled to room temperature, but dissolved when water was added. This was extracted with chloroform, dried over magnesium sulfate, and concentrated to obtain 11.2 g of a brown solid. This was separated and purified by silica gel column chromatography (using chloroform alone) to obtain 4.90 g of compound B (yield 43%). (Step 2) 1.15 g (0.005 mol) of Compound B was dissolved in 10 cc of acetic acid, and the mixture was heated under reflux at 80 ° C. for 40 minutes. The reaction solution was poured into ice water, neutralized with diluted NaOH water, and extracted with ethyl acetate. After drying over magnesium sulfate and concentration, 1.19 g of a brown solid was obtained. This was purified by silica gel column chromatography to obtain 0.90 g of Compound C (yield 85%). (Step 3) 6.35 g (0.03 mol) of Compound C in 6
0 cc of acetic anhydride was added, and the mixture was heated under reflux for 25 minutes. The reaction solution was poured into ice, warmed to room temperature, and neutralized with 5% aqueous NaOH. After extraction with ethyl acetate, drying over magnesium sulfate, and concentration, 15.4 g of a dark brown viscous liquid was obtained. This was purified by silica gel column chromatography to obtain 0.72 g (yield 10%) of Compound D. (Step 4) 0.25 g (1 mmol) of Compound D was added to 10
Dissolve in cc of ethanol and add 0.27 g of 4- (N, N-diethylamino) -2-acetylaminoaniline.
(1.2 mmol) of ethanol solution was added, and then 1.27 g (12.0 mmol) of anhydrous sodium carbonate was added to 5 c.
An aqueous solution dissolved in water of c was added, and the mixture was stirred at room temperature. Ammonium persulfate 0.27 g (1.2
A 10 cc aqueous solution containing (mmol) was gradually added dropwise.
After stirring well at room temperature for 1 hour, 50 cc of ethyl acetate and 30 cc of water were added for extraction. The ethyl acetate phase was washed well with saturated brine, the solvent was evaporated, and the residue was separated and purified by silica gel column chromatography to obtain 0.39 g of compound 1 (yield 89%).

Synthesis Example 2 Synthesis of Compound 2

[0085]

[Chemical 40]

0.5 g (2.36 mmol) of compound C
Was dissolved in 5 cc of toluene, and 0.69 cc (5.9 mmol) of benzoyl chloride and 0.82 cc (5.9 mmol) were dissolved.
(Mmol) of triethylamine was added and the mixture was heated under reflux for 1 hour. The reaction mixture was cooled to room temperature, neutralized with 5% aqueous NaOH solution, and extracted 3 times with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 1.22 g of a brown solid. This was separated and purified by silica gel column chromatography and then recrystallized from acetonitrile to obtain 0.05 g (yield 7%) of Compound E. 0.45 g (yield 90%) of Compound 2 was obtained in the same manner as in Step 4 of Synthesis Example 1 except that Compound E was used.

The heat transferable dye of the present invention is contained in the dye-providing layer on the support to prepare a heat-transfer dye-providing material, which is used for image formation in the thermal transfer system. Next, for the case where the heat transferable dye of the present invention is used for image formation in a thermal transfer system,
The details will be described below. Usually, three color dyes of yellow, magenta, and cyan are necessary to form a full-color image. Therefore, the compound of the present invention can be used as a cyan dye, and yellow and magenta dyes can be selected from known dyes to perform full-color image formation. For the same color, the dye of the present invention and a conventionally known dye may be mixed and used. Further, two or more of the dyes of the present invention may be mixed and used in the same color.

The method of using the heat transferable dye of the present invention will be described. The thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. The cyan dye of the present invention and the yellow and magenta dyes used in combination therewith are usually arranged on a support so as to form independent areas. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. Further, it is also possible to prepare three types of thermal transfer dye-donor materials in which the above-mentioned yellow dye, magenta dye, and cyan dye are provided on different supports, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be carried out sequentially. .. The cyan dye of the present invention and each of the yellow and magenta dyes used in combination with the cyan dye are dissolved or dispersed in a suitable solvent together with a binder resin and then applied on a support, or a support is obtained by a printing method such as a gravure method. Can be printed on.
The thickness of the dye-donor layer containing these dyes is usually about 0.2 to 5 μm, preferably 0.4 to 2 μm, as a dry film thickness. Dye coating amount is 0.03 to 1.0
g / m ² is preferred. Among them, 0.1-0.6 g /
m ² is more preferred.

As the binder resin used together with the above-mentioned dye, any of the binder resins known in the related art for such purpose can be used, and usually has high heat resistance,
Moreover, one that does not interfere with the migration of the dye when heated is selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resins (eg polyvinyl alcohol, polyvinyl) Acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene) and the like. In the present invention, such a binder resin is preferably used in a proportion of, for example, about 20 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be used as the ink solvent for dissolving or dispersing the above dye and binder resin. Any conventionally known support can be used as the support of the thermal transfer dye-providing material. For example polyethylene terephthalate,
Examples thereof include polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone and cellophane. The thickness of the support of the thermal transfer dye-donor element is generally 2 to 30 μm.

A slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof.
In order to prevent sticking due to heat from the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to carry out anti-sticking treatment on the side of the support on which the dye-donor layer is not provided. For example, it is preferable to provide a heat resistant slip layer mainly containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 110 ° C.
From the viewpoint that there are many reaction sites with isocyanate, the weight% of the vinyl butyral portion is 15 to 40%.
I like the one. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac® manufactured by Toho Kagaku
D720 or the like is used, and it may be used in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, based on the polyvinyl butyral resin. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The dye-donor element may be provided with a hydrophilic barrier layer for preventing the dye from diffusing toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. In general, excellent results have been obtained with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate grafted gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired effect, but preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate). / 2-aminoethyl methacrylate / -2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example, Bostic 7650 (M Heart Company, Bostic Chemical Group) Or chlorinated high density poly (ethylene-trichloroethylene) resin. The coating amount of the undercoat layer is not particularly limited, but it is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material and heat is applied in accordance with the image information from either side, preferably the back side of the thermal transfer dye-providing material, by means of heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image having excellent sharpness and resolution gradation can be obtained. An anti-fading agent can also be transferred in the same manner. The heating means is not limited to the thermal head, and known means such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In the case of using a laser as the heat source, the thermal transfer dye-donating material preferably contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into thermal energy, transfers the heat to the dye in the immediate vicinity, and is heated to a temperature at which the dye transfers to the thermal transfer image-receiving material. The absorbent material is layered below the dye and / or is mixed with the dye. For a more detailed description of this process, see British Patent 2,083,7.
26A. As the above laser,
Ion gas lasers such as Argon and Krypton,
Metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby and YAG, or 750-87.
Several lasers, such as semiconductor lasers such as gallium-arsenide, which emit in the infrared region of 0 nm can be used. Among them, the semiconductor laser is preferable because of its small size, low cost, stability, reliability, durability and ease of modulation. As a specific example, for example, Spectrodiode Lab (Sp
Laser model SDL-2420-H2 (registered trademark) manufactured by Electrodiode Labs) or laser model SLD-304v / w (registered trademark) manufactured by Sony Corporation.
Is mentioned.

In the present invention, the thermal transfer dye-donor material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system and the like. It can be used to make prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention comprises a support and an image-receiving layer for receiving the dye transferred from the dye-providing material. This image-receiving layer contains a substance capable of receiving a heat-transferable dye having a function of dyeing the heat-transferable dye, which receives the heat-transferable dye transferred from the heat-transfer dye-providing material during printing. Or with other binder substances, it is preferable that the coating has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive a heat transferable dye.

(A) those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group) and ethylene. Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyon Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used. (B) Those having a urethane bond, such as polyurethane resin. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the synthetic resin as described above, a mixture or copolymer of these may be used.

In the thermal transfer image-receiving material, especially in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in No. -30247 and No. 62-136646 can be mentioned. The image receiving layer of the thermal transfer image receiving material is
A substance capable of receiving the heat transferable dye may be dispersed in a water-soluble binder and carried. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a crosslinking reaction by a hardening agent is preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having a higher dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used as the outermost layer. Using a synthetic resin with a higher point, or sticking the surface to other substances, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents failures such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to 50.
μm, particularly preferably in the range of 3 to 30 μm. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer depends on the material
It is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, and also serves as an adhesive in some cases. The dye diffusion preventing layer plays a role of preventing the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat. The image receiving layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, and the like, which constitute the thermal transfer image receiving material, include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, and synthetic zeolite. Fine powder of zinc oxide, lithopone, titanium oxide, alumina or the like may be contained.

If the support used for the thermal transfer image-receiving material can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer, etc. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. Films or sheets that have been treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. As an example, K. Veenkatarama
n edition "The Chemistry of Synth
"tic Dyes", Volume V, Chapter 8, JP-A-61-14
The compound described in No. 3752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the present invention, in order to improve the releasability between the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably, the surfaces where both materials come into contact with each other. It is preferable to add a release agent to the outermost layer corresponding to the above. Solid release agents such as polyethylene wax, amide wax, and Teflon powder: Wax-like substances: Fluorine-based or phosphate-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. Although any of the above releasing agents can be used, silicone oil is particularly preferable. As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used. As an example, 6-of the technical data of "modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Examples include various modified silicone oils described on page 18B. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd. product name: X-22-371)
0) is effective.

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The dura mater described in No. 8 can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in the publications are suitable for use. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners (compounds of the following chemical formula 41), vinyl sulfone type hardeners (N, N'-ethylene- Bis (vinylsulfonylacetamide) ethane, etc.), N-methylol type hardener (dimethylolurea, etc.), or polymer hardener (JP-A-62-23415).
7) and the like).

[0104]

[Chemical 41]

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681
No.), benzophenone compounds (JP-A-56-27)
No. 84, etc., and JP-A-54-48535 and 6
There are compounds described in Nos. 2-136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-7556
8 and the compounds described in JP-A-63-199248. Examples of useful anti-fading agents are disclosed in JP-A-62-2
15272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image receiving material may be contained in the image receiving material in advance, or may be supplied to the image receiving material from the outside by a method of transferring from the dye providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicones Polyethylene oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc., nonionic surfactants: alkyl carboxylates, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, and other carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups Anionic surfactants containing acidic groups such as:
Amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides: alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazo Multiple rings such as lithium 4th
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing aliphatic or multiple rings can be used. Specific examples of these are disclosed in JP-A Nos. 62-173463 and 62-18345.
No. 7 etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. Typical examples of the organic fluoro compound include JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the matting agent, in addition to the compounds described in JP-A-61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-27.
There are compounds described in Nos. 4944 and 63-274952.

[0109]

【Example】

Example 1 The absorption characteristics of the dye of the present invention in ethyl acetate are shown in FIG. At the same time, the absorption characteristics of Dye II-1 are also shown in FIG. 1 for comparison. In FIG. 1, the solid line shows the absorption characteristics of Dye 1 of the present invention, the broken line shows the absorption characteristics of Dye 2 of the present invention, and the alternate long and short dash line shows the absorption characteristics of Dye II-1. Further, the maximum absorption wavelength and the full width at half maximum of Dye 1 and Dye 2 of the present invention are as follows. Dye 1 of the present invention: λmax: 603 nm (in ethyl acetate) Half-width: 60 nm (in ethyl acetate) Dye 2 of the present invention 2 λmax: 622 nm (in ethyl acetate) Half-width: 60 nm (in ethyl acetate)

From FIG. 1, the dye of the present invention has a sharp absorption and a small unnecessary absorption in the yellow part,
Also, it is found that it has an absorption maximum suitable as a cyan dye.

Example 2 A solution system of the dye of the present invention was tested for light fastness. The dyes tested and the results are shown in Table 1. Conditions: Xenon irradiator (output 500W, 170,000 lux, UXL-500D-O type manufactured by Ushio Electric Co., Ltd.) Cell: Quartz cell Solvent: Ethyl acetate Residual rate: Expressed by change in concentration at λmax before and after forced fading test It was (Unit:%) Concentration: 4.0 × 10 ^-5 (mol / liter)

[0112]

[Table 1]

Example 3 (Preparation of Thermal Transfer Dye-donating Material (3-1)) A polyethylene terephthalate film (manufactured by Teijin) having a thickness of 6 μm, the back surface of which was subjected to heat-resistant lubrication treatment, was used as a support, and the surface of the film was used. A coating composition for a thermal transfer dye-donating layer having the following composition was applied to the above by wire bar coating to give a dry thickness of 1.
A thermal transfer dye-providing material (3-1) was prepared by coating so as to have a thickness of 5 μm. Coating composition for thermal transfer dye-donating layer: Dye 1 10 mmol Polyvinyl butyral resin (Denka Butyral 5000-A manufactured by Denki Kagaku) 3 g Toluene 40 cc Methyl ethyl ketone 40 cc Polyisocyanate (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) 0.2 cc In the same manner as above except that the other dyes described in -2 were used, the thermal transfer dye-donor materials of the present invention and the comparative thermal transfer dye-donor materials (3-2) to (3-14) were prepared.

(Preparation of Thermal Transfer Image Receiving Material) Synthetic paper having a thickness of 150 μm as a support (YUPO-FPG manufactured by Oji Yuka Co., Ltd.)
-150) and a coating composition for an image receiving layer having the following composition on the surface by wire bar coating to a dry thickness of 8
A thermal transfer image receiving material was prepared by coating so as to have a thickness of μm.
Drying was carried out for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition for image-receiving layer: Polyester resin (Vylon-280 manufactured by Toyobo) 22 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 85 cc Toluene 85 cc Cyclohexanone 15 cc

The thermal transfer dye-donor materials (3-1) to (3-14) obtained as described above and the thermal transfer image-receiving material were
The thermal transfer dye-donor layer and the image-receiving layer are superposed so that they are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donor material, the output of the thermal head is 0.25 W / dot, the pulse width is 0.15 to 15 milliseconds, Printing was performed under the condition of a dot density of 6 dots / mm, and a cyan dye was dyed imagewise on the image receiving layer of the image receiving material. As a result, clear image recording without transfer unevenness was obtained. Next, each of the recorded thermal transfer image-receiving materials obtained as described above was kept at 17,000 for 7 days.
The stability of the color image was examined by irradiating it with a fluorescent lamp of 0 lux. The status A reflection density after irradiation of the portion showing the status A reflection density of 1.0 was measured, and its stability was evaluated by the residual rate (percentage) with respect to the reflection density of 1.0 before irradiation. The results are shown in Table-2.

[0116]

[Table 2]

From the above results, the color image derived from the dye of the present invention shows the conventionally known imidazole dyes II-9 and II-2.
It is clear that the light fastness is high as compared with the color image derived from 0. The color image derived from the dye of the present invention has an equivalent level of light fastness as compared with the color image derived from the conventionally known phenol indoaniline dye II-1 which is known to have high light fastness. You can see that

Example 4 The dyes shown in Table 3 were used in place of the dye 1 of the coating composition for the heat transfer dye donating layer of Example 3, and the heat transfer dye donating materials (4-1) to (4-15) were used. )made. When printing was performed using the image receiving material prepared in Example 3, clear image recording without transfer unevenness was obtained and the density was high in all cases. The light fastness was also excellent.

[0119]

[Table 3]

Example 5 A thermal transfer dye-donating material (5-1) was prepared by using the resins and dyes shown in Table 4 instead of the polyvinyl butyral resin and the dye in the coating composition for a thermal transfer dye-donating layer of Example 3. , (5-
2) and (5-3) were prepared. When printing was carried out using the same image receiving material as in Example 3, clear image recording without transfer unevenness was obtained as shown in Table 4. The light fastness was also excellent.

[0121]

[Table 4]

The following are Examples 6 to 7 regarding combinations of other thermal transfer image-receiving materials with the above-mentioned thermal transfer dye-donor elements of the present invention.
9 is shown. Example 6 (Preparation of thermal transfer image-receiving material) 150 μm thick as a support
Of the synthetic paper (YUPO-FPG-150 manufactured by Oji Oil Chemical Co., Ltd.) is applied to the surface by a wire bar coating so that the thickness when dried is 10 μm, and a thermal transfer image is received. The material was made. Drying is done temporarily with a dryer, then in an oven at a temperature of 100 ° C for 30
I went for a minute. Coating Composition for Image Receiving Layer: Polyester Resin No. 1 (Compound of Chemical Formula 42 below) 2.0 g Amino-modified silicone oil (KF-857 made by Shin-Etsu Silicone) 0.5 g Epoxy-modified silicone oil (KF-100T made by Shin-Etsu Silicone) 0 0.5 g methyl ethyl ketone 85 cc toluene 85 cc cyclohexanone 30 cc

[0123]

[Chemical 42]

When printing was carried out in combination with the thermal transfer dye-donor materials using the dyes of the invention of Examples 3 and 4, clear image recording was obtained. Also, the light fastness was excellent.

Example 7 (Preparation of Thermal Transfer Image Receiving Material) Resin coated paper prepared by laminating polyethylene of 15 μm and 25 μm on both sides of 200 μm paper was prepared, and an image receiving layer having the following composition was formed on the laminated surface of 15 μm thickness. The coating composition for coating was applied by wire bar coating to a dry thickness of 10 μm and dried to prepare a thermal transfer image receiving material. Coating composition for image receiving layer: Polyester resin No. 1 (compound of the above chemical formula 42) 25 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) 0.8 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Methyl ethyl ketone 100 cc Toluene 100 cc When printing was performed in the same manner as in Example 6, clear and high-density image recording was obtained. Also, the light fastness was excellent.

Example 8 (Preparation of Thermal Transfer Image Receiving Material) An organic solvent solution of the dye-receptive polymer having the composition (B ′) was emulsified and dispersed in an aqueous gelatin solution having the composition (A ′) shown below by a homogenizer. A gelatin dispersion of was prepared. (A ') Aqueous gelatin solution: Gelatin 2.3 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 cc Water 80 cc (B') Dye-receptive polymer solution: Polyester resin (Vylon 300 manufactured by Toyobo) 7.0 g Carboxy-modified silicone oil ( Shin-Etsu Silicone X-22-3710) 0.7 g Methyl ethyl ketone 20 cc Toluene 10 cc Triphenyl phosphate 1.5 g The dispersion prepared in this manner was added with the fluorine-based surfactant (a) of the following chemical formula 43. A solution prepared by dissolving 5 g in a mixed solvent 10 cc of water / methanol (1: 1) was added to obtain a coating composition for an image receiving layer.

[0127]

[Chemical 43]

A surface of this coating composition was corona-discharged and a synthetic paper having a thickness of 150 μm (manufactured by Oji Yuka: YUPO-SG) was used.
G-150) was applied by a wire bar coating method to a wet film thickness of 75 μm and dried to obtain a thermal transfer image receiving material. Images were recorded in the same manner as in Example 3 by using the thermal transfer dye-donor elements using the dyes of the present invention in Examples 3 and 4 and the thermal transfer image-receiving material. The obtained image had high density, was clear, and had high fastness.

Example 9 (Production of Thermal Transfer Image Receiving Material) A thermal transfer image receiving material was produced in the same manner as in Example 3 using the following coating composition for image receiving layer. Image-receiving layer coating composition: The same composition as the image-receiving layer coating composition of Example 3 except that 7 g of the ultraviolet absorber represented by the following chemical formula 44 is added.

[0130]

[Chemical 44]

Printing was carried out in the same manner as in Example 3 using the thermal transfer dye-donor materials containing the dyes of the present invention in Examples 3 and 4, and a clear and high-density image was obtained. The fastness was also higher than that when the image receiving material of Example 3 was used.

Example 10 Dye 1 (1 of the coating composition for the thermal transfer dye-donor layer of Example 3)
2 mmoles (5 mmoles each) shown in Table 5 instead of 0 mmoles), and the thermal transfer dye-donor element (10-
1) to (10-18) were prepared. Further, thermal transfer dye-donor materials (10-19) and (10-20) were prepared using one kind of dye (10 mmol) shown in Table-5. In order to examine the storage stability of the prepared thermal transfer dye-donor material, it was stored in an oven under dry conditions at 50 ° C. for 1 week and tested for thermal stability. The evaluation criteria are as follows. ○: Aggregation and crystallization of the dye are not observed even under a microscope. Δ: Aggregation or crystallization of the dye is slightly observed with a microscope. ×: Aggregation or crystallization of the dye on one surface is visually observed. The results are shown in Table-5.

[0133]

[Table 5]

As is clear from the comparison between Nos. 19 and 20 and Nos. 1 to 18, the dyes of the present invention are used as a mixture of dyes rather than being used alone in the thermal transfer dye-donor element. It is understood that the storage stability of the thermal transfer dye-providing material is better, and that it is more preferable.

Further, the thermal transfer dye image-receiving material of Example 3,
Thermal transfer dye-providing material (10-1) after thermal stability test
Printing was performed in the same manner as in Example 3 using (10-20), and the thermal transfer dye-providing materials (10-1) to (1) of the present invention were obtained.
Nos. 0 to 19) provided clear image recording without transfer unevenness. On the other hand, the thermal transfer dye-providing material (10-
In 20), the image was uneven.

Example 11 Thermal transfer dye-donor element (10-1) prepared in Example 10
~ (10-20) and the thermal transfer dye image-receiving material produced in Example 3 were used to perform dye transfer in accordance with Example 3. In order to examine the storage stability of the images on the obtained image receiving materials (11-1) to (11-20), 60 ° C. and 70% humidity were used.
% Forcibly stored for 2 weeks. The evaluation is the same as in Example 10. The results are shown in Table-6.

[0137]

[Table 6]

As described above, the dye of the present invention is better in storage stability of an image on the heat transfer dye image-receiving material when the dyes are used in combination than when used alone in the heat transfer dye-donor material. Recognize.

[0139]

INDUSTRIAL APPLICABILITY The imidazole azomethine dye of the present invention is easy to synthesize, has a sharp absorption waveform, has a small unnecessary absorption on the short-wave side, and is excellent in fastness, which is not possible with conventional dyes. Was given. Further, when an image is formed using the thermal transfer dye-donor material containing the imidazole azomethine dye of the present invention, there is an effect that a high-density image free from fading or discoloration can be obtained. Furthermore,
In the transferred images on the thermal transfer dye-donor material and the thermal transfer dye image-receiving material, the imidazole azomethine dyes of the present invention are more effective in storage stability when used in combination of two or more than when used alone. The use was also advantageous in terms of color reproduction.

[Brief description of drawings]

FIG. 1 shows the absorption characteristics of the dye of the present invention and comparative dye a in acetic ester. In FIG. 1, the solid line shows the absorption characteristics of Dye 1 of the present invention, the broken line shows the absorption characteristics of Dye 2 of the present invention, and the alternate long and short dash line shows the absorption characteristics of Dye II-1.

Claims (5)

[Claims] 1. An imidazole azomethine dye represented by the following general formula (I). [Chemical 1] In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a non-metal atomic group. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. A and B each independently represent a hydrogen atom or a non-metal substituent. However, B
Is not a substituted or unsubstituted phenyl group. R ¹ and R ² ,
And / or R ² and R ⁵ , and / or R ⁵ and R ⁶ , and / or R ⁶ and R ³ , and / or R ³ and R ⁴ may be bonded to each other to form a ring structure. .. 2. The imidazole azomethine dye according to claim 1, wherein A in the general formula (I) is an aryl group or a heterocyclic group. 3. A thermal transfer dye-donating material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer contains at least one imidazole azomethine dye represented by the following general formula (I). A thermal transfer dye-donor material characterized by: [Chemical 2] In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a non-metal atomic group. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. A and B each independently represent a hydrogen atom or a non-metal substituent. However, B
Is not a substituted or unsubstituted phenyl group. R ¹ and R ² ,
And / or R ² and R ⁵ , and / or R ⁵ and R ⁶ , and / or R ⁶ and R ³ , and / or R ³ and R ⁴ may be bonded to each other to form a ring structure. .. 4. The thermal transfer dye-donor element according to claim 3, wherein A in the general formula (I) is an aryl group or a heterocyclic group. 5. The dye-donor layer contains a mixture of two or more dyes, and at least one of the dye mixtures is an imidazole azomethine dye represented by the general formula (I). The thermal transfer dye-donor element as described.