JP2655212B2 - Azomethine dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyrrolopyrimidin-5-one azomethine dye and pyrrolopyrimidine-7.
-Relates to onazomethine dyes. Further, the present invention relates to a thermal transfer dye donating material containing the dye.

[0002]

BACKGROUND OF THE INVENTION Azomethine dyes, especially azomethine dyes in which a p-dialkylaminophenyl group is bonded to the nitrogen atom of an imine, are subjected to an oxidative coupling reaction between active methylenes or phenols and N, N-dialkyl-p-phenylenediamines. And widely used as an image forming dye in a silver halide color photographic light-sensitive material using a color reduction method based on a mixture of three colors of yellow, magenta, and cyan because the color tone ranges from yellow, red, magenta, blue, and cyan. Have been Blue or cyan dyes are formed from phenols, naphthols, 2,4-diphenylimidazoles and the like, 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, etc., form magenta or blue dyes, acylacetanilides, diacylmethanes , Malondianilides and the like form yellow dyes. Such dyes are described in JP-A-60-186567 and JP-A-63-14528.
No. 1 and Nos. 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, with the development of electronic imaging, the demand for solid-state image pickup tubes and filters for color liquid crystal televisions has been increasing. With the increase, azomethine dyes have come to be applied and studied not only for color photography but also for various systems or products. Dyes having absorption in the infrared region are disclosed in JP-A-3-81192, JP-A-3-81193, and JP-A-3-8193.
No. 1194 and No. 2-172794.

[0003]

However, these azomethine dyes have a number of disadvantages. For example, there has been a problem that the pigment has low stability to heat, moisture, light, chemicals, the atmosphere, etc., and is difficult to synthesize and expensive.
In particular, many azomethine dyes having absorption in the near infrared region have particularly low stability, and the development of a dye having high stability has been strongly desired. In order to solve the above-mentioned problems, the present inventors have developed completely new pyrrolopyrimidin-5-oneazomethine dyes and pyrrolopyrimidin-7-oneazomethine dyes. Furthermore, when this dye was used as a dye for thermal transfer, it was found that an excellent thermal transfer dye-providing material could be obtained, and the present invention was completed. Desirable properties as a thermal transfer dye include, for example, excellent transferability, sharp absorption, high light, heat fastness, that the sharpness does not decrease, that the ink sheet is easy to produce, that the image receiving layer does not bleed out, May not decrease the light fastness of the dye.

It is an object of the present invention to provide a dye having high stability to light, heat, moisture, air, and chemicals. Another object of the present invention is to provide a dye which can be easily synthesized and can be supplied in large quantities at low cost. Another object of the present invention is to provide a dye having excellent performance as a dye for image formation or a filter. Another object of the present invention is to provide a novel dye having absorption in the near infrared region. Another object of the present invention is to provide a dye having excellent performance as a dye for thermal transfer.

[0005]

The present invention has been achieved by an azomethine dye represented by the following general formula (I) or (II).

[0006]

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Wherein R ¹ , R ² , R ³ and R ⁴ are
Each independently a hydrogen atom or a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group (including a substituted amino group), an alkoxy group, an aryloxy group, an acylamino group, Aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, A carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, a carboxylic acid group (including its salt), and a sulfonic acid group (including its salt). Express. X
It is, -OH or represents a ^-NR 5 ^{R 6.} R ⁵ and R
⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an aryl group, a heterocyclic group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group. Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heteryloxy group, Alkylthio group, arylthio group, heterylthio group, halogen atom, hydroxy group, nitro group, sulfamoyl group, sulfonyl group, azo group, acyloxy group, carbamoyloxy group, imide group, sulfinyl group, phosphoryl group, carboxylic acid group, sulfonic acid group The table It is. 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 and / or R ⁹ and R ¹⁰ may combine with each other to form a ring structure.

The general formulas (I) and (II) are described in detail below. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group (including a substituted amino group ), An alkoxy group,
Aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group,
Arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group,
Sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, carboxylic acid group (Including its salts), sulfonic acid groups (including its salts), and the like.

Preferred examples thereof include a hydrogen atom,
Alkyl group (preferably having 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, butyl), alkoxy group (preferably having 1 to 30 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy), a halogen atom (for example, bromine, Fluorine, chlorine), an acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (for example, formylamino, acetylamino, propionylamino, cyanoacetylamino), preferably having 7 to 3 carbon atoms
0 arylcarbonylamino group (eg, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, eg, methoxycarbonyl, ethoxycarbonyl), cyano Group,
A sulfonylamino group (preferably having 1 to 30 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), a carbamoyl group (preferably an alkylcarbamoyl group having 2 to 30 carbon atoms (eg, methylcarbamoyl, dimethylcarbamoyl, Butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl,
Ethyl cyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, 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 a hetenylcarbamoyl group having 4 to 30 carbon atoms (For example, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methylphenyl) 1,3,4- Thiadiazolylcarbamoyl)], a sulfamoyl group (preferably having 0 to 30 carbon atoms) such as methylsulfamoyl and dimethylsulfamoyl), an aminocarbonylamino group (preferably having 1 to 30 carbon atoms) 0, for example, methylaminocarbonyl, dimethylamino carbonyl amino), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms)
For example, methoxycarbonylamino, ethoxycarbonylamino), a hydroxy group, an amino group (preferably having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino), an aryl group (preferably having 6 to 3 carbon atoms)
0, for example, phenyl, m-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 3 carbon atoms)
0, for example, 2-pyridyl, 2-furyl, 2-tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 30 carbon atoms, for example, phenoxy, p-methoxyphenoxy, o-chlorophenoxy), sulfamoylamino Groups (preferably having 0 to 30 carbon atoms such as methylsulfamoylamino and dimethylsulfamoylamino), alkylthio groups (preferably having 1 to 30 carbon atoms) such as methylthio and ethylthio, and arylthio groups (preferably having 6 to 30 carbon atoms). 30) For example, phenylthio, p-methoxyphenylthio, o-chlorophenylthio), a sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, p-toluenesulfonyl), an acyl group (preferably having 1 to 30 carbon atoms, for example, Formyl, acetyl, benzoyl, p-toluyl), Heterocyclic oxy group (preferably having 3 to 30 carbon atoms), an azo group (preferably having 3 to 30 carbon atoms,
For example, p-nitrophenylazo), an acyloxy group (preferably having 1 to 30 carbon atoms such as acetyloxy and benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms such as methylcarbamoyloxy), a silyloxy group (preferably (C3-30) such as trimethylsiloxy), aryloxycarbonyl group (preferably C7-30) such as phenoxycarbonyl), imide group (preferably C4-30 such as phthalimide), heterocyclic thio group (preferably Has 3 or more carbon atoms
30), a sulfinyl group (preferably having 1 to 30 carbon atoms,
For example, diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 30 carbon atoms, for example, diaminophosphoryl), a carboxylic acid group (including a sodium salt and a potassium salt thereof), a sulfonic acid group (a sodium salt and a potassium salt thereof), and the like Is mentioned.

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 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom (fluorine, chlorine, bromine),
An acylamino group having 1 to 20 carbon atoms, a sulfonylamino group having 1 to 20 carbon atoms, an aminocarbonylamino group having 1 to 20 carbon atoms, and an alkoxycarbonylamino group having 2 to 20 carbon atoms. Among them, R ¹ is most preferably a hydrogen atom, an alkyl group, or an acylamino group.

[0011] X represents the -OH or ^-NR 5 ^{R 6.} R
⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 30 carbon atoms, 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-methylaminocarbonyl) ethyl, 3- (N, N
-Dimethylaminocarbonyl) propyl, 2-acetylaminoethyl, 3- (ethylcarbonylamino) propyl, 2-acetyloxyethyl, allyl, homoallyl,
Prenyl, n-dodecyl), aryl group (preferably having 6 to 30 carbon atoms, for example, 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 having 3 to 30 carbon atoms), for example, a group represented by the following formulas 6 and 7.

[0012]

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[0013]

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X is preferably -NR ⁵ R ⁶ .

Preferred among R ⁵ and R ⁶ are an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, 2-cyanoethyl, 2-acetyloxyethyl, 2-ethoxycarbonyl). Ethyl, 2-
Methoxyethyl, allyl, homoallyl, prenyl). Examples of the ring that may be formed by combining R ⁵ and R ⁶ include groups represented by the following 8, 9, and 10,
The ring which may be formed by combining R ² and R ⁵ and / or R ³ and R ⁶ includes, for example, a group represented by the following formula 11, and is a preferred example.

[0016]

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[0017]

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[0018]

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[0019]

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R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an aryl group, a heterocyclic group, an alkyl group, a cyano group,
Acyl group, carbamoyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, Silyloxy group, heteryloxy group, alkylthio group, arylthio group, heterylthio group, halogen atom, hydroxy group,
Nitro group, sulfamoyl group, sulfonyl group, azo group,
It represents an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, a phosphoryl group, a carboxylic acid group (including its salt), a sulfonic acid group (including its salt), and the like.

Preferred specific examples of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a hydrogen atom, an aryl group (preferably having 6 to 30 carbon atoms, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), An alkyl group (preferably having 1 to 30 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, n-octyl, n-dodecyl), a cyano group, an acyl group (preferably having 1 to 30 carbon atoms, for example, acetyl, pivaloyl, Benzoyl, furoyl, 2-pyridylcarbonyl), carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl), alkoxycarbonyl group (preferably having 1 to 30 carbon atoms)
30, for example, 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 having 1 carbon atom)
-30 alkylcarbonylamino groups (for example, formylamino, acetylamino, propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (for example, benzoylamino,
p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a hetenylcarbonylamino group having 4 to 30 carbon atoms (e.g., 2
-Pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably Has 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m
-Chlorophenoxycarbonylamino, o-chlorophenoxycarbonylamino), a sulfonylamino group (preferably having 1 to 30 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, toluenesulfoniamino), an aminocarbonylamino group (preferably having 1
-30, for example, methylaminocarbonylamino, ethylaminocarbonylamino, anilinocarbonylamino,
Dimethylaminocarbonylamino), a sulfamoylamino group (preferably having 1 to 30 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino,
Anilinosulfonylamino), an amino group (including anilino group, preferably having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, anilino), an alkoxy group (preferably carbon Number 1 to 30, for example, methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), aryloxy group (preferably having 6 to 30 carbon atoms, for example, phenoxy, m-chlorophenoxy, p-methoxyphenoxy) , O-methoxyphenoxy), a silyloxy group (preferably having 3 to 3 carbon atoms)
0, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, cesyldimethylsilyloxy, phenyldimethylsilyloxy), a heteryloxy group (preferably having 3 to 30 carbon atoms, 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), an arylthio group (preferably having 6 to 30 carbon atoms, 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 Hajime Tamaki (preferably having 3 to 30 carbon atoms, such as 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl -
2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-
Pyridyl), a halogen atom (fluorine, chlorine, bromine), a hydroxy group, a nitro group, a sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl and dimethylsulfamoyl), a sulfonyl group (preferably having 1 carbon atom) To 30, for example, methanesulfonyl, benzenesulfonyl, and toluenesulfonyl), an azo group (preferably having 3 carbon atoms).
To 30, for example, p-nitrophenylazo), an acyloxy group (preferably having 1 to 30 carbon atoms, such as formyloxy, acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms, such as methylcarbamoyloxy), Diethylcarbamoyloxy),
Imide group (preferably having 4 to 30 carbon atoms, for example, succinimide, phthalimide), sulfinyl group (preferably having 1 to 30 carbon atoms, for example, diethylaminosulfinyl), phosphoryl group (preferably having 0 to 30 carbon atoms, for example, diaminophosphoryl) ), Carboxylic acid groups (such as sodium salts and potassium salts), and sulfonic acids (such as sodium salts and potassium salts).

The pyrrolopyrimidin-5-oneazomethine dyes and pyrrolopyrimidin-7-oneazomethine dyes of the present invention are represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
Depending on how R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are selected, it is possible to have various hues. Pyrrolopyrimidin-5-one azomethine dye and pyrrolopyrimidine-7 of the present invention
In order for the onazomethine dye to be a blue or cyan dye, at least one of R ⁷ and R ⁸ must be an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.15 or more. is required. Further, in order to obtain a dye having red and magenta hues, R ⁷ R ⁸ must be a group having σp of less than 0.15.

In order for the dye of the present invention to be a near-infrared absorbing dye, R ¹ is an alkyl group, —OR ¹¹ , —NR ¹² —CO
It is necessary that -R ^13. R ¹¹ is an alkyl group,
Represents an aryl group or a heterocyclic group. R ¹² is a hydrogen atom,
Represents an alkyl group. R ¹³ represents an alkyl group, an aryl group, a heterocyclic group, —OR ¹¹ , or —NR ¹² R ¹⁴ . R
¹⁴ has the same meaning as R ^12. At least one of R ⁷ and R ⁸ must be an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.15 or more.

When the dye of the present invention is used by dissolving it in a lipophilic polymer or solvent, the sulfonic acid group (and its salt), carboxylic acid group (and its salt), quaternary amino group and the like are substituted. Those that do not are preferred. On the other hand, when dispersed in gelatin or used as an aqueous solution, those in which a sulfonic acid group (and a salt thereof), a carboxylic acid group (a salt thereof), and a quaternary amino group are substituted are preferable.

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

The dyes of the present invention, in the case of those dyes represented by the formula (I), absorption maximum than towards what R ¹⁰ is substituted is unsubstituted is long wave. Then, the absorption waveform becomes broad. On the other hand, stability to dye of heat towards that R ¹⁰ is unsubstituted have superior those substituted. Then, the absorption waveform becomes sharp. Therefore, when using the dye of the present invention, if it is high fastness is desired, it is preferred that R ¹⁰ is chosen for an unsubstituted. Also, when a sharp absorption waveform is desired, R
Those in which ¹⁰ is unsubstituted are preferred. On the other hand, if the absorption of long wavelength is desired, from among the dyes of the present invention, it is preferable to select those which R ¹⁰ is substituted. Here, knowledge related to the present invention will be described. As another method for converting the dye of the present invention into a near-infrared absorbing dye, there is a method of simultaneously introducing a substituent into R ¹ and R ⁴ . In general, it is known that the absorption of azomethine dyes becomes extremely long when a substituent is introduced into both ortho positions of the imino group of the benzene ring of the developing agent at the same time, and the molecular extinction coefficient decreases at the same time. About this technology, for example, Photographic Scie
nce and Engineering VoLome 8, Number 3, May-June
1964 p125. The pyrrolopyrimidin-7-one azomethine dye and the pyrrolopyrimidin-5-one azomethine dye of the present invention can be extended in wavelength by the above-described method, without being affected by the general rules of the azomethine dye. However, when the wavelength is increased by the above-described method, the light and heat fastness of the dye is remarkably reduced, and the dye is not suitable for forming an image or for a filter. On the other hand, when the fastness of the dye is not required, the absorption wavelength may be increased by using the above method.

Here, the Hammett's substituent constant used in the present specification will be described briefly. Hammett's rule was used in 1935 to describe quantitatively the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean
Hen, "Lange's Handbook of Chemistry", 12th edition, 1
997 (McGraw-Hill) and extra editions in the field of chemistry, 12
No. 2, pages 96 to 103, 1979 (Nankodo). In the present invention, each substituent is limited or described by Hammett's substituent constant σ _p, but this is limited to only those substituents having a value known in the literature, which can be found in the above-mentioned books. Of course, it does not mean that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule. From now on, the σ _p value and σ _m value indicate 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 fastness of an image is required. The atomic group having the effect of suppressing fading is represented by R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^It may be bound to any of the ¹⁰ sites. As the atomic group having the effect of suppressing fading, all of those described in Japanese Patent Application No. 2-277665 can be used. Specific examples of atomic groups having an effect of suppressing fading are given below.
The present invention is not limited by this.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Specific examples of the dye of the present invention are described below. They are,
The present invention is described in detail, and the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The dye of the present invention is synthesized by oxidative coupling of the following couplers A and B and the following developing agent C.

[0054]

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[0055]

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In the above formula, Q is a hydrogen atom or an elimination that is eliminated during the coupling reaction. Of course, couplers A and B may be their tautomers. Alternatively, the dye of the present invention is synthesized by dehydrating and condensing the above couplers A and B with the following compound D.

[0057]

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When X is OH, it can be synthesized by condensing couplers A and B with the following compound F.

[0059]

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The couplers represented by A and B can be easily synthesized from the corresponding pyrroles. Next, a synthesis example of the dye of the present invention will be shown, and the synthesis method will be described.

(Synthesis Example 1) Synthesis of Compound 1

[0062]

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It can be easily obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali. 18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 25.3 g of diethyl ethoxyethylidenemalonate (compound b) were added to ethanol 30.
The mixture was dispersed in 0 ml, and 22.0 ml of a 28% methanol solution of sodium methylate was added thereto. The mixture was refluxed for 5 hours. After cooling, ethyl acetate was added, washed with water, the organic solvent was concentrated, a small amount of ethyl acetate was added, and the precipitated crystals were collected by filtration.
11.6 g (yield 36%) of compound c was obtained. Next, 10 ml of ethyl acetate and 6 ml of ethanol were added to 0.64 g of compound c.
Was added thereto, and an aqueous solution in which 1.5 g of sodium carbonate was dissolved in 10 ml of water was added. Furthermore, compound D1.
After adding 5 g, 1.4 g of ammonium persulfate was added to 1 part of water.
An aqueous solution dissolved in 0 ml was added dropwise over 2 minutes. After the dropwise addition, the mixture was further stirred for 5 minutes, and ethyl acetate and water were added, and the mixture was separated. After washing the organic layer with water, the solvent was distilled off, and the crude product obtained was purified by silica gel chromatography to obtain 0.65 g of Compound 1 (55% yield).

[0064] Gum of ¹ HNMR spectra melt beginning 120 ° C. from mp 117 (200MH _Z, COCl
During _{3) 1.10 (t, 3H,} J = 6H Z), 1.40 (t, 3
H, J = 6H _Z ), 2.40 (s, 3H), 2.75
(S, 3H), 3.05 (s, 3H), 3.30 (m,
2H), 3.45 (m, 4H), 4.45 (q, 2H,
_{J = 6H Z), 5.30 (} d, 1H, J = 8H Z),
5.80 (dd, ₁ H, J ₁ = 8 H _Z , J ₂ = 2
_{H Z), 6.00 (d,} 1H, J = 2H Z), 6.55
(Bs, 1H), 7.10 (m, 2H), 7.25
The (m, 3H) ¹ H NMR spectrum was represented by the following abbreviations. s = single line d = double line t = triple line q = quadruple line m = multiple line bs = broad single line

(Synthesis Example 2) Synthesis of Compound 2

[0066]

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Compound c (1.0 g) and ethyl acetate (100 ml)
And 100 ml of water and stirred at 20 ° C. Further, 2.60 g of potassium carbonate and 20 ml of ethanol were added. Thereafter, 1.23 g of compound e and 1.0% of ammonium persulfate were added.
6 g were slowly added alternately. Thereafter, the mixture was reacted for 30 minutes, and then extracted. The organic layer was washed twice with water, dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure using an evaporator. The crude product was purified using silica gel column chromatography. (Ethyl acetate: hexane 1: 10-1: 2). 0.41 g of compound 2 (54.
6%). mp. It is amorphous and does not show a clear melting point. Mass spectrum analysis value (only main peak is described) 481, 461, 448, 446, 409, 249, 1
49

Synthesis Example 3 Synthesis of Compound 8

[0069]

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1.0 g of compound f and 1.0 g of triethylamine were dissolved in 20 ml of methylene chloride, and the mixture was stirred at 20 ° C. while adding 0.66 ml of N-bromosuccinimide.
g, compound e and 0.98 g were alternately added in portions.
After reacting for 30 minutes, 50 ml of water and 50 ml of ethyl acetate were added.
ml was added for extraction. The organic layer was washed twice with water, dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure using an evaporator. The crude product was purified using silica gel column chromatography. (Ethyl acetate: hexane = 1: 10-1: 2). Compound 8 with 0.32
g (20.8%). Mass spectrum analysis value (only the main peak is shown) 467, 450, 237, 221, 149

Synthesis Example 4 Synthesis of Compound 12

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Compound f, 0.5 g, compound g, 0.43
g was dissolved in 10 ml of ethanol, and 0.20 g of acetic anhydride was added while stirring at 20 ° C. After reacting for 30 minutes, 100 ml of water and 100 ml of ethyl acetate were added for extraction. Since crystals precipitated during the extraction, the crystals were filtered to obtain crystals. The crude product was purified using silica gel column chromatography. (Ethyl acetate: chloroform = 1: 4). 0.40 g (43.8%) of compound 12.

Mp. Does not dissolve even at 210 ° C. ¹ HNMR spectrum (200MH _Z, CDCl
During _{3) 1.30 (t, 6H,} J = 6H Z), 1.40 (t, 3
_{H, J = 6H Z),} 3.55 (q, 4H, J = 6
_{H Z), 3.80 (s,} 3H), 4.40 (q, 2H,
J = 6H _Z ), 6.30 (d, d, 1H), 7.60
(M, 3H), 7.70 (d, d, 1H), 7.90
(M, 2H), 8.90 (bs, 1H)

(Synthesis Example 5) Synthesis of Compound 23

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18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 46.0 g of ethyl p-octadecyloxybenzoyl acetate (compound H) were added to acetic acid 3
The mixture was dispersed in 00 ml and heated under reflux for 8 hours. After cooling, 1 liter of ethyl acetate and 1 liter of water were added, and the precipitated crystals were collected by filtration to obtain 29.0 g of Compound I (MW579) (yield: 5).
0%). Subsequently, 20 ml of ethyl acetate and 12 ml of ethanol were added to 1.16 g of the compound I, and a solution prepared by dissolving 1.5 g of sodium carbonate in 10 ml of water was added thereto. After 1.5 g of compound D was further added, a solution of 1.4 g of ammonium persulfate dissolved in 10 ml of water was added dropwise over 2 minutes. After the addition, the mixture was further stirred for 5 minutes, and ethyl acetate and water were added to carry out liquid separation. After washing the organic layer with water, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 1.07 g of compound 23 (yield 63%).

Mp. 166~167 ℃ ¹ HNMR spectral analysis values (200MH _Z, CDC
During _{l 3) 0.90 (t, 3H} , J = 6H Z), 1.25 (t, 3
_{H, J = 6H Z),} 1.30 (bs, 30H), 1.8
5 (tt, 2H), 2.45 (s, 3H), 3.00
(S, 3H), 3.40 ( t, 2H, J = 6H Z),
3.50 (t, 2H, J = 6H Z), 3.60 (t, 2
H, J = 6H _Z ), 4.05 (t, 2H, J = 6)
_{H Z), 4.60 (t,} 1H), 6.35 (d, 1H,
J = 8H _Z ), 6.60 (dd, 1H, J ₁ = 8)
_{H Z, J 2 = 2H Z} ), 6.70 (bs, 2H), 7.
00 (d, 2H, J = 8H Z), 7.60 (m, 3
H), 8.05 (m, 2H), 8.10 (d, 2H, J
= 8H _Z) Mass spectrometry value (only main peaks) 845,740,739,580,579,271,1
63,

(Synthesis Example 6) Synthesis of Compound 7 18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 24.0 g of diethyl ethoxymethylenemalonate were dispersed in 400 ml of ethanol. 22.0 ml of a 28% methylate methanol solution was added, and the mixture was heated under reflux for 1 hour. After cooling, the precipitated crystals were collected by filtration, and 28.0 g of Compound f (MW307) was obtained (yield 9).
1%). Next, 10 ml of ethyl acetate and 6 ml of ethanol were added to 0.62 g of the compound f, and a solution of 1.5 g of sodium carbonate dissolved in 10 ml of water was added thereto. After 1.5 g of compound D was further added, a solution of 1.4 g of ammonium persulfate dissolved in 10 ml of water was added dropwise over 2 minutes. After the addition, the mixture was further stirred for 5 minutes.
Water was added and the layers were separated. After washing the organic layer with water, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.98 g of Compound 7 (yield: 85%).

Mp. 210-213 ° C. ¹ HNMR analysis (200MH _Z, in _{CDCl 3) 1.25 (t, 3H} , J = 6H Z), 1.40 (t, 3
H, J = 6H _Z ), 2.40 (s, 3H), 3.00
(S, 3H), 3.35 (q, 2H), 3.60 (m,
4H), 4.35 (q, 2H , J = 6H Z), 5.45
(T, 1H), 6.35 ( d, 1H, J = 8H Z),
_{6.55 (d.d, 1H, J 1} = 8H Z, J 2 = 2
_{H Z), 6.75 (d,} 1H, J = 2H Z), 7.60
(M, 3H), 8.10 (m, 2H), 8.90 (s,
1H). Mass spectrum analysis value (only main peaks are described) 574,466,392,364,307,262,2
11

The dye of the present invention can be used as a dye for image formation. Typical applications include dyes for printing inks, dyes for hot-melt thermal transfer, dyes for thermal transfer thermal transfer dyes, and ink-jet dyes. The dye of the present invention is used as a dye for a filter. Typical applications include filter dyes for silver salt photography, anti-irradiation dyes, filter dyes for solid-state image pickup tubes, dyes for micro color filters used in color liquid crystal televisions, and the like.

In particular, in the case of a photosensitive material for writing, using infrared rays, on silver halide spectrally sensitized using a semiconductor laser, which has been actively studied recently, a filter dye having absorption in the near infrared is required. The dye of the present invention can be preferably used for such applications.

The dye of the present invention is contained in a dye-donating layer on a support to form a thermal transfer dye-providing material, which is used for image formation by a thermal transfer system. Next, the case where the dye of the present invention is used for image formation of a thermal transfer system will be described in detail below. Usually, in order to form a full-color image, dyes of three colors, yellow, magenta and cyan, are required. Therefore, a full-color image can be formed by using the compound of the present invention as a cyan dye or a magenta dye and selecting the other two colors from known dyes. Further, from the dyes of the present invention, two types of dyes, cyan and magenta, may be used, and the yellow dye may be selected from known dyes and used. For the same color, the dye of the present invention and a conventionally known dye may be mixed and used. Further, two or more kinds of the dyes of the present invention may be mixed and used as the same color.

The use of the dye of the present invention as a heat transfer dye will be described. The thermal transfer dye-providing material can be used in the form of a sheet, a continuous roll, or a ribbon. The cyan dye and magenta dye of the present invention and the yellow dye used in combination therewith are usually disposed on a support so as to form independent regions. 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. Alternatively, three types of thermal transfer dye-providing materials in which the above-described yellow dye, magenta dye, and cyan dye are respectively provided on separate supports are prepared, and thermal transfer of the dye to one thermal transfer image-receiving material can be sequentially performed from these materials. . Each of the cyan dye and magenta dye of the present invention and the yellow dye used in combination therewith are each dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or supported by a printing method such as a gravure method. Can be printed on the body. The thickness of the dye-donor layer containing these dyes is usually about 0.2 to 5 μm, especially 0.4 to 2 μm in dry film thickness.
Is preferably set in the range. The amount of dye applied is 0.0
3 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 conventionally known for such a purpose can be used.
In addition, one that does not hinder the transfer of the dye when heated is selected. For example, vinyl resins such as polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (for example, polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), polyvinylpyrrolidone, and polychlorinated resins 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-based resin (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, for example, at a ratio of 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 an ink solvent for dissolving or dispersing the above-mentioned dye and binder resin. As the support of the thermal transfer dye-providing material, any of conventionally known supports can be used. For example, polyethylene terephthalate,
Polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide,
Examples include polyphenylene sulfide, polypropylene, polysulfone, cellophane and the like. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm.

A slipping layer may be provided to prevent the thermal head from sticking to the dye-providing material. The slipping layer is composed of a lubricating material with or without a polymer binder, such as a surfactant, a solid or liquid lubricant or a mixture thereof.
In order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve the slip, the dye donating material is preferably subjected to a sticking preventing treatment on the side of the support on which the dye donating layer is not provided. For example, it is preferable to provide a heat-resistant slip layer mainly composed of a reaction product of a polyvinyl butyral resin and an isocyanate, an alkali metal salt or an alkaline earth metal salt of a phosphate ester, and a filler. Polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 110 ° C.
And from the viewpoint that there are many reaction sites with the isocyanate, the weight% of the vinyl butyral portion is 15 to 40%.
Is better. As the alkali metal salt or alkaline earth metal salt of phosphate ester, Toho Chemical's Gaffa®
D720 or the like is used, and it may be used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. The heat-resistant slip layer is desirably accompanied by heat resistance in the lower layer, and a combination of a synthetic resin curable by heating and a curing agent thereof, for example, 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-providing material may be provided with a hydrophilic barrier layer for preventing the diffusion of the dye toward the support. The hydrophilic dye barrier layer contains a hydrophilic substance useful for the intended purpose. Excellent results are generally achieved with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate-grafted gelatin,
Ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly (vinyl alcohol),
Poly (ethylene imine), poly (acrylic acid), mixture of poly (vinyl alcohol) and poly (vinyl acetate), mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) )). Particularly preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-providing material 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. Preferred examples thereof 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 such as Bostick 7650 (Mhart Co., Bostick Chemical Group) Alternatively, a chlorinated high-density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the undercoat layer is not particularly limited, but 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 superimposed on the thermal transfer image-receiving material, and from either side, preferably from the back side of the thermal transfer dye-providing material, heat is applied according to image information by a 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 in accordance with the magnitude of the heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be transferred in the same manner. The heating means is not limited to a thermal head, and a known means such as a laser beam (for example, a semiconductor laser), an infrared flash, and a hot pen can be used. In the case of using a laser as the heat source, the thermal transfer dye-providing material preferably contains a material that strongly absorbs laser light. When the thermal transfer dye-providing material is irradiated with laser light, the absorbing material converts the light energy into thermal energy, transfers that heat to the nearby dye, and is heated to a temperature at which the dye transfers to the thermal transfer image-receiving material. The absorbent material is present in a layer below the dye and / or is mixed with the dye. A more detailed description of the process can be found in UK Patent 2,083,7.
No. 26A.

As the above laser, an ion gas laser such as argon or krypton, a metal vapor laser such as copper, gold and cadmium, a solid laser such as ruby or YAG, or an infrared ray of 750 to 870 nm is used. Several types of lasers, such as semiconductor lasers such as gallium-arsenic, can be used. Among them, semiconductor lasers are preferable in terms of small size, low cost, stability, reliability, durability, and ease of modulation. As a specific example, for example, a laser model SDL-2420-H2 (registered trademark) manufactured by Spectrodiode Labs or a laser model SLD-30 manufactured by Sony Corporation.
4v / w (registered trademark).

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material, so that printing using various thermal printing printers, facsimile, or magnetic recording, magneto-optical recording, optical recording, etc. Can be used to create prints from television, television, and CRT screens. For details of the thermal transfer recording method, reference can be made to JP-A-60-34895.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention has a support provided with an image-receiving layer for receiving a dye transferred from the dye-providing material. The image receiving layer receives a heat transfer dye which is transferred from the heat transfer dye providing material at the time of printing, and is made of a substance capable of receiving the heat transfer dye having a function of dyeing the heat transfer dye alone. Or a film having a thickness of about 0.5 to 50 μm, which is contained together with another binder substance. Examples of the polymer which is a typical example of the substance capable of accepting the heat transferable dye include the following resins.

(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, a carboxyl group, etc.); Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: Polyacrylate resin or polymethacrylate 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
Nos. 63-7971, 63-7972, 63
-7973 and 60-294862. Also, commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, and Byron GK-14 manufactured by Toyobo.
0, Byron GK-130, Kao ATR-200
9, ATR-2010 and the like can be used. (B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond, such as polyamide resin. (D) Those having a urea bond, such as a urea resin. (E) Those having a sulfone bond, such as polysulfone resin. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin and the like. In addition to the above synthetic resins, mixtures or copolymers thereof can also be used.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of accepting a heat transferable dye or as a dye diffusion aid. Specific examples of the high boiling point organic solvent and the hot solvent are described in JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
Nos. 62-8145, 62-9348, 62
-30247 and 62-136646. The image receiving layer of the thermal transfer image receiving material is
It is also possible to adopt a configuration in which a substance capable of accepting a heat transferable dye is dispersed and supported in a water-soluble binder. 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 cross-linking reaction with a hardener is preferable. The image receiving layer may be composed of two or more layers. In this case, the layer closer to the support is made of a synthetic resin with a low glass transition point, or a high boiling point organic solvent or a hot solvent is used to enhance the dyeing properties of the dye.The outermost layer has a glass transition point Use a synthetic resin with a higher point, minimize the amount of high-boiling organic solvent or thermal solvent used, or use it without sticking on the surface, bonding with other substances, and transferring to other substances after transfer. It is desirable to adopt a configuration that prevents failures such as retransfer and blocking with the thermal transfer dye donating material. The thickness of the image receiving layer is 0.5 to 50 in total.
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 image receiving layer may optionally contain a dye fixing agent. As a dye fixing agent, JP-A No. 3
Mordant described in JP-A-833685 and JP-A-Heisei 1-1
Any of those described in No. 88391 can be used.
Particularly, when the X moiety of the dye of the present invention is -OH, preferable results can be obtained.

The heat transfer image receiving material may have an intermediate layer between the support and the image receiving layer. The intermediate layer depends on the constituent material,
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 in some cases also serves as an adhesive. The dye diffusion preventing layer serves to prevent 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 is preferably a water-soluble binder, and examples thereof include the water-soluble binder described above as the binder for the image receiving layer, particularly gelatin. The porous layer is a layer that prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support, and plays a role of effectively using the applied heat. For the image receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer, etc. constituting the thermal transfer image receiving material, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, Fine powders such as zinc oxide, lithopone, titanium oxide, and alumina may be contained.

If the support used in 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 and dents after transfer, etc. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based synthetic paper), high-quality 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 backing, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), and various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, and polycarbonate. A film or sheet treated to give white reflectivity to the plastic, or a laminate of any combination of the above can also be used.

The thermal transfer image-receiving material may use a fluorescent whitening agent. As an example, K.K. Veenkataraman ed. "The C
hemistry of Synthetic Dyes｝ Vol. V, Chapter 8, JP 6
Compounds described in, for example, JP-A-1-143752 can be exemplified. More specifically, stilbene compounds, coumarin compounds, bisphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, 2,5-dibenzooxazolethiophene compounds, etc. Is mentioned. The fluorescent whitening agent can be used in combination with the anti-fading agent.

In the present invention, in order to improve the releasability between the thermal transfer dye-providing material and the thermal transfer image-receiving material, the surface of the layer constituting the dye-providing material and / or the image-receiving material, particularly preferably the surface where both materials are in contact with each other It is preferable to include a release agent in the outermost layer corresponding to the above. Examples of the release agent include solid or wax-like substances such as polyethylene wax, amide wax, and Teflon powder: surfactants such as fluorine-based and phosphate-based agents: paraffin-based, silicone-based, and fluorine-based oils. Any release agent can be used, but silicone oil is particularly preferred. As the silicone oil, a modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used in addition to the unmodified silicone oil. For example, see “Modified Silicone Oil” published 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, product name: X-22-371 manufactured by Shin-Etsu Silicone Co., Ltd.)
0) is valid.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be cured by a hardener. In the case of curing an organic solvent-based polymer, JP-A-61-199997 and JP-A-58-21439.
Hardening agents described in No. 8, etc. can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin. For curing of a water-soluble polymer, see U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
No. 55, No. 62-245261, No. 61-18942
The hardeners described in the above items are suitable for use. More specifically, aldehyde-based hardeners (such as formaldehyde), aziridine-based hardeners, epoxy-based hardeners (such as the compound of the following formula (44)),

[0101]

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A vinyl sulfone hardener (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (such as 62-23415
No. 7, etc.).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective. Benzotriazole compounds (U.S. Pat. No. 3,533,794, etc.),
Thiazolidone compounds (US Pat. No. 3,352,681)
Benzophenone-based compounds (JP-A-56-27)
No. 84, etc.) and JP-A Nos. 54-48535 and 6
There are compounds described in 2-136441, 61-88256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,24,155.
Nos. 5,018, columns 3 to 36; 4,254,195, columns 3 to 8; JP-A Nos. 62-174741 and 61-8.
No. 8256 (27) to (29), JP-A-1-7556
No. 8, JP-A-63-199248 and the like. Examples of useful anti-fading agents are described in JP-A-62-2.
No. 15272, pages (125) to (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 supplied from the outside to the image receiving material by a method such as transferring from a dye donating material. You may. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

In the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development. 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 and the like nonionic surfactants: alkyl carboxylate, 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, sulfo, phospho, sulfate, sulfate, and phosphate groups Anionic surfactant containing an acidic group such as:
Ampholytic surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters, alkylbetaines, amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium The fourth ring such as
Cationic surfactants such as quaternary ammonium salts and aliphatic or multiple ring phosphonium or sulfonium salts can be used. Specific examples thereof are described in JP-A-62-173463 and 62-18345.
No. 7, etc. Further, when dispersing a substance capable of accepting a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent whitening agent and other hydrophobic compounds in a water-soluble binder, an interface is used as a dispersing aid. Preferably, an activator is used. For this purpose, in addition to the above surfactants, surfactants described in JP-A-59-157636, pp. 37-38, are particularly preferably used.

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, JP-A-61-20944 and JP-A-62-13.
No. 5,826, 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 ethylene tetrafluoride resin.

A matting agent can be used for the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin and polymethacrylate, and JP-A-63-27 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
Nos. 4944 and 63-274952.

Hereinafter, the present invention will be further described with reference to specific examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

[0108]

【Example】

Example 1 The absorption characteristics of the dye of the present invention (compounds 1, 2, 8, 12, and 23) in ethyl acetate are as shown in FIGS. 1 to 5, and the absorption maximum wavelength (λmax) of the dye of the present invention is shown in FIGS. Was as follows. (In ethyl acetate). Compound 1 697 nm Compound 2 685 nm Compound 8 694 nm Compound 12 698 nm Compound 23 658 nm Among these dyes, for example, when looking at the absorption characteristics of Compound 12, the absorption at around 700 nm is sufficient, and the sharp absorption characteristic is 800 nm or more. Almost no absorption. Therefore, it can be seen that it has good performance as a filter dye used for a photosensitive material using infrared rays.

Example 2 (Preparation of Thermal Transfer Dye Donor Material (1-1)) A 6 μm-thick polyethylene terephthalate film (manufactured by Teijin) having a heat-resistant lubricating treatment applied to the back surface was used as a support. A coating composition for a thermal transfer dye-providing layer having the following composition was dried by wire bar coating to a thickness of 1.
It was applied and formed so as to have a thickness of 5 μm to prepare a thermal transfer dye-providing material (1-1). Coating composition for thermal transfer dye-donor layer: Dye 2 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.) 0.2 cc Thermal transfer dye-providing materials of the present invention and comparative thermal transfer dye-providing materials (1-2) to (1-11) were prepared in the same manner as described above except that the other dyes described in 1 were used.

(Preparation of Thermal Transfer Image Receiving Material) Synthetic paper having a thickness of 150 μm (YUPO-FPG manufactured by Oji Oil Chemical Co., Ltd.)
-150), a coating composition for an image receiving layer having the following composition having a thickness of 8 when dried by wire bar coating on the surface.
μm was applied to prepare a thermal transfer image-receiving material.
Drying was carried out in a oven at a temperature of 100 ° C. for 30 minutes after preliminary drying with a drier. 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 15cc

The thermal transfer dye-providing materials (1-1) to (1-11) thus obtained and the thermal transfer image-receiving material were
The thermal transfer dye-donor layer and the image receiving layer are superposed so as to be 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 ms, Printing was performed under the conditions of a dot density of 6 dots / mm, and a cyan dye was dyed on the image receiving layer of the image receiving material in an image form. 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 subjected to 17,000 for 7 days.
Lux was illuminated with a fluorescent lamp to examine the stability of the color image. or,
The color image was stored for 7 days under the condition of drying at 60 ° C., and the heat fastness of the color image was examined. The reflection density of the portion showing the reflection density of 1.0 after the test was measured, and the stability was evaluated by the residual ratio (percentage) to the reflection density of 1.0 before the test. The results are shown in Table 1. The measurement was performed at the λmax part.

[0112]

[Table 1]

[0113]

Embedded image

From the above results, it can be seen that the color image derived from the dye of the present invention has higher light fastness than the color image derived from the conventionally known azomethine dye a. Thermal transfer dye-providing material 1-4
As can be seen from the ～1-8, be those represented by the general formula (I) Among the dyes of the present invention, those R ¹⁰ is unsubstituted, the remarkably high heat fastness.

Example 3 Dyes shown in Table 2 were used in place of Dye 2 of the coating composition for a thermal transfer dye-donor layer in Example 2, and the thermal transfer dye-donor materials (2-1) to (2-7) were used. It was created. When printing was performed using the image receiving material prepared in Example 1, clear image recording without transfer unevenness was obtained and the density was high in each case. Light fastness was also excellent.

[0116]

[Table 2]

Example 4 In place of the polyvinyl butyral resin and the dye of the thermal transfer dye-donor layer coating composition of Example 2, the resin and the dye shown in Table 3 were used to prepare the thermal transfer dye-providing material (3-1). (3-
2) and (3-3) were prepared. When printing was performed using the same image receiving material as in Example 1, clear image recording without transfer unevenness was obtained as shown in Table 3. Light fastness was also excellent.

[0118]

[Table 3]

The following Examples 4 to 9 show combinations of other thermal transfer image-receiving materials and the above-mentioned thermal transfer dye-providing materials of the present invention.
8 is shown.

Example 5 (Preparation of Thermal Transfer Image-Receiving Material)
Thermal transfer image receiving by applying a coating composition for an image receiving layer having the following composition to the surface by wire bar coating so as to have a thickness of 10 μm when dried using synthetic paper (YUPO-FPG-150 manufactured by Oji Oil Chemical Co., Ltd.) Materials were made. Drying was carried out in a oven at a temperature of 100 ° C. for 30 minutes after preliminary drying with a drier. Coating composition for image receiving layer: Polyester resin No. 1 (compound represented by Chemical Formula 46) 2.0 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) 0.5 g Epoxy-modified silicone oil (KF-100T manufactured by Shin-Etsu Silicone) 0 0.5g methyl ethyl ketone 85cc toluene 85cc cyclohexanone 30cc

[0121]

Embedded image

When printing was performed in combination with the thermal transfer dye-providing material using the dye of the present invention in Examples 2 and 3, clear image recording was obtained. Also, light and heat fastness were excellent.

Example 6 (Preparation of Thermal Transfer Image Receiving Material) Resin-coated paper was prepared by laminating polyethylene to a thickness of 15 μm and 25 μm on both sides of a 200 μm paper, and an image receiving layer having the following composition was formed on the laminated surface having a thickness of 15 μm. The coating composition for coating was applied by wire bar coating so as to have 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 formula 41) 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 When printing was carried out in the same manner as in Example 2 with toluene 100 cc, a clear and high-density image record was obtained. Also, light and heat fastness were excellent.

Example 7 (Preparation of thermal transfer image-receiving material) An organic solvent solution of a dye-receptive polymer of the composition (B ') was emulsified and dispersed in a gelatin aqueous solution of the following composition (A') with a homogenizer to obtain a dye-receptive substance. Was prepared. (A ') Gelatin aqueous solution: Gelatin 2.3 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 cc Water 80 cc (B') Dye-receiving polymer solution: Polyester resin (Toyobo Viron 300) 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 treated with 0% of a fluorine-based surfactant (a) represented by the following formula (47). A solution of 0.5 g in 10 cc of a mixed solvent of water / methanol (1: 1) was added to obtain a coating composition for an image receiving layer.

[0125]

Embedded image

This coating composition was corona-discharged on its surface into a 150 μm-thick synthetic paper (YUPO-SG manufactured by Oji Oil Chemical Co., Ltd.).
G-150) by a wire bar coating method so as to have a wet film thickness of 75 μm, and dried to obtain a thermal transfer image-receiving material. An image was recorded in the same manner as in Example 2 using the thermal transfer dye-providing material using the dye of the present invention and the thermal transfer image-receiving material of Examples 2 and 3. The resulting image was high in density, sharp, light and heat fast.

Example 8 (Preparation of Thermal Transfer Image-Receiving Material) A thermal transfer image-receiving material was prepared in the same manner as in Example 2, except that the following coating composition for an image-receiving layer was used. Coating composition for image receiving layer: The same composition as the coating composition for image receiving layer of Example 2 except that 7 g of an ultraviolet absorber represented by the following formula (48) is added.

[0128]

Embedded image

When printing was performed in the same manner as in Example 2 using the thermal transfer dye-providing material using the dye of the present invention in Examples 2 and 3, clear and high-density images were obtained. The light fastness was higher than when the image receiving material of Example 2 was used.

Example 9 Dye 2 (1) of the coating composition for a thermal transfer dye-donor layer in Example 2
0 mmol) and the two dyes shown in Table 4 (5
Mmol) of the thermal transfer dye-providing material (9-1) to
(9-7) was created. Further, using one type of dye (10 mmol) shown in Table 4, a thermal transfer dye-providing material (9-
8) to (9-9) were prepared. Using the prepared thermal transfer dye-providing material, the thermal transfer dye image-receiving material of Example 2 was used.
The transfer was performed by the following method. In order to examine the storage stability of the color image on the image receiving material, 1
Stored for a week and tested for wet heat stability. The evaluation criteria are as follows. ：: No aggregation or crystallization of the dye was observed at all 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 4.

[0131]

[Table 4]

As is clear from the comparison between Nos. 8 and 9 and Nos. 1 to 7, the dyes of the present invention are used in a mixture of dyes rather than used alone in a thermal transfer dye-providing material. It can be seen that the color image has better storage stability of the color image and is more preferable.

[0133]

The pyrrolopyrimidin-5-one azomethine dyes and pyrrolopyrimidin-7-one azomethine dyes of the present invention are inexpensive and easy to synthesize. Also, light,
Stable to heat, moisture, air, etc. Further, depending on the substituent, the dye may have various hues and effectively absorb near-infrared rays. Furthermore, when used as a thermal transfer dye, it transfers efficiently and gives an image with high light and heat fastness. The formed image is clear, has high saturation, and has high storage stability.

[Brief description of the drawings]

FIG. 1 shows the absorption characteristics of Compound 1 of the present invention in ethyl acetate.

FIG. 2 shows the absorption characteristics of Compound 2 of the present invention in ethyl acetate.

FIG. 3 shows the absorption characteristics of Compound 8 of the present invention in ethyl acetate.

FIG. 4 shows the absorption characteristics of Compound 12 of the present invention in ethyl acetate.

FIG. 5 shows the absorption characteristics of Compound 23 of the present invention in ethyl acetate.

Claims (4)

(57) [Claims] An azomethine dye represented by the following formula (I) or (II): Embedded image Wherein R ¹ , R ² , R ³ , and R ⁴ are each independently
A hydrogen atom or a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group,
Amino group (including substituted amino group), alkoxy group, aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl Group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group,
Silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group,
Represents an acyl group, a carboxylic acid group (including its salt), and a sulfonic acid group (including its salt). X is -OH or-
Represents NR ⁵ R ⁶ . R ⁵ and R ⁶ are each independently:
Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an aryl group, a heterocyclic group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group. Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heteryloxy group, Alkylthio group, arylthio group, heterylthio group, halogen atom,
Represents a hydroxy group, a nitro group, a sulfamoyl group, a sulfonyl group, an azo group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, a phosphoryl group, a carboxylic acid group, and a sulfonic acid group. R ¹ and R ² , and / or
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 and / or R ⁹ and R ¹⁰ bind to each other To form a ring structure. 2. The azomethine dye represented by the following formula (I) or (II) according to claim 1, wherein
^7. An azomethine cyan dye, wherein at least one of R ⁸ is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.15 or more. Embedded image 3. An azomethine dye represented by the following general formula (I) or (II) according to claim 1, wherein R ¹ is an alkyl group, —OR ¹¹ , —NR ¹² —CO—
It represents R ^{13, R 11} is an alkyl group, an aryl group, or a heterocyclic group, ^{R 12} is a hydrogen atom, an alkyl group, ^{R 13} is an alkyl group, an aryl group, a heterocyclic group, -O
R ^11, represents ^{-NR 12, R 14, R 14} has the same meaning as ^{R 12.} A near-infrared absorbing azomethine dye, wherein at least one of R ⁷ and R ⁸ is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.15 or more. 4. A thermal transfer dye-providing material having a dye-providing layer comprising a heat-migrating dye-containing dye-providing layer on a support, wherein the dye-providing layer comprises the following general formula (I):
Alternatively, a thermal transfer dye-providing material comprising at least one azomethine dye represented by the general formula (II). Embedded image