JP2676656B2 - Pyrrolotriazole azomethine dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

2. Description of the Related Art 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, in combination with the development of electronic imaging, solid-state image pickup tubes and Demand for filters for color LCD TVs has increased, and azomethine dyes are used for various systems as well as for color photography.
It has come to be applied and considered in products. Phenol and naphthol azomethine dyes are known as cyan azomethine dyes used therein.
860, 1-110985, 2-59395.
No. 2-98492 and the like. Further, imidazole azomethine dye is disclosed in JP-A-63-113077.
No. 2, JP-A-2-668, No. 2-53865, and No. 2-
28264, 2-155693, 2-5386.
No. 6, No. 2-181747, and No. 1-110565. Further, Japanese Patent Application No. 1-240968 discloses a hydroxypyridine azomethine dye. Further, a pyrazoloazole azomethine dye is disclosed in JP-A-63-1.
No. 45281 and JP-A-3-51188. Further, a pyrazolopyrimidin-5-one azomethine dye is disclosed in JP-A-2-178088. A pyrazoloquinazolone azomethine dye is disclosed in JP-A-2-17519.
No. 0. Further, a pyrazolotriazine azomethine dye is disclosed in JP-A No. 2-310087. Further, JP-A-2-172793 and JP-A-2-17273.
No. 92 and No. 2-67187 disclose azomethine dyes having a cyan color.

[0002]

However, these known azomethine dyes have various drawbacks. For example, phenol and naphtholazomethine dyes have broad absorption as dyes for image formation or filters. In addition, the imidazole azomethine dye has a drawback of low light fastness. Further, the absorption of the pyrazolopyrimidin-5-one azomethine dye, the pyrazoloquinazolone azomethine dye, and the pyrazolotriazine azomethine dye was broad. In addition, the pyrazolotriazole azomethine dye had low light fastness. Furthermore, the hydroxypyridine azomethine dye was difficult to synthesize and had low light fastness. As described above, conventionally known azomethine dyes have no dye having an absorption waveform suitable as a cyan color and having good light and heat fastness. Therefore, development of an azomethine dye having sharp absorption and high fastness has been strongly desired. To solve the above problem, the present inventor
A new azomethine dye was studied. As a result, they have found that a pyrrolotriazole azomethine dye having a previously unknown specific structure has sharp absorption and high light fastness, and has completed the present invention. Here, the relationship with the conventional technology will be described. JP 6
No. 2-279340 and No. 62-278552 describe pyrrolotriazole couplers. Even if the above technique is known, the present invention is not limited at all. Although the above-mentioned known couplers are believed to give azomethine dyes by color development, according to the above-mentioned document, the color of the dye formed is magenta. According to the study by the present inventors, the pyrrolotriazole azomethine dye has a Hammett's substituent constant σ _p of R ⁷ of the coupler moiety of 0.15.
When the sum of the Hammett's substituent constants σ _p of R ⁷ and R ⁸ is 0.65 or more, a cyan color is obtained. Also, R ⁷ is-
When CONHR ¹⁰ , the cyan color is obtained even if the sum of Hammett's substituent constants σ _p of R ⁷ and R ⁸ is 0.65 or less. The above document does not describe any couplers that would give these azomethine dyes exhibiting a cyan color. Further, there is no description for predicting a specific structure exhibiting a cyan color. That is, the fact that the novel pyrrolotriazole azomethine dye of the present invention exhibits a good cyan color was first revealed by the present inventors who studied the relationship between the substituents of R ⁷ and R ⁸ and the absorption characteristics of the dye. However, it was extremely difficult to predict from the above literature.

[0003]

OBJECT OF THE INVENTION It is an object of the present invention to provide a pyrrolotriazole azomethine dye having sharp absorption and high light and heat fastness.

[0004]

The above objects of the present invention have been achieved by a pyrrolotriazole azomethine dye represented by the following general formula (I) or (II).

[0005]

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In the formulas (I) and (II), R ¹ , R ² ,
R ³ and R ⁴ each independently represent a hydrogen atom or a non-metallic atomic group. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁷ represents an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.15 or more. R ⁸ and R ⁹ each independently represent a hydrogen atom or a nonmetallic atomic group. Where R
^{When 7} is other than -CONHR ¹⁰ , the sum of Hammett's substituent constant σ _p values of R ⁷ and R ⁸ is 0.65 or more.
R ¹⁰ is a hydrogen atom or a substituent. 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 .

The general formulas (I) and (II) will be described in detail below.

Here, the Hammett's substituent constant used in the present specification will be briefly described. Hammett's rule was used in 1935 to describe quantitatively the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Hammett
It is a rule of thumb advocated by, which is widely accepted today. Substituent constants obtained by the Hammett's rule 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 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. In the future, the σ _p value will have this meaning.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a non-metallic atomic group, and the non-metallic atomic group includes a halogen atom, an alkyl group, an aryl group and a heterocycle. Group, cyano group, hydroxy group, nitro group,
Carboxy group, sulfonic acid group, amino group (including substituted amino group), alkoxy group, aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonyl Amino 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, Represents a phosphoryl group, an acyl group and the like .

Specific examples of R ¹ , R ² , R ³ and R ⁴ include a hydrogen atom and 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),
A halogen atom (eg, bromine, fluorine, chlorine), an acylamino group [preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (eg, formylamino, acetylamino,
Propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (eg, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)), an alkoxycarbonyl group (preferably carbon Number 2
-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) To 30 alkylcarbamoyl groups (e.g., 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 having 4 carbon atoms
To 30 heterocyclic carbamoyl groups (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 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, carboxy group (salt thereof), sulfonic acid group (salt thereof), amino group ( Preferably, it has 0 to 30 carbon atoms, for example, amino, methylamino,
Dimethylamino, anilino), an aryl group (preferably having 6 to 30 carbon atoms such as phenyl, m-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 30 carbon atoms such as 2-pyridyl, 2-pyridyl) Frills, 2
-Tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 30 carbon atoms, such as phenoxy, p-
Methoxyphenoxy, o-chlorophenoxy), a sulfamoylamino group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoylamino, dimethylsulfamoylamino), and an alkylthio group (preferably having 1 to 3 carbon atoms)
0, for example, methylthio, ethylthio), an arylthio group (preferably having 6 to 30 carbon atoms, for example, phenylthio, p
-Methoxyphenylthio, o-chlorophenylthio),
Sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, p-toluenesulfonyl), acyl group (preferably having 1 to 30 carbon atoms, for example, formyl, acetyl, benzoyl, p-toluyl), heterocyclic oxy group (preferably Is C3-30), an azo group (preferably C3-30, such as p-nitrophenylazo), an acyloxy group (preferably C1-30, such as acetyloxy, benzoyloxy), a carbamoyloxy group ( Preferably, it has 1 to 30 carbon atoms, for example, methylcarbamoyloxy), silyloxy group (preferably 3 to 3 carbon atoms).
0, for example, trimethylsiloxy), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, for example, phenoxycarbonyl), an imide group (preferably having 4 to 3 carbon atoms).
0, for example, phthalimide, a heterocyclic thio group (preferably having 3 to 30 carbon atoms), 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). ) 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 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. Among them, R ¹ is most preferably a hydrogen atom, an alkyl group or 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, allyl, homoallyl, prenyl, n-dodecyl, 2-acetyloxyethyl), 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 3
Represents a group).

[0013]

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Preferred among R ⁵ and R ⁶ is an optionally substituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, propyl, 2-cyanoethyl, 2-acetyloxyethyl, 2-ethoxycarbonyl). Ethyl, 2-
Methoxyethyl, allyl, homoallyl, prenyl). The ring which may be formed by combining R ⁵ and R ⁶ includes, for example, a group represented by the following chemical formula 4,
Examples of the ring which may be formed by combining ² and R ⁵ and / or R ³ and R ⁶ include groups represented by the following chemical formula 5, which can be mentioned as preferable examples.

[0015]

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[0016]

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R ⁷ has a Hammett substituent constant σ _p of 0.
It is an electron-withdrawing group of 15 or more. Examples of R ⁷ are acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group. , Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, sulfonyloxy group, acylthio group, sulfamoyl group, isocyanate group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogen Aryloxy group, halogenated alkylamino group, halogenated alkylthio group, σ _p 0.
An aryl group substituted with 15 or more other electron-withdrawing groups,
Examples thereof include a heterocyclic group, a halogen atom, or a selenocyanate group.

More specifically, R ⁷ is an acyl group (eg acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg acetoxy), a carbamoyl group (eg N.
-Ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N-methyl-N-dodecylcarbamoyl, N- {3-
(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), Cyano group, nitro group, dialkylphosphono group (for example, dimethylphosphono), diarylphosphono group (for example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenylsulfinyl), alkylsulfonyl group (for example, methanesulfonyl, octanesulfonyl),
Arylsulfonyl group (for example, benzenesulfonyl,
Toluenesulfonyl), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-t-butylphenoxy) propylthio), an arylthio group (eg, phenylthio, 2-butoxy-5-
t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio, benzoylthio) , A sulfamoyl group (for example, N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), isocyanate group, thiocyanate group, thiocarbonyl group (Eg, methylthiocarbonyl, phenylthiocarbonyl), halogenated alkyl group (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy group (eg, trifluoromethyloxy), halogenated aryloxy group (eg, pentafluorophenyloxy) ), A halogenated alkylamino group (eg, N, N
-Di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,
2,2-tetrafluoroethylthio), an aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.15 or more (eg,
2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example,
2-benzoxazolyl, 2-benzothiazolyl, 1-
Phenyl-2-benzimidazolyl, 5-chloro-1-
It represents tetrazolyl, 1-pyrrolyl), a halogen atom (eg, chlorine atom, bromine atom), or a selenocyanate group. The group capable of further having a substituent among these substituents may further have a substituent or a halogen atom which is linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferable R ⁷ is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. , An arylsulfonyl group, a sulfamoyl group, a halogenated alkyl group,
A halogenated alkyloxy group, a halogenated alkylthio group, a halogenated aryloxy group, two or more σ _p 0.
An aryl group substituted with 15 or more other electron-withdrawing groups,
And a heterocyclic group.

R ⁸ and R ⁹ each independently represent a hydrogen atom or a non-metallic atomic group. More specifically, R ⁸ and R ⁹ are each independently a hydrogen atom, an aryl group, a heterocyclic group, an alkyl group, a cyano group, a carboxyl 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, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, halogen atom, hydroxy group, nitro group, It represents a sulfamoyl group, a sulfonyl group, an azo group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group or a phosphoryl group .

Preferable specific examples of R ⁸ and R ⁹ include a hydrogen atom and an aryl group (preferably having 6 to 3 carbon atoms).
0, 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), cyano group, carboxyl group, 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 carbon). 1 to 30, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, such as phenoxycarbonyl, p-methoxyphenoxycarbonyl group, m-chlorophenoxycarbonyl, o-methoxy. Phenoxycarbonyl), an acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (eg formylamino, acetylamino, propionylamino, cyanoacetate Arylamino), preferably having a carbon number of 7
To 30 arylcarbonylamino groups (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably heterocyclic carbonylamino groups having 4 to 30 carbon atoms (for example, 2-pyridylcarbonyl). Amino, 3-pyridylcarbonylamino, furoylamino)], alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7-30,
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, toluenesulfonylamino), an aminocarbonylamino group (preferably having 1 to 30 carbon atoms, such as methylamino) Carbonylamino, ethylaminocarbonylamino, anilinocarbonylamino, dimethylaminocarbonylamino), a sulfamoylamino group (preferably having 1 to 30 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), Amino group (including anilino group, preferably having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, anilino),
Alkoxy group (preferably having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), aryloxy group (preferably having 6 to 30 carbon atoms, such as phenoxy, m
-Chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), a silyloxy group (preferably having 3 to 30 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, ceryldimethylsilyloxy, phenyldimethylsilyloxy), a heterocycle Oxy group (preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), 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 heterocyclic thio group (preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2- (1,3) -Benzoxazolyl) thio, 1-hexa Sill 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, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl,
2-pyridyl, 3-pyridyl), halogen atom (fluorine, chlorine, bromine), hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl), sulfonyl group (Preferably having 1 to 30 carbon atoms, such as methanesulfonyl, benzenesulfonyl, and toluenesulfonyl), an azo group (preferably having 3 to 30 carbon atoms, such as p-nitrophenylazo), an acyloxy group (preferably having 1 to 3 carbon atoms).
0, for example, formyloxy, acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), an imide group (preferably having 4 carbon atoms).
30, for example, succinimide, phthalimide), a sulfinyl group (preferably having 1 to 30 carbon atoms, for example diethylamino sulfinyl), a phosphoryl group (preferably include 0 to 30 carbon atoms, such as di-amino phosphoryl), etc. is.

Specific examples of the dye of the present invention are described below. The dyes in the specific examples are for explaining the present invention in detail, and the present invention is not limited thereby.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[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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[0040]

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[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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The dye of the present invention is synthesized by oxidatively coupling the coupler A or B and the developing agent C.

[0047]

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In the above formula, X is a hydrogen atom or a leaving group which is eliminated during the coupling reaction. Of course, couplers A and B may be their tautomers. Alternatively, the dye of the present invention comprises the above coupler A or B and the following compound D
And are dehydrated and condensed to synthesize.

[0049]

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In this case, X is a hydrogen atom.

Next, an example of synthesizing the dye of the present invention will be shown to explain the synthesizing method. (Synthesis Example 1) Synthesis of Exemplified Compound (2)

[0052]

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3-cyanomethyl-5-methyl-1,2,
4-triazole (compound a) 1.5 g (12.3 mm)
ol) is dissolved in 30 ml of tetrahydrofuran, and 1.0 g of sodium hydride (60% in oil) is dissolved therein.
(24.6 mmol) was added and heated to 50 ° C. In addition, 1.9 ml of ethyl bromopyruvate (14.7 mmo
1) was added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, saline and a 2N hydrochloric acid solution were added to acidify the liquidity, the mixture was extracted twice with ethyl acetate, dried and the ethyl acetate was evaporated under reduced pressure. The residue was purified by silica gel chromatography to obtain 1.20 g (4
5%). Incidentally, the synthesis of the compound (a) is
"Journal of the Chemical Society (J
individual of the Chemical So
ciety), 5149, (1962). Compound (b) 1.0 g, ethyl acetate 20
While stirring cc, 20 cc of ethanol, 24 cc of water, 6.6 g of sodium carbonate and 3.1 g of the compound (c), a solution prepared by dissolving 4.6 g of ammonium persulfate in 5 cc of water was added. After reacting at 20 ° C. for 1 hour, the mixture was extracted with ethyl acetate, the organic layer was washed twice with water, dried over magnesium sulfate, filtered, and the solvent was evaporated. The crude crystals were purified by silica gel column chromatography and recrystallized from methanol to obtain 0.82 g of Exemplified compound (2). (Yield 37%) m. p. 223 ~ 224 ℃

[0054]

【Example】

Example-1 The absorption characteristics of the dye 2 of the present invention in a solution are shown in FIG. At the same time, the absorption characteristics of the comparative dye a are also shown in FIG. In FIG. 1, the solid line shows the absorption characteristics of the dye 2 of the present invention, and the dotted line shows the absorption characteristics of the comparative dye a. Further, the maximum absorption wavelength (λmax) and the half-value width of the dye 2 of the present invention and the comparative dye a are as follows. Dye 2 of the present invention: λmax: 602.3 nm (in ethyl acetate) Half-width: 94.9 nm Comparative dye λmax: 562.6 nm (in ethyl acetate) Half-width: 88.1 nm The following comparative dye a is used for comparison. Using.

[0055]

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From FIG. 1, it can be seen that the dye of the present invention has sharp absorption, less unnecessary absorption in the yellow portion, and has an absorption maximum suitable as a cyan dye. On the other hand, it is understood that the comparative dye a in which the substituent of the coupler moiety R ⁷ is a phenyl group (σ _p is smaller than 0.15) does not have cyan color.

Example-2 Maximum absorption wavelength (λmax in ethyl acetate of the dye of the present invention
) Was written. Compound 22 618 nm Compound 4 606 nm Compound 7 619 nm Compound 10 616 nm

Example 3 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. Condition: Merry-go-round type xenon irradiator (manufactured by Dojunkoki Co., Ltd.) (output 500 W, 100,000 lux) Cell: Quartz cell Solvent: Acetonitrile Concentration: 3.0 × 10 ^-5 (mol / l) Remaining Rate: Expressed as a change in concentration (unit:%) at λmax before and after the forced fading test.

[0059]

[Table 1]

[0060]

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Example 4 In order to show the usefulness of the dye of the present invention as a filter dye, the following model filter was prepared and its light fastness was examined. A 100 μm-thick polyethylene terephthalate film (manufactured by Teijin) having a heat-resistant lubrication treatment applied to the back surface is used as a support, and a coating composition for a pigment dispersion layer having the following composition is applied on the surface of the film by wire bar coating. A model filter was manufactured. The coating thickness was adjusted so that the concentration after drying was 2.0.

Dye dispersion layer coating composition: Dye 1 1.0 g Polyvinyl butyral resin (Denka Butyral 5000-A manufactured by Denki Kagaku) 3.0 g Toluene 50 cc Methyl ethyl ketone 50 cc Polyisocyanate (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) 0.2 cc

Next, a model filter was prepared in the same manner as described above except that the dye 1 was changed to the other dyes shown in Table 2. I made the model filter for 17 days for 17 days.
The stability of the dye was examined by irradiating it with a fluorescent lamp of 000 lux. The concentration was measured before and after irradiation, and the stability was evaluated based on the ratio. The results are shown in Table 2.

[0064]

[Table 2]

As described above, it is clear that the dye of the present invention has significantly higher light fastness than the dye for comparison.

Example 5 Commercially available uncoated base paper (basis weight 64 g / m ² ) was coated with styrene-
Hollow fine particles of acrylic acid ester copolymer (particle size: 0.
3 to 0.4 μm) 43 parts (weight part of solid content, the same applies hereinafter),
A coating solution consisting of 17 parts of vapor-phase anhydrous silica (particle diameter 12 nm), 12 parts of styrene-butadiene copolymer latex, 18 parts of polyvinyl acetate latex, and 10 parts of polymethylmethacrylate fine particles (particle diameter of about 8 μm) was used as a solid content. Of 10 g / m ² was applied using a wire bar to prepare an inkjet recording paper. Ink jet recording was performed on the recording paper with an ink liquid A made of the following components at a dot number of 8 / mm by using an electrostatic acceleration type inkjet device in which a head having a nozzle hole diameter of 50 μm was installed.

Ink liquid A: Dye 1 of the present invention 16 g Diethyl phthalate 30 g Diisopropyl adipate 44 g N, N-diethyldodecane amide 20 g

The dischargeability of this ink liquid was good, and a clear and high-density cyan image was obtained. The same recording was carried out using the same number of dyes 7 and 10 as the dye 1 of the ink liquid A. As a result, each of the dyes had good ink liquid ejection properties, and a clear, high-density cyan image was obtained. The ratio below the density after leaving this image in room light for 3 months was 1% or less.

Example 6 (Preparation of Thermal Transfer Material) Materials having the following compositions were sufficiently mixed and dispersed to prepare a coating solution for a slip heat resistant protective layer. Composition of coating liquid: Methyl methacrylate 10 g n-Butyl acrylate 2 g Benzoyl peroxide 0.1 g Silica 2.5 g Toluene 35 g Isopropyl alcohol (IPA) 15 g To this coating liquid, a mixture of toluene and IPA is appropriately diluted and diluted. , A substrate of 6 μm thick polyethylene terephthalate film (hereinafter abbreviated as PET) is coated with a wire bar and dried at 100 ° C. for 1 minute to give a thickness of about 1.5 μm.
m, a heat-resistant lubricating protective layer was formed.

Next, a hot melt ink having the following composition was prepared. Composition of hot-melt ink: Dye 1 10 g Lanolin fatty acid barium salt 30 g Carnauba wax 20 g Paraffin wax 20 g Dispersant 0.5 g Liquid paraffin 5 g Ink having the above composition was treated with methyl ethyl ketone 100 at 68 ° C.
The mixture was sufficiently dispersed in a ball mill for about 48 hours together with a mixture of cc and 130 cc of toluene. Next, 300 g of a 20% by weight vinyl chloride-vinyl acetate copolymer resin solution (10 parts of resin, 20 parts of toluene, 20 parts of methyl ethyl ketone) was added to the ink dispersion, and the mixture was dispersed by a ball mill for about 1 hour. A paint was prepared. This coating material is applied to the surface of the PET film having the back surface provided with the slip resistant heat-resistant layer using a wire bar, and the drying temperature is 100.
After drying at 0 ° C for 1 minute, a hot-melt ink layer having a thickness of about 5 µm was formed.

Plain paper was used as the obtained thermal transfer material and thermal transfer image receiving material, and the transfer layer (hot-melt ink layer) of the thermal transfer material and plain paper were superposed, and printing was carried out with a thermal head from the support side of the thermal transfer material, and transfer was performed. As a result, clear cyan color recording could be obtained. Further, instead of the dye 1 of the hot melt ink, the same number of dyes 7 and 10 were used to prepare a similar ink to prepare a thermal transfer material. When this thermal transfer material was used to perform transfer in the same manner as above, clear cyan recording could be obtained.
Further, when the optical image stability of these recorded sheets was examined, very good results were obtained.

[0072]

INDUSTRIAL APPLICABILITY The novel pyrrolotriazole azomethine dye of the present invention, when used as an image forming dye in ink jet, thermal transfer, etc., provides a high density image free from fading or discoloration due to its remarkably excellent light fastness. Was given.
Further, even when the azomethine dye of the present invention was used as a dye for various filters, it was possible to obtain a filter having excellent stability and excellent reduction in concentration due to its excellent light fastness.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum of an ethyl acetate solution of Exemplified Compound (2) and Comparative Dye a.

Claims (1)

(57) [Claims] 1. A pyrrolotriazole azomethine dye represented by the following general formula (I) or (II): In formulas (I) and (II), R ¹ , R ² , R ³ and R ⁴
Are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, acylamino group, alkoxycarbonyl group, cyano group, sulfonylamino group, carbamoyl group, sulfamoyl group, aminocarbonylamino group, alkoxycarbonylamino group, hydroxy group. , Carboxy group (salt thereof), sulfonic acid group (salt thereof), amino group,
Aryl group, heterocyclic group, nitro group, aryloxy group, sulfamoylamino group, alkylthio group, arylthio group, sulfonyl group, acyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group,
Silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group or phosphoryl group
Representing the. R ⁵ and R ⁶ are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group. R ⁷
Represents an electron-withdrawing group having a Hammett substituent constant σ _p of 0.15 or more. R ⁸ and R ⁹ are each independently a hydrogen atom, an aryl group, a heterocyclic group, an alkyl group, a cyano group, a carboxy group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonyl group. Amino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, alkylthio group , Arylthio group, heterocyclic thio group, halogen atom, hydroxy group, nitro group, sulfamoyl group, sulfonyl group, azo group, acyloxy group, carbamoyloxy group, imide group, sulfinyl group or phosphoryl group . However, when R ⁷ is other than -CONHR ¹⁰ , the sum of Hammett's substituent constant σ _p values of R ⁷ and R ⁸ is 0.6.
5 or more. R ¹⁰ is hydrogen atom. 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. .