JPH0253865A - Imidazole-based dye - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1 and R2 are H, (substituted) alkyl or R1 and R2 are mutually bonded to form 5-membered or 6-membered ring; R3-R6 are halogen, amido, (substituted) alkyl, etc.; R7 and R8 are monofunctional organic group; m is 0-4; n is 0-5; B is bonded through C, N, O or S to imidazole ring or directly to imidazole ring]. USE:Dye suitable for image medium of photography, heat-sensitive transfer, etc., having low pH dependence, requiring no mordant and showing absorption characteristics preferable as a cyan dyestuff. PREPARATION:A coupler shown by formula II and a developing agent of p- phenylenediamine base shown by formula III are subjected to oxidation coupling reaction in the presence of an oxidizing agent such as silver halide under a basic condition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel imidazole dye useful for color image formation, filter use, etc.

[Background of the invention]

British patents 1 and 5 show that diphenylimidasoles form pigments through oxidative coupling with aminophenols.
No. 45,507. These diphenylimidasols are useful as photographic couplers, and it has been shown that oxidized nocot-bling dyes with aminophenols can be mordanted with quaternary ammonium mortants to produce images with good light resistance.

However, the color tone of oxidatively coupled dyes with aminephenols is highly dependent on pH, and at neutral pH the absorption wavelength is shortened to λmax or 1], so when used as images, the presence of quaternary mordants is important. Required.

Therefore, in systems where these moltans do not exist, the light absorption λmax of these dyes is in the line region of the visible light region, and it is difficult to reproduce colors by subtractive color reproduction methods such as photography, thermal transfer, inkjet, and printing. It cannot be used as a cyan dye in various image forming means.

As a result of various studies, the present inventors replaced the above-mentioned amine/phenol with a specific para-phenylene diamine compound and bonded the 2-position to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom, or sulfur atom. By introducing an anilino group into the 0-position of the organic group and the 4-position phenyl group, there is less pH dependence, there is no need for a mordant, it has more preferable spectral absorption characteristics as a cyan dye, and it has excellent heat resistance. The present inventors have discovered that a compound suitable as a cyan dye in the above-mentioned image forming means can be obtained, leading to the present invention.

[Purpose of the invention]

The purpose of the present invention is to reduce pH dependence, eliminate the need for a mordant, have more preferable absorption characteristics as a cyan dye, and provide excellent light resistance for photography, thermal transfer, ink cyanide,
The purpose of the present invention is to provide a dye suitable for printing and other image media.

[Structure of the invention]

The above objects of the present invention are achieved by an imitasol dye represented by the following general formula (I).

In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a substituted alkyl group, and R1 and R2 are bonded to each other to form 5
or a six-membered ring.

R3, R4, R5 and R6 each represent a halogen atom, amide group, alkyl group, substituted alkyl group, alkoxy group or substituted alkoxy group, R7 and R8 each represent a monovalent organic group, and m is 0 to 4, n represents an integer from 0 to 5,
When m and n are 2 or more, R7 and R8 may each represent two or more different groups. B represents an organic group bonded directly to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom.

The present invention will be explained in more detail below.

In general formula [I], R1 and R2 are preferably hydrogen atoms, alkyl groups, and substituted alkyl groups such as hydroxyalkyl groups, alkoxyalkyl groups, alkoxyalkoxyalkyl groups, and alkylsulfonamidoalkyl groups. Examples of these groups include alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl, 5ee-butyl, butyl, isobutyl, t-butyl, octyl, dodecyl, octadecyl, cyclohexyl, hydroxyethyl, Examples include substituted alkyl groups such as methoxyethyl, methoxybutyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and β-methanesulfonamidoethyl.

Examples of the 5-membered ring or 6-membered ring formed by combining R1 and R2 include groups such as pyrrolidino, pipezilino, pipe'radino, and morpholino.

R3, R4, R5 and R6 may be the same or different, preferably a hydrogen atom, a halogen atom, an alkylamido group, an arylamido group, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylsulfonamidoalkyl group , alkoxy group, etc. Examples of these are chlorine, bromine, acetamide, propionamide, benzamide, tolylamide, methyl, ethyl,
Examples include atoms or groups such as hydroxymethyl, hydroxyethyl, methoxyethyl, methanesulfonamidoethyl, methoxy, and ethoxy.

Further, as the organic group via a carbon atom represented by B, an alkyl group (for example, methyl, 1-propyl, t-butyl, trifluoromethyl, benzyl, 3-(4-aminophenyl)propyl, Allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, 3-(4-(4-dodecyloxybenzene)sulfonamidophenyl]propyl, ■Methyl-2-CC
2-octyloxy-5-t-octylphenyl)sulfonamidophenyl]ethyl, ■-methyl-2-[2-
Octyloxy-5-(2-octyloxy-5L-octylphenylsulfonamide) phenylsulfonamide 1-]ethyl, 2-[2-octyloxy-5(2-octyloxo-5-t-ocdylphenylsulfone) (amido) phenylsulfonamido]ethyl, etc.), aryl groups (for example, phenyl, naphthyl, 2,4 dichlorophenyl, 2-hydroxy-5-methylphenyl, 2-acetamidophenyl, 2-methanesulfonamidophenyl,
2-Butanamidophenyl, 2(N,N-dimethylsulfamoylamino)phenyl, 2-(4-dodecyloxybenzenesulfonamido)phel, 2-C2-C2
, 4-di-t-amylphenoxy)hexaneamido]phenyl, 2-(2-octyloxy-5-toctylphenylsulfonamido)phenyl, 4carbamoylphenyl, 4-cyanophenyl, 4-carboxyphenyl,
4-ethoxycarbonylfer, etc.), heterocyclic groups (e.g., 4-pyridyl, 2-pencyimigzolyl, etc.), cyano group, carboxyl group, acyl group, carbamoyl group, alkoxycarpol group2. Examples include aryloxycarbonyl group.

Examples of organic groups via a nitrogen atom include acylamino groups (e.g., acetamide, benzamide, 24-cy[-amylphenoxyacetamide, 2,4-dichlorobenzamide, etc.), alkoxycarbonylamino groups (e.g.,
methoxycarbonylamino, propoquinecarbonylamino, L-butoxycarbonylamino, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino), sulponamide groups (e.g., methanesulfonamide, octanesulfonamide, benzenesulfonamide, 4 -dodecyloxybenzenesulfonamide, etc.)
, anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-4-tetradecanamide anilino, etc.), ureido group (e.g., N-methylureido, N-
butylureido, N-phenylureido, N,N-dibutylureido, etc.), sulfamoylamino groups (e.g.
N, N-diethylsulfamoylamino, N-phenylsulfamoylamino, etc.), amino groups (e.g., unsubstituted amino, N-methylamino, N, N-diedylamino, etc.), heterocyclic groups (e.g., 3 .5-dimethyl-1-pyrazolyl, 2,6-dimethylmorpholino, etc.).

Examples of organic groups via an oxygen atom include alkoxy groups (e.g., methoxy, ethoxy, l-propoxy, butoxy,
2,2.2-) trifluoroethoxy, 3,3.3 trifluoropropoxy, 2-chloroethoxy, 2cyanoethoxy, 2-butanesulfonylethoxy, etc.), aryloxy groups (e.g., phenoxy, 4-methoxyphenoxy, 2.4-dichlorophenoxy, 4-(2ethylhexaneamido)phenoxy, etc.), silyloxy groups (e.g., trimethylsilyl oxine, dimethylphenylsilyloxy, dimethyl-E-butylsilyloxy, etc.), heterocyclic oxy groups (e.g., Tetrahydrobilanyloxy, 3-
Pyridyloxy, 2-(L,3-pencyimigzolyl)
oxy, etc.).

Examples of organic groups via a sulfur atom include alkylthio groups (for example, methylthio, ethylthio, butylthio, 3-C
4-C4-dodecyloxybenzene)sulfonamidophenyl]glopythio, 4-(2-butoxy-5-t-
octylphenylsulfonamide) benzylthio, etc.),
Arylthio groups (e.g., phenylthio, 2-naphthylthio, 2,5-dichlorophenylthio, 4-dodecylphenylthio, 2-butoxy-5-octylphenylthio, etc.), heterocyclic thio groups (e.g., 2-pyridylthio, 2-butoxy-5-octylphenylthio, etc.),
-(1,3-benzoxasilyl)thio group, ■-hexadecyl 1,2.3.4-tetrazolyl-5-thio group, 1
-(3-N-octadecylcarbamoylphenyl-1.
2,3.4-tetrazolyl-5-thio, etc.).

The substituents represented by R7 and R8 are not particularly limited, but
For example, halogen atoms and cyan, nitro, carboxy, alkyl, sulfamoyl, acyl, acyloxy, alkoxycarbonyl, -NHCOR,, -NHSO,R,
, etc. can be mentioned.

The alkyl group represented by R7 and R8 is preferably a straight chain or branched alkyl group having 1 to 22 carbon atoms, such as methyl, ethyl, butyl, dodecyl, and the like. These alkyl groups also include cycloalkyl groups such as cyclohexyl groups, and may be substituted. Preferred substituents include halogen atoms, hydroxy groups, carboxy groups, cyano groups, sulfo groups, and alkoxy groups having 1 to 22 carbon atoms.

The alkoxy group is preferably a linear or branched alkoxy group having 1 to 22 carbon atoms, such as methoxy, ethoxy,
Examples include 1-propyloxy, octyloxy, dodecyl oxine groups, and the like.

Examples of the carbamoyl group include unsubstituted alkylcarbamoyl groups such as ethylcarbamoyl and dodecylcarbamoyl groups, and substituted alkylcarbamoyl groups such as diethylcarbamoyl, butyloxyglopyruhamoyl and dodecyloxyfurobylcarbamoyl groups.

Similarly, regarding sulfamoyl groups, unsubstituted alkylsulfamoyl groups such as ethylsulfamoyl, ethylsulfamoyl, and todenylsulfamoyl groups, substituted alkylsulfamoyl groups such as dodecyloxypropylsulfamoyl groups, etc. The following groups can be mentioned.

Examples of the arylcarbamoyl group include phenylcarbamoyl x and a timed phenylcarbamoyl group, and examples of the arylsulfamoyl group include a phenylsulfamoyl group and various substituted phenylsulfamoyl groups.

Also, acyl groups such as acetyl, benzoyl, butanesulfonyl, benzenesulfonyl groups, acyloxy groups such as acetoxy, lauroyl oxine, butanesulfonyloxy groups, alkoxy groups such as ethoxycarbonylpyroxycarbonyl, 2-ethylhexyloxycarbonyl groups, etc. Examples include quincarbonyl group.

The NHCOR+ group represents an alkylamide group having 1 to 22 carbon atoms, and representative examples of unsubstituted alkylamide groups include acetamide, butanamide, laurylamide, stearylamide groups, and the like.

Further, it may be an alicyclic amide group such as a cyclohexanecarbonamide group, a branched structure such as a 2-ethylhexaneamide group, or it may contain an unsaturated bond.

Examples of the substituted alkylamide group include halogen-substituted alkylamide groups such as monochloroacetamide, trichloroacetamide, perfluorobutanamide F group, m-pentadecylphenoxyacetamide, α-(2,4-di-t-
Examples include phenoxy-substituted alkylamide groups such as amylphenoxy)pentanamide, α-(2,4-di-L-acylphenoxy)acetamide, and 0-chlorophenoxymyristic acidamide groups.

In addition, the -NHCOR9 group represents an arylamide group, typically an unsubstituted arylamide group such as benzamide or naphthamide F group, and a substituted arylamide group such as p
Alkyl-substituted benzamide groups such as -t-butylbenzamide and p-methylbenzamide groups, alkoxy-substituted benzamide groups such as p-methquinbenzamide and 0-dodecyloxybenzamide groups, p-ace[-amidebenzamide groups] AmiF, m-lauroylamide benzamide, m-(2.
Amide-substituted benzamide groups such as 4-di[-amylphenoxyacetamito)benzamide groups, sulfonamide-substituted benzamide groups such as O-hexadecanesulfonamidobenzamido F, p-butanesulfonamidobenzamide groups, etc. etc. are representative examples.

The NHCOOR 9 group represents a substituted or unsubstituted alkoxycarbonylamino group having 1 to 22 carbon atoms, and typical examples include ethoxycarbonylamino, l-propoquinecarbonylamino, octyloxycarbonylamino, decyloxycarbonyl, and methoxyethoxycarbonyl. Examples include amino groups. The NHCOOR9 group also represents an aryloquine carbonyl group, and a typical example thereof is a phenoxycarbonyl group.

Typical examples include dimethylcarnohamoylamino, ethylhamoylamino, and the like.

The NH302R9 group represents an alkylsulfonamide group or an arylsulfonamide group.

Examples of the alkylsulfonamide group include methanesulfonamide, butanesulfonamide 1, unsubstituted alkylsulfonamide groups having 1 to 22 carbon atoms such as dodecanesulfonamide group, and substituted alkylsulfonamide groups such as benzylsulfonamide group. can be mentioned.

Further, as the arylsulfonamide group, unsubstituted arylsulfonamide groups such as pencenesulfonamide and naphthalenesulfonamide groups, or p-luenesulfonamide, 2,4.6-1-limethylbensenesulfonamide, p- Examples include substituted arylsulfonamide groups such as alkyl-substituted benzenesulfonamide groups such as F-decylbenzenesulfonamide groups, and alkoxy-substituted benzenesulfonamide groups such as p-dodecyloxybenzenesulfonamide and butyloxybenzenesulfonamide groups.

Typical examples include dimedyl sulfamoylamino,
Dialkylsulfamoylamino groups such as dibutylsulfamoylamino groups are preferred.

Among the compounds represented by the general formula (I), the following general formulas (II:l, (III:l) and [■] are representative).

General formula (IT,) General formula [■] General formula [■] Preferred compounds include the following general formula (Vl).

General formula CV) In the general formula [:n)-(IV:], R7, R8, m
and n have the same meanings as R7, R8, m and n described above, R11 represents a monovalent organic group, and Q represents an integer of 0 to 5. When a is 2 or more, R7 may represent two or more different groups. R12, R13 and R1 each represent a substituent, and L represents an oxygen atom or a sulfur atom. Also, R
12 and R13 may be combined with each other to form a heterocycle.

In the general formula [■], the monovalent organic group represented by R11 can specifically include the atoms and substituents described for R7 and R8 in the general formula [I].

Further, among the compounds represented by the general formula (II), the general formula [
■], R7, R8, R1□ and m1n, Q are R7, R8, RI, and m in general formula (II),
They are synonymous with n and Q, respectively.

R15 is a hydrogen atom, an alkyl group, or an aryl group. The alkyl group represented by R15 is preferably a straight chain or branched alkyl group having 1 to 32 carbon atoms, and also includes cycloalkyl groups such as cyclohexyl group. Further, these alkyl groups may be substituted, and representative examples of preferred substituents include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a sulfo group, and an alkoxy group having 1 to 22 carbon atoms. I can do it.

The aryl group represented by R1 is preferably a phenyl group, and the phenyl group may be substituted with a nitro group, 7miFM, sulfonamide group, or the like.

Also, NHR+5 is -NHCOR, group, -NHCOO
The R9 group has the same meaning as R9 and Rlo in the general formula [■], respectively.

In addition, in the general formula (III), the alkyl group or aryl group represented by R12 or R13 includes the above-mentioned general formula (
Specific examples include the alkyl group and aryl group explained in RI5 of V).

The heterocycle formed by combining R12 and R13 is preferably 5- or 6-membered, and these heterocycles may have a substituent and may be further fused with a carbon ring.

Next, in the general formula [■], Ro represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group;
As for the aryl group, the argyl group and the aryl group explained in the above general formula [■] can be specifically mentioned.

The heterocyclic group represented by R1 is preferably 5- or 6-membered, specifically 2-pyridyl, 4-pyridyl,
2-hensoimitazolyl, 35-dimethyl-1-pyrazolyl, 4-morpholino, 35-dimethyl-2furyl, 24
-dimethyl-5-thiazolyl, 2-acetamido-4-
Examples include groups such as methyl-5-pyrimidinyl.

Typical specific examples of the imitasol-based N'an dye of the present invention are shown below, but the present invention is limited thereby.Next, typical synthetic examples of the N'an dye of the present invention will be shown.

Synthesis Example 1 (Synthesis of Compound Example ■3) Patents filed on August 12, 1986 by the present inventors (
4) Coupler 2-(2-oxycarbonylaminophenyl)-4-C2- described as Synthesis Example 8 in the specification of "Silver halogenide photographic material containing a novel cyan coupler" Anilino-5-(α-(2,4G-L
-amylphenoxy)-α-1-propylacetamido)phenylcy 3H-imidazole (1.3 g) was dissolved in 50 mQ of ethyl acetate, and 40 g of 5% sodium carbonate aqueous solution was added.
m+1゜4-Amino-N-ethyl-N-β-methanesulfonamidoethyl-nr Toluidine sulfate 2.0g dissolved in 20ml of water was added, and a catalytic amount of silver powder was added.
5% hydrogen peroxide solution was added little by little over 4 hours. The ethyl acetate layer immediately becomes cyan colored, but after confirming that the coupler is completely consumed by thin layer chromatography,
Separate the ethyl acetate layer and wash thoroughly with water.

The ethyl acetate layer was dehydrated with anhydrous magnesium sulfate, concentrated, and the residue was purified by column chromatography and further recrystallized from ethanol to obtain 1.8 g of the desired product.

Melting point: 211-214°C0 Other imidazole dyes represented by the general formula [I] include couplers represented by the following general formula [■] and couplers represented by the following general formula [■], as in the synthesis example above. It can be similarly synthesized by oxidative coupling of a paraphenylenecyamine-based developing agent in the presence of an oxidizing agent.

General formula [■] (Here, R7, R8, m and n represent the same meaning as defined in the above general formula [■].) General formula [■] (Here, R1, R2, R3 , R6 and R6
represents the same meaning as defined in the general formula [■]. ) This coupling reaction is preferably carried out under basic conditions, and the reaction medium may be an organic solvent, an aqueous organic solvent, or an aqueous solution. Further, the oxidizing agent may be any one having a potential capable of oxidizing p-phenylenediamine, whether organic or inorganic.
Inorganic oxidizing agents such as silver halide, hydrogen peroxide, manganese dioxide, potassium peroxide, oxygen, NBS, chloramine T
Various organic oxidizing agents such as oxidizing agents can be used.

As described above, the cyan dye of the present invention is obtained by oxidative coupling of an imidazole coupler and p-phenylenediamine.

The imidazole dye of the present invention uses a coupler represented by the general formula (Vl) as a cyan coupler used in silver halide color photographic materials, for example,
(2) Developing with a color developer containing a p-phenylenediamine color developing agent represented by [2], and coupling the p-phenylenediamine developer oxidized by exposed silver halide with the coupler. It is particularly useful as a photographic cyan dye to obtain cyan images. At this time, the coupler is normally contained in the photographic light-sensitive material, but it can also be used in an external color development method in which the coupler is dissolved together with a color developing agent in the developer.

The imidazole dye of the present invention can also be used for photography as a filter dye,
No. 8-18169, No. 58-205798, No. 58-
It is also useful as a cyan dye for images in thermal transfer processes, inkjet systems, color electrophotography, printing, etc. as shown in No. 219086.

In order to improve the stability of the dye of the present invention against light or heat, known stabilizers can be used in combination. Such stabilizers include, for example, the hydroquinone derivatives described in U.S. Pat. Nos. 3,935,016 and 3,982,944, U.S. Pat.
Hydroquinone diether derivatives described in JP-A No. 5-21004, phenol derivatives described in JP-A-54-145530, spiroinquin derivatives and methylene described in GB-A Nos. 2,077.455 and 2062.888. Dioxybenzene derivative, US Patent 3
, No. 764,337, No. 3,432,300, No. 3,
No. 574,627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973
No. 1-152225, No. 53-20327 and No. 53
Chroman derivatives, spirochroman derivatives and coumaran derivatives described in No.-17729, JP-A-55-632
No. 1, British Patent No. 1,347,556, British Patent Publication No. 2
, 066.975 and Japanese Patent Publication No. 54-12337, the hisphenol derivatives described in Japanese Patent Publication No. 48-31625 and U.S. Pat. No. 3,700,455, and Examples include metal complexes as described in Japanese Patent No. 4,245,018 and the like.

〔Effect of the invention〕

The dye of the present invention is useful as a dye for color image formation by a subtractive color method, and can also be used as a green or blue filter by mixing with yellow or magenta dye as a filter dye for solid-state image pickup tubes, color LCD televisions, etc. Can be used.

At least in the above applications, the dye of the present invention has an extremely good hue as a cyan dye, and has a molar extinction coefficient (
ε) is also high.

The dye of the present invention has a sharp cut in hue at the short wavelength side of the spectral transmittance curve compared to known phenolic and naphtholic in-1-aniline dyes, and therefore has a large sub-absorption in the linear region. The molar extinction coefficient in the red region is more than twice as large, with less irregular absorption. It also has good light resistance and heat resistance, and has extremely favorable properties in terms of color reproduction for color photography based on the subtractive color method.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to examples, and the present invention is not limited by these examples.

Example 1 Exemplary compounds (13), (16), (23) of the dye of the present invention
) and (31), the absorption spectra in the visible light region in ethyl acetate or methanol solvent were measured and the results are shown in the table below.

As shown in the table above, the new imidasol dye of the present invention is 640
It is found that it has absorption in the wavelength range of nm or more and is useful as a two-color dye of blue-9, especially as a dye for cyan image formation, and as a near-infrared dye.

Example 2 A coloring agent layer coating solution using a dispersion A having the following composition was coated on a polyethylene terephthalate film base having a thickness of 6 μm using a wire bar and dried to prepare a thermal transfer recording medium sample 1. Next, Samples 2゜3.4 and 5 were prepared in the same manner as Sample 1 using the compounds (13), (16), (23) and (31) of the present invention in place of the comparative dye (A). did.

(Dispersion A) Comparative dye (A) Ig and tricresyl phosphate 0
．． After dissolving 5 g in ethyl acetate (3 mO), 10% gelatin aqueous solution (12 mff1) and 3.75% alkanol XC (
De,.

4.5 ml of an aqueous solution (manufactured by Bonn Co., Ltd.) was added and dispersed for about 20 minutes using an ultrasonic disperser. After dispersion, heat to approximately 80°C to remove ethyl acetate, and add water to bring the total volume to 30ml.
It was set to 0.

Each sample obtained was thermally transferred onto plain paper using a thermal head. However, the heating time is constant and the heating temperature is 10
It was varied in the range of 0 to 200°C. FIG. 1 shows the relationship between transfer temperature and transfer density.

As is clear from FIG. 1, by using the dyes of the present invention, the reduction in dye concentration required to obtain the same transfer density is achieved.

Comparative dye (A)

[Brief explanation of the drawing]

FIG. 1 is a temperature-density curve when thermal transfer was performed using the thermosensitive recording medium in Example 2.

Claims (1)

[Claims] An imidazole dye characterized by being represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. may form a ring. R_3, R_4, R_5 and R_6 each represent a halogen atom, an amide group, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group, R_7 and R_8 each represent a monovalent organic group, and m is 0 to 4 and n represent an integer of 0 to 5, and when m and n are 2 or more, R_7 and R_8 may each represent two or more different groups. B represents an organic group bonded directly to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom. ]