JPH0234373B2 - HAROGENKAGINSHASHINKANKOZAIRYO - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material containing a 2,5-diacylaminophenol type cyan coupler. Prior art and its problems As is well known, subtractive color photography uses an oxidation product of a color developing agent, which is produced when an aromatic primary amine color developing agent reduces exposed silver halide grains, and a yellow color developing agent. A dye image is formed by oxidative coupling of couplers forming , cyan, and magenta dyes in a silver halide emulsion layer. As the yellow coupler that forms the yellow dye, a compound having an open chain methylene group is generally used, and as the magenta that forms the magenta dye, compounds such as pyrazolone, pyrazolinobenzimidazole, and imidazolone are used. As a cyan coupler that forms a cyan dye, a compound having phenolic or naphtholic water oxygen is used. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion;
Alternatively, it is dissolved in an aqueous alkaline solution and added to the emulsion. The former is an oil drop dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, and color sharpness. . The basic properties required for each coupler are:
In addition to simply forming a dye, first of all, it has high solubility in high-boiling organic solvents or alkaline liquids, and has good dispersibility and stability in silver halide photographic emulsions.
Various properties such as fastness against heat and moisture, good spectral absorption characteristics, good transparency, high color density, and clear images. It is desired to have the following. In particular, cyan couplers are required to have improved spectral absorption and image storage properties such as heat resistance, moisture resistance, and light resistance. Conventionally known cyan couplers include the following compounds. That is, a coupler consisting of 6-[α-(2,4-di-tert-amylphenoxy)-butanamide]-2,4-dichloro-3-methylphenol is reported in the US Patent Publication. This coupler has good light resistance but poor heat resistance. JP-A-50-112038 discloses that the 2- and 5-positions of phenol are substituted with an acylamino group, and the acylamino group at the 2-position is substituted with an acylamino group.
Cyan couplers substituted with alkyl groups substituted with fluorine atoms have been reported. This coupler has features such as good heat resistance and little loss of density when treated with a bleaching solution with weak oxidizing power or a bleaching solution that is tired, but it has poor light resistance. Furthermore, in the cyan coupler described in JP-A-53-109630, the 2- and 5-positions of the phenolic cyan coupler are substituted with acylamino groups, and the terminal of the 5-position acylamino group is a sulfonamide group or a sulfamoyl group. This is a phenolic cyan coupler substituted with , which further enhances the features of the above-mentioned phenolic cyan coupler having an alkyl-substituted acylamino group, but it is still insufficient in terms of light resistance. 2nd or 5th place in US Patent No. 4304844
Although 2,5-diacylaminophenol type cyan couplers in which the terminal end of the position is substituted with an alkylsulfonyl group are described, the cyan couplers described as these specific compounds have insufficient light resistance; It also has the disadvantage that the absorption maximum wavelength is relatively short at 640 to 655 nm, and therefore the color reproducibility of the cyan dye image formed is poor, and the absorption in the green and blue regions of the absorption spectrum is large, and the yellow and magenta Multicolor silver halide photographic materials that use couplers in combination have the disadvantage of causing color turbidity. Object of the Invention The first object of the present invention is to contain a cyan coupler capable of forming a cyan dye whose dye absorption maximum is on the long wavelength side of the red region and with little absorption in the green and blue regions. To provide a silver halide photographic material in which a cyan dye image produced has excellent color reproducibility, and a multicolor silver halide photographic material using yellow and magenta couplers in combination has less color turbidity. be. A second object of the present invention is to provide a silver halide photographic material containing a cyan coupler, in which the cyan dye image formed has improved image storage properties such as light fastness, heat resistance, and moisture resistance in a well-balanced manner. It is in. A third object of the present invention is to provide a silver halide containing a cyan coupler that exhibits less loss in the density of coloring dyes even when processed with a bleaching solution with weak oxidizing power or a bleaching solution with a weak oxidizing power in the bleaching process after color development processing. Our objective is to provide photographic materials. The present inventors have discovered that in a silver halide photographic material having at least one silver halide emulsion layer provided on a support, a cyan coupler represented by the following general formula [] is incorporated into the silver halide emulsion layer. The inventors have discovered that the above object can be achieved by including the above-mentioned components, and have completed the present invention. General formula [] [In the formula, R ₁ represents an alkyl group, a cycloalkyl group, or an aryl group. R ₂ and R ₃ each represent a hydrogen atom or an alkyl group. Ar
represents an aryl group. Z represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. ] Detailed Description of the Invention In the present invention, the alkyl group represented by R ₁ in the general formula [] preferably has 1 to 20 carbon atoms.
linear or branched alkyl groups (e.g. methyl group, ethyl group, i-propyl group, t-butyl group,
n-butyl group, t-amyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), and when these alkyl groups have a substituent, this substituent is a hydroxyl group. , hydroxycarbonyl group, cyano group, aryl group (e.g. phenyl group, P-methoxyphenyl group, tolyl group, etc.), alkyloxycarbonyl group (e.g. ethoxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group ( (e.g., phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylsulfonamide group (e.g., methanesulfonamide group, etc.), acylamino group (e.g., acetamide group, benzamide group, etc.), alkoxy group (e.g., methoxy group) , benzyloxy group, etc.), aryloxy group (eg, phenoxy group, etc.), and sulfonyl group (eg, methanesulfonyl group, etc.). The alkyl group represented by R ₁ is preferably an unsubstituted alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, i-propyl group, t-butyl group, n-butyl group, t-amyl group). group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, etc.), alkyl group substituted with an aryl group (e.g. benzyl group, p-t-butylbenzyl group, anisyl group, phenethyl group), etc. The aryl group represented by R ₁ is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group. When the phenyl group has a substituent,
Examples of this substituent include halogen atoms (e.g. chlorine, bromine, etc.), hydroxyl groups, nitro groups,
Cyano group, hydroxycarbonyl group, alkyl group (straight chain or branched alkyl group, such as methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group) etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propoxy group,
butoxy group, pentyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc.), alkylcarbonylamino group (e.g. undecylcarbonylamino group, dodecylcarbonylamino group, etc.), succinimide group, arylcarbonylamino group (e.g. benzoylimino group), groups), alkylsulfonamide groups (e.g., dodecylsulfonamide groups, etc.), arylsulfonamide groups (e.g., benzenesulfonamide groups, etc.), alkylaminosulfonamide groups (e.g., dimethylaminosulfonamide groups, etc.), arylaminosulfonamide groups (e.g., anilinosulfonamide group, etc.), alkylcarbamoyl group (e.g., hexadecylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl group, n-dodecylsulfonyl group, etc.), Examples include an alkyloxycarbonyl group (eg, dodecyloxycarbonyl group), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), and the like. More preferably, the aryl group represented by R ₁ is an unsubstituted phenyl group, a phenyl group substituted with an alkyl group (e.g. m-tolyl group), a phenyl group substituted with a nitro group (e.g. p-nitrophenyl group), Phenyl groups substituted with halogen atoms (e.g. m-chlorophenyl group), phenyl groups substituted with alkylsulfonamide groups (e.g. methylsulfonamide phenyl group, butylsulfonamide group, benzylsulfonamide group), alkylaminosulfonamide a phenyl group substituted with a group (e.g. p-N,N-dimethylaminosulfonamidophenyl group), a phenyl group substituted with an arylsulfonamido group (e.g. phenylsulfonamidophenyl group), an alkylcarbonylamino group Examples thereof include a substituted phenyl group (for example, t-butylcarbonylaminophenyl group), a phenyl group substituted with an alkyloxycarbonyl group (for example, methoxybenzyloxyphenyl group), and the like. The cycloalkyl group represented by R ₁ is, for example, a cyclopentyl group or a cyclohexyl group. In the present invention, R ₁ is preferably an unsubstituted alkyl group having 4 to 20 carbon atoms (e.g., n-butyl group, t-butyl group, n-decyl group, n-dodecyl group, n-octadecyl group) , an alkyl group substituted with an aryl group (e.g. benzyl group, p-t
-butylbenzyl group, anisyl group, phenethyl group), unsubstituted phenyl group, phenyl group substituted with alkyl group (e.g. pt-butylphenyl group, m-methylphenyl group), phenyl group substituted with nitro group ( For example, p-nitrophenyl group),
Phenyl group substituted with alkylaminosulfonamide group [e.g. p-(N,N-dimethylaminosulfonamide) group], phenyl group substituted with halogen atom (e.g. p-chlorophenyl group, phenyl group substituted with succinimide group) (eg, p-succinimidophenyl group), a phenyl group substituted with an alkoxycarbonyl group (eg, benzyloxycarbonylphenyl group), and the like.
Particularly preferred R ₁ is an alkyl group (eg, benzyl group, phenethyl group, anisyl group, pt-butylbenzyl group) substituted with an aryl group (preferably a phenyl group). In the present invention, the alkyl group represented by R ₂ and R ₃ is linear or branched, and preferably has 1 to 20 carbon atoms.
For example, methyl group, ethyl group, i-propyl group,
n-butyl group, t-butyl group, n-propyl group,
Examples include n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, and the like. The total number of carbon atoms in the groups represented by R ₂ and R ₃ is 1
It is preferable that it is 25 pieces. Particularly preferably, one of R ₂ and R ₃ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms. In the present invention, the aryl group represented by Ar in the general formula [] is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group. These aryl groups represented by Ar may have single or multiple substituents. For example, typical substituents introduced into phenyl groups include halogen atoms (e.g. fluorine, chlorine, bromine). etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, trifluoromethyl group, etc.), hydroxyl group, cyano group, nitro group,
Alkoxy groups (e.g. methoxy, ethoxy, etc.), alkylsulfonamide groups (e.g. methylsulfonamide, octylsulfonamide, etc.), arylsulfonamide groups (e.g. phenylsulfonamide, naphthylsulfonamide, etc.), alkyl Sulfamoyl groups (e.g., butylsulfamoyl groups, etc.), arylsulfamoyl groups (e.g., phenylsulfamoyl groups, etc.), alkyloxycarbonyl groups (e.g., methoxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl groups, etc.). cycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group,
Sulfo group, aryloxy group, alkoxy group, hydroxycarbonyl group, alkylcarbonyl group,
Examples include an arylcarbonyl group and an aminocarbonyl group. Two or more of these substituents may be substituted with the phenyl group. Preferred groups represented by Ar include an unsubstituted phenyl group or halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkylcarbonyl group. A phenyl group having one or more substituents such as a group, an arylcarbonyl group, or a cyano group. In the present invention, Ar is more preferably a group represented by the following general formula []. General formula [] In the general formula [], R represents a halogen atom (eg, chlorine, fluorine, bromine, etc.), preferably a chlorine atom or a fluorine atom. n represents an integer from 1 to 5. Particularly preferred Ar is a 2,6-dichlorophenyl group or a 2,3,4,5,6-pentafluorophenyl group. The group represented by Z in the general formula [] that can be eliminated by a coupling reaction with the oxidation product of the color developing agent includes, for example, a halogen atom (e.g. chlorine,
bromine, fluorine, etc.), an alkoxy group, an aryloxy group, a sulfonylalkoxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, in which a sulfur atom, an oxygen atom, or a nitrogen atom is directly bonded to the coupling position;
Examples include a triazolylthio group, a tetrazolyl group, a carbonyloxy group, a succinimide group, and more specific examples include U.S. Pat. No. 3,471,563;
JP-A No. 47-37425, JP-A No. 48-36894, JP-A-Sho
No. 50-10135, No. 50-117422, No. 50-130441,
No. 51-108841, No. 50-120334, No. 52-18315
No. 53-52423, No. 53-105226, etc. Z is preferably a hydrogen atom or a halogen atom. Typical examples of the cyan coupler represented by the general formula [] are shown below, but the invention is not limited thereto.

【table】

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〔process〕

Processing step (30°C) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes The composition of the processing solution is as follows. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g Benzine alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1, then water Adjust the pH to 10.30 using sodium oxide. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g Add water to make 1 Lightfastness and heat resistance of the dye image thus obtained The properties and moisture resistance were evaluated by the following methods. The results are shown in Table 1. [Evaluation of light resistance] The residual density after exposing the image to a xenon fade meter for 300 hours was expressed as a percentage (%), with the density before exposure being 100. [Evaluation of Humidity Resistance] The residual density after storing the image for 3 weeks at a temperature of 60° C. and a relative humidity of 70% was expressed as a percentage (%), with the density before the test being 100. [Evaluation of Heat Resistance] The residual density after storing the image at a temperature of 77°C for 3 weeks was expressed as a percentage (%), with the density before the test being 100. (However, the initial concentration is 1.0.)

[Bleach-fix solution composition]

Ethylenediaminetetraacetate iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g hydrosulfite 5g Add water to make 1. Dye residual rate = Maximum reflection density when processed with fatigued bleach-fix solution / Maximum reflection density when processed with fresh bleach-fix solution x 100 (%)

[Table] As is clear from Table 2, the silver halide color photographic light-sensitive material of the present invention has a uniformly higher color density after bleach-fixing treatment than the conventional silver halide color photographic material, and also has fatigue It can be said that the degree of defective recoloring of the cyan dye is small even with a bleaching solution, and the decrease in image density is small. and λmax is uniformly 655nm
It is larger and has extremely high color purity. Next, the absorption spectra (wavelength-absorbance curve) of each sample obtained using each cyan coupler of Exemplified Compound [16], Comparative Coupler A, and Comparative Coupler C in Example 1 are shown in the drawing. That is, curves 1 and 2 in the drawings are absorption spectrum curves of samples using comparative couplers A and C (comparison), respectively, and curve 3 is an absorption spectrum curve of a sample using exemplified compound [16] (invention). In the drawings, the absorbance for vertical comparison is a value normalized around D=1.0 for each sample. As is clear from the drawing, comparative cyan coupler A
The cyan dye image of the sample (curve 1) using
λmax is the wavelength, and the sub-absorption in the blue region (near 400 to 450 nm) is large. The cyan dye image of the sample using comparative cyan coupler C (curve 2) is
λmax is shortwave, green part (around 500-550nm)
The sub-absorption of is large. Compared to these, in the silver halide photographic light-sensitive material of the present invention (curve 3), the cyan dye image formed has a longer wavelength λma, and has less sub-absorption in the blue and green regions, resulting in good color reproducibility. becomes.

[Brief explanation of drawings]

The drawings are curve diagrams showing the absorption spectra of the silver halide photographic material of the present invention (curve 3) and comparative silver halide photographic materials (curves 1 and 2).

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, the silver halide emulsion layer contains a compound represented by the following general formula [1]. A silver halide photographic material characterized by containing a cyan coupler. General formula [1] [In the formula, R ₁ represents an alkyl group, a cycloalkyl group, or an aryl group. R ₂ and R ₃ each represent a hydrogen atom or an alkyl group. Ar
represents an aryl group. Z represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. ]