JPH0160138B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material containing a novel cyan dye image-forming coupler. Normally, color images are produced by an aromatic primary amine color developing agent reducing exposed silver halide grains, forming oxidation products of the color developing agent and yellow, magenta, and cyan dyes. A coupler is formed by oxidative coupling in a silver halide emulsion. Couplers typically used to form cyan dyes are phenols and naphthols. Particularly in the case of phenols, considering the photographic performance of conventional couplers, the basic properties required are that the dye has good spectral absorption characteristics, that is, there is no absorption in the green region of the spectrum and it is sharp. The pigment formed has sufficient fastness against light, heat, moisture, etc. Good color development. That is, it must have sufficient color development sensitivity and color density. Furthermore
It is required that a bleaching bath or a bleach-fixing bath containing EDTA ferric salt as a main component does not lose color even when fatigued by running. Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view, this product contains a novel phenolic cyan coupler that can generate cyan dyes with high color development even without benzyl alcohol. There is a demand for the development of silver halide photographic materials. Research has been conducted so far to satisfy the above requirements, but to the best of the present inventors' knowledge, there is no silver halide photograph containing a cyan coupler that satisfies all of the above required properties. A photosensitive material has not yet been discovered. For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide]-2,4-di-chloro-3-
Although methylphenol has good light resistance, it has drawbacks in heat resistance and also suffers from large dye loss in tired bleach-fix solutions. Furthermore, color development is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from the color developing solution. US Patent No.
The 2-heptafluoroptanamide-5-[α-(2,4-di-t-amylphenoxy)hexanamide] phenol described in No. 2815826 is transparent in terms of heat resistance and dye loss in a fatigued bleach-fix bath. However, it is inferior in terms of light resistance and color development. Further, the coupler described in JP-A-53-109630 also has problems in terms of removal of benzyl alcohol and light resistance. Additionally, U.S. Patent No.
No. 3839044, JP-A-47-37425, JP-A-48-
Publication No. 36894, Japanese Unexamined Patent Publication No. 50-10135, Japanese Patent Publication No. 50-117422
No. 50-130441, No. 50-108841, No. 50-
The phenolic cyan couplers described in Publication No. 120334 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. Silver halide photographic materials containing a phenol coupler having a ureido group at the 2-position are disclosed in British Patent No. 1011940 and US Patent Nos. 3446622, 3996253, 3758308 and
As described in No. 3880661, etc., cyan dyes formed from silver halide photographic materials containing these couplers have broad spectral absorption;
Furthermore, since the absorption maximum is in the relatively short wavelength region of the red region, there is considerable absorption in the green region of the spectrum, which is unfavorable in terms of color reproduction. Although the phenol coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved green absorption in the spectral region, other properties are still insufficient. As a result of extensive research into these conventional techniques, the present inventors have found that the following coupler can be incorporated into the red-sensitive silver halide emulsion layer to achieve the various properties required for the above-mentioned phenolic cyan coupler. I have found something that satisfies me. That is, in second place, -COOR', -COR', -
SO ₂ OR′, ―SO ₂ R′,

【formula】

[Formula] A phenylureido group having at least one of -NO ₂ and -CF ₃ (R represents hydrogen, an alkyl group or an aryl group, R' represents an alkyl group or an aryl group, and R and R' are bonded together) (may form a 5- or 6-membered ring), a phenolic cyanogen having a group that can be eliminated during a coupling reaction with hydrogen or an oxidation product of a color developing agent at the 4-position, and an acylamino group at the 5-position. Coupler {However, the substituent of the above phenylureido group is -COOR-,

【formula】

[Formula] or -NO ₂ , the group capable of leaving during the coupling reaction with the oxidation product of the above color developing agent is -O-R ₄ -SO-R ₅ (R ₄ is a substituted alkylene group or a substituted alkenylene group) , R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aralkenyl group, cycloalkyl group, aryl group or heterocyclic group, and R ₄ and R ₅ are bonded directly or through a bonding group. ) may be used to form a ring. }. The cyan coupler contained in the red-sensitive silver halide emulsion layer in the present invention is more preferably represented by the following general formula []. General formula [] [In _{the formula ,}
COR′,

【formula】

[Formula] -SO ₂ OR, -CF ₃ {R represents hydrogen, an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), or an aryl group (preferably a substituted or unsubstituted phenyl group) R' represents an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms) or an aryl group (preferably a substituted or unsubstituted phenyl group), and R and R' are bonded to 5 (may form a 6-membered or 6-membered ring). Further R ₃
represents a halogen atom or a monovalent organic group, for example, an alkyl group {preferably a straight or branched alkyl group having 1 to 4 carbon atoms (particularly preferably methyl,
tert-butyl)}, aryl group {preferably substituted or unsubstituted phenyl group}, heterocyclic group {preferably nitrogen-containing heterocycle (particularly preferably pyrrolidine,
piperidine)}, hydroxy group, alkoxy group {preferably a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (particularly preferably methoxy tert-butyloxy, methoxycarbonylmethoxy group)}, aryloxy group {preferably substituted or unsubstituted alkoxy group substituted phenoxy group}, acyloxy group {preferably substituted or unsubstituted alkylcarbonyloxy group,
arylcarbonyloxy group}, mercapto group,
Alkyl group thio group {preferably a substituted or unsubstituted alkylthio group having 1 to 8 carbon atoms (especially preferably methylthio group)}, nitro group, acyl group {preferably an alkylcarbonyl group having 1 to 8 carbon atoms (especially preferably is an acetyl group, a pivaloyl group)},
Amino group, alkylamino group {preferably a linear or branched alkylamino group having 1 to 4 carbon atoms (particularly preferably methylamino group, ethylamino group, tert-butylamino group)}, dialkylamino group (preferably dimethyl R ₁ is a halogen atom (preferably chloro, bromo), an alkyl group {preferably a linear or branched alkyl group having 1 to 20 carbon atoms, (particularly preferably methyl, tert-butyl, tert - Pentyl,
tert-octyl, dodecyl, pentadecyl)}, aryl group (preferably phenyl), heterocyclic group (preferably nitrogen-containing heterocyclic group), aralkyl group (preferably benzyl, phenethyl), alkoxy group {preferably linear or A branched alkyloxy group having 1 to 20 carbon atoms (particularly preferably methoxy, ethoxy, tert-butyloxy, octyloxy,
decyloxy, dodecyloxy)}, aryloxy group (preferably phenoxy), hydroxy group,
Acyloxy group {preferably substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyloxy group (particularly preferably acetoxy, benzoyloxy)}, carboxy group, alkoxycarbonyl group (preferably substituted or unsubstituted carbon number 1)
20 straight-chain or branched alkyloxycarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted phenoxycarbonyl),
Mercapto group, alkylthio group, arylthio group, alkylsulfonyl group (preferably one carbon number
to 20 linear or branched substituted or unsubstituted alkylsulfonyl groups), arylsulfonyl groups (preferably substituted or unsubstituted benzenesulfonyl groups), acyl groups (preferably carbon atoms 1 to 20)
straight-chain or branched alkylcarbonyl group), acylamino group (preferably straight-chain or branched alkylcarboxamide having 1 to 20 carbon atoms, substituted or unsubstituted benzenecarboxamide), sulfonamide group (preferably 1 carbon number) to 20 linear or branched substituted or unsubstituted alkylsulfonamide groups, substituted or unsubstituted benzenesulfonamide groups), carbamoyl groups (preferably from 1 to 20 carbon atoms)
20 straight-chain or branched alkylaminocarbonyl, substituted or unsubstituted phenylaminocarbonyl), sulfamoyl group (preferably straight-chain or branched alkylaminosulfonyl having 1 to 20 carbon atoms, substituted or unsubstituted phenylamino Z is a group arbitrarily selected from hydrogen or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent (e.g., a halogen atom (e.g., chlorine, bromine, fluorine, etc.) ), aryloxy groups, carbamoyloxy groups in which an oxygen atom or nitrogen atom is directly bonded to the coupling position,
Examples include carbamoylmethoxy group, acyloxy group, sulfonamide group, succinimide group, etc.
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.}, n represents an integer from 0 to 3, m represents an integer from 0 to 4, and l represents an integer of 0 or 1, respectively. ] The cyan coupler according to the present invention is illustrated below, but is not limited thereto. Typical synthetic routes and synthetic examples of the couplers of the present invention are shown below. Synthesis Example 1 (Synthesis of Exemplary Coupler 3) Synthesis of 2-(3-ethoxycarbonylphenyl)ureido-4-chloro-5-{α-(4-butylsulfonylamidophenoxy)tetradecanamide}phenol 18.9 g 2-Amino-4-chloro-5-nitrophenol was dispersed in 200 ml of toluene, and a solution of 21 g of 3-ethoxycarbonylphenyl isocyanate in 100 ml of toluene was added while stirring at room temperature.
The resulting reaction mixture was boiled and refluxed for 1 hour. Thereafter, the crystals were cooled to room temperature, filtered, washed with methanol, and dried. 34 g of pale yellow solid with mp 261-266°C was obtained. 2-(3-ethoxycarbonylphenyl)ureido, -4-chloro-5-nitrophenol 19g
was added to 600 ml of alcohol, and catalytic reduction was performed using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, the catalyst was filtered off and the filtrate was concentrated under reduced pressure. 17 g of crude reaction product was obtained. 2-(3-ethoxycarbonylphenyl)ureido-4-chloro-5-aminophenol 3.5g
was added to a mixed solution of 100 ml of acetonitrile and 0.9 ml of pyridine to dissolve it uniformly, and a solution of 4.7 g of α-(4-butylsulfonylamidophenoxy)tetradekyl chloride in 50 ml of acetonitrile was added under stirring at room temperature. After the addition was completed, the reaction was continued for an additional hour, and then added to ice water and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an extract. The reaction crude product was purified using silica gel and column chromatography, and solidified using hexane. 146～149
Obtained 3.7 g of white solid.

[Table] Synthesis Example 2 (Synthesis of Exemplary Coupler 8) 2-(3-trifluoromethyl)phenylureido, 4-chlor, 5-{α-(2,4-di-tert)
-Synthesis of pentylphenoxy)hexaneamide phenol. 18.9 g of 2-amino-4-chloro,-5-nitrophenol was dispersed in 200 ml of toluene, and 20.6 g of 3-trifluoromethylphenylisocyanate was added while stirring at room temperature. The resulting reaction mixture was boiled and refluxed for 3 hours. Thereafter, it was cooled to room temperature and the crystals were filtered. After washing with methanol, it was dried. 36 g of pale yellow solid was obtained. 2-(3-trifluoromethyl)phenylureido, 4-chlor, 5-nitrophenol 18.8g
was added to 600 ml of ethanol, and catalytic reduction was performed using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, hot filtration was performed to remove the catalyst. The filtrate was concentrated under reduced pressure to obtain 16 g of crude crystals. 2-(3-trifluoromethyl)phenylureido, 4-chlor, 5-aminophenol 3.5g
was added to a mixed solution of 100 ml of acetonitrile and 0.9 ml of pyridine, and α-(2,4-di-tert-
Pentylphenoxy)hexanoyl chloride
Add a solution of 3.7 g in 50 ml of acetonitrile. After the addition, the reaction was further carried out for 1 hour, and then added to ice water and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an oil. The reaction crude product was purified using silica gel column chromatography and solidified using hexane. mp151~
3.6g of white solid at 156°C was obtained.

〔process〕

Processing steps (30°C) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes The composition of each treatment is shown below. [Color developer composition 1] 4-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl)-Aniline sulfate 5.0g Benzyl 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. [Color developer composition 2] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g 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, and use sodium hydroxide. and adjust the pH to 10.30. [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. Photographic properties were measured for each of the obtained samples. The results are shown in Table 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer [1] being 100.

[Table] As is clear from the above Table 1, the samples obtained using the coupler according to the present invention are excellent in that good sensitivity and maximum density can be obtained regardless of the presence or absence of benzyl alcohol. Furthermore, as a result of measuring the color spectrum, it was found that the dye using the coupler of the present invention has the maximum absorption in a relatively long part of the red region, and exhibits excellent color purity with little absorption on the short wavelength side. . Example 2 A sample obtained in the same manner as in Example 1 was used to examine the light resistance, heat resistance, and moisture resistance of the dye image. The results obtained are shown in Table 2.

〔process〕

Processing process (33℃) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine; 1/8 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitriloacetic acid-3 -Sodium salt 1.20g Potassium hydroxide 1.48g Add water to make 1. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10g ammonium bromide 150g glacial acetic acid 10ml Add water to make 1, then use ammonia water to pH
Adjust to 6.0. [Fixer composition] Ammonia thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1, and adjust to PH6.0 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Photographic properties of the obtained cyan colored image were measured. The results are shown in Table 3.

[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 Hydrosulfite 5g Add water to make 1. The maximum reflection density of the cyan dye of the sample obtained after the development process was measured. The results are shown in Table 4. The dye residual rate in the maximum density area was determined as follows. Dye residual rate = Fatigue bleach-fix solution treatment/new bleach-fix solution treatment x 100

[Table] It can be seen from Table 4 that the samples using the coupler according to the present invention show less fading of the cyan dye when treated with a fatigue bleach-fix solution.

Claims (1)

[Claims] 1. On the support, at the 2nd position -COOR ^- , -COR ^- ,
-SO ₂ OR ^- , -SO ₂ R ^- , [Formula] [Formula] - A phenylureido group having at least one of -NO ₂ and -CF ₃ (R is hydrogen, an alkyl group or an aryl group, R ^- is an alkyl group) or aryl group, R and R ^- may be combined to form a 5- or 6-membered ring), 4
A phenolic cyan coupler having hydrogen at the position or a group capable of leaving during the coupling reaction with the oxidation product of the color developing agent, and an acylamino group at the 5th position {provided that the substituent of the phenylureido group is -
COOR ^- , [Formula] [Formula] or - NO ₂ , when the group capable of leaving during the coupling reaction with the oxidation product of the above color developing agent is -O
-R ₄ -SO-R ₅ (R ₄ represents a substituted alkylene group or substituted alkenylene group, R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aralkenyl group, cycloalkyl group, aryl group or hetero (represents a cyclic group, and R ₄ and R ₅ may be bonded directly or via a bonding group to form a ring). A silver halide photographic material having a red-sensitive silver halide emulsion layer containing }.