JPH0332773B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide color photographic material containing a cyan dye-forming coupler and an oil-soluble urea compound or sulfamide compound. After the silver halide light-sensitive material is exposed to light, the oxidized aromatic primary amine developing agent reacts with the dye-forming coupler by color development treatment.
A color image is formed. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. Phenols or naphthols are often used as cyan image forming couplers.
However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, US patent
The color images obtained with the 2-acylaminophenol cyan couplers described in U.S. Pat. Color images obtained from aminophenolic cyan couplers generally have poor light fastness, and 1-hydroxy-2-naphthamide cyan couplers generally have poor both light and heat fastness. On the other hand, U.S. Patent No. 4124396 and JP-A-57-
The 2,5-diacylaminophenol cyan coupler described in specifications such as No. 155538 and No. 57-157246 is said to have superior robustness compared to the general cyan coupler mentioned above, but it has some drawbacks. However, the developed color image has a lot of absorption in the green region and is not at a level that is satisfactory for color reproduction of color photographs. Also, UK Patent No. 1011940, US Patent No. 3446622,
No. 3996253, No. 3758308, No. 3880611 and JP-A-Sho
The phenolic cyan couplers having a ureido group at the 2-position described in Nos. 56-65134, 57-204545, and 58-37857 are said to have good light fastness, but are insufficient. However, the developed color images tend to change depending on various conditions and are not at a level that is satisfactory as a stable color photographic material. The object of the present invention is to improve these drawbacks and provide a color photographic material having cyan absorption suitable for color reproduction. Another object of the present invention is to provide a coupler which has a high dye formation rate and a maximum color density in a color developer, and in particular has a sufficiently high rate even in a color developer excluding benzyl alcohol.
On the other hand, it is an object of the present invention to provide a color photographic material that exhibits almost no decrease in density when processed with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted. The object of the present invention is to provide a silver halide color characterized in that an internal cyan dye-forming coupler represented by the following general formula [] and an oil-soluble compound represented by the general formula [] are dispersed and contained in the same layer. This is accomplished using photographic materials. However, the oil-soluble compound represented by the general formula [] does not form a dye through an oxidative coupling reaction with a developing agent. In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and L ₁ is

[Formula] represents, L ₂ is -O- or

[Formula] Group and m each represent 0 or 1, R ₃ represents a group that can be substituted on the benzene ring, and R ₃ and
R ₂ may form a 5- or 6-membered ring, and R
represents a hydrogen atom or a substituent, and X represents a group capable of leaving in an oxidative coupling reaction with a developing agent. Y represents a carbonyl group or a sulfonyl group. When Y represents a carbonyl group, R ₄ and R ₅
represents a hydrogen atom, and R ₆ and R ₇ represent an aryl group. When Y represents a sulfonyl group, R ₄ represents a hydrogen atom or an alkyl group, R ₅ represents a hydrogen atom, R ₆ represents an alkyl group, R ₇
represents an aryl group. Hereinafter, R ₁ to R ₃ , R, X, Y, in the general formula
Next, n and m will be explained in detail. In the general formula [], R ₁ and R ₂ are each preferably a chain or cyclic alkyl group having up to 32 carbon atoms (e.g., methyl group, butyl group, cyclohexyl group, dodecyl group, etc.), an aryl group (e.g., phenyl group) , naphthyl group, etc.)) heterocyclic group (e.g., 2-pyridyl group, 2-furyl group, 2-
These include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g., methoxy groups, 2-methoxyethoxy groups, etc.), aryloxy groups (e.g., phenoxy groups, 2,4-di- tert-amylphenoxy group, 2
-chlorophenoxy group, etc.), carboxy group, carbonyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methoxycarbonyl group, phenoxycarbonyl group, acetoxy group,
benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, etc.), phosphoric acid Amide group (e.g. diethyl phosphate monoamide group, tetramethyl phosphate triamide group, etc.), hydroxy group, cyano group,
It may be substituted with a substituent selected from a nitro group, a halogen atom, a thio group (for example, an ethylthio group, a phenylthio group, etc.). In the general formula [], R represents a hydrogen atom or another substituent, and the substituent is preferably an alkyl group or an aryl group. In the general formula [], n and m represent 0 or 1. In the general formula [], R ₃ is a group that can be substituted on the benzene ring, such as a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy group, 2-methoxyethoxy group, etc.), an aryloxy group ( For example, phenoxy group, 2,4-di-
tert-amylphenoxy group, 2-chlorophenoxy group, etc.), carboxy group, carbonyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group) group, ethoxycarbonyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.),
Amide groups (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide groups (e.g., dipropylsulfamoylamino group, etc.), imide groups (e.g.,
succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, benzenesulfonyl group, etc.),
Examples include hydroxy group, cyano group, nitro group, halogen atom, thio group (eg, ethylthio group, phenylthio group, etc.), and R ₃ and R ₂ may form a 5- or 6-membered ring. In the general formula [], X is a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), and the leaving group represented by X is an alkoxy group (e.g., ethoxy group, dodecyloxy group, etc.). methoxyethylcarbamoyl group, carboxymethoxy group, methylsulfonyl ethoxy group, etc.), aryloxy group (e.g., phenoxy group, naphthyloxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetra decanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g.
(methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g. dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g. ethoxycarbonyloxy group, benzyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyloxy group, etc.), thio group (e.g., phenylthio group,
(e.g., tetrazolylthio group), imide group (e.g.,
succinimide group, hydantoinyl group), azo group (e.g., phenylazo group, etc.),
These may also contain photographically useful groups. Preferred n, L ₁ and
R ₁ is _an aryl group when n=0, and n=
1, L ₁ is

The group R ₁ is an aryl group or a heterocyclic group, and these groups may have a substituent. L ₁ is

[Formula] When R ₁ is an aryl group, preferred substituents for this aryl group are a halogen atom,
Examples include sulfonyl group, sulfonamide group, sulfamoyl group, polyfluoroalkyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, and sulfamide group. In the general formula [], preferred m and R ₂ are m=0 and R ₂ is an alkyl group or an aryl group,
These groups may have a substituent. In the general formula [], preferred R ₃ is a hydrogen atom,
Halogen atoms (e.g. fluorine atoms, chlorine atoms,
bromine atom, etc.), alkyl groups having up to 20 carbon atoms (e.g. methyl group, butyl group, dodecyl group, etc.),
Aryl groups (e.g., phenyl groups, etc.), alkoxy groups (e.g., methoxy groups, butoxy groups, etc.),
aryloxy group (e.g. phenoxy group etc.),
Acyloxy group (e.g., acetoxy group, benzoyloxy group, etc.), acylamino group (e.g.,
acetylamino group, benzoylamino group, etc.), which may be substituted with a substituent that may be substituted for R ₁ described above, and R ₂ and R ₃ form a 5- or 6-membered ring. It's okay. In the general formula [], R ₃ is particularly preferably a hydrogen atom. In the general formula [], preferable X is a hydrogen atom,
These include halogen atoms (of which fluorine atoms and chlorine atoms are particularly preferred), alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, sulfonamide groups, alkoxycarbonyl groups, and thio groups. Hereinafter, R ₄ , R ₆ and R ₇ in the general formula [] will be explained in detail. In the general formula [], R ₄ represents a hydrogen atom or a chain or cyclic alkyl group having up to 20 carbon atoms (e.g., methyl group, cyclohexyl group, etc.), and this alkyl group may be substituted with R ₁ . It may be substituted with a group. In the general formula [], R ₆ and R ₇ are each a hydrogen atom, a chain or cyclic alkyl group having up to 32 carbon atoms (e.g., methyl group, cyclohexyl group, dodecyl group, etc.), an aryl group (e.g., phenyl group, naphthyl group, etc.) groups), heterocyclic groups (e.g.
2-pyridyl group, 2-furyl group, 2-benzothiazolyl group, etc.), acyl group (e.g., acetyl group,
benzoyl group, etc.) or a sulfonyl group (e.g., methylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, etc.), which may be substituted with a substituent that may be substituted on R ₁ , and R ₆ Alternatively, at least one of R ₇ may not be a hydrogen atom, and R ₆ and R ₇ may form a ring. In the general formula [], the total number of carbon atoms of R ₄ , R ₆ and R ₇ is preferably 12 or more in order to impart oil solubility. In general formula [], R ₄ , R ₅ , R ₆ and R ₇
It is preferable that active methylene or active methine compound capable of forming a dye or the p-position of phenol is not an active cyan coupler residue, and it is particularly preferable that the total number of carbon atoms is 14 to 64. In the general formula [], R ₄ is preferably a hydrogen atom. In the general formula [], R ₆ and R ₇ are preferably substituted aryl groups. In the general formula [], Y is preferably a carbonyl group. Techniques for adding water-soluble urea compounds to photosensitive materials are known (for example, U.S. Pat.
-129780, etc.), and JP-A-57-155538 discloses a coupler having a sulfamide group. It does not even give any indication of the effects that may sometimes be obtained. That is, as described in the Examples, when the oil-soluble compound represented by the general formula [] of the present invention is used together with the cyan coupler represented by the general formula [],
The absorption of the color image obtained through development processing becomes longer wavelength, and the absorption half-width is not widened, the absorption in the green region is reduced, and the color reproduction of color photographs can be improved. Furthermore, the effect of the present invention is truly surprising, as it enhances the color development of the cyan coupler represented by the general formula [], giving it a high maximum density and a high gamma. Next, typical examples of couplers according to the present invention will be given, but the couplers used in the present invention are not limited to these. Next, typical examples of oil-soluble urea compounds and sulfamide compounds according to the present invention will be given, but the compounds used in the present invention are not limited to these. The cyan coupler used in the present invention can be synthesized by a known method using the following synthetic route. ^* When R ₁ and R ₂ are amino groups, corresponding isocyanates and phenyl urethanes can be used. Next, the present invention will be explained using specific examples, but the present invention is not limited thereto. Synthesis Example 1 Synthesis of exemplified coupler (A-1) 396 g of 2-amino-4-chloro-5-nitrophenol was suspended in 2.5 g of acetonitrile and heated under reflux to dissolve 4-tert-butylbenzoyl chloride.
418 g was added dropwise over 30 minutes. After further heating under reflux for 1 hour, the mixture was cooled, and the precipitated crystals were collected, washed with acetonitrile, and dried to obtain 580 g of crystals (melting point: 242-247°C). Add this crystal to 466g of iron powder and 350g of water.
The mixture was heated under reflux for 1 hour with 30 cc of isopropanol dihydrochloric acid. After separating the iron powder, the precipitated crystals were collected and dried to obtain 480 g of 5-amino-2-(4-tert-butylbenzoylamino)-4-chlorophenol, melting point 164-165°C. 95.7 g of 5-amino-2-(4-terrt-butylbenzoylamino)-4-chlorophenol was added to 700 c.c. of acetonitrile, and 2-(2-chlorophenoxy)tetradecanoyl chloride was heated under reflux.
124.5g was added dropwise over 1 hour. After further heating under reflux for 2 hours, 1 portion of ethyl acetate was added and washed with water. The solvent was distilled off under reduced pressure, and the residue was crystallized from 200 ml of ethyl acetate and 300 ml of acetonitrile. Further recrystallization was performed to obtain the exemplary coupler (A-1) with a melting point of 111-113°C.
I got g. Elemental analysis values C: 67.62, H: 7.31, N: 4.35% Calculated values C: 67.77, H: 7.38, N: 4.27% Synthesis example 2 Synthesis of exemplary coupler (22) 37 g of p-propylsulfonylaniline, 18 ml of pyridine, In addition to 90 ml of acetonitrile, 30.6 g of phenyl chloroformate was added dropwise under ice cooling. After stirring for 2 hours, it was poured into ice water containing 7 ml of hydrochloric acid, and the precipitated crystals were collected, washed with water-containing methanol, and then dried.
58.2g of white crystals were obtained (melting point 171.5°C). The crystals were suspended in 190 ml of acetonitrile together with 30.3 g of 2-amino-5-nitrophenol, 2.3 ml of triethylamine was added, and the mixture was heated under reflux for 6 hours.
After cooling, neutralize with hydrochloric acid and collect the precipitated crystals.
Washed thoroughly with acetonitrile. Weight after drying: 58.6
Yellow crystals of g were obtained. 27g of this crystal, 14g of reduced silver, ammonium chloride
1.2g, acetic acid 1.2ml, isopropanol 90ml, water 15
ml and heated under reflux for 2 hours. Caustic soda after cooling
5.7 g of the solution was dissolved in water, the iron powder was separated, and the precipitated crystals were collected by neutralization with acetic acid and thoroughly dried to obtain 22.8 g of pale red crystals. 13.6 g of this crystal was heated to reflux with 36 ml of acetonitrile and 4 ml of dimethylacetamide, and 2-(2,
13.5 g of 4-tertiary-amylphenoxy)-butanoyl chloride was added dropwise. After further heating and refluxing for 1 hour, 70 ml of ethyl acetate was added and washed with water. After distilling off the solvent under reduced pressure, the residue was recrystallized twice from acetonitrile to obtain 19.8 g of the desired coupler (A-22). Melting point: 130-133°C Elemental analysis values: C: 66.31, H: 7.56, N: 6.30% Calculated values: C: 66.33, H: 7.58, N: 6.45% The urea compound and sulfamide compound used in the present invention are produced by the following synthetic route. , can be synthesized by a known method.

When [formula] is used, use (D) and (E) instead of (C) above. can be done.

[Formula] R ₆ N=C=O (R ₄ =H) (E) Next, specific examples will be explained, but the present invention is not limited thereto. Synthesis Example 3 Synthesis of Exemplified Compound (B-4) 36.8 g of m-methanesulfonamide aniline was dissolved in 24 ml of pyridine and 200 ml of tetrahydrofuran, and 16.5 g of phenyl chloroformate was added dropwise under ice cooling. 30
After a few minutes, the mixture was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected to obtain 59.8 g of white crystals. Add 200 ml of acetonitrile to 58 g of this crystal and 40 g of 2-amino-4-tert-octylphenol.
2.8 ml of triethylamine was added. After refluxing for 3 hours, 300 ml of ethyl acetate was washed with water. After the solvent was distilled off under reduced pressure, the residue was recrystallized from ethyl acetate-hexane to obtain 60 g of crystals with a melting point of 183-184°C. Elemental analysis values: C: 61.08, H: 7.32, N: 9.58% Calculated values: C: 60.94, H: 7.21, N: 9.69% Other compounds could be synthesized in a similar manner. In the present invention, in addition to the coupler of the present invention, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in other color development processing is used in combination. It can be used as As magenta couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
There are cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include:
There are naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. A known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the coupler and the oil-soluble urea compound and sulfamide compound into the silver halide emulsion layer. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. di- butoxyethyl succinate, dioctyl azelate), phenols (e.g. 2,4-di-tertiary-amylphenol), trimesic acid esters (e.g. tributyl trimesate), or organic solvents with a boiling point of about 30°C to 150°C, For example, it is dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, P-alkoxyphenols, P-oxyphenol derivatives, and bisphenols. Specific examples of hydroquinone derivatives are US patents
No. 2360290, No. 2418613, No. 2675314, No.
No. 2701197, No. 2704713, No. 2728659, No. 2701197, No. 2704713, No. 2728659, No.
No. 2732300, No. 2735765, No. 2710801, No.
No. 2816028, British Patent No. 1363921, etc., and gallic acid derivatives are described in US Patent No. 3457079.
No. 3069262, etc., and those of P-alkoxyphenols are described in U.S. Patent No. 2735765,
It is described in U.S. Patent No. 3698909, U.S. Pat.
No. 3574627, No. 3764337, JP-A-52-35633,
No. 52-147434 and No. 52-152225, and the bisphenols are described in the US patent
Described in No. 3700455. The photosensitive material of the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc. Other solvents, ultraviolet absorbers, protective colloids, binders, which can be introduced together with the coupler of the present invention and an oil-soluble urea compound or sulfamide compound,
Antifoggants, sensitizing dyes, dyes, bleaching agents, etc., methods for forming silver halide photosensitive materials (methods for forming photographic emulsions, methods for introducing couplers, etc., supports, layer structure of each photosensitive layer, etc.), and photographic processing. For more information, see Research Disclosure, December 1978, item
17643 (Industrial Opportunies Ltd., UK) JP-A-56-65134 and JP-A-56-104333, or the materials and methods described in the cited documents, etc. can be used. The amount of the coupler of the general formula () used in the present invention is generally 1x per mole of silver in the emulsion layer.
10 ⁻³ mol to 7×10 ⁻¹ mol, preferably 1×
The amount is 10 ^-2 mol to 5×10 ^-1 mol. The amount of oil-soluble urea compound or sulfamide compound used in the present invention is 1 mole of coupler.
It can be used in an amount of x10 ^-2 mol to 10 mol, preferably 1 x 10 ^-1 mol to 5 mol, and an oily or low melting point one can also be used as a high boiling point organic solvent. Further, it can be used in the same layer as the coupler or in an adjacent layer. EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Examples 0.015 mol of coupler of the invention according to Table 1,
A solution obtained by heating 0 or 0.015 mol of the oily compound of the invention, a high-boiling solvent (1 volume/weight relative to the coupler) and 20 ml of ethyl acetate to 50°C is a 10% solution containing 0.4% of sodium dodecylbenzenesulfonate.
It was passed through a colloid mill with 100 g of an aqueous gelatin solution to emulsify and disperse it finely. The entire emulsion was added to silver iodobromide emulsions for samples 1 to 8 and to silver chlorobromide emulsions for samples 9 to 14 (all emulsions containing 13 g of silver) as a hardening agent. - Add 30 ml of a 2% aqueous solution of dichloro-4-hydroxytriacine and 25 ml of a 1% aqueous solution of sodium dodecylbenbensulfonate as a coating aid, and apply the coupler uniformly onto the polyethylene terephthalate base so that the coupler coating amount is 1 mmol/ ^m2. did. High boiling point solvent C-1 Tricresyl phosphate C-2 Dibutyl phthalate

【table】

[Table] These films were subjected to continuous exposure using a sensitometric wedge, and were subjected to any of the following treatments A to C. Color development process A (38℃) 1 Color development...3 minutes 15 seconds2 Bleaching...6 minutes 30 seconds3 Washing with water...3 minutes 15 seconds4 Fixing...6 minutes 30 seconds5 Washing with water... 3 minutes 15 seconds 6 Stable...3 minutes 15 seconds The composition of the processing solution used in each step is as follows. Color developer Sodium nitrotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methylaniline sulfate 4.5 g Add water 1 Bleach solution Ammonium bromide 160g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175ml Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0ml Add water 1 Color development Processing step B (33°C) 1 Color development...3 minutes 30 seconds2 Bleach-fixing...1 minute 30 seconds3 Washing with water...2 minutes 30 seconds The processing steps used in each step are as follows. Color developer Benzyl alcohol 15.0ml Diethylene glycol 8.0ml Ethylenediaminetetraacetic acid 5.0g Sodium sulfite 2.0g Anhydrous potassium carbonate 30g Hydroxylamine sulfate 3.0g Potassium bromide 0.6g 4-Amino-N-ethyl-N-(β-methanesulfonamide) Ethyl)-m-toluidine sesquisulfate monohydrate 5.0g Add water 1 (PH10.2) Bleach-fix solution Ethylenediaminetetraacetic acid 4.0g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5.0g Sodium thiosulfate (70%) Add 150ml water 1 Color development process C Process Temperature Time 1 Color development 36℃ 3'00'' 2 Stop 25-30℃ 0'40'' 3 First fixing 25-30℃ 0'40'' 4 Bleaching 25-30°C 1'00" 5 Second fixing 25-30°C 0'40" 6 Water washing 25-30°C 0'30" The processing steps used in each step are as follows. Color developer Sodium sulfite 5.0g 4-Amino-3-methyl-N,N-diethylaniline 3.0g Sodium carbonate 20.0g Potassium bromide 2.0g Add water 1 (PH10.5) Stop solution Sulfuric acid (6N) 50.0ml Add water 1 (PH1.0) Actual solution ammonium thiosulfate 60.0g Sodium sulfite 2.0g Sodium hydrogen sulfite 10.0g Add water 1 (PH5.8) Bleach solution Potassium ferricyanide 30.0g Potassium bromide 15.0g Add water 1 (PH6.5) When the absorption spectra of the films obtained after the treatment were measured, the results shown in Table 2 were obtained.

【table】

[Table] In the combinations with couplers other than the present invention shown in the comparative examples of film samples No. 15 to 18, there is almost no change depending on whether or not they are added, whereas in the combinations of the present invention, there is no difference in any of the cases compared to the couplers alone. The absorption maximum is at a long wavelength without widening the half-value width, and samples 2 to 8 have absorption suitable for color negative films, and samples 10, 12, and 14 are color positive films.
It can be seen that the film has a preferable absorption as a film for paper. When the optical density against red light was measured for each of the samples obtained after the treatment, the results shown in Table 3 were obtained.

[Table] When these samples were examined for fastness to heat and light, the combination of the present invention showed no difference from each comparative sample, and all had excellent fastness. From these results, it can be seen that the combination of the present invention is excellent in that it has absorption characteristics favorable for color reproduction in color photographs and high color development (high gamma, high maximum density). Example 2 On a triacetyl cellulose film support,
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; 1st red-sensitive emulsion layer; odor Silver emulsion (silver iodide: 5 mol%) ......Silver coating amount 1.7 g/ ^m2 Sensitizing dye......6 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...... 1 mol of silver 1.5×10 ^-5 mol for Coupler A-24...0.04 mol for 1 mol of silver Either urea compound (B-6) (B-14)......0.04 mol for 1 mol of silver Coupler C: 0.003 mol Coupler ...Silver coating amount: 1.4 g/ ^m2 Sensitizing dye: 3 x 10 ^-5 mol per mol of silver Sensitizing dye: 1.2 x 10 ^-5 mol per mol of silver Coupler A-24 ...... 0.02 mol per mol of silver Either urea compound (B-6) (B-14) ...... 0.02 mol per mol of silver Coupler C... 0.0016 mol per mol of silver Oil...dibutyl phthalate 0.5cc/1g of coupler 5th layer; intermediate layer 6th layer same as the 2nd layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol%)...Silver coating amount 1.5g/ ^m2 Sensitizing dye......3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...... 1 x 10 ^-5 mol per 1 mol of silver Coupler M-...For 1 mol of silver 0.05 mol Coupler M - 0.008 mol per 1 mol of silver Coupler %) 1.6g/ ^m2 Sensitizing dye......2.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...... 0.8 x 10 ^-5 mol per 1 mol of silver {Coupler M- Coupler M- }Total of both 0.02 mol per mol of silver Coupler M-...0.002 mol per mol of silver 8th layer; Yellow filter layer Yellow colloidal silver and 2,5-
Ninth layer of gelatin layer containing an emulsified dispersion of di-t-octylhydroquinone; first blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol %)...Coated silver amount 1.5 g/m ² Coupler Y-1...0.25 mol per mol of silver Coupler X...0.015 mol per mol of silver 10th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol% ) Coated silver amount: 1.1 g/m ² Coupler Y-... 0.06 mol per mol of silver 11th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ) ) Coated silver amount 0.5g 12th gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; 2nd protective layer Trimethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, a gelatin hardening agent (1,3-vinylsulfonyl-2-propanol) and a surfactant were added to each layer. Example 3 Compounds used to prepare samples Film samples 20 to 35 listed in Table 6 were prepared in the same manner as in Example 1. Film sample 1,
Regarding 10, 16, 18 (listed in Table 1) and 20 to 35,
After exposure with a sensitometric wedge, color development process A or B described in Example 1 was performed. Table 7 shows the results of measuring the visible absorption spectrum of each film sample obtained. Table 7 shows that in the samples of the present invention, the absorption maximum is at a sufficiently long wavelength without widening the half-width. Furthermore, each film sample was subjected to sensitometry using red light, and the results are shown in Table 8. From Table 8, it can be seen that the samples of the present invention have high gamma and high maximum density, and are excellent in color development.

【table】

【table】

【table】

[Table] Sensitizing dye: Anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4',5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropyl)ethoxy]
Ethylimidazolocarbocyanine hydroxide sodium salt

Table 4 shows the urea compounds used in combination with coupler A-24 for each sample. The above-coated sample was exposed to red light at 2000 lux 1/100 seconds using a continuous wedge, and then development processing step A was performed. The optical density against red light was measured for each sample obtained after the treatment, and the sensitivity, fog, and gamma were determined as shown in Table 5.

[Table] It is clear that by using the present invention, a color sensitive material with low fog, high sensitivity, and high gamma can be obtained. Furthermore, dark heat fastness and light fastness tests were conducted on each developed film sample, and no deterioration was observed due to the combined use of a urea compound, indicating good fastness. Furthermore, this film sample was processed into a color negative photographic material, and landscapes, people, and various color patches were photographed and printed on color paper for visual evaluation. The prints showed good color reproduction with no turbidity throughout, and reds in particular were reproduced clearly.

Claims (1)

[Claims] 1. A silver halide comprising an internal cyan dye-forming coupler represented by the following general formula [] and an oil-soluble compound represented by the general formula [] dispersed and contained in the same layer. Color photographic material. however,
The oil-soluble compound represented by the general formula [] does not form a dye through an oxidative coupling reaction with a developing agent. In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, L ₁ represents [Formula], L ₂ represents -O- or [Formula] group, and m represents Each represents 0 or 1, R ₃ represents a group that can be substituted on the benzene ring, and R ₃ and
R ₂ may form a 5- or 6-membered ring, and R
represents a hydrogen atom or a substituent, and X represents a group capable of leaving in an oxidative coupling reaction with a developing agent. Y represents a carbonyl group or a sulfonyl group. When Y represents a carbonyl group, R ₄ and R ₅
represents a hydrogen atom, and R ₆ and R ₇ represent an aryl group. When Y represents a sulfonyl group, R ₄ represents a hydrogen atom or an alkyl group, R ₅ represents a hydrogen atom, R ₆ represents an alkyl group, R ₇
represents an aryl group.