JPH03220554A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material having high coupling reactivity and high absorption density of a dye by incorporating a specified cyan dye forming coupler into a silver halide emulsion layer on a substrate. CONSTITUTION:A cyan dye forming coupler represented by formula I is incorporated into a silver halide emulsion layer on a substrate. In the formula I, each of R<1> and R<2> is H, optionally substd. alkyl, alkenyl, cycloalkyl or aryl, R<3> is optionally substd. aryl and Z is H or a group releasable by coupling. A sensitive material having high coupling reactivity and high color density is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel phenolic cyan dye-forming coupler.

(Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer and a dye-forming coupler (hereinafter referred to as coupler) react to form a color image. be done. 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. Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images. In color photography, color-forming couplers are added to the developer solution or incorporated into a light-sensitive photographic emulsion layer or other color image-forming layer and react with the oxidized form of the color developer formed by development. This forms a non-diffusible dye.

The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and a coupler having a hydrogen atom at the active site is a 4-equivalent coupler, i.e. stoichiometrically requires 4 moles of development to form 1 mole of dye. It requires silver halide with a nucleus.

On the other hand, those having a group that can leave as an anion at the active site are 2-equivalent couplers, that is, couplers that stoichiometrically require only 2 moles of silver halide having a development nucleus to form 1 mole of dye. Therefore, compared to a 4-equivalent coupler, the amount of silver halide in the photosensitive layer can be generally reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. improves.

By the way, among cyan couplers, naphthol type couplers are used because the absorption of the generated dye image is at a sufficiently long wavelength and there is little overlap with the absorption of the magenta dye image, and the coupling reactivity with the oxidized form of the color developer is low. Since it can be selected up to high prices, it has been widely used for photographic purposes, mainly color negative films. However, dye images obtained from naphthol-type couplers tend to be reduced and faded by divalent iron ions that accumulate in tired bleach or bleach-fix baths (referred to as reductive fading), and their heat fastness is poor. , improvements were strongly desired.

On the other hand, U.S. Patent No. 4,333,999 has a p-cyanophenylureido group at the 2-position and a ballast group (
A phenol type cyan coupler having a carbonamide group which is a diffusion resistance imparting group) is disclosed. These couplers undergo a bathochromic shift when the dyes associate in the film, giving dye images with excellent hue, and are also excellent in fastness, so they are widely used as couplers to replace the naphthol-type cyan couplers. It's starting to happen.

(Problem to be Solved by the Invention 8) However, in recent years, the performance requirements for photographic materials have been severe, and even for these couplers, higher coupling reactivity and higher dye absorption density are being sought.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material containing a cyan coupler which provides high coupling reactivity and high dye absorption density.

(Means for Solving the Problems) In order to achieve the above-mentioned problems (objects), the present inventors have conducted extensive research and have found that the following silver halide color photographic materials may be distantly related to the problems. I found it.

That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a halogen-based color photographic material is characterized by containing at least one cyan dye-forming coupler represented by the following general formula (I). Silver chemical color photographic material.

General formula (I) [wherein R1 and R1 are hydrogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, cycloalkyl groups, or aryl groups, R3 is substituted or unsubstituted aryl groups, and Z is By the way, in the exemplified compound 1-XXI [l) of JP-A No. 55-57843, which represents a hydrogen atom or a coupling-off group, respectively, a pyrazolone core magenta coupler having an α-cyano-substituted carbonamide group is known. ing. An α-cyano substituted carbonamide group is used as a substituent for an anilino group, and only examples in which this substituted anilino group is bonded to a pyrazolone core are disclosed. There is no description of an example in which an α-cyano-substituted carbonamide group is substituted on a directly substituted pyrazolone core.On the other hand,
The object of JP-A-55-57843 is to provide a novel photographic magenta coupler which has high fastness, high solubility in organic solvents, and is easy to manufacture.

Therefore, it can be inferred from JP-A-55-57843 that a cyan coupler in which an α-cyano-substituted carbonamide group is bonded to a phenol core has high coupling activity and provides a high dye absorption density. It is extremely difficult. Therefore, the present invention provides a completely new cyan coupler.

The cyan coupler represented by the general formula (+) will be explained in detail below. In the general formula (+), R1 is preferably a linear or branched alkyl group having a total number of carbon atoms (hereinafter referred to as the number of C) of 1 to 36 (more preferably 6 to 24), or a straight or branched alkyl group having a total number of carbon atoms of 2 to 36 ( More preferably a linear or branched alkenyl group having 6 to 24 carbon atoms, a 3 to 12-membered cycloalkyl group having 3 to 36 carbon atoms (more preferably 6 to 24 carbon atoms), or a 3 to 12-membered cycloalkyl group having 6 to 36 carbon atoms (more preferably 6 to 24 carbon atoms) represents an aryl group (6 to 24), and these represent substituents (e.g. halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group) , aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloquinecarbonyl group, carbonamide group,
Even if it is substituted with a sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkylsulfonyl group ξ) group, sulfamoylamino group, alkoxysulfonyl group, imide group or heterocyclic group (hereinafter referred to as substituent group A) R1 is preferably linear, branched, or a substituent (alkoxy group, alkylthio group, aryloxy group, arylthio group, alkylsulfonyl group, arylsulfonyl group, aryl group, alkoxycarbonyl group, epoxy group, cyano group, or halogen atom) [e.g. n-octyl, n-decyl, n-dodecyl, n-hexadecyl, 2-ethylhexyl, 3,
5.5-)limethylhexyl, 3.5.5-trimethylhexyl, 2-ethyl-4-methylpentyl, 2-hexyldecyl, 2-hebutylundecyl, 2-octyldodecyl, 2,4.6-dodecyl Methylheptyl, 2°4.
6.8-Tetramethylnonyl, benzyl, 2phenethyl, 3-(t-octylphenoxy)propyl, 3-(2
, 4-di-t-pentylphenoxy)propyl, 2-(
4-biphenyloxy)ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl, 9.10-epoxyoctadecyl, dodecyloxycarbonylmethyl, 2-
(2naphthyloxy)ethyl], unsubstituted or having a substituent (e.g. halogen atom, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group or alkoxycarbonyl group) alkenyl group [e.g. allyl, 10-undecenyl, oleyl, citronellyl, cinnacl], unsubstituted or cycloalkyl groups having a substituent (halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group or aryloxy group) [e.g. cyclopentyl, cyclohexyl, 3
．． 5-dimethylcyclohexyl, 4[-butylcyclohexyl], or an aryl group that is unsubstituted or has a substituent (halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, carbonamide group, alkylthio group, or sulfonamide group) [For example, phenyl, 4-dodecyloxyphenyl, 4-biphenylyl, 4-dodecanesulfonamidophenyl, 4t-octylphenyl, 3-pentadecylphenyl], and particularly preferably the linear, branched or substituted alkyl group It is.

In general formula (I), Rz has the same meaning as R1. R1
may be different from R1, but may be the same,
However, it is not preferable that R1 and Rz are both hydrogen atoms.

In general formula (I), R3 preferably has 6 to 36 carbon atoms,
More preferably, it represents an aryl group of 6 to 15, and may be substituted with a substituent selected from the above substituent group A, or may be a fused ring. Here, as a preferable substituent, a halogen atom (F, C1, Br, cyano group, nitro group, acyl group (e.g. acetyl, benzoyl), alkyl group (e.g. methyl, t-butyl, trifluoromethyl,
trichloromethyl), alkoxy groups (e.g. methoxy,
ethoxy, butoxy, trifluoromethoxy) alkylsulfonyl groups (e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (e.g. phenylsulfonyl, p-
), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), sulfonamide groups (e.g. methanesulfonamide, trifluoromethanesulfonamide,
trienesulfonamide), carbamoyl group (e.g. N
, N-dimethylcarbamoyl, N-phenylcarbamoyl) or a sulfamoyl group (for example, N,N-diethylsulfamoyl, N-phenylsulfamoyl). R2 is preferably a halogen atom, a cyano group, or a sulfonamide group. , an alkylsulfonyl group, an arylsulfonyl group, and a trifluoromethyl group, and more preferably 4-cyanophenyl, 4-dia2-3-halogenophenyl, 3-cyano- 4-halogenophenyl, 4-
Alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3
-Alkoxyphenyl, 3-alkoxy-4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4
-halogenophenyl, 3,4.5-trihalogenophenyl, 3.4-dicyanophenyl, 3-Schiff/-4,5-
Dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-dia-2-3-halogenophenyl, 3.4-
Dicyanophenyl or 4-alkylsulfonylphenyl.

Preferred examples of the coupling-off group include a halogen atom, -OR
', -SR', -0CR', 1 Q OCNHI? ', an arylazo group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms and bonding to the coupling active position (position where Z is bonded) with a nitrogen atom (e.g. succinimide, phthalimide, hydantoinyl, Pyrazolyl, 2
-benzotriazolyl) and the like. Here R4
is an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 ClI, a cycloalkyl group having 3 to 36 carbon atoms, and a cycloalkyl group having 6 to 36 carbon atoms.
It represents a 36-aryl group or a C2-36 heterocyclic group, and these groups may be substituted with a substituent selected from Group A. Z is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an alkylthio group, and particularly preferably a hydrogen atom, a chlorine atom, a group represented by the following general formula (I[), or a group represented by the following general formula ([[ It is a group represented by [).

General formula (■) (wherein, R5 is a halogen atom, cyano group, nitro group, alkyl group, alkoxy group, alkylthio group, alkylsulfonyl group, arylsulfonyl group, carbonamide group, sulfonamide group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group or carboxyl group,
m represents an integer from 0 to 5. Here, when m is plural, R5
may be the same or different,) General formula (I In the general formula (It), R5 is preferably a halogen atom, an alkyl group (e.g. methyl, t-butyl, t-octyl, pentadecyl), alkoxy groups (e.g. methoxy, n-butoxy, n-octyloxy, hensyloxy, methoxyethoxy), carbonamide groups (e.g. acetamide, 3-carboxybrobanado) or 0m is preferably an integer from 0 to 2, more preferably O or 1, which is a sulfonamide group (e.g. methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably an alkyl group or an alkoxy group. is an integer.

In general formula (III), when R'' and/or R? represent a monovalent group, preferably an alkyl group (e.g. methyl, ethyl, n-butyl, ethoxycarbonylmethyl, benzyl, n-decyl, n-dodecyl ), aryl groups (e.g. phenyl, 4-chlorophenyl, 4-methoxyphenyl), acyl groups (e.g. acetyl, decanoyl, benzoyl, pivaloyl) or carbamoyl groups (e.g. N-ethylcarbamoyl, N-phenylcarbamoyl)
And R6 and R? is more preferably a hydrogen atom, an alkyl group or an aryl group. In the general formula % (Ill), Y is preferably 10- or -SI 1 , more preferably -C-. General formula (I[
In l), R'' is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted amino group, and more preferably an alkoxy group or a substituted or unsubstituted amino group.

In the general formula (I[l), n preferably represents an integer of 1 to 3, more preferably 1.

Specific examples of R1 or R2 in general formula (I) are shown below.

H, CHz, Ctl(s, -CJw(n), CsH+ + (n), C
sH+7(n), C+oHz+(n).

C+Jzv(n), -C+J33(n)-cs
nt(n), CJw3(n), -C1□His(n), -C+@H3y(n) C1l.

CHC+Jt+ (n) General formula (I) below R3 in Here is an example.

1 1 -OCCII.

0S(hcHi OCHzCLOCHi OCR2COOCH3 OCHzC) IzCOOCHz OCI(COOCI+3 C11゜0CR2COOH -OCR1CII2S02CH3 OCHzCONHCII□(jl, 0HOC HiCON
HCHiCHzOCH:+0CHCOOCJs OCJCHzOH CHzCOOCJs QC)IzcI(zSCHzcOo)IOCHzCHz
NFISO□C)13 SCHzCOOH -5CHCOOH CI.

SCHzCHzCOOH 5CHiCHtOH CJCHzCOOH -OCR,C00C,)It-sec OClbCOOCJw-t Note that when Z is a coupling-off group, it is preferable that it does not contain a photographically useful group (for example, a development inhibitor residue, a dye residue).

Specific examples of the cyan coupler represented by the general formula (I) are shown below.

General Formula (I) The cyan coupler of the present invention represented by general formula (I) can be synthesized by various synthetic routes, and typical synthetic routes are shown below.

(R''=ll) Here, R is a methyl group or an ethyl group, and X is a leaving group such as a halogen atom, mesyloxy group, tosyloxy group, etc. Compound b' is a combination of cyanoacetic ester and R' -X. Bases include sodium metal, sodium hydride, n-butyllithium, and methyllithium.

lithium diisopropylamide sodium methoxide,
Preferably, potassium methoxide, sodium amide, potassium amide, etc. are used. In a similar manner, b' can be guided to b.

It is common to use an aqueous solution of an inorganic base such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or an aqueous sodium carbonate solution.As the reaction solvent, a water-miscible solvent such as water, methanol, ethanol, or tetrahydrofuran is selected. The temperature is usually -20'C-100'C1, preferably 0°C to 80'C.

Induction from C to d can be achieved using thionyl chloride, phosphorus oxychloride,
For reactions using phosphorus pentachloride, oxalyl chloride, etc., use solvent-free or methylene chloride, chloroform, carbon tetrachloride,
carried out in a solvent such as dichloroethane, toluene, N,N-dimethylformamide, NN-dimethylacetamide, etc.
The reaction temperature is usually -20°C to 150°C, preferably -10°C.
'c~80°C.

Compound e is disclosed in U.S. Patent No. 4,333.999 and Japanese Patent Publication No. 6
No. 0-35731, No. 61-2757, No. 61-42
658 and 63-208562 and the like.

The reaction between d and e can be carried out without solvent or with acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N,
In a solvent such as N-dimethylimidacylin 2-one, usually -
20°C to 150°C1 preferably -lO°C to 80'C
It is carried out over a temperature range of At this time, a weak base such as pyridine, imidazole, N, N dimethylaniline, etc. may be used.

The cyan coupler represented by the general formula (+) can also be formed by a direct dehydration condensation reaction of C and e. As the condensing agent, N N'-dicyclohexylcarbodiimide, carbonyldiimidazole, etc. are used.

Examples of synthesis of couplers of the present invention are shown below.

Synthesis Example 1 Sodium metal (2.3 g, 0°10 mo
1) is dissolved in anhydrous methanol (loose) and ethyl cyanoacetate (I1, 3 g, 0.10 m) is added dropwise at room temperature over 10 minutes. After stirring for 15 minutes, benzylpromyF (I8.8 g, 0°11 mol) was added dropwise over 10 minutes at room temperature, and the mixture was heated under reflux at 80°C for 20 hours. After cooling, O8
Add 1 normal basic acid and extract three times with ethyl acetate. The organic layer is washed with water and saturated brine, and dried over anhydrous sodium sulfate.

The solvent is distilled off under reduced pressure. Ethanol with residual fragrance (I00-)
A 5N aqueous sodium hydroxide solution (I0
Add 0d) and stir for 2 hours. Add water and extract twice with ethyl acetate. The organic layer was washed with 0°1N diluted hydrochloric acid, water, and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, methylene chloride (I00m) and N,N-dimethylformamide (0.5m) were added, oxalyl chloride (I6cc) was added dropwise at room temperature over 15 minutes, and the mixture was stirred for 2 hours. When the solvent was distilled off under M pressure, the crude product of 2-cyano-3-phenylpropionic acid chloride (I3.0 g
, 75%) was obtained.

5-Amino-2-(3-(4-cyanophenyl)ureido)phenol (20.1 g, 0.075
s+ol) of N,N-dimethylacetamide (200
d) A crude product of 2-cyano-3-phenylpropionic acid chloride is added dropwise to the solution at room temperature over 30 minutes, and after the dropwise addition, the solution is stirred at 60'C for 2 hours. After cooling, add water and extract twice with ethyl acetate. The organic layer was washed with 0.1N diluted hydrochloric acid, water, and saturated brine, and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure, and the residual aroma was recrystallized from acetonitrile to obtain Exemplified Compound 2 (I5, 2 g, 50%). The melting point was 105°C.

In the present invention, the cyan coupler is generally used in an amount of 0.002 to 0.3 mol, preferably 0.002 to 0.3 mol, per 1 mol of photosensitive halide km. Ol to 0.2 mol is used. The coating amount per square meter is 0.01 to 5 mmol, preferably 0.1 to 2 mmol.

The cyan coupler of the present invention can be introduced into a photosensitive material by an oil-in-water dispersion method. A high boiling point organic solvent having a weight ratio of 2.0 to 0 to coupler can be used. Preferably 1.
A solvent having a high boiling point of 0 to 0 can be used, and compared to other cyan couplers having a similar structure, it can be stably dispersed even with a small amount of a high boiling point organic solvent of 0.1 to 0. A feature of the color photographic material of the present invention is that a stable dispersion can be obtained without using a high-boiling organic solvent.

In the present invention, the following can be used as the coupler solvent, and for the cyan coupler, phthalate esters (e.g. dibutyl phthalate di-2-ethylhexyl phthalate, didodecylphthalate, ethyl phthalyl ethyl glycol, etc.), Fatty acid esters (e.g.
2-ethylhexyl tetradecanoate, di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, 2-ethylhexyl-9,10-epoxy stearate, benzoic acid esters (e.g. 2-ethylhexylbenzoate, dodecyl Benzoate, hexadecyl
4-hydroxybenzoate, etc.), phenol M (e.g., 2,4-di-L-pentylphenol, 2,4-dinonylphenol, 2°4-didodecylphenol, etc.), and chlorinated paraffins (e.g., 4
High boiling point organic solvents such as paraffins (0 to 70% by weight) are preferred.

The cyan coupler of the present invention can be used in any of the light-sensitive emulsion layer, non-light-sensitive emulsion layer, and intermediate layer, but it is preferable to add it to the light-sensitive emulsion layer, and use it in the red-sensitive emulsion layer. It is more preferable to use it by adding it inside.

The cyan coupler of the present invention may be used alone as a cyan coupler, or may be used in combination with other cyan couplers. Preferred cyan couplers that can be used in combination include ■-funator type cyan coupler, 5-amide-
1-Naphthol type cyan coupler (U.S. Pat. No. 690,
No. 899, described in JP-A No. 64-78252! 2-Ureidophenol type cyan coupler (JP-A-64-20
No. 44).

The coupler of the present invention can be used, for example, in color paper color reversal vapor, color positive film, color negative film,
Color reversal film, color can be directly applied to positive photosensitive materials. Application to color negative film is particularly preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride.

The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen &lI power distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and those surrounding it. shell
A particle with a so-called layered structure in which the halogen composition differs between layers or multiple layers; or a structure with a non-layered portion of different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, an edge, corner or surface of the particle); Particles having a structure in which portions of different compositions are bonded to the top thereof can be appropriately selected and used.

In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

The halogen composition differs depending on the type of photosensitive material to which it is applied. For example, printing materials such as color paper are mainly based on silver chlorobromide emulsions, while photographic materials such as color negatives are mainly based on silver iodobromide emulsions. used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is taken as the particle size, and in the case of cubic particles, the particle size is taken as the particle size, and it is the average based on the projected area.

In the case of tabular grains, it is also expressed in terms of spheres. ) is preferably 2 μm or less and 0.1 μm or more, particularly preferably 1.
It is 5 μm or less and 0.15 μm or more.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r ) crystals or coexistence of these crystals, or irregular (irre) crystals such as spherical
It may have a crystalline form (gular), or it may have a composite form of these crystalline forms. Also, tabular grains may be used.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N [117643
(December 1978), pp. 22-23.

“1. Emulsion preparation
ion andtypes, )', and the same NCL1
87-16 (November 1979), p. 648, "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.
, Glafkides.

Chemie et Ph1sique Photog
Rahique, Paul included (ontel, 1
967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic Emul'5ion Che
mistry (Focal Press.

1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L.

Making
and CoatingPhotographic Em
uldion, Focal Press,
(1964) and others.

U.S. Patent No. 3,574. ．． No. 628, 3,655,3
Monodisperse emulsions such as those described in No. 94 and British Patent No. 1.413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Cutoff, Photographic Sc.
engineering), 1st
4, pp. 248-257 (I970); U.S. Patent No. 4
, 434°226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure Na1
7643 and K18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD 17643 RD 1871
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649 Right Column 4 Brightener Page 24 5 Antifoggant Pages 24-25 Page 649 Right Column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column~
Ilter dye page 650 left column UV absorber 7 stain inhibitor page 25 right column 8 dye image stabilizer page 25 9 hardener page 26 10 binder page 26 11 plasticizer, lubricant page 27 12 coating aid, 26-27 Page Surfactant 13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent No. 4. 411. No. 987 and No. 4
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 1 7643, ■-C-G.

Examples of yellow couplers include U.S. Pat. No. 024, No. 4,401゜752,
British Patent No. 4,428,961, Japanese Patent Publication No. 10739/1973, British Patent No. 1,425,020, British Patent No. 1,476.
No. 760, U.S. Patent No. 3973.968, U.S. Patent No. 4,
Preferred are those described in No. 314,023, No. 4,511,649, European Patent No. 249°473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3. 725. No. 067, Research Pad Disclosure N (L24220 (June 1984), Japanese Unexamined Patent Publication No. 6
No. 0-33552, Research Disclosure N (
I24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4.500,630, U.S. Patent No. 4.540.6
No. 54, No. 4,556,630, International Publication WO38
Examples include phthol couplers described in U.S. Pat. No. 4,052.212 and U.S. Pat.
No. 46,396, No. 4,228,233, No. 4.
296. No. 200, No. 2,369,929, No. 2,801.171, No. 2.77.2,162, No. 2,895,826, No. 3. 772. 0
No. 02, No. 3,758,308, No. 4,334.
No. 011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121.365A, European Patent No. 249,453A, US Patent No. 3.446,6
No. 22, No. 4.333゜999, No. 4,775,
No. 616, No. 4゜451.559, No. 4,427
, No. 767, No. 4,690,889, No. 4,25
4', No. 212, No. 4,296,199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure Seed 17643.
- Section G, U.S. Patent No. 4,163゜670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146,
The one described in No. 368 is preferred. Also, U.S. Patent No. 4
, 774°181, which corrects unnecessary absorption of coloring dyes by the fluorescent dye released during coupling, and couplers that react with developing agents to form dyes, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576.910, British Patent No. 2,102
．． It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors are described in RD l 764 as previously described.
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4248.962, U.S. Patent No. 4,782,012
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing coupler D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,30
2A, 11449 to couplers R, D, and N that release dyes that restore the color of the separation liquid described in No. 313,308A;
No. 24241, a bleach accelerator releasing coupler described in JP-A No. 61-201247, etc., U.S. Patent No. 4,553,47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that emit leuco dyes described in US Pat. No. 5,747, couplers that emit fluorescent dyes as described in US Pat. No. 4,774,181, and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. The process and effects of latex dispersion as one of the polymer dispersion methods, as well as specific examples of latex for impregnation, are described in U.S. Patent No. 4,199,363 and West German Patent Application (○LS) No. 2.
．． 541. No. 274 and No. 2.541,230
Regarding dispersion methods using organic solvent-soluble polymers, PCT International Publication No. WO38100723 describes, for example, phthalic acid alkyl esters (') butyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, etc.). , tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g.
2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate), alkylamides (e.g. diethyl lausolamide), fatty acid esters (e.g. dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-tetradecanoate) -hexyldecyl, tributyl citrate, diethyl azelate), chlorinated paraffins (paraffins a> with a chlorine content of 10% to 80%).

trimesic acid esters (e.g. tributyl trimesate), or organic solvents with a boiling point of about 30°C to 150°C,
For example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol,
C1,Q per mole of methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosol silver
Ol to 1 mol, preferably 0.01 to 0.01 for yellow couplers. 5 moles, 0.003 to 0.3 moles for magenta couplers, and 0.002 to 0.3 moles for cyan couplers.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-Benzinthiazoline-3 described in No. 0941
-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

The photographic material used in the present invention is coated on a commonly used plastic film (such as cellulose cellulose, cellulose acetate, polyethylene terephthalate), a flexible support such as paper, or a rigid support such as glass. . For details on the support and coating method, see Research Disclosure Volume 176 Item I T
643 Section XV (p.

27) Described in Section X (p, 28) (December 1978 issue).

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminephenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are covered by U.S. Patent No. 2. 360. 290
No. 2,418,613, No. 2,700.45
No. 3, No. 2,701', No. 197, No. 2,728,
No. 659, same No. 2.732. No. 300, No. 2, 73
No. 5,765, No. 3.982.944, No. 4,4
30,425, British Patent No. 1.363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,02
No. 8, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3゜43.
2.300, 3,573,050, 3,5
No. 74,627, No. 3.698,909, No. 3,
No. 764,337, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,360,589, and p-alkoxyphenols are described in U.S. Patent No. 2,73.
No. 5,765, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 10539/1982, and Japanese Patent Publication No. 19765/1983, and hindered phenols are described in US Patent No. 3.700.
No. 455, JP-A-52-72224, U.S. Patent No. 4,2
No. 28,235 and Japanese Patent Publication No. 52-6623, and US Pat. No. 3,457,079 for gallic acid derivatives, methylenedioxybenzenes, and aminophenols, respectively.
No. 4,332.886, Japanese Patent Publication No. 56-21144, etc., hindered amines are disclosed in U.S. Pat.
No. 135, No. 4,268,593, British Patent No. 1.
No. 326,889, No. 1,354,313, No. 1
, 410,846, JP 51-1420, JP 58-114036, JP 59-53846, JP 59-78344, etc. Metal complexes are described in U.S. Pat.
No. 050,938, British Patent No. 4,241,155, British Patent No. 2,027, British Patent No. 731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314°794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. Nos. 3,705,805 and 3,707,395), (as described in U.S. Pat. No. 4,045,229), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (eg, as described in U.S. Pat. No. 3. TOo, 455). An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidinediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N,N, -
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and their sulfates, hydrochlorides, p-toluenesulfonates, etc. can be mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and fogging agents such as competitive couplers sodium borohydride and dryide. agent, auxiliary developing agent such as l-phenyl-3-pyrazolidone, viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
l-diphosphonic acid, nitrilo-N, N, N-)rimethylenephosphonic acid, ethylenediamine-N, ,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air loss by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The tear-whitening treatment may be performed simultaneously with the fixing treatment (bleach-fixing treatment), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Further, depending on the purpose, treatment may be carried out using two consecutive white-white fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (I).
II), compounds of polyvalent metals such as chromium (■), copper (■), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Aminopolycarboxylic acids such as l, 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates, bromates, permanganates, dinitrobenzenes, etc. Can be used. Among these, aminopolycarboxylic acid iron(I[I) complexes and persulfates, including ethylenediaminetetraacetic acid iron(II[,) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(II[) complex salts also have the following properties in bleaching solutions:
It is also particularly useful in bleach-fix solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron(II[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful tear white enhancers are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, JP-A-53-95630, Research Disclosure No. Nα17.129 (I97
Compounds having a mercapto group or disulfide bond described in JP-A-50-140129; U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2,748°430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat. No. 3,893,858 and West Patent No. 1.
, 290° 812 and JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4.552゜8
Compounds described in No. 34 are also preferred. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially ammonium thiosulfate. Most widely used. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, 9.248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J (1986), Sankyo Publishing, complete collection of sanitary technology, "Sterilization of microorganisms, sterilization, anti-mold technology J (I982), Society of Industrial Technology, Japan anti-bacterial control system “Encyclopedia of antibacterial and fungicidal agents J (I)” edited by the academic society
It is also possible to use the fungicides described in 1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various hair growth agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14. ,． 8
Schiff base type compounds described in No. 50 and No. 15.159, aldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No.-135628.

The silver halide color light-sensitive material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 5B-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

EXAMPLES Next, the effects of the present invention will be specifically explained by examples, but the present invention is not limited thereto.

Example 1 Light-sensitive materials (samples 101 to 115) having the following compositions were prepared on an undercoated cellulose triacetate support, which developed monochromatic colors with two layers: an emulsion layer and a protective layer. Values other than couplers are expressed in g/nf units. (
Regarding silver halide, values are shown in terms of silver. ) Emulsion layer Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 μm) Silver 0.8 gelatin
1.2 coupler (I) (see Table 1) Mol/po unit 0.001 Dibutyl phthalate 0. 3 Protective layer Gelatin 0.9 Polymethyl methacrylate particles (1.5 μm in diameter) 0.4 Sodium 1-oxy-3,5-dichloro-s-triazate 0. ．． 04 The photosensitive materials (samples 101 to 115) prepared in this way were
After cutting into pieces with a width of 20cm and a width of 35m and exposing them to white light with an exposure intensity of 40CMS using a continuous density wedge,
The following color development process was performed.

Color development processing Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds fixing
Wash with water for 4 minutes and 20 seconds 5
Stable for 1 minute The treatment solution used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1. 0g 1-Hydroxyethylidene 1,1-diphosphonic acid 2° Sodium sulfite 4° Potassium carbonate
30゜potassium bromide
l.

Potassium iodide l.

H('roxylagone sulfate 2゜4-(N-
-ethyl-N-β- hydroxyethylamino) 2-methylaniline sulfate 4° Add water
1゜g 1 phi 10゜bleach solution 1, 3-diaminopropanetetraacetic acid secammonium salt 105゜aqueous ammonia
3゜ammonium bromide; rum
150° ammonium nitrate
10° Add water 1° pH 4
゜Fixer ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Add sodium bisulfite water and add 1゜4゜175゜4゜l.

pH 6゜g g Stabilizing liquid formalin (40%) 2゜〇-Polyoxyethylene-P-monononylphenyl ether (average degree of polymerization ÷ IO) Add 0゜3g water 1. On! Regarding the samples (I01 to 115) that developed cyan color in the color development process C, the gamma value (center I/density 0 on the metric curve)
．． 5 and the concentration of 1, 0) and Dm
ax (maximum color density) was measured. The results are shown in Table 1. Each value is expressed as a relative value when the measured value of sample 101 is set as 1.

Comparative coupler (described in U.S. Pat. No. 4,333°999) Table 1 shows that when the compound of the present invention is used, the coupling reactivity is higher than when the comparative coupler is used, and the maximum color development is It can be seen that an image with high density is provided.

Example 2 Multilayer silver halide photosensitive materials (samples 201 to 215) were prepared by coating a photosensitive layer having the following composition on an undercoated cellulose triacetate support.

(Photosensitive layer & l command) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, halogenated 1 of the same -m
jl The coating amount per mole is shown in moles.

No. 111 (Antihalation layer) Black colloidal silver! I O,18 Gelatin 2nd layer (middle layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 EX-30,02 X-12 -1 -2 -3 BS-1 B5-2 Third layer of gelatin (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Coupler (see Table 2) 3, 1xlO-' 6.3 3 X-4 X-10 B5-1 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye l Sensitizing dye■ Sensitizing dye■ X-3 X-4 X-2 B5-1 B5- 2 Gelatin 6th layer (intermediate layer) 1.4X10-'2.3X10-' ?, 5 4X10-'4X10-'4X10-' 0,010 0,080 0.097 0,22 0.10 1,39 X-5 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Increase Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X-8 B5-1 B5-3 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ 0.040 0.020 0,68 0,15 0.15 0XIO-'0XIO-'8X10-' 0.260 0.021 0.030 0.025 0.100 0.010 0,53 Silver 0.45 2, lXl0-' 7, 0XIO-' 2° sensitizing dye■ EX-6 EX-8 EX--7 B5-1 11 B S-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitization Dye V Sensitizing dye ■ Sensitizing dye ■ EX-13 EX-14 EX-1,1 EX-1 B5-1 B5-2 Gelatin 1st O layer (yellow filter layer) 6X10-' Q, 094 0.01B 0. 026 0.160 0,00B 0,43 1,2 5X10-'oxio-'0XIO-' 0.015 0.015 o, io.

O,025 0, 25 0, 10 1, 31 color color silver 已X-5 B5-1 gelatin 11th layer (111th emulsion N) Emulsion A Emulsion B Emulsion F Sensitizing dye■ EX-9 EX-8 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye■ EX-9 EX-10 BS-1 gelatin 0,08 0,07 0,07 5XlO”’ 0, V2 0.042 0, 28 0,94 Silver 0.45 2.Ixto-' 0, 154 0.007 0,05 0,66 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ EX-15 BIN gelatin No. 141 (first protective layer) Emulsion I J-4 [No 5 B5-1 gelatin No. 1511 (Second Protection N) polymethyl acrylate particles (Diameter approximately 1.5μm) -1 gelatin ul　0,77 2.2X10”’ 0, 20 0,07 0,69 0,54 0.20 1,02 In addition to the above ingredients, each layer contains 1 and a surfactant were added.

Gelatin hardening agent H EX-1 EX-2 1 H EX-3 H EX-4 H EX EX-7 EX-13 EX-9 X 10 X H X-12 X 3 X-14 X-15 -2 H H ( jJ aH drop U-4 UV-5 B5-1 Tricresyl phosphate BS Butyl phthalate (tJL:5H11 Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye Sensitive pigment■ -1 -1 cnx=bow HSow CHx C0NHCutCH
! -C1l-5o-CHg C0NII CH!
The dry film thickness of all coated layers except for the support and the undercoat layer of the support for Samples 201 to 215 prepared at this time was 16.5 μ to 1
It was 8.4μ.

The prepared samples (201-215) were cut into 35-inch widths, processed, and subjected to wedge exposure of red light.

Next, processing was performed using a cine-type automatic processor according to the processing recipe shown below. However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developer reached three times the volume of the mother solution tank, and then the samples were processed.

Processing process Processing time Processing temperature Replenishment! "Color development 3 minutes 15 seconds 37.8℃ 23d bleaching 4
0 seconds 38.0°C 5d fixation 1 minute 30 seconds 38.0°C 30d washing (I130 seconds 38
．． 0℃ water washing (2) 30 seconds 38.0"C stable 30 seconds 38.0℃ drying 1 minute
55°C ``The amount of replenishment is per 1 meter length of 35M width.Water washing is a countercurrent method from (2) to (I).

0Ii tank capacity 10i! 2 0ffi 1 1 1 0d The composition of the treatment liquid is shown below.

(Mother solution developer) Diethylenetriagon 5 acetic acid l-hydroxyethylide Thor 1. t-diphospho acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate 2-methyl-4-[N-e Chill-N-(β-hydro xyethyl)amino]a Niline sulfate add water pH Mother liquor (8) 1.0 3.0 4.0 30.0 1.4 1, F+sg 2.4 4.5 1.02 to, os Replenisher (8) 30.0 1.01 to, t.

(Bleach solution) Mother liquor (8) Replenisher (8) 1, 3 Propylenediaminetetraacetic acid ferric ammonium hydrate 1.3-Propylenediaminetetraacetic acid Ammonium bromide Ammonium nitrate Acetic acid (98%) Add water to pHC Ammonia Water (27χ) Table adjustment] 144.0 2.8 84.0 30.0 50.0 1, Ol 4.0 206.0 4.0 120.0 41.7 72.5 1.0ffi 3.2 ( Fixer) Common to mother solution and replenisher (8) Ethylenediaminetetraacetic acid diammonium salt ammonium sulfite ammonium thiosulfate aqueous solution (700g/j2) Add water to pH 1°14°340, C1I & 1, OF! 7゜ (Washing water) mother liquor, replenisher common tap water, H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong basic anion exchange resin (Amberly 1-IRA manufactured by Rohm and Haas) −
400) to reduce the concentration of calcium and magnesium ions to 3/1 or less,
Subsequently, sodium dichloride isocyanurate 20μ/Il
and 150 μ/l of sodium sulfate were added. p of this liquid
H was in the range 6.5-7.5.

(Stable solution) Mother solution, replenisher common formalin (37%) Surfactant (C+Jt+ Q -(-CHtCHtO-)T-f
-H) Add ethylene glycol water to pH 5゜ (unit: g) 1.2- 0.4 1゜1゜1 7゜ The red density of the sample (201-215) developed by the development process was measured using a Fuji densitometer. was measured.

In Table 2, a concentration of 1°0 is given for sample 201. The density of each sample at the given exposure amount is shown.

From the results shown in Table 2, it can be seen that when the compounds of the present invention are used, high color development can be obtained even in multilayer photosensitive materials.

(Effects of the invention) As is clear from the above results, when the cyan coupler of the present invention is used, the force/711177 reactivity is high;
Photosensitive materials with high color density can be obtained.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, containing at least one cyan dye-forming coupler represented by the following general formula (I). Characteristic silver halide color photographic material. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 are hydrogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, cycloalkyl groups,
or an aryl group, R^3 represents a substituted or unsubstituted aryl group, and Z represents a hydrogen atom or a coupling-off group, respectively. )