JPH03192349A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photogrpahic sensitive material contg. cyan couplers which impart high coupling reactivity and high dye absorbing density to the material by incorporating the specific cyan dye forming couplers into the material. CONSTITUTION:The cyan dye forming couplers expressed by general formula (I) are incorporated into the silver halide color photographic sensitive material having silver halide emulsion layers on a base. (In the formula, R<1> denots and alkyl group, alkenyl group, cycloalkyl group or aryl group; R<2> denotes a group which can be substdd. on a benzene ring; R<3> denotes an aryl group; R<4> denotes an aryl group; Z denotes a hydrogen atom or coupling elimination group.) The photosensitive material formed by using this invention may contain a hydroqui none deriv., aminophenol deriv., gallic acid deriv., ascorbic acid deriv., etc., as a color fogging preventive agent.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic material containing a novel phenolic cyan dye-forming coupler. [Prior art] After exposing a silver halide photographic light-sensitive material to light, color development is performed to form an oxidized aromatic-grade amine developed mulberry and a dye-forming coupler (hereinafter referred to as coupler) to form a one-color image. be done. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, color images of yellow, macenta, 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, five-color forming couplers are added to the developer solution or incorporated into the light-sensitive photographic emulsion layer or other color image-forming layer, and react with the oxidized product 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 couplers with hydrogen atoms at this active site have 4
Equivalent couplers, ie, require schematically 4 moles of silver halide to form 1 mole of dye. - On the other hand, those with a group that can leave as an anion at the active site are 2-equivalent couplers, that is, chemically only 2 moles of silver halide with development nuclei are required to form 1 mole of dye. Therefore, compared to 4-equivalent couplers, silver halide m 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 color image formed. The sharpness increases towards -L. By the way, among cyan couplers, naphthol type couplers have a sufficiently long wavelength absorption of the formed dye image, have little crosstalk with the absorption of the magenta dye image, and have low coupling reactivity with the oxidized form of the color developer. It has been widely used for photographic purposes, mainly color negative films, because it can be selected from low to high prices. but,
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 they also have poor heat fastness. was strongly desired. On the other hand, U.S. Pat.
A phenol type cyan coupler having a carbonamide group which is a diffusion resistance imparting group) is disclosed. These couplers are widely used as couplers to replace the above-mentioned naphthol-type cyan couplers because they undergo bathochromic shift when the dyes associate in the film, giving a dye image with excellent hue, and are also excellent in fastness. It's starting. [Problems to be Solved by the Invention] However, the performance requirements for photographic light-sensitive materials in recent years are severe, and even for these couplers, higher coupling reactivity and higher dye absorption density are being sought. Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material in which a cyan coupler is gold-plated and provides high coupling reactivity and high dye absorption density.

[Means to solve the problem]

The present inventors have conducted extensive research to achieve the above-mentioned object, and as a result, have found that one object can be achieved in the following silver halide color photographic light-sensitive material. That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the following formulas is used.

[! A silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by the following formula. General formula [! ] 0'#1 In formula 1, 11' is an alkyl group, alkenyl group, cycloalkyl group, or aryl group, R1 is a group that can be substituted with a penzene ring, R1 is an aryl group, and Z is a hydrogen atom or a coupling group. The leaving group represents an integer from θ to 4.] In the tenth alphabet, the R'-R" group includes those having a substituent. Below, regarding the cyan coupler represented by the formula [3] In the general formula H), R1 preferably represents the total number of carbon atoms (
(hereinafter referred to as C number) 1 to 36 (more preferably 6 to 24)
) linear or branched alkyl group, C2-36
(more preferably 6 to 24) linear or branched alkenyl groups. It represents a 3- to 12-membered cycloalkyl group having 3 to 36 carbon atoms (more preferably 6 to 24 carbon atoms) or an aryl group having 6 to 36 carbon atoms (more preferably 6 to 24 carbon atoms), and these represent substituents (
For example, halogen atoms, hydroxyl groups, carboxyl groups, sulfo groups, cyano groups, nitro groups, amino groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups,
Aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group,
R1 is preferably a linear , an alkyl group having a branched or substituted group (alkoxy group, alkylthio group, aryloxy group, arylthio group, alkylsulfonyl group, arylsulfonyl group, aryl group, alkoxycarbonyl group, epoxy group, cyano group or halogen atom) [For example, n-octyl, n-decyl, n-dodecyl, n-hexadecyl, 2
-ethylhexyl, 3.5.5-trimethylhexyl,
3.5.5-trimethylhexyl, 2-ethyl-4-methylpentyl, 2-hexyldecyl, 2-hebutylundecyl, 2-octyldodecyl, 2.4.6-trimethylhebutyl, 2.4゜6 .8-tetramethylnonyl, benzyl, 2-phenethyl, 3-(L-octylphenoxy)propyl, 2-(2,4-di-t-pentylphenoxy)propyl, 2-(4-biphenylyloxy)ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl, 9.10-epoxyoctadecyl, dodecyloxycarbonylmethyl, 2-(2-naphthyloxy)ethyl], unsubstituted or substituted (e.g. halogen atom,
an alkenyl group having an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, or an alkoxycarbonyl group)

[For example, allyl, 10-undecenyl, oleyl, citronellyl. Cinnamyl], unsubstituted or substituent-containing cycloalkyl group (e.g. halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group or aryloxy group) [e.g. cyclopentyl, cyclohexyl, 3
．． 5-dimethylcyclohexyl, 4-t-butylcyclohexyl], or unsubstituted or having a substituent (e.g., halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, carbonamide group, alkylthio group, or sulfonamide group) Aryl groups [e.g. phenyl, 4-dodecyloxyphenyl, 4-biphenylyl, 4-dodecanesulfonamidophenyl, 4-
t-octylphenyl, 3-pentadecylphenyl], particularly preferably the linear, branched or substituted alkyl group. general formula

In [1], R3 is a group that can be substituted on the benzene ring, preferably a group selected from the substituent group A, and when there is a plurality of fans, R3 may be the same or different. R3 is more preferably a halogen atom (F, Cfi, Br, 1), an alkyl group having 1 to 24 carbon atoms (e.g. methyl, butyl, butyl, t-octyl, 2-dodecyl), 3 to 24 carbon atoms. 24 cycloalkyl groups (
For example, cyclopentyl, cyclohexyl), C number 1-2
4 alkoxy groups (e.g. methoxy, butoxy, dodecyloxy, benzyloxy, 2-ethylhexyloxy, 3-dodecyloxypropoxy, 2-dodecylthioethoxy, dodecyloxycarbonylmethoxy), C number 2
~24 carbonamide groups (e.g. acetamide, 2-
ethylhexanamide, trifluoroacetamide) or a sulfonamide group having 1 to 24 carbon atoms (for example, methanesulfonamide, dodecanesulfonamide, toluenesulfonamide). general formula

In [1], the fan is preferably an integer of 0 to 2, more preferably an integer of 0 or 1. -Mathematical formula

In [1], R3 preferably has a C number of 6 to 36,
More preferably, it represents an aryl group having 6 to 15 atoms, and may be substituted with a substituent selected from the above substituents mA, or may be a condensed ring. Here, as a preferable substituent, a halogen atom (F, 6-base , rsr, 1), cyano group, nitro group, acyl group (e.g. acetyl, benzoyl), alkyl group (e.g. methyl, t-butyl, trifluoromethyl, trichloromethyl), alkoxy group (e.g. methoxy, ethoxy, butoxy, tri fluoromethoxy), alkylsulfonyl groups (e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl)
, arylsulfonyl groups (e.g. phenylsulfonyl,
p-1lylsulfonyl, p-chlorophenylsulfonyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), sulfonamide groups (e.g. methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carbamoyl groups (
For example, N,N-dimethylcarbamoyl, N-phenylcarbamoyl) or sulfamoylj! (For example, N, N
-diethylsulfamoyl, N-phenylsulfamoyl). 1 to 3 are preferably halogen atoms,
Cyano group, sulfonamide group, alkylsulfonyl group,
A phenyl group having at least one substituent selected from an arylsulfonyl group and a trifluoromethyl group, more preferably 4-cyanophenyl, 4-
Cyano-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
-cyano-4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl%3-cyano-4-yakuchiganophenyl, 3-chloro-4-cyano phenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.・In formula [1], 2 represents a hydrogen atom or a coupling-off group (including #l deatomization, the same applies hereinafter); a preferred example of a coupling-off group is a halogen atom%
-OR'-3R'-0CR' -03Ot R'
, -NHCOR' may also be used. 2 is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an alkylthio group, particularly preferably a hydrogen atom, a chlorine atom, or the following formula [! 1] or a group represented by the following formula [nll]. General formula [111 C number 6-30 arylazo group, C number 1-30, and coupling active position at nitrogen atom (position where 2 is bonded)
Heterocyclic groups bonded to (eg, cohelyimide, phthalimide, hydantoinyl, pyrazolyl, 2-benzotriazolyl), and the like. Here, R4 is C number 1 to 36
Alkyl group with 2 to 36 carbon atoms, alkenyl group with 3 to 36 carbon atoms
36 cycloalkyl group, a C6-36 aryl group, or a C2-36 heterocyclic group, and these groups are substituted with a substituent selected from Group A, [wherein R
1 is a halogen atom, a cyano group, a nitro group, an alkyl group,
Alkoxy group, alkylthio group, alkylsulfonyl group, arylsulfonyl group, carbonamide group, sulfonamide group, alkoxycarbonyl group, carbamoyl group,
a sulfamoyl group or a carboxyl group, m is 0 to 5
1 represents an integer of the general formula (ml (wherein, W represents an oxygen atom or a nitrogen atom, R6 and R7
each represents a hydrogen atom or a monovalent group, R'' and R9 each represent a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted amino group, an integer from nGjl to 6. 11), R'' preferably represents a halogen atom, an alkyl group (e.g. methyl, t-butyl, octyl, pentadecyl), an alkoxy group (e.g. methoxy,
n-butoxy, n-octyloxy, benzyloxy,
methoxyethoxy), carbonamide groups (e.g. acetamide, 3-carboxypropanamide) or sulfonamide groups (e.g. methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably alkyl or alkoxy groups. It is. n is preferably an integer of θ to 2, more preferably 0
or an integer of l. When %R@ and/or R7 represents a monovalent group in general formula [I11], 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 group (e.g. N-ethylcarbamoyl, N-phenylcarbamoyl), and R6 and R7 are more preferably hydrogen atoms,
It is an alkyl group or an aryl group. General formula [ITl
], Y is preferably -6-. General formula [n+1
In, R8 is preferably an alkyl group, an alkoxy group,
alkenyloxy group. An aryloxy group or a substituted or unsubstituted amino group, more preferably an alkoxy group or a substituted or unsubstituted amino group. In the general formula [III], n preferably represents an integer of 1 to 3, more preferably l, and in the general formula [I[1], W is preferably an oxygen atom. H3 CH3 Examples of R3 in general formula (1) are shown below. Examples of 2 in general formula (1) are shown below. -0CH3 0C2H5 -OCH2CH20CHa -OCHzCOOCHs -OCHzCHzCOOCH3 -OCH2CH2SO2CH3 -OCH2CONHCH2CH20H -OCH2CONHCH2CH20CH3-OCI(2
CH=CH2 -OCH2CH2SCH2COOH -OCH2CH2NH5OiCH3 -SCH2COOC2H5 -5CH2COOH -3C)12CH2COOH -SCHCOOH H3 -5CH2CH20H H ■ -SCH2CHCH20H CH2CH2COOH , Z is a coupling-off group, a photographically useful group (e.g. development inhibitor residue, dye residue ) is preferably not contained. Specific examples of the cyan coupler represented by the formula [I] are shown below. The cyan coupler of the present invention represented by the formula [I] can be synthesized by various synthetic routes. Typical synthetic routes are shown below. Here R is a hydrogen atom, a methyl group or an ethyl group,
X is a leaving group such as a halogen atom, mesyloxy group, or tosyloxy group. The compound S is synthesized by a nucleophilic substitution reaction between thiosalicyl [n or thiosalicylic acid ester and r('-X. Preferred examples include potassium methoxide, lithium methoxide, P-methyldimethylaminopyridine, DABCO (diazabicyclooctane), N-methylmorpholine, DBL+ (diazabicycloundecene), and DBN (diazabicyclononene). One reaction solvent may not be used, but a solvent such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N,N'-dimethylimidazolidin-2-one, acetone, or toluene may be used. The reaction temperature is usually -20°C to 150°C, preferably 20°C to 100°C. When R is an alkyl group, it is induced to C by hydrolysis. Sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, It is common to use an aqueous solution of an inorganic base such as an aqueous sodium carbonate solution, and a water-miscible solvent such as water, methanol, ethanol, or tetrahydrofuran is selected as the reaction solvent.The reaction temperature is usually -20°C to 100"C, preferably O ℃～
The temperature is 80°C. Induction from C to d is thionyl chloride, oxychloride ~
9 React using phosphorus, phosphorus pentachloride, oxalyl chloride, etc., either without solvent or in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N,N-dimethylformamide, N,N-dimethylacetamide, etc. The temperature of the 0 reaction is usually -20°C to 1
The temperature is 50°C, preferably -10°C to 80°C. Compound e is disclosed in U.S. Pat.
No. 0-35731, No. 61-2757, No. 61-42
It can be synthesized by the synthesis methods described in No. 658 and Japanese Patent Application Laid-Open No. 63-208562. The reaction between d and e can be carried out without solvent or with acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimeg-ruacetamide,
In a solvent such as N,N'-dimethylimidazolidin-2-one, usually -20°C to 150°C, preferably -10°C.
It is carried out at a temperature range of ~80°C. At this time, pyridine,
A weak base such as imidazole, N,N-dimethylaniline may be used, and the cyan coupler represented by the formula [+1 can also be synthesized by a direct dehydration condensation reaction between C and e, in which case the condensing agent as N,N'-dicyclohexylcarbodiimide. Carbonyldiimidazole and the like are used. Synthesis Example 1 Synthesis of Exemplified Compound 3 Under a nitrogen stream, 2-hexyldecanol (24.2 g. 0.1 Gmol) was added to a methylene chloride (200-) solution.
Triethylamine (12, Ig, 0.12+g+ol
) in the presence of methanesulfonyl chloride (12.6 g%
After dropping 0.11 mol) at room temperature over 15 minutes, the mixture was stirred for 1 hour, water was added, and the mixture was extracted with methylene chloride. Wash with 0.1N diluted hydrochloric acid, water, and saturated saline, and dry over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the remaining N,
A solution of N-dimethylformamide (1G (bd) was added to a solution of thiosalicylic acid (15.4g, 0.1 Ornol) in N,N-dimethylformamide (100ml) in the presence of potassium carbonate (20.0g, 0.145+mol), Stir at 80°C for 2 hours. After cooling, add water and extract twice with ethyl acetate. The organic layer is diluted with 1N diluted hydrochloric acid, water,
Wash with saturated saline and dry with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and methylene chloride (100 mft) was added.
Add N,N-dimethylformamide (0,5d),
Oxalyl chloride (16 cc) was added dropwise at room temperature over 15 minutes and stirred for 2 hours. When the solvent was distilled off under reduced pressure, 2-
A crude product of (2-hexyldecylthio)benzoic acid chloride (31.5 g, 83%) was obtained. 5-amino-2-[3-(4-cyanophenyl)ureido]phenol (22.2 g, 0.08
3n+ol) of N,N-dimethylformamide (200
r+t) solution at room temperature, 2-(2-hexyldecyl)
The crude product of thiobenzoic acid chloride was added dropwise in 30 minutes,
After the dropwise addition, the mixture was stirred at 60°C for 2 hours. Add water and extract twice with ethyl acetate. The organic layer was treated with 0.1N diluted hydrochloric acid, water,
Wash with saturated saline and dry with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain Exemplified Compound 3 (38, Ig, 73%). In the present invention, the cyan coupler is used in an amount of usually 0.002 to 3 mol, preferably 0.01 to 0.2 mol, per N mol of photosensitive silver halide. The coating ij1 per square meter is O, Ol to 5 mmol. Preferably it is 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. High boiling organic solvents having a monomer ratio of 2.0 to 0 to coupler can be used. Preferably 1.
A high boiling point organic solvent of 0 to 0 can be used, and it can be stably dispersed even with a small amount of high boiling point organic solvent of 0.1 to 0 compared to other cyan couplers having a similar structure. 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 coupler solvents listed below can be used, but for cyan couplers, phthalate esters (e.g. dibutyl phthalate, di-2-ethylhexyl phthalate, didodecylphthalate, ethyl phthalylethyl glycolate) etc.), fatty acid esters (e.g. 2-ethylhexyl tetradecanoate, di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, 2-ethylhexyl, 9.10-epoxystearate), benzoic acid esters (e.g. -ethylhexylbenzoate, dodecylbenzoate, hexadecyl-4-hydroxybenzoate, etc.), phenols (for example, 2.4-di-pentylphenol, 2.
High boiling organic solvents such as 4-dinonylphenol, 2,4-didodecylphenol, etc.) and chlorinated paraffins (eg, paraffins with a chlorine content of 40 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 as a cyan coupler in China, Germany, or in combination with other cyan couplers. Preferred cyan couplers that can be used in combination include 1-naphthol type cyan couplers, 5-amide-
1-Naphthol type cyan coupler (U.S. Patent No. 6908
No. 99, JP-A-64-78252), 2-ureidophenol type cyan coupler (JP-A-64-2044)
(described in ). The coupler of the present invention can be used, for example, color vapor, color reversal vapor, color positive film, color negative film,
It can be applied to color reversal film, color 1ci, and 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 composition 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 a shell surrounding it. (Shell) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) 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 vapor 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) Nα17643
(December 1978), pp. 22-23. “1. Emulsion preparation
tion and types, and the same N (L187
16 (November 1979), 648 pages, graphic [
"Physics and Chemistry of Photography", published by Ballmontel (P, Gl.
afkides. Chemie et Ph1sique Photog
Rahique, Paul Mantel, 19
B? ), “Photographic Emulsion Chemistry” by Duffin. Published by Focal Press (G, F, Duffin. Photographic Ernulsion Che
Mistry (Focal Press. 1966)), "Manufacture and Coating of Photographic Emulsions" by V. L. Zelikman et al +l Making
and CoatingPhotographic E+
nuldion, Focal Press, l
964) and others. U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 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 in Cutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (19'lO); U.S. Pat. No. 4,434゜226, U.S. Pat.
, 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 N11
17643 and N (118716), 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 following The relevant entries are shown in the table below.
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right Column 4 Brightener Page 24 5 Antifog Agent Pages 24-25 Page 649 Right Column ~
and stabilizer 6 Light absorber, 7 pages 25-26 page 649 right column - Ilter dye page 650 left column ultraviolet absorber 7 stain inhibitor page 25 right column page 650 left - right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10 Binder page 26 Same as above 11 Plasticizer,
Lubricant Page 27 Page 650 Right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 35,503. Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) N11l 7643, described in the patent described in ■-〇-G. As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401゜752, No. 4,
428,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1.476.760, U.S. Patent No. 3973.968, British Patent No. 4.314,
No. 023, No. 4,511,649, European Patent No. 24
9°473A, etc. are preferred. As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. 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 Disclosure N1124220 (June 1984), Japanese Patent Publication No. 6
No. 0-33552, Research Disclosure Nα
24230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Patent No. 4,500,630, U.S. Patent No. 4゜540.65
No. 4, No. 4,556.630, International Publication W0881
Examples include phthol couplers described in U.S. Pat. No. 4,052.212 and U.S. Pat.
No. 6,396, No. 4.228,233, No. 4.
296. No. 200, No. 2,369,929, No. 2.801.171, No. 2,772,162, No. 2,895.826, No. 3. 772. 002
No. 3,758.308, No. 4,33/1,0
No. 11, No. 4,327,173, West German Patent Publication No. 3
, 329,729, European Patent No. 121.365A,
No. 249,453A, U.S. Patent No. 3.446,62
No. 2, No. 4,333゜999, No. 4,775,6
No. 16, No. 4 451.559, No. 4,427,
No. 767, No. 4,690,889, No. 4,254
, No. 212, No. 4,296,199, JP-A-61-
Preferred are those described in No. 42658 and the like. Colored couplers for correcting unwanted absorption of color-forming dyes are disclosed in Research Disclosure Na17643, Section 1-G, U.S. Pat. No. 4.16:1. No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,
No. 004,929, No. 4. 138. No. 258, British Patent No. 1,146,368 are preferred. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Pat. No. 4,774.181, and U.S. Patent No. 4,777.1.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 20. 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 described in U.S. Pat. No. 3,451.820; O80.211, 4,367.282, 4,409,320
No. 4.576.910, British Patent No. 2,102
, No. 173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, No. 63-37350, U.S. Patent No. 4゜2/18,962, No. 4,782.012
Preferably, those listed in No. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, 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 photosensitive material of the present invention include U.S. Patent No. 4. 130. Competitive couplers described in U.S. Pat. No. 427, etc., U.S. Pat.
Multi-equivalent coupler described in JP-A-60-18595
DIR redox compound releasing coupler, DIR coupler releasing coupler DIR coupler releasing redox compound or DIR described in No. 0, JP-A No. 62-24252, etc.
Redox-releasing redox compound, European Patent No. 173,
No. 302A, RoD, N [L1144
9, No. 24241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553,
Ligand releasing coupler described in No. 477 etc., JP-A-63
Examples include couplers that release leuco dyes as described in US Pat. No. 4,774,181 and couplers that release fluorescent dyes as described in US Pat. 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. Further, the process, effects, and specific examples of latex for impregnation as one of the polymer dispersion methods are described in U.S. Patent No. 4,199,363 and West German Patent Application (OLS) No. 2.
．． 541. No. 274 and No. 2,541,230
Dispersion methods using solvent-soluble polymers are described in PCT International Publication No. WO 38100723 (butyl, diethyl azelate), chlorinated paraffins (
paraffins with a chlorine content of 10% to 80%). Trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β -Ethoxyethyl acetate, methyl serotonin, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. 2-ethylhexyl benzoate, 2.4
-2-ethylhexyl dichlorobenzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl coherate, amber di-2-ethylhexyl, 2-hexyldecyl tetradecanoate, silver trogenide citrate) 0.0O1 per mole of
The amount ranges from 1 to 1 mol, preferably 0.01 to 0.5 mol for yellow couplers, 0.003 to 0.3 mol for magenta couplers, and 0.002 to 0.3 mol 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 described in No. 0941. 2-benzisothiazoline-
Various preservatives or antifungal agents such as 3-one, n-butyl, p-hydroxy, dibenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2-(4-thiazolyl)penzimidazole, etc. It is preferable to add an agent. The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), 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 1764
3 Described in Section XV (p. 27) Section X■ (p. 28) (December 1978 issue). The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. 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, aminophenols, 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 disclosed in U.S. Patent No. 2,360,290;
Go No. 2,418.613, Go No. 2.7, Go No. 453, Go No. 2,701,197, Go No. 2,728,659
No. 2. 732. No. 300, No. 2,735,
No. 765, No. 3,982.944, No. 4.430
．． 425, British Patent No. 1.363,921, U.S. Patent No. 2,710.8014, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are Patent No. 3゜4:12
, No. 300, No. 3.573.050, No. 3,57
No. 4,627, No. 3,698.909, No. 3,7
No. 64,337, JP-A-52-152225, etc.
Spiroindanes are described in U.S. Pat. No. 4,360,589, and p-alkoxyphenols are described in U.S. Pat. No. 2,735.
, 765, British Patent No. 2,066.975, JP-A-59-10539, JP-B-19765, etc.;
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,22
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457,079, U.S. Pat. No. 56-21144, etc., hindered amines are disclosed in U.S. Patent No. 3,336,1.
No. 35, No. 4,268,593, British Patent No. 1.3
26.19, 1.354.313, 1.4
No. 10,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983
-114036, 59-53846, 59
-78344 etc., metal complexes are disclosed in U.S. Patent No. 4,05
No. 0,938, British Patent No. 4,241,155, British Patent No. 2,027 and 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. 3,700,455). 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 on 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-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N,-diethylaniline, 3 -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid Examples include salt. Two or more of these compounds can be used in combination depending on the purpose. The color developer may contain 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. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium poron hydride, Auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as °ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1
, 1-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 di-7droxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. can be used alone or in combination. The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the replenishment rate of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 31 per square meter of photosensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500.
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation 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 bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (m) and cobalt (I).
Compounds of polyvalent metals such as II), chromium (■), and copper (II), peracids, quinones, nitro compounds, and the like are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (m) or cobalt (I[[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromate-permanganates; nitrobenzenes, etc. may be used. can. Among these, aminopolycarboxylic acid iron(m) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (m) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. . A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, JP-A-53-95630, Research Disclosure Fish No. 17.129 (1978
Compounds having a mercapto group or a disulfide bond as described in J.P. 1987-140129; Thiazolidine derivatives as described in JP-A No. 50-140129; U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; JP-A-58-16235
Iodide salts described in No. 2,748゜430; polyoxyethylene compounds described in West German Patent No. 2,748゜430;
Polyamine compounds described in No. 836; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect.
In particular, U.S. Patent No. 3,893,858, West Patent No. 1,
Compounds described in No. 290°812 and JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4,552゜83
Compounds described in No. 4 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, with ammonium thiosulfate being the most widely used. Can be used for 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 water-wash type in the water-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, inthiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorinated disinfectants such as chlorinated sodium incyanurate,
Others, such as benzotriazole, by Hiroshi Horiguchi [Chemistry of Bacterial and Mildew Prevention J (1986), Sankyo Publishing, edited by Hygiene Technology Society [Microbial Sterilization, Disinfection, and Mildew Prevention Technology J (1982), Industrial Technology Society, Japan Antibacterial Prevention “Encyclopedia of antibacterial and fungicidal agents J” edited by the Hui Gakkai (1)
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 20 minutes.
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 the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-22'0345 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 chelating 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 14.850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． 719.4! Metal salt complex described in No. J2, JP-A-53-
Examples include urethane compounds described in No. 135628. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 5B-115438. The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification. (Example) Next, the effects of the present invention will be specifically explained using examples, but the present invention is not limited thereto. Example 1 A monochrome photosensitive material consisting of two layers, an emulsion layer and a protective layer, on a subbed cellulose triacetate support (Sample 1)
01-117) was prepared with the composition shown below. The numbers are
Items other than couplers are expressed in units of g/m''. (For silver halides, 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 Seratin
1.2 coupler (see table 1) m
ol/go unit 0.001 dibutyl phthalate
0.3 Protective layer Seratin 0.9 Polymethyl methacrylate particles (diameter 1.5 μm) 0.41 Sodium 3.5-dichloro-S-triazate 0.04 Color photosensitive material thus prepared ( Samples 101-117),
After exposure using a continuous density wedge at an exposure intensity of 40 cm5, the following standard color development process was performed. Standard color development treatment (temperature 38°C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Fixing 4 minutes 20 seconds Washing 5 minutes Stability 1 minute The composition of the processing solution used in each step was as follows. Color developer Diethylenetriamine 5 vinegar M 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-〇 - Hydroxynige Ruamino) 2-Methylaniline @ Add salt water and bleach solution Propylene diamine tetraacetic acid ferric ammonium salt Ammonia water Ammonium bromide Ammonium nitrate Add water and fix solution Ethylene diamine tetra acetic acid 30.0 g 1.4 g 1.3 mg 2, 48 4, 5 g Eyes, 0f2 pHIO, 0 105, 0g 3, 0m12 150, 0g 10.0g I, 0 flood pH 4,2 Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0m12 Add 4.6g of sodium sulfite water
1.0 pH 6.6 Stable formalin (40%) 2. omg polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 410) Add 0.3g of water and add 1.0g of cyan color in the standard color development process (10m-117)
The gamma value (slope of the sensitometric curve) and Dmax (maximum color density) were measured using a Fuji densitometer (FSD). The results are shown in Table 1, and the multivalues are for sample 1.
It is expressed as a relative value when the measured value of 01 is taken as 1. 1 part thorium salt. g Table 1 Comparative coupler A Described in U.S. Pat. High ring reactivity and maximum color density. Example 2 Multilayer silver halide photosensitive materials (samples 201 to 217) were prepared by coating a photosensitive layer having the following composition on an undercoated cellulose triacetate support. (Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/g, and for silver halide, it indicates the coating amount in terms of silver (4). However, for sensitizing dyes, the coating amount in the same layer The coating amount per mole of silver halide is not shown in moles. 1st layer (antihalation layer) Black colloidal silver Silver 0.18 Seratin 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone EX -1 EX-3 EX-12 -t l-2 -3 B5-1 B5-2 Ceratin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye 1 Sensitizing dye 11 Sensitizing dye ■ Coupler (see Table 2) EX-10 B5-1 Ceratin 0.18 0.07 0.02 o, ooz O2O3 0.08 0.10 8.10 0.02 0.88 Silver 0.25 Silver 0. 25 6.9XIO-' 1.8X 10-' 3, IX 1G-'6.3XIO-'(mol/s") 0.020 0, 060 0.73 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye II Sensitizing dye■ Coupler (see Table 2) EX-3 EX-4 EX-10 B5-1 Seratin 5th layer (3rd red-sensitive emulsion layer) Milking sensitizing dye 1 Sensitizing dye 11 Sensitizing dye ■ EX-3 EX-4 EX-2 ) IBS-1 Silver 1.0 5.1XlO-''1.4XlO-'2.3XlO-'7.5XlO-' (mol/ ) 0.020 0,030 0.0+5 0,060 1.1 Silver 1.60 &, 4XIO-'' 1.4X 10-'2.4XIO-' o, ot. o, oe. O,09? 0.22 HBS-2 Gelatin 6th layer (intermediate layer) EX-5 HB S -1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX -6 EX-1 EX-7 EX-8 B5-1 1-IBS-3 Gelatin 8th layer (second green emulsion layer) 0.10 1.39 0, Mouth 40 0,020 0.68 Silver 0. 15 silver 0. +5 3, [1XIG-'1.0XIO-' 3.8XI low 4 0, 260 0.02+ 0, 030 0, 025 0.100 0, 010 0.53 Emulsion C Sensitizing dye V Sensitizing dye Dye ■ IX-6 1': X-8 EX-7! 11'3s-1 11B S-3 Ceratin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye■ Sensitizing dye■ E:X-13 EX-14 F, X-eye [miss - Straight B5-1 Silver 0.45 2, IX! O-'? , 0XIO-'' 2.6X 10-' 0, Mouth 94 0.0+8 0, 026 0.160 0, 008 0.43 Silver!, 2 3.5X IQ-' 8, OX +0"'3.0XlO"' 0.015 0.015 0.100 0,025 0.25 B5-2 Seratin 10th layer (yellow filter layer) Yellow colloidal silver 1 x-5 II 133-1 Gelatin 11th layer (first blue-sensitive emulsion layer) ) Emulsion Δ Emulsion I3 Emulsion I: Sensitizing dye ■ L': X -9 EX-8 1! B S -1 Seratin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ EX-9 0, 10 1,31 Silver 0.05 0.08 0.03 0.81 0.08 0.07 0.07 3.5XlO-' 0.72 0,042 0.28 0.94 Silver 0.45 2.1X 10-' 0.154 EX-10 HBS-1 Seratin 13th layer (3rd Pt-sensitive emulsion layer) Emulsion)-1 Sensitizing dye EX-15 B5-1 Seratin 14th layer (1st protective layer) Emulsion I -4 l-5) IBs-1 Ceratin 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) -1 Ceratin 0,007 0.05 0.56 Silver 0.77 2.2XlG- ' 0.20 0.07 0.69 Silver 0.5 0.11 O,1? 0.05 0.85 0.54 0,20 1.20 In addition to the above components, each layer contains Ceratin hardener H -1 and surfactant were added. EX-15 C EX-10 庳X-12 -1 J-2 -3 lI CellsO5Ose υ-4 - Butylfucrate sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye I Sensitizing dyes Enhanced dyes Normal sensitizing dye ■ -1 CI. -1 Supports and supports of samples 201 to 217 prepared at this time The dry film thickness of all coating layers excluding the undercoat layer of the body is !6.5μ~
It was 17.4μ. The prepared samples (201 to 217) were cut into 351 width pieces.
It was processed to give a 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 treated with imagewise exposure until the amount of replenishing color developer was three times the volume of the mother solution tank. Fixed 2! ] 1 minute and 30 seconds washing (1) 30 seconds washing +21 30 seconds stability 30 seconds drying 1 minute $ Supplementary light amount is 35m + - width l Washing is from (2) to (1) 37.8℃ 23m ( 38.0℃ 5m!2 38.0℃ 30rn II. 38.0℃ 38.0℃ 30m 1 38.0℃ 20m x 55℃ It is a self-flowing method in the amount per meter. The composition of the processing solution is shown below. (Mother liquor Developer solution) Mother solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.0 +, 1!-
Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 3G, 0 30.0 Potassium bromide Potassium iodide Hydroxylamine fEm salt 2-Methyl-4-[N- Add ethyl-N-(0-hydroxyethyl)aminocoaniline sulfate solution to pH (bleach solution) 1.4- ], 5 mg - 2,4 3,6 4,5 6,4 1,02 1, Oi 10 .05 +0.10 Mother liquor (g) Replenisher (8) 1.3-Propylenediaminetetraacetic acid ferric ammonium hydrate 1.3-Propylenediaminetetraacetic acid Ammonium bromide Ammonium nitrate Acetic acid (98%) Add water +44.0 206.0 2.8 B4.0 30.0 50.0 1.0 4.0 +20.0 41.7 72.5 bu 1.0bu pH [adjusted with aqueous ammonia (27%)] 4 .0 3.
2 (Fixer) Common to mother solution and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g/fan) 340.0
Add m water 1. OR. pH 7,11 (Washing water) Mother liquor and replenisher Common tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-320B, manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite I RA, manufactured by Rohm and Haas). −
Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3 mg/R or less, followed by sodium dichloride isocyanurate 20+.
sg/J! and 150 mg/J of sodium sulfate were added. The p)l of this solution was in the range of 6.5 to 7.5. (Stabilizing solution) Common to mother liquor and replenisher solution (Unit: g) Formalin (37%) 1.2 mbu Surfactant 0.4 [C+oll*+
-0→CII, CII s 0hv-11] Ethylene glycol 1.0 Add water
1.0I2pH5.0-7.0 The red color density of the samples (201 to 217) which were colored by the development process was measured using a Fuji densitometer. Table 3 shows the density of each sample at the exposure dose that gave a density of 1.0 in sample 201. From the results in Table 2, the samples of the present invention show high color development even in multilayer photosensitive materials. I understand that. (Effects of the Invention) As is clear from the above results, in the silver halide color photographic light-sensitive material of the present invention, the coupling reactivity of the cyan coupler is high and the color density of the image is high, which is an excellent effect. Written amendment (method) % formula % 1. Indication of the case 1999 Patent Application No. 334006 2. Name of the invention Silver halide color photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address Kanagawa Prefecture 210 Nakanuma, Minamiashigara City Name (520)
Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent address: 7th floor, 6th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo, Subject of amendment 7, Contents of amendment: 4 sentences in the specification - Procedures …Authentic book (0 quotation io month 30, 1990)

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] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 is an alkyl group, alkenyl group, cycloalkyl group, or aryl group, R^2 is a group that can be substituted on the benzene ring, R^3 represents an aryl group, Z represents a hydrogen atom or a coupling-off group, and l represents an integer of 0 to 4, respectively. ]