JPH04199047A - Halogenated silver color photosensitive material - Google Patents

Abstract

PURPOSE:To satisfy a demand for higher coupling reactivity and higher pigment absorbing density by containing a specific cyanic pigment forming coupler. CONSTITUTION:This halogenated silver color photosensitive material contains a cyanic pigment forming coupler indicated in an expression I. In the expression I, R<1> indicates an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, R<2> indicates a substitutional group for a benzene ring, R<3> indicates an aryl group, L indicates an expression II, Z indicates a hydrogen atom or a coupling detaching group, and l indicates an integer 0-4. This results in obtaining the material containing the cyanic coupler for providing high coupling reactivity and high pigment absorbing density.

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 with an anionically detachable group at the active site are 2-equivalent couplers, i.e., stoichiometrically only 2 moles of silver halide with development nuclei are required to form 1 mole of dye. It is a coupler, and 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, which makes it possible to shorten the processing time of the photosensitive material and improve the sharpness of the color image formed. will improve.

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.

(Problems to be Solved by the Invention) However, the performance requirements for photographic light-sensitive materials in recent years are severe, and even these couplers continue to be required to have higher coupling reactivity and higher dye absorption density.

JP-A Nos. 57-204544, 57-204545, and 1-172951 disclose phenolic cyan couplers having a 3-arylureido group at the 2-position and an m-alkoxycarbonylbenzamide group at the 5-position, respectively. is disclosed. However, the cyan couplers described in these documents did not meet the requirements for higher coupling reactivity and higher dye absorption density.

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 problems can be achieved in the following silver halide color photographic light-sensitive materials. Ta.

That is, in a silver halide color photographic light-sensitive material having a small number of silver halide emulsion layers on a support, at least one cyan dye-forming coupler represented by Funazo (I) below is included. This was achieved using a distinctive silver halide color photographic light-sensitive material.

General formula (I) (wherein, R1 is an alkyl group, alkenyl group, cycloalkyl group, or aryl group, and R2 is a
, t represents a water-based Novona Yota or Totsu I ring leaving group, and Shinobi represents an integer from O to 4, respectively. ) In the above, the group R'-R3 includes not only an unsubstituted group but also a group having a substituent.

Below, the cyan coupler represented by -Funzo (I) will be explained in detail. - In ship stock (I), R1 is preferably a linear or branched alkyl group having a total number of carbon atoms (hereinafter referred to as C number) from 1 to 36 (more preferably from 6 to 24), and from 2 to 36 C atoms. (more preferably 6 to 24) linear or branched alkenyl group, 3 to 12-membered cycloalkyl group having 3 to 36 carbon atoms (more preferably 6 to 24 carbon atoms), or 3 to 12-membered cycloalkyl group having 6 to 36 carbon atoms (more preferably 6 to 24 carbon atoms) Preferably represents an aryl group (6 to 24), which is a substituent (e.g. halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amine group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group). group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group,
It may be substituted with a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group, or a 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 alkyl groups [e.g. 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-(t-octylphenoxy)propyl, 3
- (2,4-di-t-pentylphenoxy)propyl, 2-(4-biphenylyloxy)ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl, 9.10
-Epoxyoctadecyl, dodecyloxycarbonylmethyl, 2-(2-naphthyloxy)ethyl, 7-pentadecyl, 8-heptadecyl, 9-nonadecyl, 2-dodecylsulfonylethyl, 1-(2,4-di-t-pentylphenoxy) ) propyl], unsubstituted or substituted (
For example, an alkenyl group having a halogen atom, an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, or an alkoxycarbonyl group [e.g. allyl, 10-undecenyl, oleyl, citronellyl, cinnamyl], unsubstituted or substituted (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 substituted An aryl group having a group (halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, carbonamide group, alkylthio group or sulfonamide group) [e.g. phenyl, 4-dodecyloxyphenyl, 4-biphenylyl, 4-dodecane sulfonamidophenyl, 4-t-octylphenyl, 3-pentadecylphenyl], and particularly preferably the linear, branched or substituted alkyl group.

In general formula (I), R2 is a group that can be substituted on the benzene ring, preferably a group selected from the above substituent group A, and when C is plural, R2 may be the same or different. It's okay. R2 is more preferably a halogen atom (F, CJ2, Br, I), a C1-24 alkyl group (e.g. methyl, butyl, t-butyl, t-octyl, 2-dodecyl), a C3-24 alkyl group, Cycloalkyl group (
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).

In general formula (I), β is preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

In general formula (I), Rs 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-mentioned substituent group A, or may be a fused ring. Here, preferred substituents include halogen atoms (F, 0°C, Br, trichloromethyl), alkoxy groups (e.g. methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl)
, arylsulfonyl groups (e.g. phenylsulfonyl,
p-tolylsulfonyl, p-chlorophenylsulfonyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), sulfonamide groups (e.g. methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carbamoyl groups (e.g. N, N- dimethylcarbamoyl, N-phenylcarbamoyl) or sulfamoyl groups (e.g. N,N-diethylsulfamoyl, N-phenylsulfamoyl)
can be mentioned. R3 is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamido group, an alkylsulfonyl group, 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-)dihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-
4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano-3-halogenophenyl,
3.4-dicyanophenyl or 4-alkylsulfonylphenyl.

- In Shipzou (I), Z represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Preferred examples of coupling-off groups include halogen atoms, -O
R', -3R', -0CR', -0SO,R'
, -NHCOR4, C6-30 arylazo group, C
number 1 to 30, and the coupling active position (2
heterocyclic group (e.g., succinimide, phthalimide, hydantoinyl, pyrazolyl,
2-benzotriazolyl) and the like. Here R
4 is an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, a cycloalkyl group having 3 to 36 carbon atoms, and a cycloalkyl group having 6 to 3 carbon atoms
6 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, particularly preferably a hydrogen atom, a chlorine atom,
The group represented by - Funazou (n) below or below - Funazou (I
II).

- Shipura (II) (wherein R5 is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, an 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 (III) (In the formula, W represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R6 and R7 each represent a hydrogen atom or a monovalent group, Y represents 10-, each represents 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, and n represents an integer of 1 to 6.Here, n represents a compound in general formula (II). , Ra is preferably a halogen atom, an alkyl group (e.g. methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (e.g. methoxy, n-butoxy, n-octyloxy, benzyloxy, methoxyethoxy), a carbonamide group m is preferably an alkyl group or an alkoxy group. It is an integer of 0 to 2, more preferably an integer of O or 1.

In general formula (III), when R6 and/or R7 represents 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 group (e.g. N-ethylcarbamoyl, N-phenylcarbamoyl), and R6 and R? is more preferably a hydrogen atom,
It is an alkyl group or an aryl group. - In Funazura (III), Ra is preferably an alkyl group, an alkoxy group, an 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 ship stock (m), n preferably represents an integer of 1 to 3, more preferably 1.

C3HI3 C1lH17 6HI3 H3 6H13 2H5 ■ Examples of R3 in general formula (I) are shown below.

-0CH2CONHCH2CH20H-OCH2CON
HCH2CH20CH3-0CHCOOC2H5-0C
H2CH20H□ CH2C00C2H5 QCH2CH2S CHz C0OH-0CH2CH2
NHS 02 CH3CONHCH2CH20H 5till t -5CH2COOC2H5-5CH2COOH-OCH
aCONH☆NHCOCR2G) (-COOH-OCH
aCOOC<Hs-see -0CH2CO
OC4H9-t-OCLCOOOO-0CH2COOCH
2CH20CH3-OCH2CONH-()OCH3-
OCH2COOC)I2CH2SO□C1”+3
When 2 is a coupling-off group, it is preferable not to carry photographically useful groups (eg, development inhibitor residues, dye residues).

Specific examples of the cyan coupler of the present invention represented by general formula (I) are shown below, but the present invention is not limited thereto.

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

Compound A is synthesized by the reaction of salicylic acid A with a carboxylic acid chloride, a sulfonic acid chloride, or an acid anhydride. Although it is not necessary to use a reaction solvent, a solvent such as ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidin-2-one, or toluene may be used. good. It is preferred to use a base in this reaction, including sodium hydride, rhiziumamide, potassium t-butoxy, potassium carbonate, sodium carbonate, DBU
(diazabicycloundecene), DBN (diazabicyclononene), etc. are suitable. The reaction temperature is -78℃
~150°C, preferably -30°C to 50°C.

Induction from b to C uses thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride, etc., with or without solvent.
Methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N,N-dimethylformamide, N,
The reaction is carried out in a solvent such as N-dimethylacetamide. The reaction temperature is usually -20°C to 150°C, preferably -10°C to 80°C.

Compound d is disclosed in U.S. Patent No. 4,333,999 and Japanese Patent Application Publication No.
No. 0-35731, No. 61-2757, No. 61-42
It can be synthesized by the synthesis methods described in No. 658 and JP-A No. 63-208562.

The reaction between C and d can be carried out without a solvent or in acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N
, N'-dimethylimidacylin-2-one, etc., usually from -20°C to 150°C, preferably from -10°C to 80°C.
It is carried out in 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 Funazo (I) is b
It can also be synthesized by a direct dehydration condensation reaction between and d, using N as a condensing agent.

N'-dicyclohexylcarbodiimide, carbonyldiimidazole, etc. are used.

Examples of synthesis of the cyan coupler of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplary Coupler 1 13.8 g of salicylic acid and 150 ml of tetrahydrofuran
was added, stirred under water cooling, and 60% sodium hydride 8.4
g and stirred for 30 minutes. After the reaction solution was cooled to -10° C., 24.7 g of tetradecanoyl chloride was added dropwise little by little. After stirring for 1 hour, the mixture was further stirred at room temperature for 2 hours. Pour the reaction solution into 9,500 Trl of dilute salt containing ice, and add 300 ml of ethyl acetate. Extracted with. After drying the ethyl acetate solution, the ethyl acetate solution was dried and concentrated, and acetonitrile was added to crystallize it to obtain crystals of O-tetrazokayloxybenzoic acid.
．． I got 4g.

N to 17.2 g of 0-tetrazokayloxybenzoic acid,
0.5 ml of N-dimethylformamide and 50 ml of methylene chloride were added, and 6.5 ml of oxalyl chloride was added dropwise with stirring at 10°C. After stirring for 1 hour, excess oxalyl chloride and methylene chloride were distilled off under reduced pressure to obtain oily tetrazokayloxybenzoyl chloride.

5-Amino-2-[3-(4-cyanophenyl) synthesized by the method described in U.S. Patent No. 4,333,999
Ureido] 1.3.4 g of phenol to 80 m of N,N-dimethylacetamide! The entire amount of 0-tetrazokayloxybenzoyl chloride was added dropwise to the solution under stirring at room temperature. After stirring for 3 hours, 300 ml of ethyl acetate and 5
00 ml of water was added for extraction, and the mixture was further washed with water, and then sodium sulfate was added to the ethyl acetate solution for drying. The ethyl acetate solution was concentrated under reduced pressure, and the crystals precipitated by adding acetonitrile were filtered and dried to obtain 14.5 g of the desired exemplary coupler 1. The structure of this compound was confirmed by 'HNMR spectrum, mass spectrum and elemental analysis. Note that the melting point was 159 to 165°C.

Synthesis Example 2 Synthesis of Exemplary Coupler 3 The target example coupler 3 was prepared in the same manner as in Synthesis Example 1, except that the same number of moles of 2-hexyldecanoyl chloride was used in place of the tetradecanoyl chloride in Synthesis Example 1. 15.6g of crystals were obtained. The structure of this compound is 'H
Confirmed by NMR spectrum, mass spectrum and elemental analysis. In addition, the melting point was 169 to 171°C.

In the present invention, the cyan coupler is used in an amount of usually 0.002 to 0.3 mol, preferably 0.0 to 0.2 mol, per mol of photosensitive silver saponide.

The cyan coupler of the present invention can be introduced into a light-sensitive material by an oil droplet dispersion method in ice. 2.0 to 0 parts by weight of high boiling organic solvent can be used to coupler. Preferably 1.
A high boiling point organic solvent of 0 to 0 can be used, and compared to other cyan couplers having a similar structure, even a small amount of high boiling point organic solvent of 0.1 to 0 can be stably dispersed. 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, as the coupler solvent, the following can be used. For cyanide carbs, phthalate esters, fatty acid esters, and salts with a high boiling point of 6.5 or less, preferably 6.5 to 5 are used. Organic solvents are preferred, and phthalate esters of long-chain alkyl alcohols with a dielectric constant of about 5.2 are preferred because the resulting hues are of long wavelength.

The coupler of the present invention can be applied to, for example, color vapor, color reversal vapor, color positive film, color negative film, color reversal film, and color direct positive light-sensitive materials. Particularly preferred is application to color negative film.

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 by using an emulsion having the same halogen composition among the grains, 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) [-
Particles with a so-called laminated structure in which the halogen composition differs between layers (layer or multiple layers), or structures with different halogen compositions in a non-layered manner inside or on the surface of the particle (if present on the particle surface, on the edges, corners or surfaces of the particle) Particles having a structure in which parts of different compositions are joined to each other 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.

Further, so-called high-silver chloride emulsions having a high silver chloride content are preferably used for 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, it is 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.
o is 5 μm or less, and is μm or more.

The particle size distribution can be narrow (or wide),
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.

A silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (RD) N.

17643 (December 1978), pp. 22-23.

``1. Emulsion preparation
ion andtypes, )', and the same N(I1
87-16 (November 1979), p. 648, "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.
Glafkides.

Chemie et Ph1sique Photog
Rahique, Paul Montel, l
967), "Photographic Emulsion Chemistry" by Duffin.

Published by Focal Press (G, F, Duffi).

Photographic Emulsion Chem
istry (Focal Press.

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

Zelikman et al., Mak
ing and coatingPhotogra
hic Emulsion, Focal P
It can be prepared using the method described in J. ress, 1964).

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 in Cutoff, Photographic Science and Engineering.
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. The additive used in such processes is Research Disclosure Nα1.
7643 and No. 18716, 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.

Additive type 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 Antifog Agent Pages 24-25 Page 649 Right Column ~
and stabilizer 6 Light absorber, fu Page 25-26 Page 649 right column - Ilter dye Page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25 right @ page 650 left - right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO binder page 26 Same as above II 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 include the aforementioned Research Disclosure (
RD) No. 11643, ■-C-G.

As a yellow coupler, for example, U.S. Patent Box 3.93
No. 3,501, No. 4,022,620, 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 Box 3°973.968, British Patent No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
9°473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
0,619, European Patent No. 4,351°897, European Patent No. 73,636, US Patent Box 3,061,432, European Patent No. 3,061,432; 725. No. 067, Research Disclosure Nα24220 (June 1984), Japanese Unexamined Patent Publication No. 1986
-33552, Research Disclosure Nα2
4230 (June 1984), JP-A-60-43659
No. 61-"12238, No. 60-35"+30, No. 55-118034, No. 60-185951,
U.S. Patent Box 4,500,630, U.S. Patent No. 4,540.6
No. 54, No. 4,556,630, International Publication W088
Examples include phthol couplers described in U.S. Pat.
No. 46,396, No. 4,228,233, No. 4.
296. No. 200, No. 2,369,929, No. 2,801.171, No. 2,112,162,
Same No. 2,895,826, Same No. 3. 772. 00
No. 2, No. 3,758,308, No. 4,334.0
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 Box 3.446,62
No. 2, No. 4,333゜999, No. 4,775,6
No. 16, No. 4 451.559, No. 4,427,
No. 76T, 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 Research Disclosure No.

Section 17643 - G, U.S. Patent Box 4,163°670
No., Special Publication No. 57-39413, U.S. Patent Box 4,004
, No. 929, No. 4. 138. No. 258, British Patent No. 1,146,368 are preferred. Also, US Patent Box 4. No. 774°181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and U.S. Patent Box 4,777.120.
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 the above-mentioned issue.

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. 2.1.0
It is described in No. 2,173, 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. , multi-equivalent couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR redox compound late couplers IR couplers releasing couplers,
DIR coupler releasing redox compound or 1]R redox releasing redox compound, European Patent No. 173,3
No. 02A, a coupler that releases a dye that restores the color of the separation liquid described in No. 313,308A, R, D, No. 114
49, No. 24241, bleach accelerator-releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553
, No. 477, etc.;
Examples thereof include a coupler that releases a leuco dye described in US Pat. No. 3-75747 and a coupler that releases a fluorescent dye described in US Pat. No. 4,774,181.

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 (○LS) No. 2.
, 541,274 and 2,541,230, etc., and PCT International Publication No. WO38100723 describes dispersion methods using organic solvent soluble polymers, for example, phthalic acid alkyl esters (dibu nano 4 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. benzoic acid M 2-ethylhexyl) , 2-ethylhexyl 2,4-dichlorobenzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, di-2-ethylhexyl succinate, tetradecane a2-hexyldecyl, citric acid) triphthyl, diethyl acelate), chlorinated paraffins (
paraffins with a chlorine content of 10% to 80%), trimesic acid esters (e.g. tributyl trimenoate), 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, propion It is in the range of 0.001 to 1 mole per mole of ethyl acid, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, silver methyl cellosol, preferably 0.001 to 1 mole for yellow couplers. Ol to 0.5 mol, magenta coupler from 0.003 to 0.3 mol, and cyan coupler from 0.002 to 0.3 mol.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A No. 1999-
1,2-benzisothiazoline described in No. 80941
3-one, n-butyl, p-hydroxybenzoate,
Phenol, 4-chloro-3,5-dimethylphenol, 2-phenoquineethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or antifungal agents such as penzimidazole.

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 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 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 covered by U.S. Patent No. 2. 360. 290
No. 2,418.613, No. 2,700.45
No. 3, - No. 2,701,197, No. 2,728,
No. 659, same No. 2. 732. No. 300, No. 2, 7
No. 35,765, No. 3,982.944, No. 4,
430,425, British Patent No. 1,363,921;
U.S. Patent No. 2,710.801, U.S. Patent No. 2.816,0
No. 28, etc., 6-hydroxychromans, 5-hydroquine coumarans, and spirochromans are disclosed in U.S. Patent No. 3.4.
32.300, same No. 3,573,050, same No. 3,
574,627, same No. 3. 698. No. 909, No. 3,764,337, JP-A-52-152225, etc.; spiroindanes are disclosed in U.S. Patent No. 4,360,5;
No. 89, p-alkoxyphenols are disclosed in U.S. Pat.
, 735,765, British Patent No. 2,066,! 1J7
No. 5, JP-A-59-10539, JP-A-57-197
No. 65, etc., hindered phenols are covered by U.S. Patent No. 3.
Gallic acid derivatives, methylene dioxybenzenes,
-aminophenols are each U.S. Pat. No. 3,457
, No. 079, No. 4,332.886, Special Publication No. 1979-
No. 21144, etc., and hindered amines are disclosed in U.S. Patent No. 3. 336. 135, British Patent No. 4,268,593, British Patent No. 1,326,889, British Patent No. 1,354,
No. 313, No. 1,410,846, Special Publication No. 1984-1
420, JP-A-58-114036, JP-A No. 59-5
3846, U.S. Pat. No. 59-78344, etc., and metal complexes are disclosed in U.S. Pat.
No. 155, British Patent No. 2,027.731 (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 hendioxidole 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 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-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, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2.2]octane), various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, foggers such as sodium boron hydride. agents, auxiliary developing agents such as I-phenyl-3-pyrazolidone, viscosity-imparting agents, various calcinates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, e.g. , ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroquinethylidene-1
, ], -diphosphonic acid, nitrilo-N, N, N-
trimethylenephosphonic 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. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or 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 is generally less than 3J2 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0 mf or less. 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 (■) and cobalt (I).
II), compounds of polyvalent metals such as chromium (■), copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide: dichromate, organic complex salts of iron (I[I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l, 3 - Using diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc., persulfates: bromates; permanganates: nitrobenzenes, etc. I can do it. Among these, aminopolycarboxylic acid iron(III) 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(II[) complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (rfi) complex salts is usually 5.5 to 8, but it can be processed at an even lower pH to speed up the processing. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, 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 No. Nα17.129 (I97
Compounds having a mercapto group or disulfide bond described in JP-A No. 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
Polyoxoethylene compounds described in No.

Polyamine compounds described in Japanese Patent Publication No. 45-8836; 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, and in particular, compounds having a mercapto group or a disulfide group are preferred, and are particularly preferred in US Pat.
West Patent No. 1. No. 290゜812, JP-A-53-95
．． Compounds described in No. 630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552.834. 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 fixatives 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 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
Motion Picture andTe
levision Engineers Vol. 64, p.
248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, and the residence time of water in the tank increases, causing bacteria to propagate and the resulting floating matter to 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,
Chlorinated disinfectants such as chlorinated sodium incyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J' (I986), Sankyo Publishing, edited by Hygiene Technology Society [Sterilization of microorganisms, sterilization, antifungal technology J (I982) Industrial Technology Society, Japan Antibacterial Edited by the Antifungal Society [Encyclopedia of Antibacterial and Antifungal Agents J (I9
The fungicides described in 1986) can also be used.

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 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 at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can be directly processed with a stabilizing solution instead of the above-mentioned washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-14834
All known methods described in No. 6(]-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 chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other 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 compounds described in No. 7, No. 3□ 371
No. 2,599, Research Disclosure 14, 8
50 and 15,159, aldol compounds as described in 13.924, metal salt complexes as described in U.S. Pat. No. 3,719,492, and 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. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 339C to 38C, 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. I can do it. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2.226.7TO or US Pat. No. 3,674.499 may be carried out.

(Example) Next, the effects of the present invention will be specifically explained by examples, but the present invention is not limited to these.

Example 1 Photosensitive materials (samples 101 to 113) having the following layer configurations were prepared on a subbed cellulose triacetate support.

(Layer structure) Support cellulose triacetate film Emulsion layer Silver iodobromide emulsion (silver iodide 2 mo1%) 0.8 g in terms of silver / Gelatin resistance 1.2 g / Gokubura (see Table 1) O, 1 mmol / idyptyl Phthalate 0.3g/protective layer gelatin 0.9g'/b Polymethyl methacrylate particles (diameter 1.5μm) 0.4g/m'1-oxy-3.5-dichloro-8-triazine sodium 0.04g /Resistance Samples 101 to 113 thus prepared were exposed using a continuous exposure wedge at an exposure intensity of 40 cm s, and then subjected to the following standard color development process.

(Standard color development process) Color development 3 minutes 15 seconds 38℃ Bleaching 6 minutes 30 seconds Arrival: 4 minutes 20 seconds Wash with water 5 minutes Stable 1 minute The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
300g potassium bromide
1.4g potassium iodide
1.3mg hydroxylamine sulfate 2
．． 4g 4-(N-ethyl-N-β-hydroxyethylamino) 2-methylaniline sulfate 4.5g Add water 1.0ρpH 10.0 Bleach solution Propylenediaminetetraacetic acid ferric ammonium salt 105.0g Aqueous ammonia 3 , OTl′i! ! Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water
1.0 flood p84.2 Constant @ liquid ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 Sodium bisulfite 4.6 g Add water
i, o Flood pH 6,6 Stable formalin (40%) 2.0d polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) Add 0.3g water i, og standard color development process Sample that developed cyan color (I01-113)
The gamma value (slope of the sensitometric curve) and Dmax (maximum color density) were measured using a Fuji densitometer (FSI). The results are shown in Table 1. Each value is expressed as a relative value when the measured value of sample 101 is taken as 1.

From Table 1, it can be seen that when the compound of the present invention was used, both the gamma value and D wax were higher than when the comparative compound was used.

Example 2 On a subbed cellulose triacetate film support,
Sample '101, which is a multilayer color light-sensitive material, was prepared by layering 11 layers each having the composition shown below.

(Te!!, Photo II composition) The number corresponding to each component is g/rr? For silver halide, the coating amount is shown in terms of silver; however, for aggravating dyes, the coating amount is shown in moles per mole of silver halide in the same layer.

(Sample 201) 1st N (Antihalation N) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (intermediate layer) 2.5-Gy-pentadecylhydroquinone 0.18EX-
10,0?0 EX-30,020 E Layer (1st Red Emulsion N) Emulsion A Silver 0.25 Emulsion B
Silver 0.25 Sensitizing dye 1
6.9X10″5 sensitizing dye II
1.8X10-' Exacerbating Dye I
[13,lX10-' coupler (A of Example 1) 0.38E
X-100,020 HB S -10,060 Gelatin 0.87 4th NC
2nd Red Emulsion Layer) Emulsion IG
S 1.00 sensitizing dye [5, lX10
-5 Exacerbating Pigment II 1.4X],
0-' Exacerbating Dye 1[12,3X10-' Coupler (A of Example 1) 0.4SE
X -30,050 E X -100,015 Gelatin 1.30 No. 5N
Emulsion D Silver 1.60 Sensitizing Dye 1 5.4X10-' Sensitizing Dye ■ 1.4X10-' Sensitizing Dye I [12,4X10-' E X -20,097 E X -30,010 E X -40,080 HBS-10,22 HB S -20,10 Gelatin 1.63 No. 6N
(Intermediate layer) E
V 3.0X10 bow sensitizing dye V1.0X10-' Sensitizing dye Vl 3.8xlO
-'EX-10,021 E X -60,26 Eχ-70,030 E
'i (second green emulsion stone) Emulsion C silver o, 45 Sensitizing dye IV 2.1X10-
'Sensitizing dye V7. OX10
Bow sensitized color accumulation ■ 2.6
Third green emulsion N) Emulsion E Silver 1.20 Sensitizing dye TV 3.5 X 10-
S-enhancing dye V8.0X10-' Sensitizing dye Vl 3.0X10
-'EX-10,025 Eχ-110,10 Eχ-130,015 HBS~1 0.25HB
S-20,10 Gelatin 1.54 No. 10
1 (Yellow Milter 1) Yellow colloidal silver silver o, os.

EX -50,080 HB S -10,030 Gelatin 0.95 No. 11
N (first blue emulsion layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 Enhancing dye■ 3.5X10-'EX
-80,042 EX -90,72 HBS-10,28 Gelatin 1.10 No. 12
7i (second blue emulsion layer) Emulsion G silver o, 45 enhancing dye ■ 2. lX10-'E
X -90,15 E X-107,0xlO-" HB S -10,050 Gelatin 0.78 No. 13
Layer (third blue emulsion layer) Emulsion H silver o, 77 Sensitizing dye ■ 2.2X10-'
EX -90,20 HBS-10,070 Gelatin 0.69 14th layer (1st protection N) Emulsion I Silver 0.20U-4
0,11 U -50,17 HB S -15,0X10-' Gelatin 1.00 No. 15
N (second protection N) H10,40 B-1 (diameter 1.7 urr+) 5.0
X10-”B-2 (diameter 1.7 am)
0.10B-30,10 S-10,20 Gelatin 1.20 Furthermore,
W-1, W-2,
W-3, B-4, B-5, F-1, F-2, F-3, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-12, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

X-1 Eχ-2 Eχ-3 H Ex-4 H X-5 CJ+3(n) X-6 Eχ-7 X-8 Eχ-9 X-10 H I X-12 CJsO5O*O 13 Shil 1 (BS-1) Recresyl Phosphate HBS-2 G-n-butyl phthalate Sensitizing Dye ■ Sensitizing Dye ■ Sensitizing Dye ■ Sensitizing Dye ■ Sensitizing Dye ■ Sensitizing Dye ■ Sensitizing Dye ■ CH.

C) It"CHSOz<lh C0NH-CHzCHz
``'H-5(h-clh C0N)l-cHz-I W-2 n=2~4 Next, sample 202 was prepared in which the couplers added to the third and fourth layers were changed as shown in Table 2. ~213 was prepared. At this time, the coupler was added so that the coating amount per one photosensitive material was equimolar. The prepared sample was cut and processed into a width of 35 mm and subjected to wedge exposure with white light. Exposure The completed samples were subjected to continuous processing (running test) using an automatic developing machine according to the processing method described below until the tank capacity for color development was replenished three times.Next, each sample (201 to 213)
The sample was subjected to continuous wedge exposure with red light, and developed using the processing solution used in the running test. The color density of the cyan dye of each sample after treatment was measured using a Fuji densitometer (FS).
Measured in D).

Table 2 shows the density of each sample at the exposure amount that gave a density of 2.00 in sample 201.

7// // Processing method Color development 3 minutes 15 seconds 38℃ 45 print 10I
2 Bleach 1 minute 00 seconds 38℃ 20
m1 4℃ bleaching chamber @ 3 minutes 15 seconds 38℃
30 m 18°C tube system % formula % Replenishment amount per 35 mm width and 1 m length Next, write down the composition of the processing solution.

(I'm sorry for the inconvenience) Mother liquor (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid ], f) 1.11
-Hydroxyethylidene- 1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium rehydrate 30.0 37.0 Potassium bromide
1.4 0.7 Potassium iodide
1.5 mg -Hydroxylamine sulfate 2.4 2.84-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 5.5 Add water 1.1 1. 0℃pH10.05
10,10 ('Pa, '肚゛'di) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide ioo.

Ammonium nitrate 10.0 Aqueous ammonia (27%) 15.0171 Add water 1.0 β pH 6,3 .0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 d Aqueous ammonia (27%) 6.0 d Add water
1.0βp8
7.2 ('', ``A hot bed column filled with tap water and an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) Water was passed through the solution to reduce the concentration of calcium and magnesium ions to 3 mg/IL or less, and then 20 mg/j2 of sodium incyanurate dichloride and 5 g/j2 of sodium sulfate were added.The pH of this solution was 6.5. It was in the range of ~7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2.0d polyoxyethylene-p
- Monononylphenyl nityl (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.02 pH 5.0 to 8.0 From the results 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.

/ /'' Table 2 Comparative Compounds (A) Described in U.S. Pat. ) Described in JP-A-57-204545 1" IM (E) Described in JP-A-1-172951 H (G) H Example 3 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, A gelatin undercoat layer containing sodium dodesolbenzene sulfonate was provided, and various photographic constituent layers were further applied to prepare a multilayer color photographic paper (sample 301) having the layer structure shown below. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (C
pd-7) Add and dissolve 27.2 cc of ethyl acetate and 4.1 g each of 1 volume (Sol Sea 3) and (Solv-7) to 0.7 g, and dissolve this solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. Emulsified dispersion A was prepared by emulsifying and dispersing it in 185 cc of a 10% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion A (cubic, 3-near mixture (silver molar ratio) of large size emulsion A with an average grain size of 0.88 layers and small size emulsion A with an average grain size of 0.70 layers. Coefficient of variation of grain size distribution were 0.08 and 0.10, respectively, and each size emulsion contained IJW 0 bromide (3 mol % localized on a part of the grain surface). This emulsion contains a blue color enhancer dye A shown below.

B was added in an amount of 2.0 x 10-' mol to the large-sized emulsion A, and 2.5 x 10-' mol to the small-sized emulsion A, per mol of silver. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold enhancer. The emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the -Nth layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-nochloro S-triazine sodium salt was used.

In addition, the total amount of Cpd-10 and Cpd-II in each layer was 25.0 mg/bo and 50.0 mg/bo, respectively. It was added so that it became Otag/A.

The following spectral enhancing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

Enhanced dye A for the blue-sensitive emulsion layer Sensitizing dye B for the blue-sensitive emulsion layer (per mol of halide kn, 2.0 x 10-' mol each for the large-sized emulsion layer, and 2.0 x 10-' mol for the small-sized emulsion layer, and sensitizing dye B for the blue-sensitive emulsion layer)
(2.5xlO-' mol for each) for green-sensitive emulsion layer) Enhanced dye C for green-sensitive emulsion layer (4.0x10-' mol for large size emulsion B, 4.0x10-' mol for small size emulsion B per mol of silver halide) is 5
．． 6X10-' mol) and multiplying dye D for the glaucolato emulsion layer (per mole of silver halide, for large size emulsion B ?, 0XIO-S mol and for small size emulsion B 1. 0x10-' mol) Enhanced dye for red-sensitive emulsion layer E II CzHs Ie CsH++ (0.9x10 per mol of silver halide for large size emulsion C)
-' moles, and for small size emulsion C 1. IX
For the red-sensitive emulsion layer, 2.6 x 10-' moles of the following compounds were added per mole of silver halogenide.

Furthermore, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, ]-(5-methylureidophenyl)-5-mercaptotetrazole was added to each mole of 8.5 x 10-' moles of halogenated 8. , 7X10-' moles, 2.
5 x 10-' moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added per mole of silver halide, respectively, to lXl0-'
mol and 2X10-' mol were added.

In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

(Long/a") (I0 mg/m") and (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/n()). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Tilt) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A-0,30 Gelatin 1,86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1>0.19
Solvent (Solv-3) 0.
18 solvent (Solv-7)
0.18 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol Sea 1) 0.1
．． 6 solvent (Solv-4)
0.08 Fifth layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1 of large size emulsion B with average grain size 0.554 and small size emulsion B with 0.39*)
The coefficient of variation of the 0 particle size distribution of the 3 mixtures (Ag molar ratio) is 0.10 and 0.08, respectively, and each size emulsion is AgB.
rO, 8 mol% was locally contained in a part of the particle surface)
0.12 gelatin
1.24 magenta coupler (ExM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.1.6 Color image stabilizer (Cpd-
4) 0.02 color image stabilizer (Cp
d-9) 0.02 solvent (Sol
v-2) 0.40 fourth layer (
Ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47
Color mixing inhibitor (Cpd-5) 0.
05 Solvent (S01 Sea 5)
0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.584 and small size emulsion C with an average grain size of 0.45 - 1:
The coefficient of variation of the grain size distribution of the 4 mixtures (Ag molar ratio) is 0.09 and 0.11, and each size emulsion is AgBr 0.09 and 0.11.
(6 mol% was locally contained on a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-6
) 0.18 color image stabilizer (Cpd
-7) 0.40 color image stabilizer (C
pd-8) 0.05 solvent (So
lv-6) 0.14 Sixth layer (ultraviolet absorption li) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.0
2 solvent (Solv-5)
0.08 Seventh layer (protection N) Gelatin Acrylic modified copolymer of 1,33 holvinyl alcohol (denaturation degree 17%) 0.17 Liquid paraffin 0.03 (Ex
Y) 1:1 mixture (molar ratio) with yellow coupler (ExM) Magenta coupler (ExC) 1:1 mixture (molar ratio) with cyan coupler L (Cpd-1) Color image stabilizer (cpd-2) ) Color Image Stabilizer 0QCJs (Cpd-3) Color Image Stabilizer (NiPD-4) Color Image Stabilizer (Cpd-5) Color Mixing Preventer 0H IJI'I (Cpd-6) Color Image Stabilizer 2:4 :4 mixture (weight ratio) (Cpd-7) Color image stabilizer-fc)l-CH)i- C0NIIC4)1ψ(I) Average molecular weight 60,000 (Cpd-8) Color image stabilizer 1: 1 mixture (weight ratio) (Cpd-9) Color image stabilizer CH3CH3\/H Cl13 CH3 (Cpd-10) Preservative (Cpd-11) Preservative (U Sea 1) Ultraviolet absorber CsH+, (L) 4 :2:4 mixture (weight ratio) (Solv-1) Solvent (Solv-2) W! (Solv-3) Solvent (Sol Sea 4) Solvent (Solv-5) Solvent C00C1H+ff (CHz)s C00CsH+.

(Solv-6) Solvent C+H+tC)ICH(CHz)tcOOc*H+t\
1 and 80:20 mixture (volume ratio) (Sol Sea 7) Solvent CsH+, CHCH (CHz)*C00CJ+t\1 Next, cyan coupler (ExC) in the fifth layer of sample 301
Sample 302 was prepared in which 15 was substituted with equimolar amount of 15 in the compound side. After each sample was wedge exposed to red light, development processing was performed according to the following processing steps. When comparing the cyan coloring density of the maximum exposure area, Sample 302 was 1.
It was 68 times more concentrated.

38℃ 45 seconds bleach fixing 35℃ 45 seconds rinse ■ 35℃ 30 seconds rinse 0 35℃ 30 seconds rinse ■ 35℃ 30 seconds drying 80℃ 60 seconds (rinse) (3-tank countercurrent force type.) The composition of each treatment liquid is as follows.

Tatenojiritakaj water 800m
1 Ethylenediamine-N,N.

N,N-tetramethylenephosphone'#1 3.0g Triethanolamine 8.0g Potassium chloride
3.1g potassium bromide
0.015g potassium carbonate 25
gHydrazinoniacetic acid 5.0gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0gFluorescent brightener (
WHITEX-4 Add water 10007 ipH (add potassium hydroxide) 10.05 concentrated a base water 400
ml ammonium thiosulfate solution (700g/J2) 100ml ammonium sulfite 45g ethylenediaminetetraacetic acid iron(III) ammonium 55g ethylenediaminetetraacetic acid 3g ammonium bromide
Add 30g water 1
ooOTnil pH5,8 Jou Zsu Yomu ion exchange water (calcium, magnesium 3pp each
m or less) (Effects of the Invention) The above results show that by using the compound of the present invention, a silver halide photographic material with high coupling reactivity and 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 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 is an aryl group, L is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, Z is a hydrogen atom or a coupling-off group, l is 0 to 4 Each represents an integer.)