JPH0375744A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce an amount of organic solvent to be used and to prevent deterioration of color development density by processing with a color developing solution of a pH of >= 11 the color photographic sensitive material having a photosensitive silver halide emulsion layer having a specified cyan dye forming coupler dispersed in the presence of a specified amount of a high-boiling organic solvent and a nonphotosensitive layer. CONSTITUTION:The photosensitive silver halide emulsion layer has the cyan dye forming coupler represented by formula I good in hue and image fastness dispersed in the presence of the high-boiling organic solvent in a coupler to solvent weight ratio of <= 1. In formula I, R1 is H, an aliphatic, aromatic, or heterocyclic group, alkoxy, aryloxy, or substituted amino; each of R2 and R3 is same as R1 but not H; X is H or a group to be repleased by the coupling with the oxidation product of a color developing agent; each of Y1 and Y2 is a divalent or single bonding group; X may form a ring together with Y1 or R1; one of each of R1 - R3 and X may form a polymer of the coupler; and when Y2 is single bonding group and R2 is an aliphatic group, its carbon number is >=2. This photosensitive material is processed with the color developing solution having a pH of >= 11.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for processing silver halide color photographic materials. (Prior art) After a silver halide photosensitive material is exposed to light and subjected to color development processing, a developing agent such as an aromatic primary amine oxidized by silver halide reacts with a dye-forming coupler. An image is formed. Generally, in this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and red, yellow magenta and cyan color images, which are complementary colors, are formed, respectively. Phenols or naphthols are often used as cyan image forming couplers (hereinafter abbreviated as cyan couplers). However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, U.S. Patent Nos. 4,327,173 and 4,564.5.
86 and U.S. Pat. No. 4,430.
．． No. 423, 4- described in Japanese Patent Application No. 141060/1983
The color images obtained from hydroxy-5-acylaminooxindole couplers and 4-hydroxy-5-acylamino-1,3-benzimidazolin-2-one couplers have excellent light fastness and heat fastness. However, light and heat tend to cause yellow or red stains on the unexposed white background area, which is not yet satisfactory. Furthermore, the color image obtained from 4-hydroxy-5-acylamino-1,3-benzimidazolin-2-one is susceptible to density dependence, and has large sub-absorption in blue and edge regions, resulting in poor color image development. I didn't like it. On the other hand, in color photographic light-sensitive materials, reducing the dry film thickness of the light-sensitive material improves image quality, especially sharpness.
This is important in terms of improvement or imparting suitability for rapid processing. Usually, the coupler is dissolved in a high-boiling organic solvent and coated on the support after emulsification and dispersion, so reducing the amount of the high-boiling organic solvent used is important in achieving thin layers. However, in general, reducing the amount of high-boiling organic solvent reduces color development. Various attempts have been made to solve this problem by changing the structure of the coupler, but although the color development can be improved, there have been side effects such as deterioration of hue or deterioration of color image storage stability. JP-A-64-32261 discloses a new cyan coupler with excellent color image fastness and good hue. However, it is necessary to use a high boiling point organic solvent used as a solvent for the cyan coupler in a weight ratio of 1 or more,
When a smaller amount of solvent is used, there is a problem in that the color development is reduced. (Problems to be Solved by the Invention) Therefore, an object of the present invention is to reduce the amount of a high boiling point organic solvent coexisting with the cyan coupler having good hue and good image fastness, and to reduce the coloring density. An object of the present invention is to provide an image forming method that prevents a decrease in image quality. (Means for Solving the Problems) As a result of intensive research, the present inventors found that the object of the present invention can be achieved by the following means. That is, it has a photographic constituent layer including at least one light-sensitive silver halide emulsion layer and at least one light-insensitive layer, and at least one cyan dye-forming coupler represented by the following general formula (I). A silver halide color photographic light-sensitive material, comprising the light-sensitive silver halide emulsion layer or non-light-sensitive layer, wherein the cyan dye-forming coupler is dispersed in the coexistence of a high-boiling organic solvent in an amount of less than 1 in weight ratio. A method for processing a silver halide color photographic light-sensitive material, which comprises processing the following with a color developing solution having a pH of 11 or more. General formula (I) (wherein R8 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, or a substituted amino group, and R2 represents an aliphatic group, aromatic group, heterocyclic group,
represents an aliphatic oxy group, an aromatic oxy group, or a substituted amino group, R8 represents an aliphatic group, an aromatic group, a heterocyclic group, or a substituted amino group, and X represents a hydrogen atom or a cup with an oxidized developing agent. Indicates a vine group that leaves due to a ring reaction, and Y
, and Y2 each represent a divalent linking group or a single bond, and X may form a ring with either Y+ or R+. In addition, R+, Ri, R8 in the formula
, X may form a dimer or more multimeric coupler. Further, when Y2 is a single bond and R2 is an aliphatic group, the number of carbon atoms is 2 or more. ) Below, R8, Ri, R3, X in general formula (I),
Y, , y* will be explained in detail. In formula (I), when R+, Ri and R1 represent any of an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, and an aromatic oxy group, these may be unsubstituted or substituted. You can. The term "aliphatic group" as used herein refers to a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups. Representative examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group,
1so-propyl group, tert-butyl group, tert-
Examples include octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, benzyl group, 2-hexadecenyl group, and propargyl group. Further, the term "aromatic group" refers to a monocyclic or condensed ring aryl group. A "heterocyclic group" is a 3- to 8-membered, preferably 5- or 6-membered group containing 1 to 4 O%N%S as heteroatoms. Examples of preferable ring constituent atoms are 4C10, 4CIN, 3CIN10.3C2
N. 2C2NlO, 4NIC, etc. In formula (I), when R+, Ri and R3 represent a substituted amino group, they represent a group in which the amino group nitrogen is substituted with one or two aliphatic groups, aromatic groups or heterocyclic groups, and these are unsubstituted. may have a substituent. The substituent groups allowed for the aromatic oxy group below the aliphatic group of R, R, and R5 and the substituent groups allowed for the amino group substituent of the above-mentioned substituted amino group are as follows. : That is, for example, an alkyl group, an aryl group, a heterocyclic group,
Alkoxy groups (e.g. methoxy, 2-methoxyethoxy), aryloxy groups (e.g. 2,4-di-ter
t-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), alkenyloxy groups (e.g. 2-
propenyloxy), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy)
, amino groups (e.g. acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide,
butylsulfamoyl), sulfamide groups (e.g. dipropylsulfamoylamino), imide groups (e.g.
succinimide, hydantoinyl), ureido groups (e.g. phenylureido, dimethylureido), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl,
phenylsulfonyl), aliphatic or aromatic thio group (
For example, ethylthio, phenylthio), hydroxy group,
A cyano group, a carboxy group, a nitro group, a sulfo group, or a halogen atom, which may be substituted with one or more of these substituents, and when they have two or more substituents, they may be the same or different. You can. In general formula (I), R1 represents a hydrogen atom, preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (e.g., phenyl, naphthyl), a heterocyclic group (
(e.g., 3-pyridyl, 2-furyl), preferably an aliphatic oxy group having 1 to 36 carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy), preferably having 6 to 36 carbon atoms.
36 aromatic oxy groups (e.g., phenoxy, 2,4-
tert-aminophenoxy, 4-methoxyphenoxy), preferably a substituted amino group having 0 to 36 carbon atoms (e.g., 4-cyanoanilino, 4-butanesulfonylanilino, 3-chloro-4-cyanoanilino, 3-cyano-
4-chloroanilino, 3-lauryloxypropylamino, 3-(2゜4-di-tert-aminophenoxy)
-propylamino, methoxyamino, hydroxyamino, butyamino), and hydrogen atoms, aliphatic groups having 1 to 36 carbon atoms, and aromatic groups having 6 to 36 carbon atoms are particularly preferred. In general formula (I), R2 preferably has 6 to 3 carbon atoms.
6 aromatic groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. 3-pyridyl, 2-furyl), preferably aliphatic oxy groups having 1 to 36 carbon atoms (e.g. 1so-butoxy, methoxy), preferably is an aromatic oxy group having 6 to 36 carbon atoms (e.g. phenoxy, 4-methoxyphenoxy), preferably a substituted amino group having 0 to 36 carbon atoms (e.g. butylamino, hydroxyamino, methoxyamino,
4-cyanoanilino, 3-lauryloxypropylamino), preferably an aliphatic group having 2 to 36 carbon atoms

【for example,
Ethyl, propyl, 4-lauryloxybenzyl, 4-
(2-(2,4-di-tert-amylphenoxy)
-hexanoylamino)benzyl] and has 6 carbon atoms.
-36 aromatic groups and C2-36 aliphatic groups are particularly preferred. In general formula (I), R1 preferably has 1 to 3 carbon atoms.
6 aliphatic groups (e.g. α-(2,4-tert-
amylphenoxy)-propyl, heptafluoropropyl), preferably an aromatic group having 6 to 36 carbon atoms [e.g.
pentafluorophenyl, 3-(2-(2,4-di-tert-amylphenoxy)butanoylamino)phenyl, 3-chloro-4-hexadecanesulfonamidophenyl], heterocyclic groups (e.g. 3-pyridyl, 2- furyl), preferably a substituted amino group having 1 to 36 carbon atoms (e.g., 4-butanesulfonylanilino, 4-cyanoanilino, 3-lauryloxypropylamino), an aliphatic group having 1 to 36 carbon atoms, Particularly preferred are 6 to 36 aromatic groups. In general formula (I), when X represents a coupling-off group (hereinafter referred to as a leaving group) other than a hydrogen atom or a halogen atom, the leaving group is coupled via an oxygen, nitrogen, sulfur or carbon atom. Groups that bond ring activated carbon to aliphatic groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups, halogen atoms, aromatic azo group, etc., and the aliphatic, aromatic or heterocyclic group contained in these leaving groups may be substituted with a substituent permissible for R+, Ri, Ri, and if these substituents are 2 When there are two or more substituents, they may be the same or different, and these substituents may further have a substituent allowed for Rt=R*, R3. Specific examples of coupling-off groups include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (e.g. acetoxy, tetradecanoyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), Acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamino, p-toluenesulfonamino), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyl) oxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio), carbamoylamino groups (e.g. N-
methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic groups (e.g. imidazolyl group, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide groups (e.g. succinimide, hydantoinyl), aromatic azo groups (e.g. phenylazo), etc.
These groups may be further substituted with a group allowed as a substituent for R1. Furthermore, there are bis-type couplers obtained by condensing equivalent couplers with aldehydes or ketones as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators. In general formula (I), X is preferably a hydrogen atom, a halogen atom, an alkoxy group, or an aryloxy group, and particularly preferably a chlorine atom. In general formula (I), Yl and Y2 each represent a divalent linking group or a single bond, and examples of the divalent linking group include a divalent amino group, an ether bond, a thioether bond,
It represents an alkylene group, an ethylene bond, an imino bond, a sulfonyl group, a sulfoxy group, a carbonyl group, etc., and a plurality of these may be combined, and these may further have a substituent. In general formula (I), Yl and Y2 are each independently preferably a sulfonyl group, a carbonyl group, or a single bond,
Single bonds are particularly preferred. The cyan coupler represented by general formula (I) (hereinafter referred to as the coupler of the present invention) is 4-hydroxy-5-acylamino-1,3 characterized by having a substituent having 2 or more carbon atoms at the 3-position. -benzimidazolin-2-one coupler, and is considered to be the reason why various good performances were obtained. That is, the dye selected from the couplers of the present invention is sensitive to light,
It exhibits excellent fastness to heat and humidity, and at the same time has the property that there is almost no decrease in density even when treated with a bleaching solution with weak oxidizing power or a bleaching solution that is exhausted. Furthermore, the dye has very good spectral absorption characteristics, and sub-absorption in the blue and edge regions is significantly reduced compared to conventional dyes, which is very favorable for color reproduction. Furthermore, the light of the unexposed area,
Yellow-1 red stains due to heat were significantly reduced. Moreover, the coupler of the present invention has excellent color development properties, can provide extremely high color density, and is suitable for processing in the absence of color development promoters such as benzyl alcohol. These features were completely unexpected and surprising. Specific compounds included in the present invention are illustrated below, but are not limited thereto. NHC0CH2CH2Co2H (11) (12) (13) (17) (18) (19) (20) (14) (15) (16) C2H. The synthesis method of exemplified compounds (1) and (6) is disclosed in Japanese Patent Application Laid-open No. 6
It is described in No. 4-32261. Other couplers can be synthesized in a similar manner. In a layer sensitive to light in approximately the same spectral range, which is the same layer as the coupler of the present invention or a separate layer, two or more of the couplers of the present invention may be used in combination, or other known cyan couplers may also be used. I can do it. A cyan coupler that can be particularly preferably used can be represented by the following general formula (n). R1 represents a substituted or unsubstituted aliphatic group, aryl group, or acylamino group, R4 is a hydrogen atom,
It represents a halogen atom, a substituted or unsubstituted aliphatic group, an aryl group, an alkoxy group, an aryloxy group, or an acylamino group, and Rlm and Rlm may form a nitrogen-containing 5- or 6-membered ring; It represents a hydrogen atom or a group that leaves in an oxidative coupling reaction with a developing agent, and n represents O or 1. Next, representative examples of cyan couplers represented by general formula (II) will be shown. In general formula (II), Ro represents a substituted or unsubstituted aliphatic, aryl, or heterocyclic group (II-1) (n-4) (■-2) (n-5) (II-3) α (n-6) α α (■-7) (II-8) α (II-9) (n-14) 5H11t (n-15) α (II-16) (n-11) (n-12 ) (n-13) (II-17) (n-18) (II-19) H (2H5 (n-23) (n-21) (U-22) C, Hll(4) In the present invention, the general formula The amount of the coupler represented by (I) added is usually 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide in the silver halide emulsion layer constituting the photosensitive layer. This coupler is preferably added to the light-sensitive silver halide emulsion layer.Next, the high boiling point organic solvent used when introducing the coupler of the present invention into a light-sensitive material will be described.In the present invention, the coupler, etc. Various known dispersion methods are used to introduce lipophilic photographic organic compounds into light-sensitive materials.The oil-in-water dispersion method described in U.S. Pat. High boiling point organic solvents above ℃, such as phthalates, phosphoric esters, benzoic quasi-esters, fatty acid esters, amides, phenols, alcohols, carboxylic acids, N,N-dialkylanilines, hydrocarbons , oligomers or polymers and/or low-boiling organic solvents having a boiling point of about 30° C. to about 160° C. at normal pressure, such as esters (e.g. ethyl acetate, butyl acetate, ethyl propionate, β
-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (e.g. secondary butyl alcohol), ketones (e.g. methyl isobutyl ketone,
methyl ethyl ketone, cyclohexanone), amides (
e.g. dimethylformamide, N-methylpyrrolidone)
A lipophilic photographic organic compound is dissolved in ethers (eg, tetrahydrofuran, dioxane), etc., and then emulsified and dispersed in a hydrophilic colloid such as gelatin. The process and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat. No. 4,199,363;
1.230 and European Patent No. 294,104A. These high boiling point organic solvents and latexes not only function as dispersion media, but also improve the physical properties of gelatin films, promote color development, adjust the hue of color images, and improve the fastness of color images by selecting their structures. It is possible to add various functions such as improvement of The high boiling point organic solvent may be in any form such as liquid, wax, or solid, and is preferably represented by the following formulas [5-11 to [5-91]. Formula (S-S) Rto(COO-Rtt)d Formula (S-4) (R, -CoochiR9 Formula (S-9) (As)at (A2)ax--・----(A
, I), n-In formula [S-1], Rt, Ri and R
1 each independently represents an alkyl group, a cycloalkyl group or an aryl group. In formula [S-2], R4 and R each independently represent an alkyl group, a cycloalkyl group, or an aryl group, and R6 is a halogen atom (F, C, Br, I and the following)
, represents an alkyl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group, and a represents an integer of O to 3. When a is plural, the plural R's may be the same or different. In formula [S-3], Ar represents an aryl group, b represents an integer of 1 to 6, and R? represents a hexavalent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond. In formula [S-4], R represents an alkyl group or a cycloalkyl group, C represents an integer of 1 to 6, and R1 represents a zero-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond. In formula [S-5], d represents an integer of 2 to 6, and RI
G represents a d-valent hydrocarbon group (excluding aromatic groups), and Ro represents an alkyl group, a cycloalkyl group, or an aryl group. In formula [5-61, Rlm, R11 and R14 each independently represent an alkyl group, a cycloalkyl group or an aryl group. R11 and RIs or Rlm and R14 may be bonded to each other to form a ring. In formula [S-7], R4 represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, or a cyano group, and R16 represents a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group. , represents an alkoxy group or an aryloxy group, and e represents an integer of 0 to 3. When e is plural, the plural Rlm may be the same or different. In the formula [5-81, Rl? and R4 each independently represent an alkyl group, a cycloalkyl group, or an aryl group, Rlm represents a halogen atom, a cycloalkyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and f is an integer of O to 4. represent. When f is a plurality of R19s, the plurality of R19s may be the same or different. In formula [S-9], At, Ax, ...An each represent a polymerized unit provided by a different non-color-forming ethylene-like monomer, and R3, R2, ...an are the weight fractions of the respective polymerized units. , and n represents an integer from 1 to 30. In formulas [5-11 to [5-81, Rt to Rts, R
When a, R++ to R1゜ is an alkyl group or a group containing an alkyl group, the alkyl group may be linear or branched, and even if it contains an unsaturated bond, it may have a substituent. You may do so. Examples of substituents include halogen atoms, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, hydroxyl groups, acyloxy groups, and epoxy groups. In formulas [S-1] to [5-81, R5 to Rs, Re
, R1+ to R1, is a cycloalkyl group or a group containing a cycloalkyl group, the cycloalkyl group is 3 to
The 8-membered ring may contain an unsaturated bond, and may also have a substituent or a crosslinking group. Examples of substituents include halogen atoms, hydroxyl groups, acyl groups, aryl groups, alkoxy groups, epoxy groups, and alkyl groups, and examples of crosslinking groups include methylene, ethylene, isopropylidene, and the like. In formulas [S-1] to [5-81, R1 to Rs s R
e When R++ to R1 is an aryl group or a group containing an aryl group, the aryl group is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, etc. Good too. In formulas [S-3], [S-4], and [S-5], Ry
, R@ or RIO is a hydrocarbon group, the hydrocarbon group may contain a cyclic structure (e.g. benzene ring, cyclopentane ring, cyclohexane ring) or an unsaturated bond, or may have a substituent. Examples of suitable substituents include halogen atoms, hydroxyl groups, acyloxy groups, aryl groups, alkoxy groups, aryloxy groups, and epoxy groups. In formula [S-9], At-Ax,...A. Examples of non-color-forming ethylene-like monomers that give
These include olefins, styrenes, vinyl ethers, acrylonitriles, etc. Next, particularly preferred high boiling point organic solvents in the present invention will be described. In formula [S-1], R+, Ra and R3 have a total number of carbon atoms (hereinafter abbreviated as C number) of 1 to 24 (preferably 4 to 18).
) alkyl groups (e.g. n-butyl, 2-ethylhexyl, 3,5.5-trimethylhexyl, n-dodecyl,
n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2.3-dichloropropyl, 2-butoxyethyl, 2-phenoxyethyl), C5-24 (preferably 6-18) cycloalkyl groups (e.g. cyclopentyl, Cyclohexyl, 4-t-butylcyclohexyl, 4
-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (eg, phenyl, cresyl, p-nonylphenyl, xylyl, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl). In formula [S-2], R4 and R6 are an alkyl group having 1 to 24 (preferably 4 to 18) carbon atoms (for example, the same group as the alkyl group mentioned above for R+, ethoxycarbonylmethyl, 1.1-diethylpropyl, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1
, 5-dimethylhexyl), a cycloalkyl group having 5 to 24 carbon atoms (preferably 6 to 1B) (for example, the same group as the alkyl group mentioned for R3 above, 3,5.5-trimethylcyclohexyl, menthyl, bornyl, l -methylcyclohexyl) or C number 6 to 24 (preferably 6 to 1 g
) aryl groups (for example, the aryl groups listed above for R1, 4-t-butylphenyl, 4-t-octylphenyl, 1°3.5-)limethylphenyl, 2.4-di-
t-butylphenyl, 2,4-di-t-pentylphenyl), and R6 is a halogen atom (preferably C1, C
Alkyl groups having 1 to 18 carbon atoms (e.g. methyl, isopropyl, t-butyl, n-dodecyl), alkoxy groups having 1 to 18 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxy, methoxyethoxy, benzyloxy), C number 6
~18 aryloxy groups (e.g. phenoxy, p-tolyloxy, 4-methoxyphenoxy, 4-t-butylphenoxy) or C2-19 alkoxycarbonyl groups (e.g. methoxycarbonyl, n-butoxycarbonyl, 2-ethyl) xyloxycarbonyl),
a is O or 1. In formula [S-3], Ar is an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (e.g., phenyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2-
naphthyl, 4-n-butoxyphenyl, 1,3.5-trimethylphenyl), and b is 1 to 4 (preferably 1
-3), and R1 is a hexavalent hydrocarbon group having 2 to 24 (preferably 2 to 18) carbon atoms [for example, the alkyl group, cycloalkyl group, or hexavalent carbon group listed for R4 above. Hydrocarbon groups having 4 to 24 (preferably 4 to 18) atoms bonded to each other through ether bonds [e.g. -CH2C
H! 0CH2CH! --CH*CHt(OCH*CH*
)s-1-CHgCH*CH*0CHiCHiCHa-
basis

[For example -CHl, -(C1,) *-1-(Ctt
*), -1 In formula [S-4], R8 has a C number of 1 to 24
(preferably 1 to 17) alkyl groups (e.g. methyl,
n-propyl, l-hydroxyethyl, l-ethylpentyl, n-undecyl, pentadecyl, 8,9-epoxyheptadecyl) or C number 3 to 24 (preferably 6 to
18) is a cycloalkyl group (e.g. cyclopropyl, cyclohexyl, 4-methylcyclohexyl), and C
is an integer of 1 to 4 (preferably 1 to 3), and R1 is 0
A hydrocarbon group having a valence of 2 to 24 (preferably 2 to 18) carbon atoms or a zero valent carbon atom number of 4 to 24 (preferably 4 to 18)
) In the formula [S-5], which is a hydrocarbon group (for example, the group listed above for R1) bonded to each other through an ether bond, d is 2 to 4 (preferably 2 or 3), and R1° is a hexavalent group. The hydrocarbons have a C number of 1 to 24 (
an alkyl group having preferably 4 to 18 carbon atoms, a cycloalkyl group having 5 to 24 carbon atoms (preferably 6 to 18 carbon atoms), or a cycloalkyl group having 6 to 24 carbon atoms (preferably 6 to 18 carbon atoms);
24 (preferably 6 to 18) aryl groups (for example, the alkyl groups, cycloalkyl groups, and aryl groups listed above for R4). In formula [5-61, R1ff1 is an alkyl group having 1 to 24 (preferably 3 to 20) carbon atoms [e.g., n-propyl,
1-ethylpentyl, n-undecyl, n-pentadecyl, 2.4-di-t-pentylphenoxymethyl, 4-
t-octylphenoxymethyl, 3-(2,4-di-t-butylphenoxy)propyl, 1-(2,4-di-t-butylphenoxy)propyl], C number 5 to 24 (
Preferably 6 to 18) cycloalkyl groups (e.g. cyclohexyl, 4-methylcyclohexyl) or C number 6
~24 (preferably 6 to 18) aryl groups (for example, the aryl groups listed above for Ar), and R4 and R
o is an alkyl group having 1 to 24 (preferably 1 to 18) carbon atoms (e.g. methyl, ethyl, isopropyl, n-butyl,
n-hexyl, 2-ethylhexyl, n-dodecyl),
A cyclohexyl group having 5 to 18 (preferably 6 to 15) carbon atoms (e.g. cyclopentyl, cyclopropyl) or a C
It is an aryl group of number 6 to 18 (preferably 6 to 15) (eg, phenyl, l-naphthyl, p-tolyl). R4
and R14, may be bonded to each other to form a pyrrolidine ring, piperidine ring, or morpholine ring together with N, and R1
1 and Rls may combine with each other to form a pyrrolidone ring In formula [S-7], R1 is an alkyl group having 1 to 24 (preferably 1 to 18) carbon atoms (e.g. methyl, isopropyl, t- Butyl, t-pentyl, t-hexyl, t-octyl, 2-butyl, 2-hexyl, 2-octyl, 2
-dodecyl, 2-hexadecyl, t-pentadecyl),
Cycloalkyl group having 3 to 18 carbon atoms (preferably 5 to 12 carbon atoms) (e.g. cyclopentyl, cyclohexyl), 2 carbon atoms
~24 (preferably 5 to 17) alkoxycarbonyl groups (e.g. n-butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl)
, an alkylsulfonyl group having 1 to 24 carbon atoms (preferably 1 to 18) (e.g. methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), an arylsulfonyl group having 6 to 30 carbon atoms (preferably 6 to 24) ( For example p-
tolylsulfonyl, p-dodecylphenylsulfonyl,
p-hexadecyloxyphenylsulfonyl), C number 6
~32 (preferably 6 to 24) aryl group (e.g. phenyl, p-tolyl) or cyano group, and R+s is a halogen atom (preferably C1, C1 to C24 (preferably 1 to 18) alkyl group (For example, the alkyl group mentioned above for R4), C number 3 to 18 (preferably 5 to 1
7) Cycloalkyl group (e.g. cyclopentyl, cyclohexyl), C6-32 (preferably 6-24) aryl group (e.g. phenyl, p-tolyl), C1-C
24 (preferably 1 to 18) alkoxy groups (e.g. methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n-hexadecyloxy) or 6 to 32 (preferably 6 to 18) C atoms 24) is an aryloxy group (e.g., phenoxy, pt-butylphenoxy, pt-butylphenoxy, pt-octylphenoxy, m-pentadecylphenoxy, p-dodecyloxyphenoxy), and e is 0 to It is an integer of 2 (preferably 1 or 2). In formula [5-81, Rtt and R4 are the above R4 and R
o, and R1, is the same as R16. The average molecular weight of the polymer represented by formula [S-9] is approximately 1
．． OOO to about 1,000,000 (preferably about 5.
OOO to about 100,000), and may be either a homopolymer or a copolymer of a non-color-forming ethylene-like monomer; in the case of a copolymer, even a random copolymer may have a specific sequence Copolymers with (block copolymers,
Examples of preferred non-color-forming ethylene-like monomers include acrylic esters [methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, , n-hexyl acrylate, 2-ethylhexyl acrylate, n-
Octyl acrylate, 2-chloroethyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, phenyl acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, polyethylene glycol monomethyl ether acetate (n=9), etc.], meth Acrylic acid esters [methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, furfuryl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-acetoxyethyl methacrylate, 2-butoxyethyl methacrylate, methacrylate of polyethylene glycol monomethyl ether (
n=6), etc.], vinyl esters [vinyl acetate, vinyl butyrate, vinyl phenylacetate, vinyl benzoate, vinyl caprolate, vinyl chloroacetate, etc.], acrylamides [acrylamide,
N-methylacrylamide, N-ethylacrylamide, N-butylacrylamide, N-1-butylacrylamide, N-cyclohexylacrylamide, N-methoxyethylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, N,N-diethyl Acrylamide, diacetone acrylamide],
Methacrylamides [methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-butylmethacrylamide, Nt-butylmethacrylamide, N-cyclohexylmethacrylamide, N-(2-methoxyethyl)methacrylamide,
N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N-phenylmethacrylamide, N-(2-cyanoethyl)methacrylamide], olefins [ethylene, propylene, vinyl chloride, vinylidene chloride, l- butene, butadiene, isoprene, chlorobrene, etc.], styrenes [styrene, methylstyrene, dimethylstyrene, chloromethylstyrene, chlorostyrene, methoxystyrene, methoxycarbonylstyrene, etc.], vinyl ethers

[
Methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-methoxyethyl vinyl ether, etc.], acrylonitrile [
Acrylonitrile, methacrylonitrile, crotononitrile, etc.] and other vinyl monomers

[Butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, N-
Examples of J include vinyloxazolidone, N-vinylpyrrolidone, and N-vinylpyridine. Specific examples of the high boiling point organic solvent used in the present invention are shown below. Compound represented by formula (S-1) C2H5 5-21 -22 Compound represented by formula (S-2) 2Hs 1 2Hs 5till''-t Compound represented by formula (S-3) 5-51 -52 - 53 n-C4HgOCO(CH2)@COC00C4H0 Compound represented by formula (S-4) -45 n Cl5H31COOC16H33-n-46 CH. CH. -55 C2H. -56 -57 CH2COOC4Hg n HOC-C00C4H@-n Last C OOC4H9- 11 S-58 S-59 -70 -84 -85 -86 L;gH17-t -83 -88 -89 -90 -91 L;still-t Compound 5-92 -93 represented by formula (S-S) -94 -95 L;fiti17-t Other compounds -100 -102 -104 Compound represented by formula (S-9) (average molecular weight 40,000') -105 -106 0M -107 Chlorinated paraffin (average composition Cl4H24C16 )'3
-108 Chlorinated paraffin (average composition CI2HCl2H1) S
-109 Poly(chlorotrifluoroethylene) average molecular weight 900
S-110 S-111 -112 -113 These high boiling point organic solvents may be used alone or in combination of several types [e.g. tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di(2-ethylhexyl) sebacate, Dibutyl phthalate and poly(N-t
Examples of compounds other than those mentioned above as high-boiling organic solvents used in the present invention and/or methods for synthesizing these high-boiling organic solvents are disclosed in, for example, U.S. Pat. No. 2,322,027, Same No. 2,533.
No. 514, No. 2,772,163, No. 2,835
, No. 579, No. 3,594.171, No. 3,67
6.137, 3,689.271, 3,7
No. 00.454, No. 3.748,141, No. 3,
No. 764,336, No. 3.765.897, No. 3
．． 912.515, 3,936.303, 4.004,928, 4,080,209, 4,127,413, 4.193.802,
Same No. 4,207,393, Same No. 4.220.711, Same No. 4,239.851, Same No. 4.278,757
No. 4,353.979, No. 4,363,87
No. 3, No. 4.430,421, No. 4,464.4
No. 64, No. 4,483,918, No. 4.540.
No. 657, No. 4,684.606, No. 4.728
, No. 599, No. 4,745,049, European Patent No. 2
No. 76.319A, No. 286.253A, No. 28
9.820A, 309.158A, 309
．． No. 159A. No. 309,160A, Japanese Patent Application Publication No. 48-47335,
No. 50-26530, No. 51-25133, No. 51
-26036, 51-27921, 51-27
No. 922, No. 51-149028, No. 52-4681
No. 6, No. 53-1520, No. 53-1521, No. 5
No. 3-15127, No. 53-146622, No. 54-
No. 106228, No. 5-64333, No. 56-818
No. 36, No. 59-204041, No. 61-84641
No. 62-118345, No. 62-247364, No. 63-167357, No. 63-214744,
It is described in 63-301941, 64-68745, and JP-A-1-101543. The amount of the high boiling point organic solvent used in the present invention is based on the amount of the cyan coupler of the general formula (I) of the present invention,
The weight ratio is less than 1. It is preferably from 0.5 or less to 0 or more, particularly preferably from 0.2 or less to 0.01 or more. The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide emulsion layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support.
A silver halide photographic light-sensitive material having at least one light-sensitive layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light; In silver color photographic materials, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-1.13440, No. 61-2
Coupler, DIR compound, etc. as described in No. 0037 and No. 61-20038 may be contained, and a color mixing inhibitor as commonly used may be contained. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57
-112751, 62-200350, 62-
As described in No. 206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/B L/G L/G )1/RH/RL, or BH/B L/G H /G L/RL/RH can be installed in this order. Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. . In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support. In addition, they may be arranged in the following order: high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer. Furthermore, even in the case of four or more layers, the arrangement may be changed as described above. To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer. As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), No. 1764.
3 (December 1978), pp. 22-23, "■, Emulsion preparation
d types)” and the same No. 18716 (
November 1979), 648 pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chea+ie et Ph1)
sique PhotographiquePaul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duff
in. Photographic Emulsion Che
mistry (Focal Press. 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
Manet al, Making and Coat
ing Photographic Emulsion,
Focal Press, 1964). U.S. Patent Nos. 3,574.628 and 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 by Gutoff, Photographic Science and Engineering.
nce and Engineering), 1st
4, pp. 248-257 (1970): U.S. Patent No. 4
, 434.226, 4.414.310, 4.433.048, 4.439.520 and British Patent No. 2,112,157. I can do it. 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 that can be used in such a process are described in the aforementioned Research Disclosure No. 17643 and Research Disclosure No. 18716, and the relevant sections are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. RD 17643 1 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Antifoggants and stabilizers 6 Light absorbers, filter dyes, ultraviolet absorbers 7 Anti-stain agents dye images Stabilizer Hardener Binder Plasticizer, lubricant coating aid, surface active agent 13 Static inhibitor 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 pages right column 25 pages 26 pages 26 pages 27 Pages 26-27 Page 27 RD 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above Page 650 Right Column Same as above Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, compounds that can be fixed by reacting with formaldehyde described in U.S. Pat. is preferably added to the photosensitive material. Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 17643, ■-C to G. As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425°020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, 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.
0.619, European Patent No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, European Patent No. 3,725.067, Research Disclosure No. 24220 (1984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure No.
24230 (-June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4,500,630, U.S. Patent No. 4,540,6
No. 54, No. 4,556,630, International Publication No. 8
Particularly preferred are those described in No. 8104795 and the like. Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
Paragraph ■-G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, No. 4,138°258, British Patent No. 1,146,
No. 368 is preferred, and also U.S. Pat.
, 774.181, which corrects unnecessary absorption of coloring dyes by the fluorescent dye released during coupling, and the couplers described in U.S. Pat. It is also preferred to use a coupler having as a leaving group a dye precursor group which reacts with a developing agent to form a dye as described in '177.120. Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.12.
No. 5,570, European Patent No. 96,570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2,102
, No. 173, etc. Couplers that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, No. 63-37350, and U.S. Pat. . 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 coupler-releasing couplers, DIR Coupler-releasing redox compound or DIR
Redox-releasing redox compound, European Patent No. 173,
No. 302A, No. 313,308A; R, D, No. 114
49, No. 24241, bleach accelerator releasing coupler described in JP-A-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 process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. (OLS) No. 2,541.274 and OLS No. 2,541,230. The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2
- It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2-(4-thiazolyl)benzimidazole. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and same No. 187
16, from the right column on page 647 to the left column on page 648. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less. Further, the membrane swelling rate Tr7m is preferably 30 seconds or less, more preferably 20 seconds or less, and the membrane thickness is 25 seconds or less.
℃ Means the film thickness measured under 55% relative humidity (2 days), and the film swelling rate T'+y* can be measured according to a method known in the art. Photographic Science and Engineering (Ph.D.
otogr, Sci, Eng, ), vol. 19, 2
It can be measured by using a swellometer (swelling film) of the type described in No., pp. 124-129, and TI/□ is the maximum swelling film reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% of the thickness is defined as the saturation film thickness, and is defined as the time required to reach the film thickness of T1/2. The membrane swelling rate Tl7m can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula = (maximum swollen film thickness - film thickness)/film thickness. pH of the color developer used in the development of the photosensitive material of the present invention
is 11.0 or more, preferably 11.5 or more. 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-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity-imparting agents. , aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acid, phosphonocarboxylic acid, phosphonocarboxylic acid, etc., such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid Typical examples include acids, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof. Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination. The pH of these black and white developers is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally 34 or less per square meter of the light-sensitive material, and by reducing the bromide ion concentration in the replenisher, the amount of replenishment can be reduced to 500 m[ It can also be less than l. 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. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, there is also a method using a movable lid as described in JP-A No. 1-82033;
The slit development method described in JP-A No. 63-216050 can be mentioned. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. . Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetic acid iron(m) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8.
However, to speed up the process, it is also possible to process at an even lower pH. 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, 2. o59.988, JP 53-32736, JP 53-57831, JP 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July 1978), etc.
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3.706,5
Thiourea derivatives described in No. 61; West German Patent No. 1.127
, 715, Iodide salts described in JP-A-58-16235: West German Patent No. 966.410, West German Patent No. 2.748.43
Polyoxyethylene compounds described in No. 0: Japanese Patent Publication No. 1973
-Polyamine compounds described in No. 8836: Other JP-A No. 4
No. 9-42434, No. 49-59644, No. 53-9
No. 4927, No. 54-35727, No. 55-2650
Compounds described in No. 6 and No. 58-163940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred, and these bleach accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pka) of 2 to
Specifically, acetic acid, propionic acid, etc. are preferable among the compounds having 5. Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. In addition, it is also preferable to use thiosulfate, thiocyanate, thioether compounds, thiourea, etc. as preservatives for fixing solutions and bleach-fixing solutions.
Preferred are sulfites, bisulfites, carbonyl bisulfite adducts, and sulfinic acid compounds described in EP 294,769A. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time for the desilvering step is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25℃~
The temperature is 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented. In the desilvering step, it is preferable that stirring be as strong as possible. A specific method for strengthening stirring is described in Japanese Patent Application Laid-Open No. 1834-1983.
No. 60 and No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183461,
No. 183461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator. The automatic developing machine used for processing the photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open Nos. 60-191257 and 60-191258,
It is preferable to have a means for transporting a photosensitive material as described in Japanese Patent No. 60-191259. The above-mentioned Japanese Patent Application Laid-Open No. 60-191
As described in No. 257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid. This is particularly effective in shortening time and reducing the amount of processing liquid replenishment. 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 (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety of
MotionPicture and Te1evis
ion Engineers Vol. 64, p. 248-2
53 (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. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal agents J (1986), Sankyo Publishing, Sanitary Technology Golden Wire, “Sterilization of microorganisms, sterilization, and antifungal technology J (1982), Society of Industrial Technology, Japan Antibacterial Antifungal Society Line “Encyclopedia of Antibacterial and Antifungal Agents J” (
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 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C is selected. moreover,
The light-sensitive material of the present invention can also be processed by direct stabilization instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-148
All known methods described in No. 34 and No. 60-220345 can be used. Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. 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. When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water. 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 a 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, Schiff base-type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include the urethane compounds described in No. 28. 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 described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438. Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. (Effects of the Invention) According to the method of the present invention, the dry film thickness of the photosensitive material can be reduced to improve the image quality, and a color photographic image with good color development and excellent hue and fastness can be formed. . (Examples) The present invention will be described in more detail below based on Examples. Example 1 Preparation of Sample 101 A multilayer color light-sensitive material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 101. The numbers represent the amount added per d. Note that the effects of the added compound are not limited to the described uses. 1st layer: Antihalation layer black colloidal silver 0.25g gelatin
1.9g UV absorber U-10,
04g Ultraviolet absorber U-20, 1g Ultraviolet absorber U-30, 1g Ultraviolet absorber U-60, Ig High boiling point organic solvent 0i1-10.1g 2nd layer: Intermediate layer gelatin 0.40g Compound Cp
d-010mg High boiling point organic solvent 0ff-340mg 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, AgI content 1 mol%) Silver amount 0.
05g gelatin 0.4g 4th layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4μ, AgI content 4.5 mol%) (a 1=1 mixture of monodisperse cubes with an average particle size of 0.3μ and a AgI content of 4.5 mol%) Silver amount: 0.4g Gelatin: 0.8g Comparison coupler A: 0.20g High-boiling organic solvent: 0il
-10,20g 5th layer: Medium red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.5μ, AgI content 4 mol% monomer) Dispersion cube) Silver amount 0.4g Gelatin 0
．． 8g comparative coupler A 0.2g comparative coupler 8 0.2g high-boiling organic solvent 0
il-10.4g 6th layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.7μ, AgI content 2 mol% monomer) Dispersed twin particles) Silver amount 0.4g Gelatin 1
．． 1g comparison coupler B 1. Og high boiling point organic solvent 0i1-11.1g 7th layer: Intermediate layer gelatin 0.6g dye D-1
0.02g 8th layer: silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, AgI
Content 0.3 mol%) Gelatin 1. Og color mixing prevention agent C
pd-A O, 2g 9th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4 μ, AgI content 4.5 mol) % monodisperse cubes and 1=1 mixture of monodisperse cubes with average particle size 0.2 μ and AgI content 4.5 mol %) Silver amount 0.5 g Gelatin 0.5 g Coupler C-40,L
og Coupler C-70, 10g Coupler C-80, iog Compound Cpd-80, 03g Compound Cpd-EO8Ig Compound Cpd-FO O, Ig Compound Cp
d-G O, Ig compound Cpd-HO,
1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodisperse cubic with average grain size 0.5 μm and AgI content 3 mol%) Silver Amount 0.4g Gelatin 0
．． 6g coupler C-40, 1g coupler C-70, 1g coupler c-go, 1g compound Cp
d-80,03g Compound Cpd-E0.1g Compound Cpd-F0.1g Compound Cpd-G O,05g Compound C
pd-80.05g High-boiling organic solvent 0il-10.01g 11th layer: Highly sensitive green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size when converted to spheres) Diameter 0.6 μ, AgI content 1.3 mol%
, a monodisperse flat plate with an average diameter/thickness of 7) silver content 0.
5g Gelatin 1.0g Coupler C-40.4g Coupler C-70.2g Coupler C-80.2g Compound Cpd-B O, osg Compound C
pd-Eo, 1g Compound Cpd-FO, Ig Compound Cp
d-G O, Ig compound Cpd-HO,
l'g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0.05g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1g Gelatin
1.1g color mixing prevention agent Cpd-A
O, 01g 14th layer: Intermediate layer gelatin 0.6g 15th layer: Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
1:1 mixture of monodisperse cubes with an average particle size of 0.4 μ and an AgI content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μ and an AgI content of 3 mol %) Silver amount 0.6 g Gelatin 0.8 g Coupler C-50
, 6g 16th layer: Medium-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Monodispersed cubes with average particle size 0.5 μm and AgI content 2 mol%) Silver amount 0.4 g Gelatin 0
．． 9g Coupler C-50, 3g Coupler C-60, 3g 17th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle diameter when converted to spheres: 0.7 μ, AgI content: 1.5 mol%,
Tabular grains with an average diameter/thickness of 7) Silver content: 0.4 g Gelatin: 1.2 g Coupler C-60.7 g 18th layer: 1st protective layer Gelatin Ultraviolet absorber U-l Ultraviolet absorber U-3 Ultraviolet absorption Agent U-4 Ultraviolet absorber U-5 Ultraviolet absorber U-6 Formalin scavenger pac Dye D-3 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer (average grain size 0. 06μ
, AgI content 1 mol%) 0.8g 0.05g 0.7g 0.04g 0.03g 0.03g 0.05g 0.05g Gelatin silver amount 0.1g 0.4g 20th layer: Third protective layer gelatin 0 .4g polymethyl methacrylate (average particle size 1.5μ) 0.1g 4=6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1g silicone oil 0.03g surfactant W- 13.0
mg In addition to the above composition, gelatin hardening agent H-1 and a surfactant for coating and emulsification were added to each layer. In addition, in the emulsion used here, monodisperse means that the coefficient of variation is 20% or less. -4 C-5 -6 pd-C pdE -7 Coupler C-8 il -1 Diptyl phthalate i1-2 Tricresyl phosphate 0-3 C2Hs\. *I (s/NCOC "1'. pd-D L -1 U-2 -3 -4 -3 -4 -5 -6 1tlc4H9 -5 -6- -1 -2 -3 H-1 Comparative coupler C -1 Comparative coupler D jl Comparative coupler A (included in U.S. Pat. and Sample 101 were prepared in the same manner as Sample 101, except that comparative coupler B was replaced with comparative coupler C in equimolar amounts, and high boiling point organic solvent 0i1-1 was added in an equal weight to the coupler. Preparation of sample 103 Coupler C used in sample 102 was replaced with comparative coupler D in an equimolar amount, and Oil-1 was added in an equal weight. Preparation of samples 104 to 106 In sample 103, the fourth layer to Sample 017 was prepared in the same manner as Sample 013, except that the coupler D added to the sixth layer was replaced with the couplers (3), (4), and (6) of the present invention in equal moles, and the same weight of Oil-1 was added. ~112 Preparation Samples 101 to 106, the amount of high boiling point organic solvent used in the fourth to sixth layers was 0.5 by weight for each coupler.
It was produced in the same manner as Samples 101 to 106 except that it was doubled. Preparation of Samples 113 to 118 In the same manner as Samples 107 to 112, except that in Samples 017 to 112, the amount of high boiling point organic solvent used in the fourth to sixth layers was increased by 0.2 times by weight for each coupler. Created. Processing process 1 Processing process Time first development 6-minute water washing 2-minute reversal 2-minute color development ・6-minute adjustment 2-minute bleaching 6-minute fixing 4-minute second washing, 4-minute stabilization 1-minute tank capacity 2I2 J2 I2 2Q I2 2I2 I2 I2 4 Temperature 38°C 38°C 38°C 38°C 38°C 38°C 38°C 38°C 25°C The composition of each treatment liquid was as follows. Kanjiri Takahi Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2.0g Sodium sulfite 30g Hydroquinone potassium monosulfonate 20g Potassium carbonate 33g 1-phenyl-
4-Methyl-4-hydroxymethyl-3-pyrazolidone 2.0g Potassium bromide 2.5g Potassium thiocyanate
1.2g potassium iodide 2.0
Add mg water to make 1000 p) (
9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. & Blue liquid nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3.0g stannous chloride.
Dihydrate salt 1. Qgp-aminophenol
0.1g Sodium hydroxide 8g Glacial acetic acid 15T1'111 Add water to 1000p pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide. Nitrilo-N,N,N-)limethylenephosphonic acid, pentasodium salt 2.0g Sodium sulfite 7.0g Trisodium phosphate dodecahydrate 36g Potassium bromide 1.0g
Potassium iodide 90mg Sodium hydroxide 3.0g Citrazic acid
1.5g N-ethyl-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g 3.6-dithiaoctane-1,8-diol Add water and adjust the pH to 4. Acetic acid/disodium/dihydrate Sodium sulfite 1-thioglycerin Water was added to pH.The pH was adjusted to pH with hydrochloric acid or sodium hydroxide. Concentrated blood Ethylenediaminetetraacetic acid, disodium, dihydrate Ethylenediaminetetraacetic acid, Fe Ammonium, dichloride Potassium bromide Ammonium nitrate 1.0g 000ml 10.8 Adjusted with hydrochloric acid or potassium hydroxide. 8.0g 2g 0.4ml 000ml 6,20 Adjust with lium 2.0g (III) 20g 00g 10g Add water to 1000 pH 5,7
0 pH was adjusted with hydrochloric acid or sodium hydroxide. L-enriched sodium thiosulfate sog sodium sulfite 5.0g sodium bisulfite
Add 5.0g water 10010
00Tn 6.60pH is
Adjusted with hydrochloric acid or aqueous ammonia. Sagittal fluid formalin (37%) 5.0m [! Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5Trl[! Add water 1ooodp)l
Processing step 2 without adjustment The same as processing step 1 except that the pH of the color developing solution was adjusted to 11.0 in processing step 1. Processing Step 3 The same as Processing Step 1 except that the pH of the color developing solution in Processing Step 1 was adjusted to 11.8. The obtained samples 101 to 106 were subjected to wedge exposure in a conventional manner and then developed in the following development steps 1 to 3. Next, the cyan density was measured and the maximum density was obtained. The results are shown in Table 1. As is clear from Table 1, when a sample using a coupler represented by the general formula (I) and an amount of a high-boiling organic solvent is processed with a developing solution having a pH of less than 9811, the maximum concentration decreases greatly, but a processing solution with a pH of 11 or more is found. When treated with , the decrease in maximum concentration can be suppressed. On the other hand, when a coupler other than the coupler represented by general formula (I) is used, the increase in maximum density is small even when processed with a developer having a pH of 11 or higher. In addition, the light described in JP-A No. 64-32261,
The color image fastness and hue to heat are similarly maintained in the embodiments of the present invention. Therefore, it can be seen that only in the examples of the present invention, when the amount of the high-boiling point organic solvent is reduced, it is possible to achieve thinning of the layer without deteriorating the color development, and it is possible to maintain color image fastness and good hue. Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating solution adjustment Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (cubic, 3:7 mixture of average grain sizes of 0.88 μm and 0.70 μm (silver molar ratio)
. The coefficient of variation of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to a large size per mol of silver. For the emulsions, 2.0 x 10'' moles were added, and for small size emulsions, 2.5 x 10'' moles were added, followed by sulfur sensitization.The above emulsified dispersion A first coating solution was prepared by mixing and dissolving this emulsion to have the composition shown below.Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3,5-dichloro-8-triazine sodium salt was used as the gelatin hardener in each layer. The following was used as the spectral sensitizing dye in each layer: Blue-sensitive emulsion layer (silver halide 1 per mole, green-sensitive emulsion layer (2.0 x 10-' mole each for large size emulsions and 2.5 x 10-' mole each for small size emulsion) green-sensitive emulsion layer (per mole of silver halide) , 4.0XIO-' moles for large size emulsions and 5.6 for small size emulsions.
X10-' mole) and (per mole of silver halide, 0.9XIO-' mole for large emulsions and 1 for small emulsions)
．． For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6X10-'' mole per mole of silver halide. 0x10-' mole, or 1 for small size emulsions
．． In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8.5 x 10-' per mole of silver halide, respectively. 'Mole, 7.7XIO-'Mole, 2.5
X10-' 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-titrazaindene was added per mole of silver halide to lXl0-'
mol and 2X10-' mol were added. The following dyes were added to the emulsion layer to prevent irradiation. and (Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g/r/). 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 (Ties) and a bluish dye (ulmarine blue)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19
Solvent (Solv-1) 0
．． 35 color image stabilizer (Cpd-7)
o, Os 2nd layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08
Solvent (Solv-1) 0
．． 16 solvent (Solv-4)
0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of average grain size of 0.55 μm and 0.39 μm (Ag molar ratio) 0 grain size distribution The coefficient of variation is 0.1O and 0.0
8. Each emulsion contained 8 mol% of AgBr O locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (ExM
) 0.20 color image stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (
Solv-2) 0.40
4th layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47
Color mixing inhibitor (Cpd-5) 0.
05 Solvent (Solv-5)
0.24 5th layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 1=4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm (Ag molar ratio) with a grain size distribution of 0 The coefficient of variation is 0.09 and 0.1
1. In each emulsion, 6 mol% of AgBr O was locally contained in a part of the grain surface) 0.23 Gelatin
1.34 cyan coupler (ExC
) 0.32 color image stabilizer (Cpd
-6) 0.17 color image stabilizer (C
pd-7) o, 40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.3
2 6th layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorption layer (UV-1) 0.16
Color mixing inhibitor (Cpd-5) 0.
02 Solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (ExY
) 1:1 mixture with yellow coupler (mole ratio) (ExC) Cyan coupler (Cpd-1) Color image stabilizer (ExM) 1:1 mixture with magenta coupler (mole ratio) (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-6) Color image stabilizer C4Hg (tl (Cpd-7) Color image stabilizer 1→CH2 -CM□- ■ C0NHC4H*(tl Average molecular weight 60,000 (Cpd-8) Color image stabilizer (Solv-1) Solvent (Solv-2) 2:1 mixture of solvents (volume ratio) (Solv-4) Solvent (Cpd-9) Color image stabilizer (UV-1) 4:2:4 mixture of ultraviolet absorbers (weight ratio) (Solv-5) Solvent (Solv-6) Solvent The sample prepared as above was 201 Next, the cyan coupler ExC in the fifth layer was replaced with the couplers (7) and (9) of the present invention in equimolar amounts, and the amounts of the solvents were made equal in weight to prepare samples 202 and 203. Samples 204 to 206 In the preparation samples 201 to 203, the fifth layer solvent (Solv-
Samples 201 to 203 were prepared in the same manner as samples 201 to 203 except that the amount of 6) was reduced to 1/2 for each cyan coupler. The obtained samples 201 to 206 were exposed to light according to the method described in Example 1. The exposed sample was subjected to continuous processing (running test) using a paper processing machine until twice the color development tank capacity was replenished in the next processing step. Color development 35℃ 45 seconds 161d 171
Bleach window 30-35℃ 45 seconds 215m [l 17
I2 rinse Φ 30-35℃ 20 seconds,
It) J2 rinse 030-35℃ 20 seconds
lO flood rinse 030-35℃ 20 seconds 350Tni!
10 fi Shoe drying 70 to 80°C for 60 seconds *The replenishment amount was per 1 rrr of photosensitive material (3 tank countercurrent system was used for rinsing ① to ②.) The composition of each processing solution was as follows. Standing two miles judgment
800d 800d Ethylenediamine-N,N. N,N-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g Triethanolamine 8.0g 12.0g Sodium chloride 1.4g - Potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g N,N-bis(carboxymethyl)hydrazine 5.5g Optical brightener (WHITEX 4B. (manufactured by Sumitomo Chemical) Add 1.0g of water
100OTIIIpH (25℃)
10.055g 7.0g 7.0g 2.0g 1000Trli! 10,45! (Tank fluid and refill fluid are the same) Water 40
0m! Ammonium thiosulfate (70%>1
00d Sodium sulfite 17g Iron (III) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide Add water and pH (25℃) 0g 1000 capacity 6.0 ±ff1 (tank liquid and replenisher are the same) Ion exchange Water (3 pp each of calcium and magnesium
(m or less) Next, the pH of the color developer was raised to 11.2, the same treatment was carried out, and the maximum density of the cyan color image of the obtained sample was measured. As a result, samples 201 to 203, in which the amount of high boiling point organic solvent was the same as that of the coupler, had almost the same maximum concentration even if the pH of the processing solution was changed, but sample 20, in which the amount of high boiling point organic solvent was reduced,
4 to 206 are p) (The decrease in maximum density was large in the developer solution of 10 and 25, but in the developer solution of pH 11.2, sample 205.206 of the present invention gave a maximum density almost equivalent to sample 202.203. In addition, the hue and color image fastness were both superior to Samples 201 and 204. Example 3 The coupler (3) added to the fourth to sixth layers was replaced with an equimolar amount of the coupler (13). On the other hand, Oil
Sample 11 of Example 1 except that the amount was 0.5 times the weight ratio.
Sample 301 is prepared in exactly the same manner as Sample 0, and the same result as Sample 110 is obtained when it is processed in Processing Step 3 of the same example.

Claims (1)

[Scope of Claims] A cyan dye-forming coupler having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer and at least one light-insensitive layer, and represented by the following general formula (I). The light-sensitive silver halide emulsion layer or the non-light-sensitive layer comprises at least one of the above-mentioned cyan dye-forming coupler dispersed in the coexistence of a high-boiling organic solvent having a weight ratio of less than 1. Color photographic material at pH 11
A method for processing a silver halide color photographic material, which comprises processing with the above color developing solution. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, or a substituted amino group. , R_2 represents an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, or a substituted amino group, and R_2 represents an aliphatic group, an aromatic group, a heterocyclic group, or a substituted amino group. represents an amino group; , R_1 may form a ring together with either R_1.In addition, R_1 in the formula
, R_2, R_3, and X may form a dimer or more multimeric coupler. Further, when Y_2 is a single bond and R_2 is an aliphatic group, the number of carbon atoms is 2 or more. )