JPS6275526A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent fogging by development by incorporating a two-equiv. yellow coupler having at least one group having -SO2- structure besides a group which is eliminated by coupling with the oxidized product of a color developing agent and a component having specified repeating units into a photosensitive silver halide emulsion layer. CONSTITUTION:A polymer compound having repeating structural units each have a group represented by formula I and a two-equiv. yellow coupler are incorporated into a silver halide emulsion layer. The yellow coupler having at least one group having -SO2- structure besides a group which is eliminated by coupling with the oxidized product of a color developing agent may be represented by formula II (where X is a group which is eliminated by coupling with the oxidized product of a color developing agent). Even when the yellow coupler is used in combination with other yellow coupler having high color developability in the layer developing yellow, fogging is reduced without lowering the sensitivity, gradient or maximum density.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a yellow image with good sensitivity, gradation, and maximum density can be obtained without the need to contain benzyl alcohol in a color developing solution. The present invention relates to an improvement in the capri of a silver halide emulsion layer of a photographic light-sensitive material having a silver halide emulsion layer containing a highly color-forming yellow coupler. [Prior Art] In subtractive color photography, which is commonly used in the photographic field to obtain color images, as is well known, an aromatic primary amine color developing agent is used to develop the exposed silver chloride. A dye image is formed by oxidative cambling of the oxidation products of a color developing agent produced by reducing the grains and couplers that form yellow, cyan, and magenta dyes in a silver halide emulsion. It has been customary to add benzyl alcohol to a color developer as an accelerator for promoting such a color development reaction. However, from the perspective of eliminating pollution, eliminating dependence on benzyl alcohol has been taken up as a major issue. Generally, when a color developing solution without benzyl alcohol added is used, the color development properties of the coupler added to the silver halide emulsion, that is, the rate of dye formation and the maximum color development density are reduced, and this reduction is remarkable in yellow couplers. Against this background, a yellow coupler called a high color-forming yellow coupler has been developed and disclosed as a yellow coupler whose color-forming property does not depend on benzyl alcohol. As such a coupler, for example, JP-A-17-2
No. 4321, No. 50-87650, No. 50-9273
No. 1, No. 55-32071, No. 52 ・-11521
No. 9, No. 54-48541, No. 55-142340, No. 58-42045, No. 55-70841, No. 5
No. 4-133329, No. 57-200037, No. 58
-42'046, 55-142340, 54-
No. 99433, No. 56-164343, No. 56-30
No. 127, No. 57-22238, No. 59-17755
No. 7, No. 59-177553, No. 59-177554
No. 59-214854, No. 59-222837, No. 60-41042, No. 60-69653, No. 5
There are those described in No. 6-30126, No. 56-92237, etc. Highly color-forming yellow couplers are known to be preferable, especially in terms of sensitization and reducing the amount of misuse, because they give high sensitivity, high gamma, and high maximum density when developed with a color developer containing benzyl alcohol. ing. However, many of these known highly color-forming yellow couplers have extremely weak light fastness of the dye images formed, or have extremely poor solubility in high-boiling organic solvents, and are therefore not suitable for reflective print colors, especially for ornamental purposes. Although there are few couplers that can be practically used in photographic light-sensitive materials, two-equivalent yellow couplers that have at least one -SO2- group in addition to the group that couples with the oxidized form of a color developing agent and leaves it are relatively rare. There are few drawbacks. As such a coupler, Japanese Patent Application Laid-open No. 5
No. 6-95237, No. 55-70841, No. 5o-9
No. 2731, No. 58-42046, No. 55-1423
No. 46, No. 54-99433, No. 56-164343
No. 56-30127, No. 57-22238, No. 54-133329, No. 59-177553, No. 5
There are those described in No. 9-177554 and No. 60-41042. However, highly color-forming yellow couplers, including this type, are prone to development fog, especially at high temperatures (35
(°C or higher) during development, and in the recent trends of high-temperature and rapid processing, it is especially desirable to suppress development fog when using highly color-forming yellow couplers. Conventionally, in order to prevent development fog, a method has generally been used in which an anti-capri agent or an anti-stain agent is incorporated into a developer or a photographic material. As antifoggants, many heterocyclic organic compounds are known, typified by mercapto heterocyclic compounds, benzotriazole compounds, and benzimidazole compounds. (These compounds are described in, for example, 19 of ``Fundamentals of the Photographic Industry, Silver Salt Photographic Network'' (edited by the Photographic Society, 1989).
It is described on pages 4-198. ) However, since these compounds generally act directly on silver halide, if they are used alone in amounts that have a sufficient antifogging effect, they may cause a decrease in development speed, decrease in maximum density and gamma, and distortion of gradation. This causes various undesirable adverse effects such as bending and a decrease in desilvering speed. In addition, as stain inhibitors, dihydroxybenzene compounds (e.g. hydroquinone, catechol, 2.5-
Dibutylhydroquinone, 2.5-dioctylhydroquinone, etc.), ascorbic acid, citrazine acids, etc. are known, and when these are included in the developer, the maximum density may be lowered by more than the rate that reduces fog, Alternatively, staining may occur in the developing solution during storage, which may contaminate the photographic material after processing, making it meaningless to use a highly colored yellow coupler, and also preventing staining when included in the photographic material. If the agent elutes into the developer, it will elute into the developer and cause similar problems.
Even if it does not dissolve into the developer, it has disadvantages such as reducing the fastness of the dye image formed. [Object of the Invention] The object of the present invention is to provide a technical means for improving the development fog, which is a drawback of the highly color-forming yellow coupler, without losing the above-mentioned features and without causing other quality deterioration as mentioned above. The goal is to provide the following. Another object of the present invention is to provide a silver halide color photographic sensitizer containing a highly color-forming yellow coupler, which has a high maximum density, high gamma, good dye fastness, and provides a yellow image with low development fog. The goal is to provide materials. [Structure of the Invention] The object of the present invention is to provide at least one photosensitive silver halide emulsion layer containing at least one -SO2- structure in addition to a group that couples with and leaves an oxidized form of a color developing agent. 2-equivalent yellow coupler having the group and the general formula [
1,1 means J? This is achieved by a photographic Le optical material characterized by containing a compound having the 11th position. General Formula [1] In the formula, R represents a hydrogen atom or an alkyl group. The present invention will be explained in detail below. In the above general formula (I), the alkyl group represented by R is preferably an alkyl group having 1 to 5 carbon atoms. The compound having a unit represented by the general formula (1) is preferably a compound represented by the following [1a] and the following (ib)
It is. a]: [1b): A polymer compound in which the repeating structural unit has a group represented by the general formula [1). Here, R has the same meaning as R in the general formula (1), and is preferably alkyl group. is a methyl group. n represents an integer from 1 to 4. R' represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent. The alkyl moiety of the above alkyl group preferably has 1 to 8 carbon atoms, such as a methyl group or a benzyl group. Examples of the alkenyl group include an allyl group, and examples of the aryl group include a phenyl group, 2
, 4-'; -tert-butylphenyl group and the like. When n == 1, Ro is a hydrogen atom, an alkyl group which may have a substituent, or one of alkylcarboxylic acid, cycloalkylcarboxylic acid, or arylcarboxylic acid, each of which may have a substituent. When n = 2, it represents an alkylene group, an alkenylene group, or a divalent residue of argyl dicarboxylic acid, cycloalkyl dicarboxylic acid, or aryl dicarboxylic acid, each of which may have a substituent. When n = 3, it represents a trivalent residue of alkyltricarboxylic acid, cycloalkyltricarboxylic acid, or aryltricarboxylic acid, each of which may have a substituent, and when n = 4,
Each represents a tetravalent residue of an alkyltetracarboxylic acid, a cycloalkyltetracarboxylic acid, or an aryltetracarboxylic acid, each of which may have a substituent. Next, specific examples of compounds having a unit represented by the above general formula [11] will be given. In addition, n in the polymer in the following specific examples is approximately 2 to 20.
Represents 0. (p-3) (p-4) (P-5) (P-6) (P-7) (p-8) (P-9) (P-10) Ichino
\ノ -0-
Low
Roy Q, C
L+ mountain ν
ν Ql
1 1
CL1 mountain
Yama-ichi
Nノ ＼ノ＋
1
'Mountain Mountain
Mountain CLI - Box (P-31) (P・-32) (p-33) (p-34) (P-35) (P-36) The above compounds are generally known, and their synthesis method is as follows: For example, JP-A No. 49-32937, JP-A No. 59-538
No. 46, No. 59-116747, No. 59-11935
No. 1, Japanese Patent Publication No. 57-20617, U.S. Patent No. 4,23
No. 3,412, No. 4,344,876, European Patent Publication No. 2,005, etc. The compound may be contained in the same silver halide emulsion layer as the yellow coupler used in the present invention, and usually, it may be added alone or together with the coupler etc. in the form of a dispersion. As the medium, an organic solvent used in known coupler dispersions can be used, and as a dispersion system, latex can be used. The content of this compound is 5% relative to the yellow coupler used.
It is used in a range of 100% to 100% by weight, preferably 10 to 60% by weight. The second generation yellow coupler (hereinafter referred to as the yellow coupler of the present invention) having at least one group having a -5O2- structure in addition to the group that couples with and leaves the oxidized form of the color developing agent in the present invention is preferably one of the following general formulas. formula(
11]. General formula [[1,I Here, R2 is an alkyl group that may have a substituent (
For example, methyl, isophyl, tert-butylene,
hexyl, 1-methylbenzyl, neobenzyl, isohexyl, dodecyl, phenyl-substituted alkyl, phenoxy-substituted alkyl, etc.), aryl groups that may have substituents (e.g. phenyl, naphthyl, alkyl-substituted phenyl, alkoxy-substituted phenyl) etc., where the number of carbon atoms of alkyl and alkoxy is 1 to 5) or a substituent.
Butyl group, phenyl group, 0-methoxyphenyl group and hip
-methoxyphenyl group, more preferably tert
-butyl group. R3 represents a hydrogen atom, a halogen atom (for example, chlorine, bromine, iodine, etc.) or an alkoxy group (for example, methoxy, ethoxy, etc.), and is preferably a chlorine atom or a methoxy group. D is a hydrogen atom or a group capable of substituting a benzene nucleus, such as a chlorine atom such as chlorine, fluorine, an alkyl group such as methyl, ethyl, ethoxyethyl, tert-butyl, dodecyl, methoxy, ethoxy, Alkoxy groups such as tert-butoxy and ethyloxyethoxy; aryloxy groups such as phenoxy and (3,5-jethoxycarbonyl)phenoxy. These include alkylthio groups such as ethylthio, hexylthio, and benzylthio, arylthio groups such as phenylthio, acylamide groups such as acetamide, penzamide, methanesulfonamide, and benzenesulfonamide, and carboxy groups. A is just a bond, -NR, -, -NR, COR, -. , where R4 represents a hydrogen atom or an alkyl group (such as methyl, ethyl, dodecyl, etc.), and this alkyl group may have a substituent, and this substituent is not particularly limited. However, typical examples include halogen atoms (e.g. fluorine, chlorine, bromine, iodine), alkyl groups (e.g. methyl, ethyl, t-butyl, octyl groups, etc.)
, aryl groups (e.g., phenyl, p-chlorophenyl, p-methoxyphenyl, p-dodecylphenyl, naphyl, etc.), alkoxy groups (methoxy, ethoxy,
-butoxy, benzyloxy, dodecyloxy, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (ethylthio, hexylthio, etc.), arylthio groups (phenylthio, etc.), alkylsulfonyl (β- and droxyethylsulfonyl, dodecylsulfonyl, etc.) , arylsulfonyl (such as phenylsulfonyl), acylami/group, carbamoyl group, acyl group, sulfonamido group, sulfamoyl group, nitrile group, and the like. Further, R5 represents an alkylene group which may have a substituent, and examples of this substituent include the groups listed above as substituents for the alkyl group of R4. ), typical examples include groups such as methylene, ethylene, 2-phenylethylene, and p-chlorophenylethylene. R6 represents an alkylene group (eg, ethylene, ethylene, etc.). B is an alkyl group (e.g., ethyl, propyl, dodecyl, etc.) which may have a substituent, an aryl group (e.g., phenyl, dodecylphenyl, dodecyloxyphenyl, etc.), or a heterocyclic group (e.g., pyridyl, pyrazinyl,
(furyl, etc.), and examples of substituents for these alkyl groups, aryl groups, and heterocyclic groups include the groups listed above as substituents for the alkyl group of R4. X is a group capable of coupling with and leaving an adapted form of a developing agent, preferably a group capable of bonding via an oxygen atom, nitrogen atom or sulfur atom, more specifically selected from the groups shown below. It is the basis. a) -0COR7 (In the formula, R7 represents an alkyl group, alkenyl group, phenyl group or terpenyl group which may have a substituent.) b) -0COR. (In the formula, R8 is an alkyl group that may have a substituent,
Table C2 aryl group or heterocyclic group?・. (In the formula, Zl represents a group of nonmetallic atoms necessary to form a saturated or unsaturated 4-, 5-, or 6-membered ring.) d) (In the formula, Z2 represents a saturated or unsaturated 4-membered, e) N43 (wherein, Z3 represents a non-metallic atomic group necessary to form a saturated or unsaturated 4-, 5-, or 6-membered ring.) Represents a group of metal atoms.) f)-8-R. In formula 4, R9 is an alkyl group which may have a substituent,
Represents an alkenyl group, an aryl group or a heterocyclic group. ) Typical examples of these groups that can be eliminated during color development are described below. (S-1) -〇C0IJI3 (S-7) 10 〇 〇 〇,. R23 (S-8) (S-IQ) (S-11) (S-12) (S-16) "(S-17)". (S-18) (S-20) (S-21) (S-24) (S-25) (S-26) (S-27) (S-28) (S-29) (S-30) (S-32) Furthermore, X may constitute a Sitechis-type compound having a structure obtained by removing X from the general formula [11J]. At this time, this bis-type compound is represented by the following general formula [1]. General formula (111 (In the formula, W represents a divalent linking group necessary to form a bis-type coupler by bonding two molecules of α-acylacedoanilide coupler at the active site substitution position.) Next Representative examples of the divalent linking group represented by W above are described below. (S-34) (S-35) (S-36) (S-37) (S-38) (S-39) C) I3H3 Next, typical examples of the yellow coupler of the present invention are shown in the table below, but the present invention is not limited thereto. In addition, specific examples are shown by the substituents in the above general formula,
The numbers in parentheses in the substituent column indicate the bonding position. The yellow coupler of the present invention can be synthesized with reference to the descriptions in JP-A-57-22238 and JP-A-58-42046. The content of the yellow coupler of the present invention is 10 silver genide 1
A range of 2 to 70 moles per mole is appropriate, preferably a range of 0 to 60 moles, and more preferably a range of 0 to 60 moles. In the light-sensitive material according to the present invention, yellow couplers other than the yellow coupler of the present invention can be used as the yellow coupler, but it is preferable that the ratio of the yellow coupler of the present invention to the yellow couplers is at least 40 mol%. More preferably, it is at least ■mol%. The photosensitive material according to the present invention preferably contains a nitrogen-containing heterocyclic mercapto compound. Particularly preferred nitrogen-containing heterocyclic mercapto compounds are mercaptooxadiazole, mercaptothiadiazole, and mercaptotriazole represented by the general formula [11], and most preferred are mercaptotriazoles. General Formula CI] (Y) In the formula, Xl is a hydrogen atom, an amine group, a hydroxyl group, a hydrazi7 group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -NHCOR,. group, -NHSO
2R,. A group or (-S R,, represents a group, Y is a hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -CONHR12 group, -COR. group, NHCOR14 group or -NH8O2R,, represents a group. Z4 represents a nitrogen atom, a sulfur atom, or an oxygen atom. m represents 1 when z4 is a nitrogen atom, and represents 0 when z4 is an oxygen atom or a sulfur atom. Rto + RII
+ R12RI3 and R14 are each an alkyl group,
Represents an alkenyl group, a cycloalkyl group or an aryl group. The alkyl group represented by Examples of the group include cyclohexyl group, cyclopentyl group, etc., and alkenyl group preferably has 2 to 18 carbon atoms, such as allyl group, octenyl group, etc., and aryl group includes:
For example, phenyl group, naphthyl group, etc. Also R10
+ R+I + R12 The alkyl group represented by RI3 and RI4 is preferably a straight chain or branched one having 1 to 18 carbon atoms, such as a methyl group, ethyl group, propyl group, puchyl group, xyl JJi, etc. Examples of cycloalkyl groups include cyclopentyl group and cyclohexyl group, and alkenyl groups include 2 carbon atoms.
-18 are preferable, such as allyl group, octenyl group, octadecenyl group, etc., and the aryl group is 1
For example, phenyl group, naphthyl group, etc. Also, X4 * Y+ RIO+ R11* R12*
The alkyl group, cycloalkyl group, alkenyl group and aryl group represented by R13 and RI4 may each have a substituent, and examples of such substituent include an alkyl group, a cycloalkyl group, an aryl group, Examples include an alkenyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, an ami7 group, a carboxyl group, and a hydroxyl group. However, the present invention also includes these tautomers. Specific examples of compounds represented by one set of general formulas are listed below. I-I CH3 1-7 -8 1-91 -t. ■ -11 Era -12 NHCOCH, NHCOCH. 1-19 1 -Nod I -
23 Seal -24 ~ OtoC''''N Yen 111H ■-33 C2H. H3 ■-40 ■ -41 ■ -45 ■-46 ■-50 l-51 ■-52 ■-53 ■-56 ■-58 ■-59 -F compounds are described in, for example, JP-A-51-107129,
No. 48-102621, No. 55-59463, No. 5
No. 9-124333 and British Patent No. 1,204,623. The above-mentioned nitrogen-containing heterocyclic mercapto compound can be added to at least one arbitrary photographic constituent layer constituting the silver halide color photographic light-sensitive material of the present invention, but the silver halide emulsion containing the yellow coupler of the present invention It is preferably contained in a layer or a layer adjacent thereto, and the amount added is 5 x IO- to 1 mole of silver halide contained in the emulsion layer.
A moderation of 10 mol is preferred. The silver hydride emulsion (in the emulsion layer containing the yellow coupler of the invention and other emulsion layers) used in the light-sensitive material of the invention will be described below. The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use any of the following. In the present invention, the silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, monocotic method, and ammonia method.
It may be allowed to grow longer, or it may be allowed to grow after creating seed particles. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding 8 g of p II r +) in a mixing pot while controlling. By this method, 710 silver denride grains with a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles. During production of the silver halide emulsion, a silver halide solvent can be used as necessary to control (d) the grain size, grain shape, grain size distribution, and grain growth rate of the silver lodenide grains. . Silver halide grains used in silver halide emulsions are
In the process of forming and/or growing particles, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (
Adding metal ions using at least one selected from rhodium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing), and containing these metal elements inside the particles and/or on the particle surfaces. By placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure
Closure) It can be carried out based on the method described in No. 17643. Silver lodenide grains used in silver halide emulsions are:
The core/shell grains may have a uniform no-% silver denide composition distribution within the grains, or may be core/shell grains in which the 710 silver denide composition differs between the inside of the grain and the surface layer. Silver lodenide grains used in silver halide emulsions are:
It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle. Z1010 silver denride used in silver halide emulsions is
It O
Any ratio of the 01 plane and the (1111 plane) can be used.Also, a single particle having a composite form of these crystal forms may be used, or grains of various crystal forms may be mixed.Silver halide grains The average grain size (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5μI11 or less, particularly preferably 3μW or less.The silver halide emulsion may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, and an emulsion with a narrow grain size distribution <-!1i is referred to as a dispersed emulsion. A dispersed emulsion is one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less.The grain size is defined as the diameter in the case of spherical silver halide. ,
In the case of particles with shapes other than spherical, the diameter is shown when the projected image is converted into a circular image with the same area. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using a noble metal compound or the like can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone, but 2'! 1
The above may be used in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a super sensitizer, which is a compound that does not substantially absorb visible light and enhances the spectral sensitization of the sensitizing dye. It's okay. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing capri during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added. As a binder (or protective colloid) for the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used. When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by baggy method). The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention contain i! ! ! Hardening can be achieved by using I or two or more of them. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. Since the photosensitive material of the present invention forms a multicolor image,
Other couplers for forming dye images such as cyan coupler and magenta coupler can be used in combination, and various known photographic additives can also be used. As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, and closed acylacetonitrile couplers can be preferably used. A specific example of a magenta coupler that can be advantageously used is disclosed in the patent application filed in 1973.
No. 8-164882, No. 58-167326, No. 58
-206321, 58-214863, 58-
No. 217339, No. 59-24653, Special Publication No. 1973-
No. 6031, No. 40-6035, No. 45-40757
No. 47-27411, No. 49-37854, JP-A No. 50-13041, No. 51-26541, No. 5
No. 1-37646, No. 51-105820, No. 52-
No. 42121, No. 53-123129, No. 53-12
No. 5835, No. 53-129035, No. 54-485
No. 40, No. 56-29236, No. 56-75648, No. 57-17950, No. 57-35858, No. 5
No. 7-146251, No. 59-99437, British Patent No. 1,252,418, U.S. Patent No. 2,600, 78
No. 8, No. 3,005゜712, No. 3,062,653
No. 3,127,269, No. 3,214゜437, No. 3,253.924, No. 3,311,476,
3,419°391, 3,519,429, 3,558,319, 3,582°3'12, 3,615,506, 3,658,544, Same 3
, 705°896, 3,725,067, 3,
No. 758,309, No. 3,823゜156, No. 3,
834, No. 908, No. 3,891,445, No. 3,
907゜571, 3,926,631, 3,9
No. 28,044, 3, 935. No. 015, No. 3,960,571, No. 4,076.5
No. 33, No. 4,133゜686, No. 4,237,21
No. 7, No. 4,241,168, No. 4,264°723
No. 4,301,235, No. 4,310. [323
This is what is written in the number etc. As the cyan dye-forming coupler, known 7-tall couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 543.040, Japanese Patent Publication No. 4B-36894, and Japanese Patent Publication No. 48-598:1.
No. 8, No. 50-137137, No. 51-146828
No. 53-105226, No. 54-115230, No. 56-29235, No. 56-104333, No. 56-126833, No. 57-133650, No. 5
No. 7-155538, No. 57-204545, No. 51
? -118843, 59-31953, 56-
No. 31954, No. 59-59656, No. 59-124
No. 341, No. 59-166956, U.S. Patent No. 2,36
No. 9,929, No. 2,423,730, No. 2,434
, No. 272, No. 2,474,293, No. 2,698,
No. 794, No. 2,772,162, No. 2, SO1,1
No. 71, No. 2,895,826, No. 3,253,92
No. 4, No. 3,311,476, No. 3,458,315
No. 3,476.563, No. 3,591,383, No. 3,737,316, No. 3,758,308,
3,767.411, 3,790,384, 3,8 SO, 661, 3,926,634, 4
, No. 004,929, No. 4,009,035, No. 4,
No. 012,258, No. 4,052,212, No. 4,1
No. 24,396, No. 4,134,766, No. 4,13
8.258, i, 146,396, 4,14
No. 9,886, No. 4.178.183, No. 4,205
, No. 990, No. 4,254,212, No. 4,264,
No. 722, No. 4,288,532, No. 4,296,1
No. 99, No. 4,296,200, No. 4,299.91
No. 4, No. 4,333,999, No. 4,334,011
No. 4,386,155, No. 4.40'l, 752
No. 4,427,767, etc. As a high-boiling oil agent, it does not react with the oxidized form of the developing agent71
Organic solvents having a boiling point of 150'C or higher, such as nol derivatives, heptatarate alkyl esters, phosphoric acid esters, citric acid esters, benzoic 1M esters, alkylamides, fatty acid esters, and trimesic acid esters are used. High boiling, +, 'K @ tE that can be used in the present invention
! As the solvent, U.S. Patent Nos. 2,322,027, 2,538.514, 2,835,579,
, No. 287,134, No. 2,353,262, No. 2.
No. 852,383, No. 3,554,755, No. 3,6
No. 76.137, No. 3゜676.142, No. 3,70
No. 0,454, No. 3,748,141, No. 3,779
．． No. 765, No. 1,837.863, British Patent No. 95
No. 8,441, No. 1゜222.753, 0LS2,5
38,889, JP-A-47-1031, JP-A No. 49-90
No. 523, No. 50-23823, No. 51-26037
No. 51-27921, No. 51-27922, No. 51-26035, No. 51-26036, No. 50-
No. 62632, No. 53-1520, No. 53-1521
No. 53-15127, No. 54-119921,
No. 54-119922, No. 55-25057, No. 5
No. 5-36869, No. 56-19049, No. 56-8
1836, Japanese Patent Publication No. 48-29060, etc. Low-boiling or water-soluble organic solvents that can be used with or in place of high-boiling, alpha-solvents include U.S. Patent PIS 2, SO 1,1
Examples include those described in No. 71 and No. 2,949,360. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate,
Examples include butyl acetate, butyl, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc. Water-soluble organic solvents include acetone, methyl imbutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, meta 7 -ol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, noethyleneglyfur monophenyl ether, 7ethyl/oxyethanol, and the like. Examples of surfactants used as dispersion aids include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl g 17 oxyethylene. Anionic surfactants such as alkyl phenyl ethers; nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives; amphoteric surfactants such as amino acid salts, aminoalkyl sulfones, and alkyl betaines; It is preferred to use cationic surfactants such as surfactants and quaternary ammonium salts. Specific examples of these surfactants are "Surfactant Handbook" (Sangyo Tosho, 1966) and rlL conversion and emulsification equipment research. It is described in Technical Data Collection 1 (Science Panronsha, 1978). Hydroquinone transparent conductor, aluminum/
Preferably, 7-ol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc., specific examples of which are described in U.S. Patent M2,3.
60,291y, 2,336.327 JJ2,40
No. 3,721, No. 2,418,613, No. 2,675
．． No. 314, No. 2,701,197, No. 2,704,
No. 713 J12, 728, 659, 2, 732
, No. 300, No. 2,735.765, No. 3,700,
No. 453, JP-A-50-92988, R50-929
No. 89, No. 50-93928, No. 50-110337
No. 50-1.56438, No. 52-146235
No. 55-95948, No. 59-5247, Japanese Patent Publication No. 50-23813, etc. Examples of ultraviolet absorbers include benzophenone compounds (for example, those described in JP-A No. 46-2784), butanoene compounds (for example, those described in U.S. Pat. No. 4,045,229), 4-thiazolidone compounds (for example, those described in U.S. Pat. Patent No. 3,314,794, Patent No. 3,35
2,681), benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,53
Nos. 3,794 and 4.323,633)
, benzoxidol compounds (e.g., U.S. Pat. No. 3,7
00,455), cinnamate ester compounds (e.g., U.S. Pat. No. 3.705, SO5, No. 3,
707.375) can be used. Furthermore, U.S. Patent No. 3,499,762, JP-A-54-
Those described in No. 48535 can also be used. Ultraviolet-absorbing couplers (e.g., cyan dye-forming couplers based on α-7-tole) and ultraviolet-absorbing polymers (e.g., JP-A-58-111942, JP-A-17835)
(described in Publication No. 1) can be used. These ultraviolet absorbers may be mordanted in specific layers. As the optical brightener, stilbene-based, triazine-based, imigsolone-based, pyrazoline-based, triazole-based, coumarin-based, acetylene-based, oxazole-based, and oxadiazole-based optical brighteners can be preferably used. These optical brighteners are described in U.S. Pat.
, No. 581,057, No. 2,818,636, No. 2,
702゜296, 2,713,054, 2,7
15,630. No. 2,723.193, No. 3,5
No. 13,102, No. 3,684,729, No. 3,78
No. 8,854, No. 3, 789, O] No. 22 British Patent No. 669,590, No. 672, No. SO3, No. 712
, 764, Dutch Patent No. 74,109, German Patent No. 911.368, German Opening Publication (OLS) 2,52
It is described in No. 5, 6SO, etc. These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion. Filter dyes, dyes used for iranoation prevention, and other purposes include oxal dyes,
Included are hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxal dyes and merocyanine dyes are useful. The shell/body side of the dye that can be used is British Patent No. 373,004.
No. 584, No. 609, No. 1,177.429,
JP 48-85130, JP 49-99620, JP 49-114420, JP 52-108115, JP 5
No. 7-185038, U.S. No. 11,878,961,
2,150,695, 2,274,782, 2,298.731, 2,533.472, 2
, No. 865,752, No. 2,956.879, No. 3.
148.187, 3.177.078, 3.2
No. 47,127, No. 3,282,699, No. 3゜54
No. 0.887, No. 3,575,704, No. 3,653
, No. 905, No. 3,718.472, No. 4,071,
No. 312 and No. 4,070,352. The support for the silver halide photographic material of the present invention includes:
Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflectors, such as plastic plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, and polycarbonates. There are films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material. Preferably, it is a reflective support, and in this case the effect of the present invention is large. To obtain a dye image using the photosensitive material of the present invention, after exposure,
After exposure, printing and development processing is performed. The color development process is a process of forming a color image, and in physical terms, it is a process of forming a color image by a coupling reaction between an oxidized color developing agent and a color coupler. Therefore, in the color development processing process, it is usually necessary to incorporate a color developing agent into the color developing solution, but it is necessary to incorporate the color developing agent into the color photographic material, and use a color developing solution or a color developing agent containing the color developing agent. It also includes treatment with an alkaline solution (activator solution). The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent.
Contains phenylenone amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, salts of acid, sulfates, P-toluenesulfonates, sulfites, oxalates, benzenesulfonates, etc. can be used. can. . These compounds are generally about 0.0% in color developer 11.
A concentration of 1 g to about 30 g, more preferably color developer 1
A concentration of about 1 g to 15 g for p is used. 0. Ig
A sufficient color density cannot be obtained if the amount added is less than . Further, the temperature of the processing solution in the color developing tank is 10"C to 65C, more preferably 25C to 45C. Examples of the amino 7-ether-based developer include O-7
Mino-7er/-el, p-amino/phenol, 5-amino-
Included are 2-oxy-toluene, 2-7minor-3-oxy-toluene, 2-oxy-3-amino-1,4-tmethylbenzene, and the like. A particularly useful primary aromatic amine color developer is N-N-
A noalkyl-p-phenylenenoamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful examples of compounds include tN-tumethyl-11-phenylenediamine [a9IX, N-methyl-p-phenylenenoamine hydrochloride, N,N-tumethyl-p-7 22enediamine hydrochloride, 2-amino/-5-(N-ethyl-N-dodecylami7)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami7aniline sulfur am, N-ethyl-N -β-hydroxyethylami7aniline, 4-amino/-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N
-ethyl-3-methylaniline-p-)luenesulfonate and the like. In addition, the above color developing agents may be used alone or in combination! ! ! More
It may be used in combination with. Furthermore, the color developing agent may be incorporated into the color photographic material. For example, a method of incorporating a color developing agent into a metal salt as described in US Pat. No. 3,719,492, US Pat. No. 3,342,55
No. 9, Research, Disclosure A--(Resear
ch Disclosure) 1976 No. 15
159, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429 and JP-A-58-65429;
No. 8-24137, etc., as a dye precursor, and U.S. Pat. No. 3,342,59.
A method of using B as a color developing agent precursor as shown in No. 7 can be used. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and immediately after the alkaline solution treatment, it is subjected to a blank fixing process. The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citranic acid, and preservatives such as citric acid, etc.
In addition, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide, and dimethylsulfoxide may be appropriately contained. 1]11 of the color developing solution is usually 7 or more, preferably about 9 to 13. In addition, the color developing solution may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anili7ethyl, nohydroxyacetone, aromatic Ml! Alcohol, hydroxamic acid, hendose or hexose, C7-1,3-methyl ether, etc. may be contained. In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylene diamine diacetic acid, diethylene triamino pentaacetic acid, nucleating phosphonic acids such as 1-hydroxyethylidene-1,1゛-nophosphonic acid, ami/tri(methylene phosphonic acid), or ethylene phosphonic acid are used. 7-minopolyphosphonic acids such as mincedtralinic acid, oxycarboxylic acids such as citric acid or glufonic acid, 2-
Phospho/butane-1,2,4-)licarvone I'i2￥
Examples include phospho/carboxylic acids of P, polyphosphoric acids such as tripolyphosphoric acid such as hexametaphosphoric acid, and polyhydroxy compounds. The bleaching agent used in the bleaching process is a metal salt of an organic acid, such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., and metals such as iron, cobalt, copper, etc. Those with coordinated ions are used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include things like daigi. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N,N'
, N'-) diacetic acid [4] propylene diamine tetraacetic acid [5]
Tori Ro Tori Vinegar Ejihi [6] Cyclohexanediaminetetraacetic acid [7] I Mi 7 Shi'
Acetic acid [8] Cyhydroxyethylglycincitric acid (
or tartaric acid)

[9] Ethyl ethernoamine thitraacetic acid [10]
] Glyfur ethernoamine tetraacetic acid (113 Ethylenediaminetetraprobionic acid (12:1 phenylenenoaminetitraacetic acid) [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] [16] Diethylenetriaminepentaacetic acid pentasodium salt (17) Ethylenediamine-N-(β-oxyethyl-
N,N',N'-) Sodium acetate salt [18] Sodium propylene diamine tetraacetate salt [19] Sodium lyloacetate salt [20] Sodium cyclohexane diamine tetraacetate These bleaches contain 5 to 450 g/l , more preferably 2
It is used in history at 0 to 250 r/1. In addition to the above-mentioned bleaching agent, the bleaching solution must contain sulfite as a preservative if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (■) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. For bleaching solutions, JP-A No. 46-2SO, JP-A No. 45-85
No. 06, No. 46-556, Belgian Patent No. 770,9
Various bleaching accelerators described in Japanese Patent Publication No. 10, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Application Publication No. 54-71634 and Japanese Patent Publication No. 49-42349, etc. can be added. ) The pH of white liquid is used at 2.0 or higher, but generally it is used at +11+4, 0 or higher and pl+9.5 or lower,
Preferably, p I+ 4 is used at 5 or more and pl+8.0 or less, and more specifically, p++ is most preferably used at 5.0 or more and 7.0 or less. The processing temperature is SO ℃ or less, and the temperature is 3 ℃ or more, preferably 5 ℃ or more lower than the temperature of the processing solution in the color developing tank.
Use at temperatures below ℃ to prevent evaporation. Silver halide fixing agents used in the fixing solution used in the fixing process include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, Typical examples include 1000 sulfates such as sodium sulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, 1000 urea, and thioether. These fixing agents are used in an amount of 971 or more, within the range that can be dissolved, but generally 70 g to
Use at 250g/l. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the constant N tank. The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. )
The H buffering agent may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, γIV foaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or nitroalcohols, stabilizers such as (i[salts, methanol, trimethylsulfamide, It is possible to contain an organic solvent such as methyl sulfoxide as appropriate. 1) The fixer is used with a p of 3.0 or more, but is generally used with a p I+ 4, 5 or more and a p 1110 or less, Preferably l) I+ is used at a pH of 5 or more and pH 9.5 or less, more preferably 11 I+ is 6 or more.
If it's less than 9, it's J! I! be done. The processing temperature is below SO'C and lower than the processing a temperature of the color developing tank by 3°C or more, preferably by 5°C or more, but preferably by 5°C or more.
Use at temperatures below 5°C to prevent evaporation. The metal complex salt of an organic acid used as a bleaching agent in the bleach-fixing solution used in the bleach-fixing process is an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid.
It is coordinated with metal ions such as. There is something like this (
The most preferred organic acids used to form the metal complex salts of carbonic acid include the polycarboxylic acids. These polycarboxylic acids or amine/polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Examples of these nine shellfish include the following: [1] Ethylenenoaminetitraacetic acid [2] Noethylenedolyaminebentaacetic acid [3] Ethylenenoamine-N-(β-oxyethyl)-N,N°
, N' -) Liacetic acid [4] Propylenenoaminetitraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7]
] Imi-7 diacetic acid [8] Hydroxyethylglycine citric acid or tartaric acid)

[9] Ethyl ethernoamine titraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylenenoamine tetrabrobionic acid [12] Phenylenenoamine titraacetic acid [13] Ethylenenoamine titraacetic acid nonodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt (16) Ethylenetriamine benkacetic acid pentasodium salt (17) Ethylenenoamine - (β ~ oxyethyl)
-N, N', N'-) lyloacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt (19) di) lyloacetic acid sodium salt [20] cyclohexane diamine tetraacetic acid sodium salt /1, more preferably 2
0 to 25 (used in '19/1. Bleach-fix solution contains i
In addition to bleaching agents such as those described in Section 17), a solution having a composition containing 10 silver denide fixing agent and, if necessary, sulfite as a preservative, is applied. Additionally, iron ethylenediaminetetraacetate (
Ill) Complex salt bleach and the above halogenated ffi constantff
Bleach-fix solutions containing a small amount of other halides such as ammonium bromide, or conversely, bleach-fix solutions containing a large amount of halides such as ammonium bromide, and even ethylenediamine. It is also possible to use a special bleach-fixing solution with a composition consisting of iron (171) tetraacetate complex salt bleach and a large amount of halogen (l) such as ammonium bromide. Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used in the ammonium pond.Contained in the bleach-fix solution. The silver halide fixing agent is a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate salt such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, which is used in ordinary fixing processing. Typical examples include thionic acid t1^ such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether.These fixing agents are used in an amount of 5 g/N or more, within the range that can be dissolved. However, generally 709-25 (1
Use in g/l. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as amide/polycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, trimethylsulfamide, trimethylsulfonate, etc. Kin 1?
It is possible to appropriately contain organic solvents such as the like. Special 111 for bleach-fix solution! 1970-2SO No. 45-8506, Belgian Patent No. 46-556, Belgian Patent No. 770,910/Special Publication No. 8836/1973, 53-
No. 9854, JP-A-54-71634 and JP-A-49-4
Recorded in issue 2349 etc. 1! Various bleach accelerators can be added. ) The pH of the brightening fixer is 4.0 or above (1), but generally it is used at a pH of 5.0 or above 1) I+ 9, 5 or below, preferably +3116.0 or above 1) 118.5 or below. , more specifically, the most preferable 1) 1] is 6
．． Processed at 5 or more and 8.5 or less. The processing temperature is SO°C or below, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank, but is preferably 55°C or below to prevent evaporation, etc. From the viewpoint of rapid processing, the processing humidity of various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc., of silver halide color photographic light-sensitive materials is set at 30°C from the viewpoint of rapid processing. It is preferable to carry out the reaction at a temperature of 35°C or higher, preferably 35°C or higher. The silver halide photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58-14
No. 834, No. 58-105145, No. 58-1346
No. 34 and No. 58-18631 and patent application No. 58-2
A stabilization treatment as an alternative to water washing as shown in Japanese Patent Application No. 709 and No. 59-89288 may also be performed. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 1709/rr? polyethylene on one side of the paper support,
Silver halide color photographic materials A1 to 24 were prepared by sequentially coating the following layers on the titanium dioxide-containing polyethylene side of a support laminated with polyethylene containing 11% by weight of anatase titanium dioxide on the other side. . Note that the amount added is expressed per 1 ml unless otherwise noted. Layer 1...1.99 gelatin, 0.399
Blue-sensitive silver chlorobromide emulsion (in terms of silver), 1.2 x 10
-3 mol of yellow coupler shown in Table-1, 0.03
0.50 # of di(2-ethylhexyl) phthalate (hereinafter referred to as DOP) in which 0.25 g of the compound having the general formula "11" of the present invention shown in Q-1 (below) and Table-1 was dissolved. Layer containing: Layer 2: 1.39 gelatin and 0.028.
Protective layer containing 2,4-dichloro-6-hydroxy-5-triazine (hardener) of No.9. Q −1 nT−+ Jti In addition, as a hardening agent, 0.04 ! 7 Added immediately before coating. Each of the photosensitive material samples A1-24 was exposed to white light through an optical wedge and then processed in the following steps. Processing process Color development A Color development B Color development C Bleach fixing Seki 1 minute 30 seconds at 33 degrees Celsius 1 minute 30 seconds at 33 degrees Celsius 1 minute 30 seconds at 33 degrees Celsius Washing with water 30-34 degrees Celsius 2 minutes 30-34 degrees Celsius 2 minutes 30-34 degrees Celsius Dry for 6 minutes
0 to SO°C 2 minutes 60 to SO°C 2 minutes 60 to SO°C 2 minutes The composition of each treatment liquid is as follows. [Color developer A] Pure water SO0 me Benzyl alcohol 15 ml Triethanolamine [OI hydroxyamine sulfate 2.0 g Potassium bromide
0.6 g sodium chloride 1
,0g Potassium sulfite 2.0N
-ethyl-N-β-methanesulfonamidoethyl-3methyl-4-ami/aniline sulfate 4.5,! ? ■
-Hydroxyethylidesu-1.1- Diphosphonic acid (60% aqueous solution) 1.5 mt
Potassium carbonate 32 gWh
itex BB (50% aqueous solution) (fluorescent brightener, manufactured by Sumira Chemical Industries, Ltd.) Add 2 mt of pure water to prepare 1e, and adjust the pH to 1o, 1 with 20% potassium hydroxide or 10% dilute sulfuric acid. [Color developer B] Same as color developer A except that potassium bromide was changed from 0.6 g to 1.3 g. [Color developer C] Same as color developer B except that benzyl alcohol was removed. [Bleach-fix solution] Pure water 600 mt 1000% diaminetetraacetic acid! (1) Ammonium 5F 2-sodium salt of diaminetetraacetic acid Ammonium thiosulfate 85g Sodium bisulfite
10. 9 Sodium metabisulfite
2g Sodium diaminetetraacetic acid 0g Sodium bromide 109 Color developer A 200mt Add pure water and 11! Adjust the pH to 7.0 with dilute sulfuric acid. Reflection measurement was performed on each of the obtained samples using blue monochromatic light, and the sensitivity and gradation (slope of reflection density from 0.5 to 1.5) were determined from the obtained characteristic curves. The sensitivity is characterized by the sensitivity when a sample that does not contain a compound having the general formula It can be seen that development fog is improved without deterioration in sensitivity and gamma compared to the comparative light-sensitive material lacking the requirements of the present invention. Example 2 The same experiment as in Example 1 was conducted, except that the compounds shown in Table 2 were used as the yellow coupler and the compound having the unit represented by the general formula [1) or its comparative compound. The results are shown in Table-2. Comparison-1 Comparison-2 Comparison-3 From these results, it can be seen that the photosensitive material according to the present invention was prepared using a polyalkylpiperazine compound having a similar chemical structure instead of the compound having the unit represented by the general formula [1]. It can be seen that fogging is significantly improved compared to photosensitive materials. Example 3 The following layers were formed on the titanium dioxide-containing polyethylene side of a 170 g/m'' paper support laminated with polyethylene on one side and anatase titanium dioxide on the other side. Sequentially coated and boiled silver halide color photographic light-sensitive material 37-4
4 was created. The amount added is 1ml unless otherwise specified.
It is shown in the amount per hit. Layer 1...1.2 & gelatin, 0.299
(in terms of silver) blue-sensitive cubic silver chlorobromide emulsion (Note-1),
0.50. ! The yellow coupler and photosensitive materials j639 and IEg 40 shown in Table 3 of 0.70.9 dissolved in the DOP of i' are, in addition, 2X per mole of silver halide.
A layer containing IO'mol of the nitrogen-containing heterocyclic compound (1-24). Layer 2...0.7I gelatin, 15m9 anti-irradiation dye (AI-1), lOw/(AI
-2) and 0.05 g of the above color stain inhibitor HQ-1
0,05,! An intermediate layer containing a DOP of 7. Layer 3...1. z5g gelatin, 0.22#
green-sensitive cubic silver chlorobromide emulsion (Note-2), 0.30
A layer containing a magenta coupler (M-1) of 0.459 dissolved in a DOP of 9. Layer 4...1.2g gelatin, 0.08.9
HQ-1 and 0.35 g DOP in which 0.5 F ultraviolet absorber (UV-1) is dissolved. Layer 5...1.4,! i' gelatin, 0.
20 g of red-sensitive cubic silver chlorobromide emulsion (Note-3),
Layer containing 0.45 g of cyan coupler (C-1) below dissolved in 0.20 g of DOP. Layer 6...1. Og gelatin and 0.20.9
0,30,! dissolved in the DOP of ! ? A layer containing UV-1. Layer 7: Layer containing 0.5 g of gelatin. As a hardening agent, 0.049 of 2.4-dichloro-6-hydroxy-5-) riazine sodium was added to each of the layers 4 and 7 immediately before coating. I V-1 CsHII(t) I-2 (Note-1) Blue-sensitive silver chlorobromide emulsion Silver bromide composition mol% Sodium thiosulfate per mol of silver halide 2.8
Chemical sensitization was carried out by adding to -5 moles of X, and optical sensitization was carried out using a blue sensitizing dye. As a stabilizer, a 1-hydroxytetrazaindene compound was added at 4.5% per mole of silver halide.
X 10-mol was added. (Note-2) Green-sensitive silver chlorobromide emulsion Silver bromide composition: 70 mol% Sodium thiosulfate: 3.5% per mol of silver chloride
Chemical sensitization was carried out by adding 10-5 mol of X to the silver chloride, and optical sensitization was carried out using a green sensitizing dye.As a stabilizer, a l-hydroxytetrazaindene compound was added to the silver halide at 4.5 X to- Added moles. (Note-3) Red-sensitive silver chlorobromide emulsion Silver bromide composition: 55 mol% Sodium thiosulfate: 3.5% per mol of silver genide
Chemical sensitization was carried out by adding to -3 moles of X, and optical sensitization was carried out using a red sensitizing dye. As a stabilizer, a 1-hydroxytetrazaindene compound was added in an amount of 4.5×10 −3 mol per 1 mol of silver genide. In addition, samples 2, 4, 6, 8, to, 12
, 14 and 16, 2.5 X to
-6 mol was added. Each of the above photosensitive material samples A 37 to 44 was exposed and developed in the same manner as in Example 1. From these results, the yellow coupler of the present invention different from the above Example and the unit of general formula i1 were determined. It can be seen that the same effects of the present invention as in the above examples can be obtained in combination with a compound having a nitrogen-containing heterocyclic mercapto compound, and that the effects of the present invention can be further enhanced by using the nitrogen-containing heterocyclic mercapto compound in combination. Example 4 Samples containing IQ-1 (A I
A ”jVx 6 A) and the sample without containing (j
618-A 6 B) was produced. These samples were exposed and processed with color development A in the same manner as in Example 1, and the sensitivity, maximum density, and fog were determined. Furthermore, the obtained sample was exposed to xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 300 hours, and the concentration before exposure (D
o = 1.0) to measure the concentration after exposure.
D/Do) X 100 was taken as the dye residual rate of the yellow dye image. The results are shown in Table 4. Note that the sensitivity is A
Table 4 From these results, the sample according to the present invention has improved light fastness, sensitivity, gamma, maximum density and It can be seen that the dye has overall excellent hardness. Example 5 The yellow coupler in Example 2 was changed from Y-2 to Y-2.
and compared coupler RY-1 (molar ratio 0.7:0.3),
The same experiment as in Example 2 was conducted except that Y-37 was changed to Y-37 and the comparative coupler RY-2 (molar ratio o, s: 0.2). The results are shown in Table-5. 2-2 - 2-2 From these results, it can be seen that the effects of the present invention can be obtained in the light-sensitive material of the present invention even when the yellow coupler of the present invention is used in combination with other yellow couplers. [Effects of the Invention] According to the present invention, the following effects (1) to 4) can be obtained in the yellow coloring layer of a silver halide color photographic light-sensitive material. (1) Even when a highly color-forming coupler is used, fogging is reduced without reducing sensitivity, gradation, and maximum density. (2) Provides good photographic performance even when developed with a color developing solution that does not contain benzyl alcohol. (3) There is little fogging even during high-temperature development, and rapid processing is possible. (4) Prevent fog without reducing image storage stability, especially light fastness. Applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment December 19, 1986

Claims (1)

[Scope of Claims] At least one photosensitive silver halide emulsion layer contains at least one group having an -SO_2- structure in addition to a group that couples with and leaves an oxidized form of a color developing agent.
A color photographic material comprising an equivalent yellow coupler and a compound having a unit represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a hydrogen atom or an alkyl group. ]