JPH0552939B2 - - Google Patents

Description

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

The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically to a method for processing silver halide color photographic light-sensitive materials, which can significantly improve processing fluctuations during color development processing and achieve low pollution. Regarding.

[Prior art]

Generally, after exposure, color photographic materials undergo processing steps including color development using a developer containing a paraphenylenediamine color developing agent, bleaching, fixing, or bleach-fixing and washing to produce a photographic image. In the color development processing step, a color image is formed by a coupling reaction between an oxidized color developing agent and a color coupler, and at the same time, metallic silver is produced in the photographic step. In a subsequent desilvering step, this metallic silver is oxidized by a bleaching agent, forms a soluble silver complex by a fixing agent, and is dissolved away. In recent years, due to environmental protection and cost issues, research has been conducted to reduce pollution, and this has been put into practical use in some treatment processes. Particularly in the color development process, various low-pollution techniques have been proposed in the past due to the high level of pollution caused by the process. For example, JP-A-54-
No. 37731, No. 56-1048, No. 56-1049, No. 56-
Regeneration method by electrodialysis described in No. 27142, No. 56-33644, No. 56-149036, etc., Japanese Patent Publication No. 55-1571,
Regeneration method using activated carbon according to JP-A No. 58-14831,
The ion exchange membrane method described in JP-A-52-105820, as well as JP-A-53-132343, JP-A-55-144240, and JP-A-57-
146249, a method using an ion exchange resin described in US Pat. No. 4,348,475, etc. are disclosed. However, in the above method, the reproducing equipment is large and expensive;
Furthermore, in order to maintain the development level at a constant level, a skilled person is required to analyze the regenerating solution, so the reality is that this method is not practiced at all except in a few laboratories. On the other hand, a method has recently come into use in which the amount of waste liquid is reduced by reducing the amount of replenisher for the color developing solution without using the regeneration method. Unlike the methods described above, this method can be said to be a preferable method for achieving low pollution without requiring large-scale, expensive equipment or skilled analysts. However, although it is possible to reduce replenishment to a certain extent by this method, concentration of the color developing solution due to evaporation, contamination of iron salts, thiosulfates, etc. due to belt and back contamination, and eluates from the emulsion, such as active This method has serious disadvantages in that processing fluctuations and processing stains increase due to outflow of agents and inhibitory components. This tendency becomes particularly noticeable when low replenishment progresses and high temperature treatment and low throughput are performed. Techniques to prevent processing fluctuations due to the contamination of iron salts, thiosulfates, etc. into the color developing solution due to low replenishment include various chelating agents and JP-A-Sho.
As described in No. 57-150847, No. 58-120250, and No. 58-121036, polyvinylpyrrolidone-based compounds and polyethylene glycol-based compounds have been disclosed; It is only effective against the contamination of iron salts and thiosulfates, and is not very effective when the level of replenishment is further reduced and the ratio of iron salts and thiosulfates mixed into the color developing solution increases. Further, it is not preferable to add a large amount of the chelating agent, polyvinylpyrrolidone, or polyethylene glycol-based polymer compound, since this greatly affects the photographic properties of the light-sensitive material.

[Purpose of the invention]

The purpose of the present invention is to significantly improve the processing fluctuations of silver halide photographic materials due to low replenishment, and the second purpose is to achieve a significant reduction in pollution using a simple and inexpensive method. Still another object of the present invention is to provide a processing method capable of forming color photographic images with high sensitivity and excellent image quality.

[Structure of the invention]

As a result of intensive research, the present inventors found that 3 mol%
A silver halide color photographic light-sensitive material containing at least one core-shell emulsion containing silver iodide as described above and containing a cyan coupler represented by the following general formulas [] to [] contains 3.0 x 10 ^-3 mol of bromide or less. The present inventors have discovered that this can be achieved by replenishing the color development replenisher contained in the silver halide color photographic light-sensitive material with 9 ml or less of the replenisher per 100 cm ² of the material. General formula [] In the formula, one of R ₁ and R is hydrogen, the other represents a linear or branched alkyl group having at least 2 to 12 carbon atoms, X represents a hydrogen atom or a group that leaves by a coupling reaction, and R ₂ is Represents a ballast group. General formula [] General formula [] In the formula, Y is −COR ₄ ,

[Formula] −SO ₂ R ₄ ,

【formula】

[Formula] -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R ₅ is a hydrogen atom,
Alkyl group, alkenyl group, cycloalkyl group,
It represents an aryl group or a heterocyclic group, and R ₄ and R ₅ may be bonded to each other to form a 5- to 6-membered ring. ), R ₃ represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent. Furthermore, as a preferred embodiment of the present invention, the color developer replenisher contains a chelating agent represented by the following general formulas [] to [], and furthermore, the bromide content of the color developer replenisher is 2.0×
10 ^-3 mol/or less, and the color developing replenisher per 100 cm ² of silver halide color photographic light-sensitive material.
The effects of the present invention become noticeable by replenishing and processing 7.5 ml or less. General formula [] A-COOM General formula [] B-PO ₃ M ₂ General formula []

[Formula] In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance or an organic substance. D represents a nonmetallic atom group necessary to form an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. The present invention will be explained in detail below. When low replenishment is carried out in order to achieve low pollution and cost reduction, processing fluctuations and processing stains of color photographic light-sensitive materials become large. Silver chemical color photographic material 9ml per ^100cm2
It has been found that processing fluctuations and processing stains become significantly larger when processing is performed with the following replenishment.
In particular, it was found that the minimum density of the red-sensitive layer fluctuated greatly when the throughput was low. In general, color negative film containing silver iodide-containing color photographic materials, such as color photographic materials for photography, is refilled with approximately 15 ml per 100 ^cm2 of color development, but in this case, since the amount of replenishment is large, iron salts, etc. There is not much of a problem other than the contamination of pre-bath components such as thiosulfates, but if the replenishment amount decreases to 9 ml or less, concentration of the color developing solution due to evaporation and accumulation of emulsion eluate become a problem as described above. . Therefore, it is important to prevent concentration of the color developing solution due to evaporation, or to ensure that concentration does not affect the color photographic material too much, and to prevent contamination of iron salts and thiosulfates due to emulsion eluates and back contamination, especially halogens. It is necessary to prevent or control the accumulation of alkali salts. Conventionally, it has been impossible to further reduce the replenishment level because almost no solution has been found to the above problem, but core-shell type halogen containing 3 mol% or more of silver iodide has been used as a silver halide color photographic light-sensitive material. At least one emulsion layer containing silver oxide grains and general formula [] ~
The composition contains a cyan coupler represented by
By setting the bromide concentration to 3.0×10 ^-3 mol/or less, it is possible to maintain the bromide concentration without causing any problems and to make it possible to replenish as low as 9 ml/100 cm ^{2 or} less. To further explain the present invention in detail, the replenishment amount of the color development replenisher of the present invention is 9 ml or less,
When considering the amount of evaporation, it is preferably replenished at 1 ml or more and 9 ml or less, particularly preferably 3 ml or more and 7.5 ml or less. The color developer replenisher can be replenished by any known method, but it is preferable to use a metering pump such as a bellows pump. The bromide content in the color developer replenisher of the present invention is 3.0×10 ^-3 mol/or less, but it is necessary to adjust the bromide concentration depending on the degree of low replenishment, but generally the amount of replenishment will decrease. Accordingly, it is necessary to reduce the bromide concentration in the color developer replenisher. The bromide concentration in the color developer replenisher is adjusted to keep the bromide concentration in the color developer (mainly determined by elution and evaporation from the emulsion) constant, but the bromide concentration is 3.0×10 ^-3 mol/or less. In addition, if the amount of color developing replenisher is 9 ml/100 cm ² or less, it is possible to stabilize the processing without significantly affecting photographic properties. Specific examples of bromide include alkali metal salts such as sodium bromide, potassium bromide, and ammonium bromide, and hydrobromic acid. The cyan dye-forming coupler according to the present invention can be represented by the above general formulas [] to [], and the general formula [] will be further explained. In the present invention, R ₁ , R of the general formula []
The linear or branched alkyl group having 2 to 12 carbon atoms represented by is, for example, an ethyl group, a propyl group, or a butyl group. In the general formula [], the ballast group represented by R ₂ is of a size that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. It is an organic group that has a shape. Typical ballast groups include alkyl groups or aryl groups having 8 to 32 carbon atoms in total, preferably 13 to 28 carbon atoms in total. Substituents for these alkyl groups and aryl groups include, for example, alkyl groups, aryl groups, alkoxy groups, allyloxy groups, carboxyl groups, acyl groups, ester groups, hydroxy groups, cyano groups, nitro groups, carbamoyl groups, and carbonamide groups. , an alkylthio group, an arylthio group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, and a halogen. Examples of substituents for the alkyl group include the substituents listed for the above-mentioned arul group except for the alkyl group. Preferred ballast groups are those represented by the following general formula. R ₇ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. Substituents include alkyl groups, hydroxy groups, halogen atoms,
Examples include alkylsulfonamide groups, and the most preferred are branched alkyl groups such as t-butyl. The coupling-off group defined by X in the general formula [] determines the number of equivalents of the coupler and influences the reactivity of the coupling, as is well known to those skilled in the art. As a representative example,
Halogens represented by chlorine and fluorine, aryloxy groups, substituted or unsubstituted alkoxy groups, acyloxy groups, sulfonamide groups, arylthio groups,
Examples include a heteroylthio group, a heteroyloxy group, a sulfonyloxy group, a carbamoyloxy group, and the like. As a more specific example,
No. 10135, No. 50-120334, No. 50-130441, No. 10135, No. 50-120334, No. 50-130441, No.
No. 54-48237, No. 51-146828, No. 54-14736,
No. 47-37425, No. 50-123341, No. 58-95346
No., Special Publication No. 48-36894, U.S. Patent No. 3476563,
Examples thereof include groups described in the respective publications of No. 3737316 and No. 3227551. Examples of cyan coupler compounds represented by the general formula [] will be listed below, but the invention is not limited thereto.

【table】

【table】

【table】

【table】

[Table] The synthesis methods of exemplary compounds of the present invention are shown below.
Other exemplified compounds can also be synthesized by similar methods. Synthesis example of exemplified compound C-5 [(1)-a] 2-nitro-4,6-dichloro-5
-Synthesis of ethylphenol 2-nitro-5-ethylphenol 33g, iodine
0.6 g and 1.5 g of ferric chloride are dissolved in 150 ml of glacial acetic acid. 75 ml of sulfuryl chloride was added dropwise to this at 40°C over 3 hours. The precipitate formed during the dropwise addition is reacted and dissolved by heating and refluxing after the completion of the dropwise addition of sulfuryl chloride. Heating to reflux takes about 2 hours. The reaction solution is poured into water and the crystals produced are purified by recrystallization using methanol. [(1)-a] was confirmed by nuclear magnetic resonance spectroscopy and elemental analysis. [(1)-b] 2-nitro-4,6-dichloro-5
- Synthesis of ethylphenol 21.2 g of the compound [(1)-a] was dissolved in 300 ml of alcohol, a desolating amount of Raney nickel was added thereto, and hydrogen was passed through the solution at normal pressure until hydrogen absorption ceased. After the reaction, Raney nickel was removed and alcohol was distilled off under reduced pressure. The residue [(1)-b] was subjected to the next acylation without purification. [(1)-c] 2[(2,4-di-tert-acylphenoxy)acetamide]-4,6-dichloro-
Synthesis of 5-ethylphenol 18.5g of the crude amino compound obtained in [(1)-b]
It is dissolved in a mixture of 500 ml of glacial acetic acid and 16.7 g of sodium acetate, and an acetic acid solution prepared by dissolving 28.0 g of 2,4-di-tert-aminophenoxyacetic acid chloride in 50 ml of acetic acid is added dropwise thereto at room temperature. Drip in 30 minutes,
After stirring for an additional 30 minutes, the reaction solution was poured into ice water. The generated precipitate is collected by filtration, dried, and then recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectroscopy.

[Table] Next, the cyan couplers represented by the general formulas [] and [] used in the present invention will be explained. In the general formulas [] and [], Y
is −COR ₄ ,

[Formula] −SO ₂ R ₄ ,

【formula】

[Formula] This is a group represented by -CONHCOR ₄ or -CONHSO ₂ R ₄ . Here, R ₄ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (for example, an allyl group, heptadecenyl group, etc.), cycloalkyl group, preferably a 5- to 7-membered ring (e.g. cyclohexyl group), aryl group (e.g. phenyl group,
tolyl group, naphthyl group, etc.), heterocyclic group, preferably one nitrogen atom, oxygen atom or sulfur atom
Represents a 5- to 6-membered heterocyclic group containing ~4 members (eg, furyl group, thienyl group, benzothiazolyl group, etc.). R ₅ represents a hydrogen atom or a group represented by R ₄ . R ₄ and R ₅ may be combined with each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. Note that any substituent can be introduced into R ₄ and R ₅ , for example, an alkyl group having 1 to 10 carbon atoms (for example, ethyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.) , aryl group (e.g. phenyl, naphthyl, etc.), halogen atom (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide group (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group (e.g. methylsulfamoyl,
phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl, carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl) etc.), acyl groups (eg, acetyl, benzoyl, etc.), heterocyclic groups (eg, pyridyl, pyrazolyl, etc.), alkoxy groups, aryloxy groups, acyloxy groups, and the like. In the general formulas [] and [], R ₃ represents a ballast group necessary to impart diffusion resistance to the cyan coupler represented by the general formulas [] and [] and the cyan dye formed from the cyan coupler. . Preferably an alkyl group having 4 to 30 carbon atoms,
It is an aryl group or a heterocyclic group. For example, straight-chain or branched alkyl groups (e.g. t-butyl, n
-octyl, t-octyl, n-dodecyl, etc.),
Examples thereof include an alkenyl group, a cycloalkyl group, a 5-membered or 6-membered heterocyclic group, and the like. In the general formulas [] and [], Z represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidation product of a color developing agent. For example, halogen atoms (e.g., chlorine, bromine, fluorine, etc.) substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio group, sulfonamide group, etc., and further specific examples include U.S. Patent No. 3,741,563, JP-A-47-37425, JP-A-48-36894, JP-A-50-10135, JP-A-50-
No. 117422, No. 50-130441, No. 51-108841, No. 117422, No. 50-130441, No. 51-108841, No.
No. 50-120343, No. 52-18315, No. 53-105226,
No. 54-14736, No. 54-48237, No. 55-32071,
No. 55-65957, No. 56-1938, No. 56-12643, No. 56-27147, No. 59-146050, No. 59-
No. 166956, No. 60-24547, No. 60-35731, No. 60
-37557. Examples include those described in each publication. In the present invention, among the cyan couplers represented by the general formula [] or [], cyan couplers represented by the following general formula [], general formula [], or general formula [] are more preferred. General formula [] General formula [] General formula [] In the general formula [], R ₇ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, examples of the substituent include _-SO2R9 , halogen atom (e.g. fluorine, bromine, chlorine, _etc. ), _-CF3 , _-NO2 , -CN, -
COR ₉ , −COOR ₉ , −SO ₂ OR ₉ ,

【formula】

[Formula] −OR ₁₀ , −OCOR ₉ ,

【formula】

[expression] and

At least one substituent selected from the formula is included. Here, R ₉ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl,
tert-butyl, dodecyl, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (e.g. allyl group, heptadecenyl group), cycloalkyl groups, preferably 5- to 7-membered ring groups (e.g. cyclohexyl group, etc.) ), aryl groups (e.g. phenyl group,
tolyl group, naphthyl group, etc.), and R ₁₀ is a hydrogen atom or a group represented by R ₉ above. A suitable compound of the phenolic cyan coupler represented by the general formula [] is one in which R ₇ is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -SO ₂ R ₁₁ (R ₁₁ (alkyl group), halogen atom, and trifluoromethyl. In the general formulas [] and [], R ₈ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl, tert-butyl, dodecyl, etc.), or an alkenyl group, preferably having 2 to 20 carbon atoms.
alkenyl groups (e.g. allyl, oleyl, etc.),
A cycloalkyl group, preferably a 5- to 7-membered ring group (e.g., cyclohexyl, etc.), an aryl group (e.g., phenyl, tolyl, naphthyl, etc.), a heterocyclic group (having 1 to 4 nitrogen, oxygen, or sulfur atoms) A 5- to 6-membered heterocycle containing 5- to 6-membered heterocycles is preferable, and examples thereof include a furyl group, a thienyl group, and a benzothiazolyl group. The above R ₉ , R ₁₀ and general formulas [] and []
An arbitrary substituent can be further introduced into R ₈ , specifically a substituent such as the one that can be introduced into R ₄ or R ₅ in the general formulas [] and []. As the substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable. In the general formulas [], [] and [], Z and R ₈ have the same meanings as in the general formulas [] and [], respectively. A preferred example of the ballast group represented by R ₈ is a group represented by the following general formula []. General formula [] In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, k represents an integer of 0 to 4, l represents 0 or 1, and when k is 2 or more, two or more R _13s may be the same. May be different, R ₁₂
represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, and _R13 represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), or an alkyl group. , preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, t-butyl, t-pentyl, t-
- octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl group (e.g. phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched carbon number 1 to 20 alkoxy groups (e.g., methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc. groups),
Aryloxy group (e.g. phenoxy group), hydroxy, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably having 1 to 20 carbon atoms. Straight chain or branched alkyloxycarbonyl group, aryl, oxycarbonyl group, preferably phenoxycarbonyl, alkylthio group, preferably 1 to 20 carbon atoms, acyl group, preferably straight chain or branched alkyl group having 1 to 20 carbon atoms Carbonyl group, preferably acylamino group having 1 to 20 carbon atoms, preferably linear or branched alkylcarboxamide having 1 to 20 carbon atoms, benzenecarboxamide, sulfonamide group, preferably having 1 to 20 carbon atoms
20 straight chain or branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group, preferably straight chain or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, sulfamoyl group, preferably carbon It represents a linear or branched alkylaminosulfonyl group or a phenylaminosulfonyl group having numbers 1 to 20. Specific examples of cyan couplers represented by the general formula [] or [] used in the present invention are shown below.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] These cyan couplers can be synthesized by known methods, such as U.S. Pat. No. 2,772,162,
Same No. 3758308, No. 3880661, No. 4124396, Same No.
No. 3222176, British Patent No. 975773, British Patent No. 8011693, British Patent No.
No. 8011694, JP-A-47-21139, JP-A No. 50-112038
No. 55-163537, No. 56-29235, No. 55-
No. 99341, No. 56-116030, No. 52-69329, No. 56
-55945, 56-80045, 50-134644, as well as British Patent No. 1011940, US Patent No. 3446622,
No. 3996253, JP-A-56-65134, JP-A No. 57-204543
No. 57-204544, No. 57-204545, Patent Application No. 1983
−131312, No. 56-131313, No. 56-131314,
No. 56-131309, No. 56-131311, No. 57-149791
No. 56-130459, JP-A-59-146050, No. 59
−166956, No. 60-24547, No. 60-35731, No.
It can be synthesized by the synthesis method described in No. 60-37557, No. 60-55340, etc. In the present invention, the general formula [], [] or []
The cyan coupler represented by can be used in combination with a conventionally known cyan coupler within the scope of the purpose of the present invention. Further, the general formula [], [] or [] can also be used in combination. When the cyan coupler according to the present invention represented by the general formulas [] to [] is contained in the silver halide emulsion layer, it is usually about
It is used in a range of 0.005 to 2 mol, preferably 0.01 to 1 mol. The aromatic primary amine color developing agents used in the color developer and color developer replenisher in the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 per 1 color developer.
g to about 30 g, preferably about 1 g to about 1.5 g per color developer. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. A particularly useful primary aromatic amino color developer is an N,N'-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, a particularly useful compound is N,N'-diethyl-
p-phenylenediamine hydrochloride, N-methyl-p
-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methane Sulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-( 2-methoxyethyl)-N-ethyl-3-methylaniline-p
-Toluenesulfonate and the like can be mentioned. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, 1-phenyl-3-pyrazolidone, metol and hydroquinone black and white developing agents, water softeners In the present invention, the following general formula [
], [], and [] are preferably used to further exhibit the effects of the present invention. General formula [] A-COOM General formula [] B-PO ₃ M ₂ General formula []

[Formula] In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance or an organic substance. D is an aromatic ring which may have a substituent,
It represents a group of nonmetallic atoms necessary to form a heterocycle, and M represents a hydrogen atom or an alkali metal atom. The general formula [ ], [ added to the present invention
Among the chelating agents represented by ] or [ ], preferred chelating agents for the present invention are compounds represented by any of the following general formulas [] to []. General formula [] MmPmO ₃ m General formula [] Mn+ ₂ PnO ₃ n+1 General formula (] A ₁ −R ₁ −Z−R ₂ −COOH General formula [] In the formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R ₇ -OR ₇
−, −R ₇ −OR ₇ OR ₇ −, −R ₇ ZR ₇ −, where Z is >
N- _R7 - _A6 ,>N- _A6 , _R1 to _R7 represent substituted or unsubstituted alkylene groups, _A1 to _A6 are hydrogen,
-OH, -COOM, _-PO3M2 , M is _hydrogen ,
represents an alkali metal atom, m is an integer of 3 to 6, n
represents an integer from 2 to 20. General formula [] R ₈ N (CH ₂ PO ₃ M ₂ ) ₂ In the formula, R ₈ is a lower alkyl group, an aryl group, an aralkyl group, a nitrogen-containing 6-membered ring group [as a substituent -
OH, -OR, -COOM], M is a hydrogen atom,
Represents an alkali metal atom. General formula [] In the formula, R ₉ to _{R 11} are hydrogen atoms, -OH, lower alkyl (unsubstituted or as a substituent -OH, -COOM,
-PO ₃ M ₂ ), B ₁ to B ₃ are hydrogen atoms, -OH,
-COOM, _-PO3M2 , _{-Nj2 ,} J represents a hydrogen atom, lower alkyl, _{C2H4OH , -PO3M2 ,}
M represents a hydrogen atom or an alkali metal, n and m are 0
Or represents 1. General formula [] In the formula, R ₁₂ and R ₁₃ are hydrogen atoms, alkali metals,
Represents a _C1 to _C12 alkyl group, alkenyl group, or cyclic alkyl group. General formula [] In the formula, _R14 is a _C1-12 alkyl group, a _C1-12 alkoxy group, a _C1-12 monoalkylamino group, a _C2-12
represents a dialkylamino group, an amino group, a C _1-24 aryloxy group, a C _6-24 arylamino group, and an amyloxy group, and Q ₁ to _{Q 3} are -OH, a C _1-24 alkoxy group, or an aralkyloxy group. , aryloxy group, _-OM3 (M is a cation), amino group, morpholino group, cyclic amino group, alkylamino group, dialkylamino group, arylamino group, and alkyloxy group. General formula [] General formula [] In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -
_OR19 , _-COOR20 , -CON< ^R21 represents _R22 or a substituted or unsubstituted phenyl group. R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom or a carbon atom number of 1 to 1
Represents 18 alkyl groups. General formula [] In the formula, R ₂₃ and R ₂₄ are hydrogen atoms, halogen atoms,
Represents a sulfonic acid group. General formula [] In the formula, R ₂₉ and R ₃₀ are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH ₂ COOH, -CH ₂ PO ₃
H ₂ or a salt thereof, X ₁ represents a hydroxyl group or a salt thereof, W ₁ , Z ₁ and Y ₁ are a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, respectively. represents a group or a salt thereof, an alkoxy salt, or an alkyl group. Also
m ₁ is 0 or 1, n ₁ is an integer of 1 to 4, I ₁ is 1 or 2, p ₁ is an integer of 0 to 3, and q ₁ is an integer of 0 to 2. Specific examples of the chelating agents represented by the general formulas [] to [] include the following.

【table】 /

(12) N−CH ₂ COOH

\

_CH2 COOH





(13)







_CH3



HOOCCH ₂ ｜ CH ₂ COOH

(14) \ /

N-CH ₂ CH-N

／ ＼

HOOCCH ₂ CH ₂ COOH

(15) (HOC ₂ H ₄ ) ₂ NCH ₂ COOH



HOOCCH ₂ CH ₂ COOH

\ /

(16) NC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ N

／ ＼

HOOCCH ₂ CH ₂ COOH

HOOCCH ₂ CH ₂ COOH

\ /

(17) NC ₂ H ₄ OC ₂ H ₄ N

／ ＼

HOOCCH ₂ CH ₂ COOH

HOOCCH ₂ CH ₂ CH ₂ CH ₂ COOH

\ /

(18) NC ₂ H ₄ N

／ ＼

HOOCCH ₂ CH ₂ CH ₂ CH ₂ COOH

[Table] ｜

H



PO ₃ H ₂



｜

HC−COOH



(27) |

HC−COOH



｜

PO ₃ H <sub>2

CH2</sub> COOH



｜

CH－COOH



(28) |

CH－COOH

｜

PO ₃ H ₂

[Table] ｜

PO ₃ H <sub>2



CH2</sub> COOH



｜

_CH2



(35) |

H ₃ C−C−COOH



｜

PO ₃ H ₂







(36)

[Table] ｜

PO ₃ H <sub>2



CH2</sub> COOH



｜

CHCOOH



(43) |

C ₄ H ₉ -C-COOH



｜

PO ₃ H ₂



CH ₂ PO ₃ H ₂

/

(44) N−CH ₂ PO ₃ H ₂

\

CH ₂ PO ₃ H <sub>2

CH2</sub> COOH

/

(45) N−CH ₂ PO ₃ H ₂

\

CH ₂ PO ₃ H ₂

[Table] ｜

PO ₃ H <sub>2



CH3</sub>



｜

(52′) H ₂ O ₃ P−C−PO ₃ H ₂



｜

OH



CH ₂ PO ₃ H ₂



｜

(53) H ₂ O ₃ P−C−PO ₃ H ₂



｜

OH

【table】 ‖

(62) HOCH ₂ CH−O−P−(ONa) ₂


｜

_CH2OH



O



‖

(63) HOCH ₂ C−CH ₂ −O−P−(OH) ₂


‖

O

【table】

【table】 ‖ ‖

(83) HO−P−CH−P−OH



｜｜ ｜

OH OH OH



OO



‖ ‖

(84) CH ₃ O−P−O−P−OCH ₃


｜ ｜

OCH ₃ OCH ₃



OO



‖ ‖

(85) C ₆ H ₅ NH-P-O-P-NHC ₆ H ₅


｜ ｜

OH OH



OO



(86) ‖ ‖

(C ₆ H ₅ COO) ₂ -P-O-P-(OCOC ₆ H ₅ ) ₂

【table】

【table】

【table】

[Table] In the present invention, general formulas [], [], [
], [], [], [], [] and [] are effective to use. The above general formulas [] to [] used in the present invention
] The chelating agent represented by any of the above can be added in an amount of 1 x 10 ^-4 mol to 1 mol per color developer, preferably 2 x 10 ^-4 to 1 x 10 ^{-1 mol.}
It can be added in a molar range, more preferably in a range of 5 x 10 ^-4 to 5 x 10 ^-2 molar. The PH value of this color developer is usually 7 or more,
Most commonly from about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching solution or bleach-fixing solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced during development and converts it into silver halide. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is made of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid, and iron,
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etheraminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)N,N',N'-triacetic acid sodium salt [18] Propylenediaminetetra Sodium acetate [19] Sodium nitrilotriacetate [20] Sodium cyclohexanediaminetetraacetate The bleaching solution used contains the metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. can. As additives, in particular alkali halides or ammonium halides,
Rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to contain metal salts and chelating agents. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixer and bleach-fixer contain ammonium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fix replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired, or as appropriate. An oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. In the process of the present invention, silver may be recovered by known methods from processing solutions containing soluble silver complexes such as washing or washing substitute stabilizing solutions, fixing solutions, bleach-fixing solutions, and the like. For example, electrolysis method (French patent
2299667), precipitation method (JP-A-52-73037, German Patent No. 2331220), ion exchange method (JP-A-51-
17114, German Patent No. 2548237) and metal substitution method (British Patent No. 1353805) can be effectively used. In the processing method of the present invention, after bleaching and fixing (or bleach-fixing) after color development processing, water washing may not be performed and a water washing alternative treatment may be performed, or water washing processing may be performed and then a water washing alternative stabilization treatment may be performed. In addition to the above steps, known auxiliary steps may be added as necessary, such as hardening, neutralization, black-and-white phenomenon, reversal, and washing with a small amount of water. A typical example of a preferred treatment method includes the following steps. (1) Color development → bleach-fixing → washing with water (2) Color development → bleach-fixing → washing with a small amount of water → washing with water (3) Color development → bleach-fixing → washing with water → alternative treatment with water (4) Color development → bleach-fixing → alternative treatment with water ( 5) Color development → bleach-fixing → water-washing alternative treatment → stabilization (6) Color development → water-washing (or water-washing alternative treatment) → bleach-fixing → water-washing (or water-washing alternative treatment) (7) Color development → stop → bleach-fixing → washing with water ( (8) Color development → bleaching → washing → fixing → washing → stabilization (9) Color development → bleaching → fixing → washing → stabilization (10) Color development → bleaching → fixing → alternative washing → stabilization (11) ) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stabilizing (12) Color development → washing with a small amount of water → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stabilizing (13) Color development → stop → bleaching → a small amount Washing → fixing → washing with a small amount of water → washing with water → stabilization (14) Black and white phenomenon → washing with water → (or alternative treatment with water) → reversal → color development → bleaching → fixing → washing with water (or omitted)
→ Stable (15) Predural mater → Neutralization → Black and white phenomenon → Stop → Color development →
Bleaching → fixing → washing with water (also omitted) → stabilization The core shell emulsion used in the present invention is described in detail in JP-A-57-154232. In the present invention, it is sufficient that the core shell emulsion contains 3 mol% or more of silver iodide, but a preferred color photographic light-sensitive material is such that the silver halide composition of the core contains no more than 3 mol% of silver iodide.
The silver halide contains 0.1 to 20 mol%, preferably 0.5 to 10 mol%, and the shell is composed of silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or a mixture thereof. Particularly preferably, the shell is a silver halide emulsion comprising silver bromide or silver iodobromide. Further, in the present invention, preferable effects can be obtained by forming the core as a monodisperse silver halide grain and setting the thickness of the shell to 0.01 to 0.5 μm. The silver halide color photographic light-sensitive material of the present invention is characterized by comprising silver halide grains containing 3 mol% of silver iodide, in particular, using silver halide grains containing silver iodide as a core, silver bromide, chloride Silver halide grains containing silver iodide are produced by hiding the core of silver halide grains made of silver, silver chlorobromide, silver iodobromide, or a mixture thereof using a shell having the specific thickness. The purpose of this method is to improve processing fluctuations, particularly processing stains, while making use of the particle's ability to increase sensitivity and concealing disadvantageous characteristics of the particle. More specifically, the core is made of silver halide containing silver iodide, and the thickness range necessary to effectively exhibit only the desirable properties of this core and to shield undesirable behavior is strictly regulated. The goal is to give Ciel to the core. The method of coating the core with a shell that has the necessary minimum absolute thickness to effectively utilize its properties has changed the purpose, and therefore the materials of the core and shell have been changed, for example, to improve processing variations, especially It is extremely advantageous in that it can be used for purposes such as improving the storage stability of treated stains or improving the adsorption rate of sensitizing dyes. The silver iodide content in the silver halide grains (cores) serving as the matrix ranges from 0.1 to 20 mol% solid solution to mixed crystal, but is preferably 0.5 to 10 mol%. The silver iodide contained within the core may be distributed unevenly or uniformly, but uniform distribution is preferred. The silver halide emulsion of the present invention having silver halide grains having a shell of a specific thickness can be produced by coating these shells with silver halide grains contained in a monodisperse emulsion as a core. can. In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 10 mol % or less. To make the core a monodisperse silver halide grain,
Particles of desired size can be obtained by the double jet method while keeping pAg constant. In addition, the production of highly monodisperse silver halide emulsions was developed by JP-A-Sho.
The method described in No. 54-48521 can be applied. A preferred embodiment of this method is a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. Therefore, it is to manufacture. At this time, the time function of addition rate, PH,
By appropriately selecting pAg, temperature, etc., a highly monodisperse silver halide emulsion can be obtained. Monodisperse core shell emulsions are preferably used in the present invention, but monodisperse silver halide grains mean that the total silver halide weight is within a grain size range of ±20% around the average grain size. Refers to 60% or more of the weight of silver halide grains. The average particle size is the product of the frequency ni of particles with particle size ri and ri ³ .
Particle size ri when ni×ri ³ is the maximum (3 significant figures)
is defined as The grain size here means the diameter in the case of spherical silver halide grains, and in the case of grains having shapes other than spherical, the diameter when the projected image is converted into a circular image of the same area. The particle diameter can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or the area of the projected image on the print. The number of particles measured is 1000 indiscriminately.
The number shall be at least 1. In the present invention, the use of a monodisperse silver halide emulsion has effects such as smaller density changes in high density areas compared to polydisperse emulsions, and is a preferred embodiment for carrying out the present invention. Next, the thickness of the shell relative to the core must be such that it does not hide the desirable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core. That is, the thickness is limited to a narrow range defined by such upper and lower limits. Such a shell can be formed by depositing a soluble silver halide solution and a soluble silver solution onto a monodisperse core by a double jet process. For example, using monodisperse silver halide grains with an average grain size of 1 μm containing 3 mol% silver iodide in the core,
According to experiments using mol% silver iodobromide as a shell and varying the coating thickness, for example, when a shell with a thickness of 0.85 μm was made, the monodisperse silver halide grains produced by this method had a low covering power and were very practical. I couldn't stand it. This was treated with a physically developing processing solution containing a solvent that dissolves silver halide, and when observed under a scanning electron microscope, it was found that no filaments of developed silver had come out. This suggests that the optical density and even the covering power are reduced. Therefore, considering the filament form of developed silver, we thinned the thickness of the silver bromide shell on the surface while changing the average grain size of the core.As a result, the thickness of the shell was determined by the absolute thickness regardless of the average grain size of the core. It has been found that a large number of well-developed silver filaments are formed at a diameter of 0.5 μm or less (preferably 0.2 μm) or less, resulting in sufficient optical density, and that the quality of the core for high sensitivity is not impaired. On the other hand, if the thickness of the shell is too thin, parts of the core material containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the chemical sensitization effect, rapid development, fixing properties, etc. will be lost. be exposed. Preferably, the thickness limit is 0.01 μm. Preferred shell thicknesses are between 0.01 and 0.06 μm, with the most preferred thickness being 0.03 μm or less, as determined by the highly monodisperse core. The above-mentioned development silver filaments are sufficiently generated to improve the optical density, the high-sensitivity properties of the core are utilized to produce a sensitizing effect, and the rapid development and fixing properties are achieved due to the high This is due to the shell whose thickness is regulated as described above by the dispersible core and the synergistic effect between the silver halide compositions of the core and shell, so if the thickness regulation of the shell can be satisfied, the shell can be As the constituent silver halide, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among these, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of compatibility with the core, processing stability, processing stain, and storage stability. In the photosensitive silver halide emulsion used in the present invention, when silver halide precipitation of the core and shell is formed,
Doping may be performed with various metal salts or metal complex salts during or after grain growth. For example, metal salts or complex salts such as platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, and combinations thereof can be used. Further, excess halogen compounds generated during the preparation of the emulsion of the present invention, and by-product or unnecessary salts and compounds such as nitrates and ammonium may be removed. As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are commonly used in general emulsions, can be used as appropriate. Furthermore, the emulsion of the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the method for optically sensitizing the emulsion of the present invention. ) can be optically sensitized.
These technologies are described in U.S. Patent No. 2,688,545;
No. 2912329, No. 3397060, No. 3615635, No.
3628964, British Patent No. 1195302, British Patent No. 1242588,
No. 1293862, OLS No. 2030326,
It is described in Japanese Patent Publication No. 2121780, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. The silver halide emulsion used in the present invention further includes a silver halide emulsion in which the core grains are monodisperse silver halide grains, in which the core grains are formed. By coating the shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained.
The particle size distribution can be used as it is, or two or more types of monodisperse emulsions with different average particle sizes can be blended at any time after grain formation to obtain a predetermined gradation. You can also serve it. The silver halide emulsion used in the present invention has a ratio equal to or higher than that of an emulsion obtained by coating a monodisperse core with a shell, to all silver halide grains contained in the emulsion. Those containing silver halide grains are preferred. However, silver halide grains other than those according to the invention may also be included within a range that does not impede the effects of the invention. The silver halide other than those of the present invention may be of the core-shell type or may be of a type other than the core-shell type, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, it is preferable that at least 65% by weight of the silver halide grains contained in the emulsion be the silver halide grains of the present invention, and almost all of them are silver halide grains of the present invention. It is desirable that Other photographic couplers used in the present invention include, as photographic magenta couplers, compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone. As pyrazolone magenta couplers, US Patent Nos. 2600788, 3062653, and
No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558318, No. 3684514, 3888680
No. 49-29639, No. 49-111631, No. 49
−129538, No. 50-13041, Special Publication No. 53-47167
Examples of pyrazolotriazole magenta couplers include couplers described in U.S. Patent No. 1247493 and Belgian Patent No. 792525, which have diffusion resistance. As the colored magenta coupler, a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is generally used.
For example, US Patent No. 2801171, US Patent No. 2983608, US Patent No.
Examples include compounds described in JP-A-49-123625 and JP-A-49-31448. Additionally, U.S. Patent No.
Colored magenta couplers of the type described in No. 3419391, in which the dye flows out into the processing solution by reaction with the oxidized form of a developing agent, can also be used. As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Furthermore, the carbon atom at the coupling position is substituted with a substituent that can leave during the coupling reaction 2
Equivalent type yellow couplers have also been used advantageously. Examples of these can be found in U.S. Patent No. 2,875,057;
No. 3265506, No. 3664841, No. 3408194, No.
No. 3277155, No. 3447928, No. 3415652, Tokko Akira
No. 49-13576, JP-A No. 48-29432, JP-A No. 48-68834
No. 49-10736, No. 49-122335, No. 50-
It is described in No. 28834, No. 50-132926, etc. together with the synthesis method. The amount of the diffusion-resistant coupler used in the present invention is generally 0.05 to 2.0 mol per mol of silver in the light-sensitive silver halide emulsion layer. In the present invention, in addition to the above-mentioned diffusion-resistant couplers,
DIR compounds are preferably used. Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as U.S. Pat. No. 3,297,445, U.S. Pat. No. 15271,
Examples include those described in No. 53-9116, No. 59-123838, and No. 59-127038. The DIR compound used in the present invention is a compound that can react with an oxidized form of a color developing agent to release a development inhibitor. A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when released from the active site is introduced into the active site of the coupler. , U.S. Patent No. 3227554, U.S. Patent No. 4095984
No. 4149886, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. In addition, the present invention utilizes US Patent No. 3,652,345,
No. 3928041, No. 3958993, No. 3961959, No.
No. 4052213, Japanese Patent Publication No. 53-110529, No. 54-13333
It also includes compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 55-161237. Furthermore, JP-A-54-145135, JP-A No. 56-
When reacted with oxidized color developing agents such as those described in No. 114946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, the present invention also includes so-called timing DIR compounds, which are compounds that release a development inhibitor through desorption reaction. In addition, as described in JP-A-58-160954 and JP-A-58-162949, the above timing group is present in the coupler core that produces a completely diffusible dye when it reacts with an oxidized color developing agent. It also includes bound timing DIR compounds. The amount of DIR compound contained in the photosensitive material is silver 1
The range of 1×10 ⁻⁴ mol to 10×10 ⁻¹ mol based on the mole is preferably used. The silver halide emulsion layer of the present invention can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based,
Hardeners such as arpodiimide, maleimide, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Chroman, Claman, bisphenol, and phosphite ester hardeners; Image stabilizer;
Lubricants include waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups.
Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion and other hydrophilic colloid layer coating solutions include:
Gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Any synthesis of copolymers, hydrophilic polymers, etc. are included. Examples of the support for the silver halide color photographic material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film,
Examples include polystyrene film, and furthermore, ordinary reflective supports (for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflective material) may also be used. It is appropriately selected depending on the intended use of the photosensitive material. Coating of the silver halide emulsion layer and other photographic constituent layers used in the present invention includes coating, air doctor coating, curtain coating,
Various coating methods such as hopper coating can be used. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,893 can also be used. The present invention is applicable to silver halide color photographic materials containing polymer couplers, such as color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper. be able to. [Example] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example (1) A multilayer color photosensitive material was prepared on a cellulose triacetate film support, consisting of each layer having the composition shown below. 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (gelatin layer) 3rd layer: 1st red-sensitive emulsion layer Silver halide (listed in Table (1))...Silver coating amount 2.0
g/m ² Sensitizing dye (below)...for 1 mole of silver
6×10 ^-5 mol Sensitizing dye (below)...for 1 mol of silver
1.5×10 ^-5 Morcian coupler (listed in Table (2))...0.044 mol per mol of silver 4th layer: Second red-sensitive emulsion layer Silver halide (listed in Table (1))...Silver coating amount 2.0
g/m ² sensitizing dye...for 1 mole of silver
3.5×10 ^-5 mol Sensitizing dye...for 1 mol of silver
1.0×10 ^-5 mol Cyan coupler (listed in Table (2))...0.020 mol per mol of silver 5th layer: Intermediate layer Same as 2nd layer 6th layer: 1st green-sensitive emulsion layer Silver iodobromide (Silver iodide: 4.0 mol% Average grain size
0.34μm spherical monodisperse emulsion)...Silver coating amount
1.8g/ ^m2 Sensitizing dye (below)...for 1 mole of silver
3.3×10 ^-5 mol Sensitizing dye (below)...for 1 mol of silver
1.1×10 ^-5 mol Magenta coupler (below)...12 g per 1 mol of silver 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide (Silver iodide: 4.5 mol% Average grain size 1.0 μm
spherical monodispersed emulsion)...Silver coating amount 1.8g/ ^m2 Sensitizing dye...per 1 mole of silver
2.65×10 ^-5 mol Sensitizing dye...for 1 mol of silver
0.89×10 ^-5 mol Magenta coupler...0.02 mol per mol of silver 8th layer: Yellow filter layer Gelatin layer containing yellow colloidal silver in gelatin aqueous solution 9th layer: 1st blue-sensitive emulsion layer Silver iodobromide (Silver iodide: 6.0 mol% Average grain size 0.4 μm
Monodisperse spherical particles)...Silver coating amount 1.5 g/m ² Yellow coupler (below)...0.25 mol per 1 mol of silver 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (Silver iodide: 6 mol% Average particle size
0.90μm monodisperse spherical particles)...Silver coating amount
1.21g/m ² Yellow coupler...0.06 mol per mol of silver 11th layer: 1st protective layer Silver iodobromide (Silver iodide: 1 mol% Average grain size
Monodispersed spherical particles of 0.07 μm)... Silver coating amount 0.5 g Gelatin layer containing an emulsified dispersion of ultraviolet absorber 12th layer: 2nd protective layer Trimethyl methacrylate particles (diameter 1.5 μm)
Gelatin layer containing In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer. Sensitizing dye: anhydro-5,5'-dichloro-
3,3'-(γ-sulfopropyl)-9-ethyl-
Thiacarbocyanine hydroxide pyridium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4',5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetradichloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]}ethylimidazolocarbocyanine hydroxide sodium salt

[Table] Magenta coupler yellow coupler After photographing the photosensitive material using a Konica FS-1 camera (manufactured by Konishiroku Photo Industry Co., Ltd.), white stepwise exposure was applied using a KS-7 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). , and was continuously processed using an automatic processor according to the following steps. The automatic developing machine is a hanging type automatic film developing machine type H4- manufactured by Noritsu Koki Co., Ltd.
A modified 220W-2 was used. Processing process (38℃) Number of tanks Processing time Color development 1 tank 3 minutes 15 seconds Bleaching 2 tanks 6 minutes 30 seconds Washing with a small amount of water 1 tank 3 minutes 15 seconds Fixing 1 tank 6 minutes 30 seconds Water washing 2 tanks 4 minutes 20 seconds Stability 1 tank 2 minutes 10 seconds The composition of the color developer used is as follows. Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 0.1g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20
Adjust the pH to 10.06 using % sulfuric acid. The composition of the color development replenishment solution used is as follows. Potassium carbonate 40g Sodium hydrogen carbonate 3g Potassium sulfite 7g Sodium bromide 2.0×10 ^-3 mol Hydroxylamine sulfate 3.1g 4-amino-3-methyl-4-ethyl-N-
(β-hydroxylethyl)aniline sulfate
6.0g Potassium hydroxide 2g Add water to make 1, potassium hydroxide or 20
Adjust the pH to 10.12 using % sulfuric acid. The composition of the bleaching solution used is as follows. Iron amminium ethylenediaminetetraacetate
100g Disodium ethylenediaminetetraacetate 10g Amminium bromide 150g Glacial acetic acid 10ml Add water to make 1, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid. The composition of the bleach replenishment solution used is as follows. Iron ammonium ethylenediaminetetraacetate
120g Disodium ethylenediaminetetraacetate 12g Ammonium bromide 178g Glacial acetic acid 21ml Add water to make 1, and adjust the pH to 5.6 using aqueous ammonia or glacial acetic acid. The composition of the fixer used is as follows. Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate
0.5g Sodium carbonate 10g Add water to make 1. The composition of the fixing replenisher used is as follows. Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate
0.8g Sodium carbonate 14g Add water to make 1. The composition of the stabilizing solution used is as follows. Formalin (37% aqueous solution) 2ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5ml Add water to make 1. The composition of the stable replenishment solution used is as follows. Formalin (37% aqueous solution) 3 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7 ml Add water to make 1. Color development replenishment solution is color negative film 100
8.0 ml per cm ² of color developing bath is replenished, bleach replenishment solution is replenished to 18 ml bleach bath per 100 cm ² of color negative film, and fixing replenishment solution is replenished to fixing bath 7.0 ml per 100 cm ² of color negative film for further stabilization. Replenishment liquid was added to the stabilizing bath at 11 ml per 100 cm ² of color negative film. In addition, 3 ml of water is replenished per ^100cm2 of color negative film in the small amount washing bath;
150ml was poured per ^100cm2 . Ammonium hydroxide or acetic acid was appropriately added to the fixing replenishing solution to maintain the pH of the fixing bath at 6.5 during continuous processing of the color negative film, and 500 m ² was continuously processed. . For the sample thus obtained, the maximum absolute gamma difference (|Δγ|) and the minimum density difference (ΔDmin) with respect to the CNK-4 standard treatment were taken as representative characteristics of treatment stability. The measuring device is Sakura optical densitometer PDA-65.
The transmission density of the model Red (manufactured by Konishiroku Photo Industry Co., Ltd.) was measured. The results are shown in Table (2).

[Table] Comparison (1) Comparison (2) As is clear from the results in Table (2), the silver halide is silver iodobromide, containing 3 mol% or more of silver iodide,
Furthermore, processing fluctuations and minimum density fluctuations (including fog and processing stain) are significantly improved by using emulsions F and M of the invention, which are core shell emulsions, and using the exemplary coupler of the invention as a coupler. I understand. The results in Table (2) show that even if the emulsion does not contain silver iodide or the silver iodide emulsion contains silver iodobromide but is not a core-shell type emulsion, the minimum density fluctuation is large and the processing stability is deteriorated. It is not very practical. Furthermore, it can be seen that when a cyan coupler other than the one according to the present invention is used, the processing stability and minimum density fluctuation are significantly inferior, as described above. In addition, as exemplary compound cyan couplers of the present invention, C-1, C-2, C-10, C-12, C-29, C-
31, C-51, C-77, and C-88 were also investigated, but the same effects as shown in Table (2) could be obtained. Example (2) In samples (21) and (23) of Example (1), the cyan coupler was changed as shown in Table (3), and the sodium bromide concentration replenishment amount in the color developer replenisher was determined as shown in Table (3). ) Evaluation was performed in the same manner as in Example (1) except as shown in (1).

【table】

[Table] Comparison (3) Comparison (4) The results in Table (3) show that even if the emulsion of the present invention is used, when a cyan coupler other than the present invention is used, if the concentration of sodium bromide is increased or the amount of replenishment is decreased, the difference in minimum density becomes smaller, but the sensitivity decreases. This is not preferable because it causes a large amount of pollution and cannot be put to practical use, or it does not meet the objective of reducing pollution, which is the objective of the present invention. It is clear that processing stability and processing stain can be significantly improved synergistically by using cyan couplers, the couplers of the present invention. Example (3) In order to see the effect of the present invention on ferric ions and thiosulfate, ferric ions were added at 0, 5, 10 ppm,
Sodium thiosulfate was added at 0, 20, and 50 ppm as a chelating agent (7), (12), (52'), (93).
，
(88) was added to each sample of Example (1) to study the processing stability (|Δγ|) and minimum concentration difference.
As a result, as in Example (1), only when the emulsion and coupler of the present invention are used, processing fluctuations and minimum concentration fluctuations due to ferric ions and sodium thiosulfate are small, and are more noticeable when the above chelating agent is used. It was effective.

Claims (1)

[Scope of Claims] 1. A cyan coupler having at least one silver halide emulsion layer containing a core-shell emulsion containing 3 mol% or more of silver iodide, and represented by the following general formula [], [] or [] When color-developing a silver halide color photographic light-sensitive material containing bromide, the color development replenisher contains 3.0×10 ^-3 mol/or less of bromide, and the silver halide color photographic light-sensitive material 100
1. A method for processing a silver halide color photographic material, which comprises replenishing 9 ml or less of the color developer replenisher per cm ² . General formula [] In the formula, one of R ₁ and R is hydrogen, the other represents a linear or branched alkyl group having at least 2 to 12 carbon atoms, X represents a hydrogen atom or a group that leaves by a coupling reaction, and R ₂ is Represents a ballast group. General formula [] General formula [] In the formula, Y is -COR ₄ [Formula] -SO ₂ R ₄ , [Formula] [Formula] -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ is an alkyl group, alkenyl group, cycloalkyl group, aryl group or hetero Represents a ring group, R ₅ is a hydrogen atom,
Alkyl group, alkenyl group, cycloalkyl group,
It represents an aryl group or a heterocyclic group, and R ₄ and R ₅ may be bonded to each other to form a 5- to 6-membered ring. ), R ₃ represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent. 2 In the color developer, the following general formula [] ~
A method for processing a silver halide color photographic light-sensitive material according to claim 1, which comprises a chelating agent represented by [ ]. General formula [] A-COOM General formula [] B-PO ₃ M ₂ General formula [] [Formula] [In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance, It may be an organic substance. D represents a nonmetallic atom group necessary to form an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. ] 3 The color developer replenisher contains 2.0×10 ^-3 mol or less of bromide, and the color developer replenisher is contained in an amount of 7.5 ml per 100 cm ² of the silver halide color photographic light-sensitive material.
A method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the material is subsequently replenished and processed.