JP2554530B2 - Image forming method for silver halide color photography - Google Patents

Description

The present invention relates to a silver halide color photographic image forming method. More specifically, it relates to a high silver chloride silver halide photographic light-sensitive material with high sensitivity and fog. The present invention relates to an image forming method having a small amount and excellent developability.

(Prior Art) In recent years, in the photographic processing of a color photographic light-sensitive material, it has been desired that the processing time be shortened as the delivery time for finishing and the labor for laboratories are reduced. As a method of shortening the time of each treatment step, temperature increase and replenishment amount increase are common methods, but in addition, many methods of strengthening stirring or adding various accelerators have been proposed.

Among them, for the purpose of accelerating color development and / or reducing the replenishment amount, a color photographic light-sensitive material containing a silver chloride emulsion in place of the silver bromide emulsion or silver iodide emulsion which has been widely used in the past is processed. It is known how to do it. For example, in International Publication WO87-04534, a silver halide color photographic light-sensitive material having a high content of silver chloride is prepared as a so-called high silver chloride color photographic light-sensitive material with a color developer containing substantially no sulfite ion and benzyl alcohol. The method of processing is described.

However, based on the above method, it was found that when a developing process was carried out using an automatic developing machine for paper, fluctuations in photographic properties (particularly minimum density) occurred and the white background was significantly contaminated.

As described above, the rapid development processing using a high silver chloride color photographic light-sensitive material has a serious problem of fluctuation of photographic properties, and it has been strongly desired to solve them.

In a rapid processing method using a high silver chloride color photographic light-sensitive material, a method for reducing fluctuations in photographic characteristics (particularly, fog) due to continuous processing is disclosed in JP-A-58-95345 and JP-A-5-35345.
It is known to use organic antifoggants in 9-232342. However, it was found that the antifoggant effect was insufficient, and it was not enough to prevent the increase of the minimum density due to the continuous treatment, and the use of a large amount resulted in the decrease of the maximum density.

Further, in JP-A-61-70552, a high silver chloride color photographic light-sensitive material is used, and a replenishment amount of an amount that does not cause overflow to the developing bath is added during development to reduce the replenishment of the developing solution. JP-A-63-106655 discloses a method of stabilizing a silver halide color photographic light-sensitive material having a high silver chloride content in a silver halide emulsion layer with a hydroxyamine compound for the purpose of stabilizing the processing. A method of developing with a color developer containing chloride at a concentration higher than the concentration is disclosed.

However, these methods do not solve the above-mentioned problems, because the photographic property variation during continuous processing, which occurs in the processing using the above-mentioned automatic developing machine, is recognized.

(Problems to be Solved by the Invention) An object of the present invention is to use a high silver chloride color photographic light-sensitive material and have excellent photographic properties with high sensitivity, high maximum density and low minimum density in rapid processing, An object of the present invention is to provide an image forming method in which variations in photographic characteristics (especially minimum density) due to processing are significantly suppressed.

(Means for Solving the Problems) The object of the present invention is to provide at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer on a support. A silver halide color photographic light-sensitive material formed by coating is provided with at least one aromatic first
An image forming method of processing with a color developing solution containing a primary amine color developing agent, wherein the red light-sensitive silver halide emulsion layer has a high silver chloride content of 0.5 mol% or more and 6 mol% or less. The silver bromide content of the blue-sensitive silver halide emulsion layer and the silver halide emulsion of the green-sensitive silver halide emulsion layer containing the silver halide emulsion is higher than that of the red-sensitive silver halide emulsion layer. Chloride ion is used for silver halide color light-sensitive material whose silver bromide content is lower than that of silver emulsion.
A silver halide color characterized by being treated with a color developing solution containing 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / mol and bromide ion of 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / mol. Achieved by a photographic imaging method.

Chloride ion is well known as one of the antifoggants, but its effect is small, and even if it is used in a large amount, it does not completely prevent the increase of fog due to continuous processing. It had the adverse effect of delaying and reducing the maximum concentration.

Bromine ions are also well known as one of the antifoggants, but depending on the addition amount, it is possible to prevent fog associated with continuous processing to some extent, but it is insufficient, and further development is suppressed and maximum The density and sensitivity were lowered, and it was not practical.

However, as a result of various investigations, the present inventors have used a high silver chloride light-sensitive material containing a compound represented by the general formula (S) with a silver chloride content of 80 mol% or more, and a chloride ion and a bromine ion. 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol /,
By processing with a color developer containing 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / content, the maximum density does not decrease, and fluctuations in photographic characteristics due to continuous processing that occurs in automatic processor processing ( It has been found that especially (minimum density) can be prevented.

Chlorine ion and bromine ion alone do not show such an effect, and it is quite unexpected and truly surprising that such an effect was obtained for the first time by the combination in the concentration range of the present invention. Met.

 Hereinafter, the present invention will be described in detail.

In the present invention, chlorine ion is added to the color developer at 3.5.
It is necessary to contain x10 ^{-2 to} 1.5 x 10 ^-1 mol / mol. It is preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / mol. If the chlorine ion concentration is more than 1.5 × 10 ⁻¹ mol / mol, it has a drawback that the development is delayed and the maximum concentration and sensitivity are lowered.
It does not achieve the object of the invention of being fast and of high maximum concentration. On the other hand, if it is less than 3.5 × 10 ⁻² mol / mol, the photographic property variation (particularly the minimum density) accompanying the continuous processing is large and the amount of residual silver is large, so that the object of the present invention is not achieved.

In the present invention, a bromine ion of 3.0 is contained in the color developer.
It is necessary to contain x10 ^-5 mol / to 1.0 x 10 ^-3 mol /. It is preferably 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /. If the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are reduced, and
If the amount is less than 0 ^-5 mol / min, it is impossible to prevent fluctuations in photographic properties (particularly minimum density) associated with continuous processing, and the object of the present invention is not achieved.

Here, the chlorine ion and the bromine ion may be directly added to the developing solution or may be eluted from the photosensitive material in the developing solution.

When added directly to the color developer, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Among them, preferred is sodium chloride. , Potassium chloride.

Also, it may be supplied in the form of a salt against the fluorescent whitening agent added to the developer. As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, potassium bromide and sodium bromide are preferable.

When it is eluted from the light-sensitive material in the developing solution, chlorine ions and bromine ions may be supplied together from the emulsion, or may be supplied from sources other than the emulsion.

JP-A-63-106655 describes a method of processing a silver chloride light-sensitive material of 70 mol% or more with a developer containing a chloride of 2 × 10 ^-2 mol or more. However, the concentration of bromide in the developing solution is a treatment outside the present invention, and further, the specific effect of the combination of an appropriate amount of bromine ion and chlorine ion of the present invention is not described at all, and the present invention will solve the problem. The above-mentioned problem is not described, and the present invention is not analogized.

The effect of suppressing photographic fluctuations associated with continuous processing by the combination of an appropriate amount of chlorine ion and bromine ion of the present invention is due to the high development activity by using a high silver chloride emulsion and the presence of an appropriate amount of bromine ion and chlorine ion. It cannot be explained only by the fact that the balance of the decrease in activity, that is, the high activity / high suppression type development, is caused by the suppression of the fluctuation in photographic properties. The significance of the combination of bromine ion and chlorine ion in the concentration range of the present invention will be clarified by future studies.

In the present invention, it is preferable that the color developing solution contains substantially no sulfite ion from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog, but in order to suppress deterioration of the developing solution. Does not use the developer for a long time, uses a floating lid to suppress the effect of air oxidation, uses physical means such as reducing the opening of the developing tank, suppresses the temperature of the developer, and maintains the organic solvent. Chemical means such as adding agents can be used. Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air, but among them, a hydroxylamine derivative (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-188619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
6559, 61-170756, 61-188742, 61-1887
No. 41, U.S. Pat.Nos. 3,615,503 and 2,494,903,
52-143020 and JP-B-48-30496.

With respect to the preferred organic preservatives, general formulas and specific compounds are shown below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / -0.5 mol /, preferably 0.03 mol /-
It is desirable to add it so as to have a concentration of 0.1 mol /.

Particularly, addition of hydroxylamine derivative and / or hydrazine derivative is preferable.

The hydroxylamine derivative is preferably represented by the following general formula (I).

General formula (I) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R ¹¹ and R ¹² are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring together with the nitrogen atom. The heterocyclic ring structure is a 5- or 6-membered ring and is composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

R ¹¹ and R ¹² are preferably alkyl or alkenyl groups, and preferably have 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the nitrogen-containing hetero ring formed by linking R ¹¹ and R ¹² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole group.

Desirable substituents for R ¹¹ and R ¹² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amido group,
A carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound The following are preferred as hydrazines and hydrazides.

General formula (II) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted, It represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amiki group. The heterocyclic group is a 5- to 5-membered ring,
It is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. X ³¹ is -CO-, -SO ₂
-Or Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In formula (II), R ³¹ , R ³² , and R ³³ are hydrogen atoms or C ₁ to C.
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (II), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Here, preferable substituents of the alkyl group include a carboxysyl group, a sulfo group, a nitro group, an amino group and a phosphono group. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

(Compound example) II-2 NH ₂ NHCH _{2 4} SO ₃ H II-3 NH ₂ NHCH _{2 2} OH _{II-6 NH 2 NHCOCH 3 II} -7 NH 2 NHCOOC 2 H 5 II-10 NH ₂ NHCONH ₂ II−12 NH ₂ NHSO ₃ H II-14 NH ₂ NHCOCONHNH ₂ II-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H II-18 NH ₂ NHCH ₂ CH ₂ COOH Use of the compound represented by the general formula (I) or (II) and the amine represented by the following general formula (III) or (IV) in combination improves the stability of the color developer. Is more preferable from the viewpoint of improving the presentation stability of continuous treatment.

General formula (III) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R
⁷³ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

(Example of compound) III-1 NCH ₂ CH ₂ OH) ₃ III-2 H ₂ NCH ₂ CH ₂ OH III-3 HNCH ₂ CH ₂ OH) ₃ III-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ III-11 NHCH ₂ COOH) ₂ III−13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ III-15 H ₂ N-CCH ₂ OH) ₂ General formula (IV) In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other. Among the general formula (IV), particularly preferable one is the general formula (IV
-A) and compounds represented by (IV-b).

In the formula, X ¹ represents N or CH. R ¹ and R ² are defined at the same time in the general formula (IV), R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (IV-a), X ¹ is preferably N. The number of carbon atoms of R ¹ , R ² and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (IV).

In the general formula (IV-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (IV-a) and (IV-b), the compound represented by the general formula (IV-a) is particularly preferable.

The above organic preservatives can be obtained as commercial products, but can also be synthesized by the methods described in Japanese Patent Application Nos. 62-124038 and 62-24374.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N- (Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per developing solution.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0.1 mol /
It is preferably at least above, and particularly preferably 0.1 mol / to 0.4 mol /.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-
Sulfosalicylic acid, 4-sulfosalicylic acid, and these chelating agents may be used in combination of two or more, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g per unit.

If necessary, any development accelerator can be added to the color developing solution.

Development accelerators include JP-A-37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, etc., p shown in JP-A Nos. 52-49829 and 50-15554. -Phenylenediamine compounds, JP-A-50-13
7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in U.S. Pat.Nos. 2,610,122 and 4,119,462, and U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Japanese Patent Sho 4
1-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in JP-B-3.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxides represented by 532, 501, etc.,
In addition, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means 2. per color developer.
It is 0 ml or less, more preferably, it is not contained at all. When the content is not substantially contained, the fluctuation of photographic characteristics during continuous processing is small, and more preferable results are obtained.

In the present invention, any antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole and 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 10 g /, preferably 0.1 to 6 g /.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

Usually, in color development, the developer is replenished. The replenishment amount depends on the photosensitive material to be processed, but is generally about 180 to 1000 ml per square meter of the photosensitive material. Replenishment is a means for keeping the components of the color developing solution constant in order to avoid a change in development finish characteristics due to a change in component concentration in a development processing method in which a large amount of a light-sensitive material is continuously processed by an automatic developing solution, For replenishment, a large amount of overflow liquid is inevitably generated, and it is preferable that the replenishment amount is small in terms of economy and pollution. This preferable replenishment amount is 1 m ² of the light-sensitive material.
It is about 20 to 150 ml. The replenishment amount of 20 ml per 1 m ² of the light-sensitive material is the amount at which the carry-out amount of the processing liquid by the light-sensitive material and the replenishment amount are substantially equal, but the overflow is substantially eliminated, although the amount is slightly different depending on the light-sensitive material. The present invention is effective even in such a treatment with low replenishment.

In the present invention, desilvering processing is performed after color development.
The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferred that they are performed simultaneously.

The bleaching solution or bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), or chloride (eg, potassium chloride,
Rehalogenating agents such as sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. These are used alone or in admixture of two or more. can do. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5.
The range is up to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is
3 to 10 are preferable, and 5 to 9 are particularly preferable. pH
If it is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing solution in the present invention, as a preservative, sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound is contained. These compounds are converted to sulfite ion
The content is preferably 0.02 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, carbonyl bisulfite adduct, sulfinic acid, carbonyl compound, sulfinic acid, etc. may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, and then washing with water and / or a stabilizing step.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers), 3 uses, and the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Terevision Engineers) Volume 64, p.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, Japanese Patent Application Nos. 61-1343, 60-220345 and 60-238832 are available.
No. 60, No. 60-239784, No. 60-239749, No. 61-4054,
All known methods described in JP-A-61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-
A stabilizing bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .

The processing time of the present invention is defined as the time from the time when the photosensitive material comes into contact with the color developer to the time when it leaves the final bath (usually a washing or stabilizing bath). The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 4 minutes or less.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support. In general color photographic printing paper, it is normal that the color printing paper is coated on the support in the above-mentioned order, but the order may be different from this. In these light-sensitive emulsion layers, a silver halide emulsion having sensitivity in each wavelength range, a dye having a complementary color relationship with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red. By incorporating a so-called color coupler to be formed, color reproduction by a subtractive method can be performed. However, the photosensitive layer and the hue developed by the coupler may not have the above correspondence.

In the present invention, the red-sensitive silver halide emulsion layer must contain a high silver chloride emulsion having a silver bromide content of 0.5 mol% or more and 6 mol% or less. High silver chloride here means
It essentially consists of silver chloride, that is, it has a silver chloride content of 80 mol% or more, preferably 94 from the viewpoint of rapidity.
It refers to a silver chlorobromide or a silver chloride containing substantially no silver iodide in an amount of not less than mol%, more preferably not less than 98% by mol. If the silver bromide content is less than 0.5 mol%, the sensitivity is likely to decrease and the photographic properties are likely to change due to continuous processing. On the other hand, if the silver bromide content is 6 mol%, a high maximum density is obtained. Not only that, the sensitivity may be lowered and the photographic properties may be deteriorated due to continuous processing.

The silver bromide content of the blue-sensitive and green-sensitive silver halide emulsions other than the red-sensitive layer must be lower than that of the red-sensitive silver halide emulsion layer. Is preferable from the viewpoint of continuous processing stability and processing dependence. The halogen composition is preferably silver chlorobromide or normal silver chloride having a silver chloride content of 94 mol% or more, more preferably 98 mol% or more.

As the silver halide emulsion of the red light-sensitive silver halide emulsion layer used in the present invention, those composed of high silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. Particles having a so-called layered structure having a different halogen composition with the (shell) [one layer or a plurality of layers], or a structure having a non-layered portion having a different halogen composition inside or on the surface (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above is preferable.
The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. And these localized layers can be inside the grain, on the edges, corners or faces of the grain surface. As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain.

On the other hand, in order to suppress the sensitivity decrease when the light-sensitive material is subjected to pressure as much as possible, even in a high silver chloride emulsion having a silver bromide content of 6 mol% or less, a grain having a uniform structure with a small halogen composition distribution in the grain. It is also preferable to use.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μ to 2 μ. preferable.

Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodisperse emulsion by blending it in the same layer, or to perform multi-layer coating.

The formation of silver halide grains contained in photographic emulsions is regular (regula-like, such as cubic, tetradecahedral or octahedral).
r) Those having a crystal form, those having an irregular crystal form such as spheres and plates, or those having a composite form thereof can be used. Also,
It may consist of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The total coated silver amount of the silver halide color photographic light-sensitive material of the present invention is preferably 0.80 g / m ² or less. When the total coated silver amount is more than 0.80 g / m ² , the rapidity and the photographic characteristics greatly fluctuate during continuous processing. It is preferably 0.75 g / m ² or less.

The silver chlorobromide emulsion used in the present invention is described in Chemi by P. Glafkides.
e et Phisique Photographique (Paul Montel, 196
7) Photographic Emulsion Chemistry by GFDuufin
(Focal press, 1966), VL Zelikman et al M
aking and Coating Photographic Emulsion (Focal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. May be. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the present invention can be introduced with various polyvalent metal ion impurities in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized.

In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 2, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity. As the spectral sensitizing dye used at this time, for example, Heterocyclic compo by FH Harmer
unds Cyanine dyes and related compounds (John Wile
y & Sons [New York, London], 1964). As specific examples of compounds, those described in the above-mentioned JP-A No. 62-215272, page 22, upper right column to page 38 are preferably used.

In the silver halide emulsion used in the present invention, the production process of the photosensitive material, to prevent fogging during storage or photographic processing,
Alternatively, various compounds or precursors thereof can be added for the purpose of stabilizing photographic performance. These are commonly called photographic stabilizers. Specific examples of these compounds are described on page 39 of the above-mentioned JP-A-62-215272.
Those described on page 72 are preferably used.

The emulsion used in the present invention may be any type of so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

As the color light-sensitive material, yellow couplers, magenta couplers and cyan couplers which are coupled with an oxidized form of an aromatic amine color developing agent to form yellow, magenta and cyan, respectively, are usually used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferable.

Among them, the following general formula [Y
-1] and [Y-2] are preferred.

For details of the pivaloyl acetanilide type yellow coupler, see U.S. Pat. No. 4,622,287, column 3, line 15 to column 8, line 39 and U.S. Pat. No. 4,623,616, column 14, line 50 to 1
It is described in column 9, line 41.

For details of the benzoylacetanilide type yellow coupler, see U.S. Pat.Nos. 3,408,194, 3,933,501,
4,046,575, 4,133,958, 4,401,752, etc.

Specific examples of the pivaloylacetanilide type yellow coupler include the 38th compound of the above-mentioned US Pat. No. 4,622,287.
The compound examples (Y-1) to (Y-39) described in Columns to 54 can be mentioned, among which (Y-1), (Y-4), (Y
-6), (Y-7), (Y-15), (Y-21), (Y-
22), (Y-23), (Y-26), (Y-35), (Y-3
6), (Y-37), (Y-38), (Y-39) and the like are preferable.

Further, the above-mentioned U.S. Pat.No. 4,623,616, columns 19 to 24
The compound examples (Y-1) to (Y-33) in the column can be mentioned, among which (Y-2), (Y-7), (Y-8),
(Y-12), (Y-20), (Y-21), (Y-23),
(Y-29) and the like are preferable.

In addition, as a preferable one, U.S. Pat.
Specific examples (34) and 3,93 in column 6 of the specification
Compound examples (16) and (1
9), compound examples (9) described in columns 7 to 8 of JP-A-4,046,575, compound examples (1) described in columns 5 to 6 of JP-A-4,133,958, and compound (1) of JP-A-4,401,752. Compound Example 1 described in column 5 and the following compounds a) to h) can be mentioned.

Among the above couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Examples of the magenta coupler used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, preferably 5-pyrzolone type and pyrazolone azole type couplers such as pyrazolotriazoles. 5-pyrazolone-based couplers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye,
Representative examples are U.S. Pat.Nos. 2,311,082 and 2,343,703.
No. 2,600,788, No. 2,908,573, No. 3,062,65
No. 3, No. 3,152,896 and No. 3,936,015. As a leaving group of a 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351,897 and WO (PC
T) The arylthio groups described in 88/04795 are preferred. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) Pyrazolotetrazoles and Research Disclosure 24)
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. Any of the couplers described above may be a polymer coupler.

These compounds are specifically represented by the following general formula (M-
1), (M-2) or (M-3).

Among the pyrazoloazole couplers, U.S. Pat.
Imidazo [1,2-b] pyrazoles described in 500,630 are preferred, and pyrazolo [1,5-b] [1,2,4] triazole described in U.S. Pat. No. 4,540,654 is particularly preferred.

In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2,3- or 6-position of a pyrazolotriazole ring, JP-A-61-65
No. 246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and a European compound. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in Japanese Patent No. 226,849.

 Specific examples of these couplers are listed below.

The most representative cyan couplers are phenol cyan couplers and naphthol cyan couplers.

U.S. Pat.
9,929, 4,518,687, 4,511,647 and 3,772,002
, Etc., which has an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position (including polymer couplers), and typical examples thereof are described in Canadian Patent No. 625,822. The coupler of Example 2, compound (1) described in U.S. Pat. No. 3,772,002, compounds (I-4) and (I-5) described in U.S. Pat. No. 4,564,590, JP-A-61-39.
Compounds (1), (2), (3) and (2) described in No. 045
4) and compound (C-2) described in JP-A-62-70846.

U.S. Patents for phenolic cyan couplers
2,772,162, 2,895,826, 4,334,011, 4,50
There are 2,5-diacylaminophenol type couplers described in U.S. Pat. No. 6,653 and JP-A-59-164555, and typical examples thereof include compounds (V) described in U.S. Pat.
Compound (17) described in JP-A-4,557,999, compounds (2) and (12) described in JP-A-4,565,777, compound (4) described in JP-A-4,124,396, and compound (I-1) described in JP-A-4,613,564.
9) and so on.

U.S. Patents for phenolic cyan couplers
No. 4,372,173, No. 4,564,586, No. 4,430,423, JP-A-6
1-390441 and Japanese Patent Application No. 61-100222 include those in which a nitrogen-containing heterocycle is condensed with a phenol nucleus, and typical examples thereof include the coupler (1) described in U.S. Pat. No. 4,327,173 and (3), compounds (3) and (16) described in 4,564,586, compounds (1) and (3) described in 4,430,423, and the following compounds.

In addition to the cyan couplers of the type described above, the diphenylimidazole-based cyan couplers described in EP 0,249,453A2 may be used.

As phenolic cyan couplers, other U.S. Pat.Nos. 4,333,999, 4,451,559, 4,444,872, 4,4
27,767, 4,579,813, European Patent (EP) 067,689B1
And the like. Typical examples thereof include couplers (7) described in US Pat. No. 4,333,999, couplers (1) described in US Pat. No. 4,451,559, and couplers described in US Pat.
Couplers (14) described in 4,444,872, couplers (3) described in 4,427,767, couplers (6) and (24) described in 4,609,619, and couplers (1) and (11) described in 4,579,813. And couplers (45) and (50) described in European Patent No. (EP) 067,689B1, and a coupler (3) described in JP-A-61-42658.

As the naphthol cyan coupler, those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, US Pat. No. 2,313,586) and those having an alkylcarbamoyl group at the 2-position (for example, US Pat.
474,293, 4,282,312), those having an arylcarbamoyl group at the 2-position (for example, Japanese Examined Patent Publication No. 50-14523), those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60-237448, 61-145557, 61-1536
No. 40), those having an aryloxy leaving group (for example, US Pat. No. 3,476,563), those having a substituted alkoxy leaving group (for example, US Pat. No. 4,296,199), and those having a glycolic acid leaving group (for example, Japanese Patent Publication No. 60-39217). )and so on.

These couplers can be contained in the dispersed emulsion layer in the presence of at least one high boiling point organic solvent. High boiling organic solvents represented by the following formulas (A) and (E) are preferably used.

Formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ -O-W ₂ (In the formula, W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloaxyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ Is W ₁ , OW ₁ or SW
Represents ₁ , and n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ form a condensed ring. May be).

In addition, these couplers are impregnated with a loadable latex polymer (for example, U.S. Pat. No. 4203716) in the presence or absence of the above high boiling point organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably the homopolymer or copolymer described on pages 12 to 30 of International Publication No. WO88 / 00723 is used,
In particular, use of an acrylamide polymer is preferable in terms of color image stabilization and the like.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as an organic anti-fading agent for cyan, magenta and / or yellow images, hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenol bonds, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. As. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents.

Hydroquinones are U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
728,659, 2,732,300, 2,735,765, and
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No. 2, U.S. Patent Nos. 2,710,801 and 2,816,028,
6-hydroxychromans, 5-hydroxycoumarans and spirochromans are described in U.S. Pat. No. 3,432,300
No. 3,573,050, No. 3,574,672, No. 3,698,909, No. 3,764,337, JP-A-52-152225, etc., spiroindanes in U.S. Pat.No. 4,360,589, p-alkoxyphenols in U.S. Pat. British Patent No. 2,0
66,975, JP-A-59-10539, JP-B-57-19765 and the like, hindered phenols are described in U.S. Pat.
JP-A-52-72224, U.S. Pat.No. 4,228,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. In Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent Nos. 1,32,889, 1,3
54,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, 59-53846, 59-78344, etc., ethers of phenolic hydroxyl groups, ester derivatives are U.S. Pat. No. 4,174,220, No. 4,254,
No. 216, No. 4,264,720, JP-A No. 54-145530, No. 55-
No. 6321, No. 58-105147, No. 59-10539, Japanese Patent Publication No. 57-3
No. 7856, U.S. Pat.No.4,279,990, Japanese Patent Publication No. 53-3263, and the like, and metal complexes are described in U.S. Pat.Nos. 4,050,938 and 4,241,1.
55 and British Patent 2,027,731 (A). These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an external ray absorbent into the layers on both sides adjacent to the cyan coloring layer.

Among the anti-fading agents, spiroindanes and hindered amines are particularly preferred.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers, especially with the pyrazoloazole coupler.

That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

The preferred compound (F) has a second-order reaction rate constant k2 (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec with p-anilidine. It is a compound that reacts with.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the residual aromatic amine-based developing agent is slow, and as a result, the side effect of the residual aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R1- (A) _n- X General formula (F II) In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents an aromatic amine-based developing agent added to the compound of the general formula (F II). Represents a promoting group. Here, R1 and X, Y and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine-based developing agent, representative ones are substitution reaction and addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in Japanese Patent Application Nos. 62-158342, 62-158643, and
62-212258, 62-214681, 62-228034 and 62
-279843 and the like.

Details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

The photosensitive material prepared using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), a 4-thiazolidone compound (for example, those described in U.S. Pat. 46-
2784), a cinnamic acid ester compound (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375), a butadiene compound (for example, those described in US Pat. No. 4,045,229), or a benzooxide compound (for example, US Those described in Japanese Patent No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

The light-sensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a binder or protective colloid which can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be lime-treated,
It may be either treated with an acid or not. The details of the method for producing gelatin are described in The Macromolecule Chemistry of Gelatin, by Arthur Wuice (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention means one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, etc.
These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, a white pigment should be sufficiently kneaded in the presence of a surfactant, and the surface of the pigment particles should not be mixed.
It is preferable to use one treated with a tetrahydric alcohol.

The occupying area ratio (%) of the white pigment fine particles per defined unit area is most typically projected by dividing the observed area into adjacent 6 μm × 6 μm unit areas. It can be determined by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R ₁ () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation s / is Can be obtained by

In the present invention, the occupied area ratio (%) of the fine particles of the pigment
The coefficient of variation of 0.15 or less is particularly preferably 0.12 or less. 0.
When it is 08 or less, the dispersibility of the particles is substantially “uniform”.
Can be said.

Example 1 A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 60.0g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) 28.0 g of ethyl acetate 150 cc and solvent (Solv-
3) Add 1.0 cc and 3.0 cc of solvent (Solv-4) and dissolve, then add 10 cc of this solution containing sodium dodecylbenzene sulfonate.
% Gelatin aqueous solution (450 cc) and then dispersed with an ultrasonic homogenizer. The resulting dispersion is 420 g of silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-Bis (vinylsulfonyl) ethane was used as a gelatin hardener for each layer.

The following were used as the spectral sensitizing dye in each layer.

Blue-sensitive emulsion layer; Anhydro-5-5'-chloro-3,3 '
-Disulfoethylthiacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5-5'diphenyl-3,3'-disulfoethyloxycarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-diethyl- 5-methoxy-9,9 '
-(2,2'-Dimethyl-1,3-propano) thiacarboxyanine iodide The following substances were used as stabilizers for each emulsion layer.

The following dyes were used as the anti-irradiation dye.

[3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-disulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7-
Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- (4 -Sulfonatophenyl) -2
-Pyrazolin-4-ylidene) -1-pentanyl) -1
-Pyrazolyl] benzene-4-sulfonato-sodium salt (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene 1st layer (blue sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic average grain size)
0.9μ) 0.27 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (anti-color mixing layer) Gelatin 0.80 Anti-color mixing agent (Cpd) -2) 0.055 Solvent (Solv-1) 0.03 Solvent (Solv-2) 0.015 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic grain size 0.45)
μ) 0.28 Gelatin 1.40 Magenta coupler (ExM) 0.67 Color mixing inhibitor (Cpd-3) 0.23 Color mixing inhibitor (Cpd-4) 0.11 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.02 Fourth layer (color mixing prevention layer) ) Gelatin 1.70 Anti-color mixing agent (Cpd-2) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red sensation) Layer) Silver chlorobromide emulsion (AgBr: 2 mol%, cube, grain size 0.5)
μ) 0.19 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Sixth layer (UV absorption) Layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (ExY) Yellow coupler α-pivalyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5 [β- (dodecylsulfonyl)
-Butylamido] acetanilide (ExM) magenta coupler 1- (2,4,6-trichlorophenyl) -3- [2-chloro-5 (3-octadecenylsuccinimide) anilino] -5-pyrazolone (ExC-1 ) Cyan coupler 2-pentafluorobenzamide-4-chloro-5
[5- (2,4-di-tert-aminophenoxy) -3-methylbutylamidophenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di −
tert-Aminophenoxy) butylamido] phenol (Cpd-1) anti-fading agent 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate (Cpd-2) anti-color mixture 2,5- Di-tert-octylhydroquinone (Cpd-3) anti-fading agent 1,4-di-tert-amyl-2,5-dioctyloxybenzene (Cpd-4) anti-fading agent 2,2'-methylenebis (4-methyl-) 6-tert-butylphenol) (Cpd-5) p- (p-toluenesulfonamide) -phenyl dodecane (Solv-3) solvent di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide Methoxy-2,4-di-t
-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5- Di-tert-butylphenyl) benzotriazole (Solv-1) solvent di (2-ethylhexyl) phthalate (Solv-2) solvent dibutylphthalate The sample thus obtained was designated as A. Samples A to B were prepared by changing the halogen composition of the silver chlorobromide emulsion in the red light-sensitive emulsion layer as shown in Table 1 to Samples A to E.

The following experiments were conducted to examine the photographic characteristics of these coated samples.

First, the coated sample was subjected to sensitometric gradation exposure using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1 /
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 10 seconds.

The coated sample was processed by an automatic processor with the following processing steps and the following processing compositions. However, the composition of the color developing solution was changed as shown in Table 2. Processing process Temperature Time Color development 38 ℃ 45 seconds Bleach fixing 30-36 ℃ 45 seconds Rinse 30-37 ℃ 30 seconds Rinse 30-37 ℃ 30 seconds Rinse 30-37 ℃ 30 seconds Dry 70-80 ℃ 60 seconds The composition of the treatment liquid is as follows.

Color developer Water 800ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0g Organic preservative A (I-1) 0.03mol Sodium chloride See Table 2 Potassium bromide See Table 2 Potassium carbonate 25g N -Ethyl-N- (β-methanesulfonamide ethyl) -3-methyl-4-aminoaniline sulfate 5.0g Triethanolamine 10.0g Fluorescent brightener (4,4'-diaminostilbene type) 2.0g Sodium sulfite 0.01g Water added 1000ml pH (25 ℃) 10.05 Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Add water to 1000 ml pH (25 ° C) 5.40 Rinse solution Ion-exchanged water (calcium and magnesium each 3ppm or less) Degree S (the reciprocal of an exposure amount required to provide cyan density 0.5 and sensitivity, the sensitivity of Sample A was displayed by a relative value of 100), the maximum density of the cyan Dma
The x and minimum density Dmin were measured and the results are shown in Table 2.

Further, the opening ratio (opening area / liquid volume) of the above color developer
After aging at room temperature at 0.02 cm ⁻¹ for 2 weeks, the sensitometric evaluation was performed using it. The minimum cyan density increase ΔDmin with time of the developer was measured, and the results are shown in Table 2.

As is clear from the results in Table 2, according to the image forming method of the present invention, the sensitivity is high, the maximum density is high, the minimum density is low, and the photographic property variation (minimum density) associated with continuous processing is
A feature with less is obtained.

Reference Example A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, silver bromide containing 0.2 mol% on the grain surface) was mixed with the following blue-sensitive sensitizing dyes at 2.0 × / mol silver. After addition of 10 ^-4 mol, sulfur-sensitized one was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1 as a gelatin hardening agent for each layer
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

(Each 2.0 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ⁻⁴ mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 1- (5-methylcladephenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer Configuration) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv -1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (1: 3 mixture (Ag mole) ratio of cubic average grain size 0.55μ and 0.39μ) . Coefficient of variation of particle size distribution 0.10 and 0.08 respectively.

0.8 mol% of AgBr was locally contained on the particle surface. 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.54 Fourth layer ( UV absorbing layer) Gelatin 1.58 UV absorbing (UV-1) 0.47 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Solvent (Solv-2) 0.05 Fifth layer (Red sensitive layer) Silver chlorobromide Emulsion (cubic, grain size 0.58μ and 0.45μ 1: 4 mixture (Ag molar ratio). Coefficient of variation of grain size distribution 0.09 and 0.11.

0.6 mol% of AgBr was locally contained in a part of the particle surface. 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer ( UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol ( Degree of denaturation 17%) 0.17 Liquid paraffin 0.03 2: 4: 4 mixture by weight of each 2: 4: 4 mixture (weight ratio) 4: 2: 4 mixture (weight ratio) 2: 1 mixture (by volume) (Solv-3) solvent _{O = PO-C 9 H 19} (iso)) 3 The sample obtained as described above was designated as F.

After subjecting the sample F to image exposure in the same manner as in Example 1, continuous processing (running test) was carried out in the following processing steps using a paper processor until the tank capacity of the color developer was replenished to twice.

Color developing solution The composition of each processing solution is as follows.

[Tank liquid]

Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3.0 g Triethanolamine 8.0 g Sodium chloride See Table 3 Potassium bromide See Table 3 Potassium carbonate 25 g N-Ethyl-N- (β -Methanesulfonamide ethyl) -3-methyl-4-aminoaniline sulfate 5.0g Organic preservative A (II-19) 0.03mol Optical brightener (Sumitomo Chemical WHITEX-4) 1.0g Water was added. 1000ml pH (25 ℃) 10.05 [Replenisher] Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3g / triethanolamine 12g / potassium chloride See Table 3 Potassium bromide See Table 3 Carbonate Potassium 26g / N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 9g / Organic preservative (II-19) 7g / Optical brightener (Sumitomo Chemical WHITEX-4) 2.5g / Add water to 1000ml pH (25 ℃ ) 10.55 (adjusted with KCH or H ₂ SO ₄ ) Bleach-fixing solution [tank solution] Water 400 ml Ammonium thiosulfate (70%) 100 ml Ammonium sulfite 38 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Glacial acetic acid 9 g Add 1000 ml pH (25 ° C) 5.40 [Replenisher] 2.5 times concentrated tank solution Concentrated water Rinse water (same as tank solution and replenisher) Ion-exchanged water (3 p each for calcium and magnesium)
pm or less) In addition, distilled water was added to the color developing solution, the bleach-fixing solution, and the washing solution in an amount of evaporated water, and continuous processing was performed while correcting the evaporation and concentration.

The maximum cyan density Dmax at the start of the running test, the minimum density Dmin, and the increase in the minimum density of cyan until the end of the running Dmin were measured, and the results are shown in Table 3.

As is clear from the results shown in Table 3, the effect of the image forming method of the present invention is recognized even in the system of the multilayer coating sample used in Example-2.

(Effects of the Invention) The present invention provides an image forming method having high sensitivity, high maximum density, low minimum density, and significantly suppressed fluctuation in photographic properties (particularly minimum density) due to continuous processing.

Claims (1)

(57) [Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
A silver halide color photographic light-sensitive material comprising at least one green light sensitive silver halide emulsion layer and at least one red light sensitive silver halide emulsion layer, and at least one aromatic primary amine color developing agent. In the image forming method of processing with a color developing solution, the red-sensitive silver halide emulsion layer contains a high silver chloride silver halide emulsion having a silver bromide content of 0.5 mol% or more and 6 mol% or less, And the silver bromide content of the silver halide emulsions of the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is the silver bromide content of the silver halide emulsion of the red-sensitive silver halide emulsion layer. Lower than silver halide color light-sensitive material, chloride ion 3.5
X10 ^{-2 to} 1.5 x 10 ^-1 mol / content and contains bromide ion
An image forming method for silver halide color photography, which comprises processing with a color developing solution containing 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / mol.