JPH06342199A - Color image forming method - Google Patents

Abstract

PURPOSE:To provide a color image forming method, with which a silver halide color photosensitive material having a low silver content can be continuously and stably subjected to development intensification by using an intensifying replenisher that contains a peroxide compound and no color developing agent and has a pH adjusted to a value within a specified range. CONSTITUTION:In this color image forming method, a silver halide color photosensitive material contg. stoichiometrically at least a >=50mol% excess amount of the coupler is continuously subjected to development intensification processing in the presence of a peroxide compound by using the replenishing method. At this time, the intensifying replenisher contg. a peroxide compound does not contain any color developing agent and the pH of the replenisher is <=7. The peroxide compound can be employed in any optional, convenient and coventional form and an inorganic peroxide compound or salt of peracid such as a perborate, percarbonate or persilicate, particularly hydrogen peroxide, is used as the peroxide compound. The peroxide compound is preferably used in >=0.01mol/l concn. as the intensifying replenisher contg. the peroxide compound and in 0.001 to 0.5mol/l concn. as the development intensifyer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silver halide color light-sensitive material containing a stoichiometric excess of a coupler with respect to silver halide in the presence of a peroxide for development intensification processing to obtain a color image. And a method for forming a color image.

More specifically, the present invention relates to a novel color image forming method capable of continuously and stably assisting development.

[0003]

2. Description of the Related Art Silver halide photographic light-sensitive materials have been widely used since they have high photosensitivity and excellent image quality. However, for silver halide photographic light-sensitive materials that use a large amount of silver, the shortage of silver resources and the resulting rise in raw material costs have become quite serious in recent years, and there is a demand for the development of a technique that can save the amount of silver. As a technique to meet this demand, we focused on the image silver obtained by developing the image after exposing the silver halide photographic light-sensitive material imagewise, and using this silver as a catalyst, the oxidation formation of the developing agent was more efficient. A so-called dye image intensifying method is known in which an object is produced to thereby form a high-density dye image. According to this method, the developed silver is recycled and used many times, so that a dye image can be obtained extremely efficiently and the amount of silver can be significantly reduced. There are many known methods for intensifying a dye image of such a silver halide photographic light-sensitive material. For example, oxidation of a para-phenylenediamine color developing agent by decomposition of hydrogen peroxide on the surface of a silver catalyst in the presence of a coupler (color former), and subsequent formation of a dye by coupling with a coupler (hereinafter, This process is called color intensification.) Is described in, for example, “History of Color Phtography” by JS Friedman, page 406.

A color intensifying method using a cobalt complex on the surface of a noble metal is disclosed, for example, in JP-A-48-9728 and JP-A-48-9728.
8-9729, 48-48130, 49-102340, 49-102341
No. and other publications. In this intensification method, a silver halide photographic light-sensitive material is developed with a black and white developing agent or a color developing agent, and cobalt (II
I) A method in which a redox reaction occurs between a complex and a para-phenylenediamine color developing agent, and subsequently, an oxidation product of the color developing agent and a coupler are coupled to form a dye.

Further, a color intensifying method using a combination of hydrogen peroxide and a cobalt complex is described in JP-A Nos. 52-20025 and 52-30430. Compounds having a strengthening action such as hydrogen peroxide and a cobalt complex are called a strengthening agent, and a liquid containing these strengthening agents is called a strengthening solution. Although the above-mentioned method has an effect of efficiently increasing the dye image density and is an effective means from the viewpoint of saving silver resources, the fact is that it has not yet been put to practical use. The color intensification method using hydrogen peroxide is
This is preferable because it has higher intensification activity than other intensification methods. But,
Perhaps because the oxidizing power of hydrogen peroxide is too strong, it is easy to oxidize the color developing agent and to form a dye by coupling the oxidant with the coupler, even in the area other than the catalytic material (for example, developed silver) distributed in the image. Therefore, fogging occurs. Further, since the color developing agent which is a reducing agent and hydrogen peroxide which is an oxidizing agent coexist, the preservability of the intensifying solution containing hydrogen peroxide is significantly deteriorated. That is, the color developing agent is decomposed and decreased by hydrogen peroxide with the passage of time, so that the intensifying activity is lowered and the maximum density (Dmax) and / or the minimum density (Dmin) is deteriorated.

Various methods have been proposed to remedy these drawbacks. For example, there is a method of adding benzotriazole or the like as an antifoggant as described in Research Disclosure No. 11660. However, these antifoggants have no effect in a small amount, and when added in an amount that is recognized to have an antifoggant effect, they also adversely affect the image-like catalyst substance, suppress the dye formation in the image area, and significantly increase Dmax. Will fall.

Further, since silver halide may act as a catalyst for decomposition of hydrogen peroxide in the silver halide photographic light-sensitive material, after the silver halide photographic light-sensitive material is subjected to development processing and before the intensifying bath. , A solution containing a silver halide solubilizer (called a fixing solution) is used to remove silver halide that was not used for image formation, leaving only the imagewise silver and then treated with an intensifying solution. How to do is presented. However, even with this method, the catalytic activity of the developed silver is significantly impaired, and the intensification of the dye image cannot be expected.

Furthermore, the American Chemical Society monograph series No. 1
As described in "Hydrogen Peroxide" on page 447, various metals catalyze the decomposition of hydrogen peroxide and reduce the stability of hydrogen peroxide. In order to shade the trace metals (magnesium, calcium, etc.) present in the intensifying bath, it has been attempted to add a chelating agent such as polyaminocarboxylic acid, but there is almost no effect of improving the preservability of the intensifying bath. The above-mentioned drawback has a fundamental cause that the color developing agent which is a reducing agent and hydrogen peroxide which is an oxidizing agent coexist in the intensifying bath. Thus, the hydrogen peroxide intensification method has not yet been put to practical use, although hydrogen peroxide has a high intensification activity.

On the other hand, the intensification method using a cobalt (III) complex has a drawback that the intensification activity is low. This is probably because the cobalt (III) complex used as the intensifying agent has a relatively weak oxidizing power in consideration of the stability of the complex itself. In addition, the phenomenon of fogging is remarkable even in the intensification method using a cobalt complex, and there is a phenomenon that Dmin is increased even in the liquid storability. To improve these shortcomings,
Add various antifoggants and stabilizers to the intensifying bath,
Alternatively, the method of incorporating in a silver halide light-sensitive material is described in JP-A-52-11034, JP-A-52-20831, JP-A-53-8135, etc., but satisfactory improvements have not been made. Absent.

Furthermore, the intensification method using hydrogen peroxide and cobalt (III) complex in combination is hydrogen peroxide, cobalt (III) complex.
The intensification activity is higher than that when each complex is used alone. However, the drawbacks of fog generation and deterioration of liquid storage stability, which have been observed with hydrogen peroxide intensification and cobalt (III) complex intensification, have become more prominent, and it is currently difficult to put them into practical use.

In addition, these methods are used in a relatively short time after preparation of the treatment liquid and the treatment liquid is a disposable system (batch system).
However, the treatment quality was unstable and unsatisfactory in the case of continuous replenishment.

When a large amount of light-sensitive materials are commercially processed, they are generally processed by a replenishing system using an automatic processor for finishing at low cost.

The replenishment method is such that the composition of the processing solution changes when the photosensitive material is processed, but the composition of the processing solution is kept constant by adding the replenishing solution to the processing solution. It is a method of processing and is well known in the industry.

International Patent Publications WO91-16666, WO92-07299, WO
92-07301 and WO92-07302 describe improvements relating to a replenishment system and a processing device for such continuous processing.

However, none of them mentions the stability of the replenisher itself containing peroxide, and the deterioration of the replenisher containing peroxide with the passage of time makes it impossible to continuously treat the replenisher. However, satisfactory and stable treatment results were not obtained.

[0016]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to continuously and stably develop a silver halide color light-sensitive material having a low silver content by a development intensifying process using a peroxide. It is to provide a method for forming a color image.

[0017]

The above object of the present invention is in the presence of a peroxide of a silver halide color light-sensitive material containing a stoichiometric excess of at least 50 mol% relative to silver halide. In the method of forming a color image in which the developing intensification process is continuously performed by a replenishing method, the peroxide-containing intensifying replenisher does not contain a color developing agent and its pH is 7
It was achieved by a method of forming a color image, characterized in that:

The present invention will be described in detail below.

The peroxide employed in the practice of the present invention can take any convenient conventional form. Generally, water-soluble compounds containing peroxy groups are preferably employed in the practice of this invention as peroxides. Inorganic peroxide compounds or salts of peracids such as perborates, percarbonates, or persilicates, especially hydrogen peroxide, can be used as peroxides in the practice of the present invention. Organic peroxide compounds such as benzoyl peroxide, percarbamide and addition compounds of hydrogen peroxide and aliphatic acid amides, polyalcohols, amines, acyl-substituted hydrazines and the like can also be employed. Hydrogen peroxide is preferred because it is highly active and easy to handle in the form of an aqueous solution.

The concentration of peroxide is preferably 0.01 mol / liter or more for the peroxide-containing intensifying replenisher, and 0.001 to 0.5 mol / liter for the developing intensifying liquid.

Of the peroxide-containing intensifying replenisher used in the present invention
The pH is 7.0 or less, preferably 5.0 to 3.0.

In order to adjust the pH, an inorganic acid, an organic acid and salts thereof can be used alone or in combination, but the acid is preferably a polyvalent inorganic acid, an organic carboxylic acid or the like. Are phosphoric acid, pyrophosphoric acid, sulfuric acid, persulfuric acid, boric acid, perboric acid, carbonic acid, peroxocarbonic acid, silicic acid, formic acid, acetic acid, citric acid, benzoic acid, etc., but the present invention is by no means limited thereto. .

The concentration of the acid in the peroxide-containing intensification replenisher should not be too high, and is preferably 0.01 to 10 mol%.

In addition to the pH adjusting agent, stabilizers such as barbital, acetanilide, uric acid and hippuric acid can be added to the peroxide-containing intensification replenisher.

Further, any compound may be added more than this, but it is preferable that the reducing substance such as a color developing agent is small, and it is more preferable not to add it at all.

When a color developing solution and a peracid are mixed and used as a color development intensifying solution, they should be mixed as soon as possible just before processing.

The silver halide color photographic light-sensitive material according to the present invention is subjected to development and intensification or development intensification processing after exposure, and is subjected to processing such as desilvering, washing and stabilization as necessary. To be done. In each step, a color developing solution and an intensifying solution or a developing intensifying solution, a bleaching solution or a bleach-fixing solution for desilvering,
A fixing solution is used for the fixing treatment, tap water or ion-exchanged water is used for the washing, a stabilizing solution is used for the anhydrous washing, and a stabilizing solution is used for the dye stabilizing treatment. A liquid having a processing performance for performing each of these processing steps is called a processing liquid. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the light-sensitive material is immersed in these processing solutions, or the processing solution is applied on the light-sensitive material in a thin layer.

As the method applied to the thin layer, the method described in JP-A-3-111844, page 14, lower left line 13 to page 15, lower left line 17, is preferably used.

The intensifying solution is a treating solution containing an intensifying agent and the like, and the intensifying agent and the like include peroxides, halohalous acids, iodoso compounds, cobalt (III) complex compounds and hydrogen peroxide. A compound that releases.

The development intensifying liquid is a processing liquid in which a liquid containing a color developing agent and a liquid containing an intensifying agent are mixed.

The color developer used in the present invention is preferably an aqueous solution containing a P-phenylenediamine type developing agent having a hydrophilicity-imparting group represented by the following general formula [A].

[0032]

[Chemical 1]

[Wherein R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, and R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a sulfo group. Base,
Represents a carboxyl group. R ₁ and R ₂ may combine to form a 5- to 7-membered nitrogen-containing heterocycle. At least one of R _{1 to} R ₆ is a substituted alkyl or substituted alkoxy group having a water-solubilizing group, and a typical example thereof is hydroxyalkyl (C ₂
~ C ₄ ), methanesulfonamidoalkyl (C ₂ ~
_{C 3), CH 2 CH 2} CO 2 H, and the like CH ₂ CH ₂ SO ₃ H. ] As the above compound, specifically, 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-3-hydroxypropylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N, N-di-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N, N-diethylaniline, 3-sulfoethyl-4-amino-N, N-diethylaniline,
3-carboxyethyl-4-amino-N, N-diethylaniline,
Examples thereof include sulfates such as 3-methyl-4-amino-N-ethyl-N-sulfoethylaniline, hydrochlorides, P-toluenesulfonates, phosphates and the like, or a mixture of two or more thereof.

Of the above P-phenylenediamine derivatives, 3-methyl-4-amino-N-ethyl-N-β-hydroxyaniline and 3-methyl-4-amino-N-ethyl-N-3 are particularly preferable.
-Hydroxypropylaniline.

4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline and 3-methyl-
A combination of 4-amino-N-ethyl-N-3-hydroxypropylaniline and two types is also a particularly preferred embodiment.

The content of the developing agent in the developer is generally 5 mmol or more, preferably 0.01 to 0.2 mol, more preferably 0.02 to 0.1 mol. For example, when processing a light-sensitive material having a silver amount of 0.6 g / m ^{2 and a} film thickness of 10 μm with a small amount of a developer of 30 cc / m ² , it is necessary to adjust the concentration to about 0.09 to 0.1 mol. The amount of 7-8
Equivalent to twice the highly concentrated amount.

High concentration can be achieved only by applying the above-mentioned developing agent having a hydrophilic group. It was also found that the development delay in the lowermost layer portion was small and the developing characteristics were greatly improved as compared with the developing agent having no hydrophilic group.

In carrying out the present invention, it is preferable to use a developing solution containing substantially no benzyl alcohol. Here, the term "substantially free from" means preferably 2
ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably benzyl alcohol concentration.
That is, it contains no benzyl alcohol.

The developer used in the present invention more preferably contains substantially no sulfite ion. The sulfite ion has a function as a preservative of the developing agent, and at the same time, has a function of dissolving a silver halide and a function of reacting with an oxidized product of the developing agent to reduce the dye forming efficiency. This kind of action
It is presumed to be one of the causes of the increase in fluctuations in photographic characteristics due to continuous processing. Here, the term "substantially free from" means preferably
The sulfite ion concentration is 3.0 × 10 ⁻³ mol / liter or less, and most preferably, the sulfite ion is not contained at all. However, in the present invention, a very small amount of sulfite ion, which is used for the oxidation prevention of the processing agent kit in which the developing agent is concentrated before preparing the use solution, is excluded.

An organic preservative is preferably added to the developer used in the present invention in order to maintain the preservative property of the developing agent.

The term "organic preservative" as used herein refers to all organic compounds which, when added to a processing solution for a color photographic light-sensitive material, reduce the deterioration rate of an aromatic primary amine color developing agent.
That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent due to air, among others, hydroxylamine derivatives (excluding hydroxylamine, the same applies below), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235, JP-A-63-44656, and U.S. Pat.
No. 03, No. 2,494,903, and Japanese Patent Publication No. 48-30496.

Other preservatives include various metals described in JP-A-57-44148 and 57-53749, and JP-A-59-180588.
The salicylic acids described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, etc. You may contain as needed. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferable.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferable, and the details thereof are described in JP-A-1-97953, JP-A-1-187557 and the like. Has been done.

Further, it is more preferable to use the above hydroxylamine derivative or hydrazine derivative in combination with amines, from the viewpoint of improving the stability of the developing solution and further improving the stability during continuous processing.

As the above-mentioned amines, JP-A-63-23944
Cyclic amines such as those described in JP-A No. 63-128340
Amines such as those described in JP-A-1-186939
And amines such as those described in No. 1-187557.

Particularly preferred as the organic preservative is paratoluenesulfinic acid or disulfoethylhydroxylamine diNa salt, and it is preferable to add 0.003 mol / liter to 0.008 mol / liter.

In the present invention, chlorine ion is added to the developer in an amount of 1
It can be contained up to × 10 ^-1 mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / liter, it has a drawback of delaying the development and is not preferable for achieving the object of the present invention that it is rapid and the maximum concentration is high.

In the present invention, the content of substantially no bromide ion is preferably 2 × 10 ⁻⁴ mol / liter or less, more preferably 2 × 10 ⁻⁵ mol / liter or less. Further, it is preferably 2 × 10 ⁻⁴ mol / liter or less, more preferably 2 × 10 ⁴ if it contains substantially no iodine ions.
^-5 mol / liter or less. Bromide ion retards development, remarkably suppresses intensification reaction, and reduces maximum density and sensitivity, so it is more preferable not to include it.

Here, the chlorine ion and the bromine ion may be directly added to the developing solution or may be eluted from the light-sensitive material to the developing solution during the development processing.

When directly added to the developing solution, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Preferred are sodium chloride and potassium chloride.

It is preferable that the developer used in the present invention does not substantially contain a fixing agent such as thiosulfate and a bleaching agent such as ferric organic salt (more specifically, 10 ^-5 mol or less).

Further, it may be supplied from an optical brightening agent added to the developing solution or the developing intensifying solution.

As the bromine ion supplying substance, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Thallium bromide may be mentioned, of which potassium bromide and sodium bromide are preferred.

When it is eluted from the light-sensitive material during development processing,
Both chlorine ion and bromine ion may be supplied from the emulsion, or may be supplied from other than the emulsion.

The developer used in the present invention is preferably
The pH is from 9 to 12, more preferably from 9 to 11.0, and the developer may contain other known compounds of the developer components.

In order to retain the above pH, it is preferable to use various buffers. As the buffer agent, carbonate, phosphate, borate, tetraborate, hydroxybenzoate,
Glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Especially, carbonate, phosphate, tetraborate and hydroxybenzoate have high solubility of pH 9.0 or higher.
It is particularly preferable to use these buffers because they have excellent buffering ability in the pH range, have no adverse effect on photographic performance (fog, etc.) even when added to a color developer, and are inexpensive.

Specific examples of these buffers include 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, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the developer is 0.01 to 0.
It is preferably 4 mol / liter, and particularly preferably 0.02 mol / liter to 0.2 mol / liter.

In addition, various chelating agents can be used in the developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, 1, 2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic 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 and the like can be mentioned.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the developing solution. For example, it is about 0.1 g / 10 g per liter.

If desired, any development accelerator can be added to the developer.

As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles,
Etc. can be added as needed.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine and adenine.

The developing solution applicable to the present invention preferably contains a fluorescent whitening agent. As optical brighteners, 4,
A 4'-diamino-2,2'-disulfostilbene compound is preferred. The addition amount is 0 to 5 g / liter, preferably 0.1
g to 4 g / liter.

If necessary, alkyl sulfonic acid,
You may add various surfactants, such as an aryl sulfonic acid, an aliphatic carboxylic acid, and an aromatic carboxylic acid.

The processing temperature of the developer applicable to the present invention is
20-80 ° C, preferably 30-60 ° C. The processing time is 30 seconds or less, preferably 10 to 20 seconds.

As described above, the processing method of the present invention is a method in which an exposed light-sensitive material is processed in a development assisting step and then subjected to a conventional method such as a desilvering step, a washing and / or stabilizing step, and a drying step. Can be processed. Also, the subsequent process can be performed by a painting method. Alternatively, it is not necessary to perform desilvering because the amount of coated silver is extremely small.

Next, the desilvering process applicable to the present invention will be described. As the desilvering step, generally, any step such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, the bleach-fixing solution and the fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). , Complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Iron (II
The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming the organic complex salts of I) are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid. , Propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thylium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, such as ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And aminopolycarboxylic acid, aminopolyphosphonic acid,
A ferric ion complex salt may be formed in a solution using a chelating agent such as phosphonocarboxylic acid. In addition, the chelating agent may be used in excess to form the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol / liter,
It is preferably 0.05 to 0.50 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, a compound having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July 1978 issue), a thiourea compound, or a halide such as iodine or bromide is preferable because of its excellent bleaching power. .

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or iodide (eg, ammonium iodide) or the like. If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
It is possible to add one or more kinds of inorganic acids having pH buffering ability such as citric acid, sodium citrate and tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
It is a water-soluble silver halide solubilizer such as thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas, and they 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, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of fixer per liter is 0.3
Is preferably 2 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or the fixing solution is 3 to 10
Is preferable, and 5-9 is particularly preferable.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like. The bleach-fixing solution or fixing solution contains sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative, It preferably contains a sulfite ion-releasing compound such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ion
It is preferable to contain 0.02 to 0.05 mol / liter,
More preferably, it is 0.04 to 0.40 mol / liter.

As the preservative, a sulfite is generally added, but ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound or the like may be added.

Further, a buffering agent, an optical brightening agent, a chelating agent,
You may add a defoaming agent, an antifungal agent, etc. as needed.

After desilvering processing such as fixing or bleach-fixing, washing and / or stabilizing processing is generally carried out. Further, it is preferable to carry out washing with water and / or stabilization treatment after development intensification.

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) and uses, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Can be set in a wide range. 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 a
nd Television Engineers) Volume 64, P.248-253 (1955)
May May issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, particularly 2
-4 are preferable.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced. For example, 0.5 liter to 1 per 1 m ^{2 of the} light-sensitive material.
Although it is possible to make it less than 1 liter, the effect of the present invention is remarkable, but due to the increase of the residence time of water in the tank, there are problems such as bacteria breeding and the generated suspended matter adhering to the photosensitive material. As a solution to such a problem, JP-A-62-288
The method of reducing calcium and magnesium described in No. 838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, and chlorine-based germicides such as chlorinated sodium isothianurate described in JP-A-61-120145, JP-A-63-12251.
Benzotriazole, copper ion and others described in No. 6 by Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal", (1986) Sankyo Publishing, Hygiene Technology Society "Sterilization, Sterilization and Antifungal Technology of Microorganisms" (1982)
Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal Agents
(1986), it is also possible to use the fungicide described in.

Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softening agent can be used.

It is also possible to carry out the treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a film pH suitable for stabilizing a dye, and an ammonium compound. In addition, in order to prevent the growth of bacteria in the liquid and impart antifungal properties to the processed light-sensitive material,
The above-mentioned various bactericides and antifungal agents can be used.

Further, a surfactant, a fluorescent whitening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without passing through a washing step, known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345, etc. , All can be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution is also used as a washing or stabilizing solution used after the desilvering process.

The pH of the washing step or stabilizing step is preferably 4-10, more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the light-sensitive material, but generally 15
-45 ° C, preferably 20-40 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. It is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute. The smaller the replenishment amount, the more preferable from the viewpoints of running cost, reduction of discharge amount, handleability and the like.

A specific preferable amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount per unit area from the pre-bath. Alternatively, it is 1 liter or less, preferably 500 ml or less per 1 m ^{2 of the} light-sensitive material. The replenishment may be performed continuously or intermittently.

The liquid used in the washing and / or stabilizing step is
Further, it can be used in the previous step. As an example of this, the overflow of washing water is reduced by the multi-stage countercurrent method,
It is possible to reduce the amount of waste liquid by flowing it into the bleach-fixing bath of the preceding bath and replenishing the bleach-fixing bath with a concentrated solution.

After washing with water and / or stabilizing treatment, the light-sensitive material is preferably dried by a conventional method, for example, at room temperature to 90 ° C. for 10 seconds to 10 minutes. Incidentally, the drying may be omitted.

The magenta coupler used in the silver halide photographic light-sensitive material of the present invention is disclosed in JP-A-63-30745.
Exemplified compounds (1) to (15) described on page 6 to 7 of No. 3, Exemplified compounds (1) to (3) described on pages 8 to 14 of JP-A-64-7041.
1), (46) to (50), (52) to (60), JP-A-64-6664
Exemplary compounds (I-1) to (I-2 described in No. 6 on pages 3 to 5)
4), Exemplified compounds (6) to (8), (10), (12) to (15), (18), described in JP-A 1-277236, pages 5 and 6.
(20), Exemplified compounds (M-4) to (M-35), (M-37), (M-50) to those described in JP-A-2-160233, pages 11-18.
(M-53), Exemplified Compounds (M-1) to (M-89) described on pages 5 to 9 of JP-A-2-61430, JP-A-2-296241 to 5-8.
Exemplified compounds (M-1) to (M-6) and (M-
8) to (M-12), (M-14) to (M-27), JP-A-3-.
Exemplified compounds (M-
2) to (M-29), (m-2) to (m-28), JP-A-3-
Exemplified Compounds (M-3) to (M-3)
-5), (M-7) to (M-12), (M-14), (M-
16) to (M-30) and the exemplified compounds (M-1) to (M-38) described in JP-A-3-138644, pages 6 to 10.

As the yellow and cyan couplers used in the silver halide photographic light-sensitive material of the present invention, a coupling reaction with an oxidant of a color developing agent to form a coupling having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm. Any compound capable of forming a substance can be used,
Particularly, as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 600 nm
Magenta coupler with spectral absorption maximum wavelength, wavelength range
A typical one is a cyan coupler having a spectral absorption maximum wavelength in the range of 600 to 750 nm.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula [Y-I] described in JP-A-4-114154, page 3, upper right. Can be mentioned.
Specific compounds are described in YC-1 to YC on pages 3 to 4 of the specification.
Those listed as -9 can be mentioned.
Among them, YC-8 and YC- described on page 4 of the same specification.
No. 9 is preferable because it can reproduce a preferable yellow color.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
JP-A-4-114154, the general formula (CI) described in the lower left of page 5,
The coupler represented by (C-II) may be mentioned. Specific compounds include CC in pages 5 and 6 of the specification.
Those described as -1 to CC-9 can be mentioned.

One of these preferably used cyan couplers is a 2-acylamino-5-ethylphenol cyan coupler, which is a compound described in JP-A-2-251845, page 5, lower right, page 14 to page 6, upper left. is there. Specific examples thereof include couplers No. II-1 to II-20 in the upper right column of page 6 to the upper left column of page 7 of the above specification. Most preferably used among these is the compound represented by II-4. Another type of cyan coupler preferably used is a 2,5 diacylaminophenol type cyan coupler, which is disclosed in JP-A-2-251845, page 3, from the upper left end to 7
It is the compound described in the 4th line from the 3rd line to the lower right. Specific examples thereof include couplers No. I-1 to I-31 in the upper left column on page 4 to the lower left column on page 5 of the above-mentioned specification. Among these, the compound represented by I-2 is most preferably used.

The coating amount of each coupler according to the present invention is not particularly limited as long as a sufficiently high concentration can be obtained, but preferably 1 × 10 6 per mol of silver halide.
^{-3 to} 5 mol, more preferably 1 x 10 ^-2 to 1 mol.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. As a high-boiling organic solvent that can be used to dissolve and disperse couplers and the like, 100
A high boiling point organic solvent having a vapor pressure at 0.5 ° C. of 0.5 mmHg or less is preferable. Specific examples of the compound include compound examples II-1 to II-9 and III-1 to III-6 described in JP-A-63-103245. Compound examples H-1 to H-22 described in JP-A 1-196048, and compound examples II-1 to II-38 described in JP-A 64-66646 can be preferably used. As a surfactant that can be used at the time of dispersion, for example, JP-A 64-26854 55
Examples thereof include the anionic surfactants A-1 to A-11 described on pages 56 to 56. Moreover, you may use the surfactant which substituted the fluorine atom in the alkyl chain.

For the purpose of shifting the absorption wavelength of the color forming dye, for example, the compound (d-11) described in JP-A-4-114154, page 9, lower left, and the compound (A'-, described in page 10, upper left of the same specification).
Compounds such as 1) can also be used.

The magenta coupler according to the present invention comprises, as a fading-preventing agent, phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541,
A phenolic compound represented by the general formula IIIB described in JP-A-3-174150 and an amine compound represented by the general formula A described in JP-A-64-90445 may be used.

As the anti-fading agent for the yellow coupler and the cyan coupler according to the present invention, the compound represented by the general formula I'described on page 8 of JP-A 1-196049 may be used. As the anti-fading agent, it is preferable to use different compounds in combination.

In the present invention, as the ultraviolet absorber, a compound having a spectral absorption maximum wavelength in the ultraviolet region (400 nm or less) and a molecular extinction coefficient of 5000 or more may be used. Examples of the compound include the compound represented by the general formula III-3 described in JP-A 1-250944 and the compound represented by the general formula I described in JP-A 4-1633.

In the present invention, a hydroquinone compound may be added in order to prevent color turbidity or adjust gradation. Moreover, you may use together the quinone body which is an oxidation body of these hydroquinone type compounds.

In the present invention, a fine particle powder (so-called matting agent) can be added to the layer farthest from the support and the surface layer. Examples of the matting agent include compounds described in JP-A-2-73250, page 4, lines 9 to 20. It is also possible to add a high boiling point organic solvent to the surface layer.

In the present invention, an oil-soluble dye can be added. An oil-soluble dye has a solubility in water at 20 ° C of 0.01
The following organic dyes are referred to, and compounds having a molecular absorption coefficient of 20,000 or more at the maximum absorption wavelength at a wavelength of 400 nm or more are preferable. Specific compounds include compounds 1 to 27 described on pages 8 to 9 of JP-A-2-842.

In the present invention, it is preferable to add a fluorescent whitening agent to the light-sensitive material. As a fluorescent whitening agent, JP-A-2-
Compounds of general formula II described in 232652 are preferred.
Specific examples of the compound include compounds 1 to 6 described on pages 6 to 7 of the above specification.

In the present invention, a water-soluble polymer compound which complements the above-mentioned optical brightening agent and enhances the optical brightening effect can be added. For example, polyvinylpyrrolidone and a polymer containing vinylpyrrolidone as a repeating unit are used. It is preferable that these are contained in the ultraviolet absorber-containing layer most distant from the support and / or in the layer further distant from the layer.

For the silver halide photographic light-sensitive material of the present invention, it is preferable to use water-soluble dyes having absorption in various wavelength regions for the purpose of preventing irradiation and halation. As a preferable anti-irradiation dye, a compound represented by the general formula II described in JP-A-62-253146 (specific examples of the compound are compounds II-1 to II-19 described on pages 12 to 13 of the above specification). Compounds represented by the general formula I described in JP-A 1-26850 (specific examples of compounds are Compound Nos. 1 to 85 described on pages 7 to 11 of the above specification), and compounds described in JP-A-2-97940 Compounds represented by Formula I (specific examples of compounds are compounds represented by Nos. 1 to 103 described on page 5, lower column to page 9, upper column of the same).
Is mentioned. As the anti-irradiation dye, it is preferable to use a dye having different maximum absorption wavelengths together, 600n
Dyes with maximum absorption in m to 700 nm and 500 nm to 600
It is preferable to use a dye having a maximum absorption wavelength in nm and a dye having a maximum absorption wavelength in 400 nm to 500 nm together.
These dyes may be added to any layer, but are preferably added to the non-photosensitive layer. The addition amount, each of the compounds per preferably 1 to 100 mg / m ^2, still more preferably is 3~60mg / m ^2. The optical reflection density of the finished light-sensitive material is preferably 0.7 or more at 680 nm and not more than the optical reflection density at 680 nm.

In the silver halide photographic light-sensitive material of the present invention, gelatin can be used as a binder for dispersion and coating liquid. In addition, the film of the finished photosensitive material
The pH is usually 5.0 to 6.5.

In the present invention, a binder hardener is used. As a hardener, vinyl sulfone type hardener,
A chlorotriazine type hardener can be mentioned. As the vinyl sulfone type hardener, the compounds described in JP-A-61-249054, page 25, upper right column, line 13 to page 27, upper right column, line 2, and as chlorotriazine-based hardeners, JP-A-61-245153 The compounds described on page 3, lower left column, line 1 to page 3, lower right column, bottom to line 4 and page 3, lower right column, line 4 to page 5, lower left can be mentioned.

In the present invention, it is preferable to add an antifungal agent to either layer. As the antifungal agent, preferred compounds include the general formula [II] described in JP-A-3-157646, page 2.
Compounds represented by are preferred. Specific examples of the compounds include the compound examples No. 9 to No. 22 described on page 19 of the above specification.
Is mentioned. Of these, a particularly preferable compound is a compound represented by No. 9.

The silver halide grains according to the present invention may have any shape. US Patent 4,183,756
No. 4,225,666, JP-A-55-26589, JP-B-55-4273
No. 7 and The Journal of Photographic
Using particles such as octahedron, dodecahedron, dodecahedron and the like, by the method described in the literature such as Science (J.Photogr.Sci.) 21, 39 (1973), etc. You can also Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes.

The particle size of the silver halide grain according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is up to 1.0 μm.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less.

There is no limitation on the coating amount of the silver halide emulsion, but if the coating amount per each photosensitive layer is too large or too small, color reproducibility is deteriorated due to problems such as color turbidity and soft gradation. because there is, in terms of the photosensitive layer per silver, preferably from 5 to 100 mg / m ^2, more 10 to 50 mg / m ²
Is more preferable. Further, the balance of the coated silver amount between the respective photosensitive layers may be any, but it is more preferable in terms of gradation balance that the coated silver amount of the photosensitive layer closer to the support is larger than that of the layer far from the support.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany. Apparatus for adding water-soluble silver salt and water-soluble halide salt aqueous solution described in Patent 2,921,164 etc. while continuously changing the concentration, and taking out the reaction mother liquor from the reactor described in JP-B-56-501776 etc. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: (IIa-1) to (IIa-8) and (IIb-1) to
Compound (IIb-7) and 1- (3-methoxyphenyl) -5
-Mercaptotetrazole and the like can be mentioned. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it was spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention.
BS-1 to 8 described on page 28 of 1840 can be preferably used alone or in combination. As the green sensitizing sensitizing dye, GS-1 to 5 described in the lower right of page 28 of the same specification are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same specification are preferably used.

A developing agent precursor can be added to the silver halide photographic light-sensitive material of the present invention. The developing agent precursor may be added to either the silver halide photosensitive layer or the non-photosensitive layer.

The developing agent precursor of the present invention is a compound represented by the following general formula (I).

General formula (I) Bl- (Time) _m -CD where Bl represents a block group and Tim
e represents a timing group, m represents an integer from 0 to 3, and CD represents an aromatic primary amine developing agent.

The compound represented by formula (I) will be described in more detail below.

The block group represented by Bl is a group capable of cleaving the bond between Bl and (Time) _m -CD by a hydrolysis reaction initiated by a component (eg, acid or base) in the treatment liquid. Examples of these include blocking groups such as acyl groups and sulfonyl groups described in JP-B-47-44805, JP-A-59-93442 and JP-A-59-104641, JP-B-54-39727,
No. 55-9696, No. 55-34927, etc., a block group whose bond is cleaved by a reverse Michael reaction, Japanese Examined Patent Publication No. 54-39727,
JP-A-57-135944, 57-135945, 57-136640,
57-154234, 58-1139, 58-1140, 58-2097
A block group in which the bond is cleaved with the formation of a quinone methide or a quinone methide-like compound by intramolecular electron transfer as described in JP 36, etc., a block group in which the bond is cleaved by an intramolecular ring closure reaction described in JP-A-55-53330 and the like. , JP-A-57-76541
No. 57-135949, No. 57-179842, etc., a block group in which the bond is cleaved by a 5-membered or 6-membered ring cleavage, and JP-A-2-296240, 4-177243, No. 4-177244,
4-177245, 4-177246, 4-177247, 4-1772
No. 48, No. 4-179948, No. 4-184337, No. 4-184338, No.
Β- or γ-ketoacyl type block groups described in 5-45816 and the like, other JP-A-59-137945, 59-140445,
59-201057, 59-202459, 59-218439, 60-
41034, 61-32839, 61-43739, 61-80239
No. 61, No. 61-83532, No. 61-95346, No. 61-95347, No. 61
-113059, 61-114238, 63-318555, and the block groups described in US Pat. Nos. 4,468,451 and 4,743,533. Among these, a preferable blocking group is a β- or γ-ketoacyl type blocking group, and a blocking group represented by the following general formula (II) is more preferable.

[0129]

[Chemical 2]

Wherein R ₁ is an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl or the atoms necessary to complete together with R ₂ and Z a ring, especially an alicyclic or heterocyclic ring. in and, Z represents the atoms necessary to complete a ring together with R ₁ and R _2, R ₂ may cause nucleophilic substitution reaction by treating in the presence of 2 nucleophilic agent A substituted or unsubstituted carbon or nitrogen atom, which thus provides a distance between the carbonyl groups, and P is 0 or 1.

Particularly preferred blocking groups are represented by the following general formula (II
It is represented by I), (IV) and (V).

[0132]

[Chemical 3]

Here, R ₃ is an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, and R ₄ , R ₅ ,
R ₆ and R ₇ are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, and R ₃ , R ₄ ,
R ₅ , R ₆ and R ₇ are preferably methyl groups.

Typical timing groups represented by Time are, for example, JP-A Nos. 52-90932, 54-145135 and 5
6-114946, 57-154234, 57-188035, 58-987
No. 28, No. 58-209736, No. 58-209737, No. 58-209738
No. 58-209739, No. 63-37346, JP-A-2-47651,
It is a timing group described in the specifications of No. 2-256047 and No. 4-216547. Of these, preferred timing groups are represented by the following general formulas (VI) and (VII).

[0135]

[Chemical 4]

Ar represents a substituted or unsubstituted phenylene group, -O- and -R ₁₁ -are bonded to the phenyl group in the ortho or para position, and R ₁₁ is substituted or unsubstituted. Represents a substituted methylene group, R ₁₂ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, R ₁₃ represents a substituted or unsubstituted alkyl group, aryl group, alkoxy group, acyl group, alkoxycarbonyl group Represents a carbamoyl group or a cyano group.

The aromatic primary amine developing agent represented by CD is preferably a p-phenylenediamine or p-aminophenol derivative, and is an alkyl group, a hydroxyalkyl group, a sulfonamidoalkyl group, a sulfoalkyl group or a carboxyalkyl group. Substituted ones are preferred.

The CD precursors of the present invention are preferably treated in the presence of a nucleophile containing two nucleophilic groups.
Such nucleophiles include H ₂ O ₂ , NH ₂ NH ₂ , NH ₂ OH, CH ₃
NHNHCH ₂ , CH ₃ NHOH, CH ₃ CONHOH, CH ₃ SO ₂ NHNH ₂ , NHCON
H ₂ , NH ₂ -C (= NH) NH ₂ , CH ₃ -C (= NH) NH ₂ , NH ₂ CH ₂ CH ₂ NH ₂ , NH
₂ CH ₂ COOH, NH ₂ —C (CH ₃ ) ₂ CH ₂ OH, NH ₂ CH ₂ CH ₂ SH, 1,2-diamine-cyclohexane and the like, and hydroxylamine, hydrogen peroxide and monosubstituted hydroxylamine preferable.

[0139] The amount of CD precursor of the present invention is preferably a 10 mmol / m ² from 0.1 mmol / m ^2.

The CD precursors of this invention can be incorporated into photographic elements by known methods. One way is
It can be added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Further, the alkali-soluble CD precursor can be added by the Fisher dispersion method. Further, it can be added to a photographic element by a solid fine particle dispersion method.

Typical examples of the CD precursor of the present invention are shown below.

[0142]

[Chemical 5]

[0143]

[Chemical 6]

[0144]

[Chemical 7]

[0145]

[Chemical 8]

[0146]

[Table 1]

[0147]

[Table 2]

As the reflective support according to the present invention, any material may be used, including white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The print sample obtained after the exposure and development treatment can be subjected to various post-treatments, for example, application of an ultraviolet curable resin or lamination with a laminating material containing an ultraviolet absorber.

[0151]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of boiling point organic solvent (DNP) to dissolve, and this solution was dissolved in 15% of surfactant (SU-1) 9.5 m.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing l using an ultrasonic homogenizer. This dispersion was stored at 60 ° C. for 30 minutes and mixed with a blue-sensitive silver halide emulsion (containing 0.868 g of silver) prepared under the following conditions to prepare a coating solution for the first layer and coating. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
In addition, (H-1) is used as a hardener in the second and fourth layers,
(H-2) was added to the seventh layer, and the first to seventh layers were simultaneously multilayer coated. As a coating aid, a surfactant (SU
-2) and (SU-3) were added to adjust the surface tension.

The layer structure is as shown in the table below.

[0155]

[Table 3]

[0156]

[Table 4]

[0157]

[Chemical 9]

[0158]

[Chemical 10]

[0159]

[Chemical 11]

[0160]

[Chemical 12]

[0161]

[Chemical 13]

[0162]

[Chemical 14]

[0163]

[Chemical 15]

[0164]

[Chemical 16]

(Preparation of blue-sensitive silver halide emulsion) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (C solution) and (D solution) to pA
Simultaneous addition was carried out over 180 minutes while controlling g = 7.3 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water was added to 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.0 mol% was obtained.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0173]

[Chemical 17]

[0174]

[Chemical 18]

Sample 101 was exposed to 0.1 sec.
After performing optical wedge exposure to obtain an exposure amount of 0 CMS, the following processing steps and processing solutions were used under the following processing conditions, and 10
Treatments were carried out continuously for 20 days at m ² / day. (Experiment 1) Processing temperature (℃) Time (sec) Replenishment rate (ml / m ² ) Development power 35 45 50 (Color development replenisher) * 2.5 (Peroxide-containing replenisher) * Bleach fixing 25 ~ 40 45 50 Stable 25-40 15 200 * Replenished constantly during heat up.

<Color development replenisher> anhydrous potassium carbonate 30.0 g 1-hydroxyethane-1,1-diphosphonic acid 0.6 g 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3 / 2 Sulfate 6.0g Disulfoethylhydroxylamine / 2Na salt 20.0g Ethylene glycol 15.0g Potassium chloride 0.6g Optical brightener 3.0g Add water to make 1 liter (pH 10.65).

<Color Development Starter> Potassium chloride 2.3 g Potassium carbonate 2.4 g Potassium hydrogen carbonate 5.7 g Water is added to make 50 ml (pH 9.5).

<Peroxide-containing intensification replenisher> Sodium dihydrogen phosphate 10.0 g 30% hydrogen peroxide water 100 g Water is added to make 1 liter (pH 4.6).

<Color Development Intensifying Solution> Color developing replenishing solution 700 ml Color developing starter 50 ml Peroxide-containing intensifying replenishing solution 50 ml (mixed just before use) Add water to make 1 liter (pH 10.3).

<Bleaching solution and its replenisher> Potassium hydrogen carbonate 25.0 g Potassium chloride 0.5 g 30% hydrogen peroxide solution 50.0 g Water is added to make 1 liter (pH 10.0).

<Fixer and Replenisher> Sodium thiosulfate 10.0 g Sodium sulfate 20.0 g Glacial acetic acid 20.0 ml Water is added to make 1 liter (pH 4.8).

<Stabilizing Solution and Replenishing Solution> Sodium hydrogen sulfite 3.0 g Sodium sulfite 2.6 g Optical brightening agent (WHITEX4B manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2-Mercaptobenzimidazole-5-sulfonate 1.0 g Water was added. Make 1 liter (pH 6.7).

Further, Experiments 2 to 5 were performed in exactly the same manner as Experiment 1 except that the following was used instead of sodium dihydrogen phosphate in the peroxide-containing replenisher.

Addition amount (g) pH Experiment 1 (Invention) Sodium dihydrogen phosphate 10 4.6 Experiment 2 (Comparison) Sodium phosphate 10 11.0 Experiment 3 (Comparison) Potassium carbonate 10 10.0 Experiment 4 (Comparison) Sodium hydrogencarbonate 10 8.0 Experiment 5 (Invention) Boric acid 10 4.8 Table 5 shows the B, G, and R concentrations at the specific exposure doses obtained in Experiments 1 to 5 on the 1st, 10th, and 20th days.

[0185]

[Table 5]

As is clear from the above table, in Experiments 2, 3 and 4 in which the peroxide-containing intensification replenisher solution was alkaline, the concentration had already decreased from the 10th day, and on the 20th day, all were large. It causes a wide concentration drop.

On the other hand, in Experiments 1 and 5 in which the peroxide-containing intensification replenisher according to the present invention was acidic, it was found that there was almost no change in concentration from day 1 to day 20, and stable treatment was performed.

Example 2 Sample No. 101 of Example 1 was continuously treated for 40 days in the same manner as in Example 1. The samples treated on the 1st, 20th and 40th days were designated as Experiment 6.

In the sample No. 101 of Example 1, the CD shown in Table 1 was used as the first layer, the third layer and the fifth layer of the photosensitive material.
The same samples were prepared except that the precursors 1, 2 and 3 were added respectively. These samples were tested in the same manner as in Experiment 6, and designated as Experiments 7, 8, and 9, respectively. For each layer
The amount of CD precursor added is 0.94 mmol for the first layer.
/ M ^2, the third layer 0.46 mmol / m ^2, the sixth layer 0.58 mmol /
It was set to m ² . The results are shown in Table 6.

[0190]

[Table 6]

Example 3 In Example 2, addition was made to the first layer, the third layer and the fifth layer.
CD precursors 1, 2, and 3 are the second layer, the fourth layer, and the sixth layer, respectively.
Identical samples were made except that they were added to the layers. These samples were exposed, processed and evaluated in the same manner as in Experiment 6 of Example 2 and designated as Experiments 10, 11 and 12, respectively. The results are shown in Table 7.

[0192]

[Table 7]

The sample of Example 3 in which the CD precursor was added to the non-photosensitive layer exhibited the effect of the present invention more effectively than the sample of Example 2.

[0194]

According to the present invention, there is provided a method for forming a color image capable of continuously and stably assisting development of a silver halide color light-sensitive material having a low silver content by a development intensification treatment using a peroxide. be able to.

Claims (1)

[Claims] 1. A development replenishing treatment in the presence of a peroxide of a silver halide color light-sensitive material containing a stoichiometrically excess of at least 50 mol% of a coupler with respect to silver halide is continuously conducted by a replenishing method. A method for forming a color image, wherein the peroxide-containing intensifying replenisher does not contain a color developing agent and has a pH of 7 or less.