JPH0743524B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it enables rapid processing and has improved processing stability in the rapid processing. The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

BACKGROUND OF THE INVENTION In recent years, there has been a demand in the art for a technique capable of rapidly processing a silver halide color photographic light-sensitive material, and having excellent processing stability and stable photographic characteristics.
In particular, a method for processing a silver halide color photographic light-sensitive material that can be processed rapidly is desired.

In other words, silver halide color photographic light-sensitive materials are run by an automatic processor provided in each laboratory. Users are required to return it, and nowadays, it is even required to return it from the reception desk within a few hours, and there is an urgent need for development of technology that can be processed rapidly.

Regarding the rapid processing of silver halide color photographic light-sensitive materials, the prior arts are examined. [1] Technology by improvement of silver halide color photographic light-sensitive material, [2] Technology by physical means during development processing, [3] Development processing The above-mentioned [1] relates to an improvement of the silver halide composition (for example, a technique for forming fine grains of silver halide as described in JP-A-51-77223 and a special technique). A technique for reducing silver bromide of silver halide as described in JP-A-58-183142 and JP-B-56-18939, and use of an additive (for example, a specific structure as described in JP-A-56-64339). A technique for adding 1-aryl-3-pyrazolidone to a silver halide color photographic light-sensitive material and a method disclosed in JP-A-57-14454
No. 7, No. 58-50534, No. 58-50535, No. 58-50536, a technique of adding 1-arylpyrazolidones to a silver halide color photographic light-sensitive material), a high-speed reactive coupler (For example, Japanese Patent Publication No. 51-10783, Japanese Patent Laid-Open No. 50-10783)
-123342, 51-102636, the technology of using a high-speed reactive yellow coupler), the thinning technology of the photographic constituent layers (for example, the thinning technology of the photographic constituent layers described in Japanese Patent Application No. 60-204992), etc. Regarding the above [2], there is a stirring technique for the processing liquid (for example, the stirring technique for the processing liquid described in Japanese Patent Application No. 61-23334), and for the above [3], a development accelerator is used. Techniques used, techniques for thickening color developing agents, techniques for reducing the concentration of halogen ions, especially bromide ions, etc. are known.

The processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilizing treatment, washing with water or stabilizing treatment as an alternative to washing with water are added as additional treatment steps. That is, in color development, exposed silver halide is reduced to silver and at the same time oxidized aromatic primary
The primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as an inhibitor contained in the light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the light-sensitive material as soluble silver salts by a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

Among the rapid processing techniques of the above [1], a technique of using a silver halide light-sensitive material containing silver halide grains having a high concentration of silver chloride (for example, JP-A-58-95345 and JP-A-60-). 1
9140, JP-A-58-95736 and the like) provide particularly excellent speed-up performance. However, the use of such a high silver chloride-containing light-sensitive material has a drawback that a sulfite salt usually contained in a color developing solution causes a physical development reaction, resulting in an insufficient dye concentration. For this reason, the high silver chloride-containing light-sensitive material is in a dead state in which it must be used in a concentration range where the amount of phosphite is extremely low. However, when a high-silver chloride-containing light-sensitive material is developed with a color developer having a low sulfite concentration, sufficient speed can be obtained, but when a bleach-fixing process is continuously performed, a preservative in the color developer is used. It has been found that the so-called bleaching fog is likely to occur due to the oxidation of the color base agent due to the low concentration of certain sulfite.

In particular, bleach-fixing solutions tend to have low replenishment or high reproducibility due to the recent demand for low pollution and cost reduction, and in such a case, the amount of the color developing solution accumulated in the bleach-fixing solution is high. Is increasing. That is, when the bleach-fixing solution is made to have a low replenishment rate or a high regeneration rate, the influence of evaporation or a regenerating operation or the difference in the processing amount of the photographic light-sensitive material (for example, between the beginning of the week when the order volume is large and the weekend when the order volume is decreasing). The amount of the color developing solution in the bleach-fixing solution increases due to the difference in processing amount or the difference in processing amount between high season and off season. Under such circumstances, photographic characteristics such as bleaching fog are further deteriorated and the photographic characteristics are significantly deteriorated.
031, British Patent 1,131,335, U.S. Patent 3,293,036
However, the actual situation is that there are more and more items that cannot be supplemented.

Another problem is that a highly silver chloride-containing light-sensitive material, which is a very effective technology for speeding up, contains hydroxylamine (which has been usually used as a preservative for color developing agents) in a color developer. In this case, there is a disadvantage that a silver developing reaction occurs and a sufficient dye concentration cannot be obtained. However, when this preservative hydroxylamine was removed from the color developing solution, a sufficient dye concentration was obtained, but the color developing solution became extremely unstable, and the color developing solution was subsequently treated with a bleach-fixing solution. In that case, there is a drawback that bleaching fog is extremely likely to occur, and there is a trade-off relationship.

[Object of the Invention] Therefore, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which uses a high chloride silver halide to provide a rapid developing property and has less fog in a bleach-fixing solution. Is provided. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material that causes less stain even when the bleach-fixing solution is replenished at a low level. A third object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material having improved processing stability. A fourth object is to provide a method for processing a silver halide color photographic light-sensitive material, in which the preservability of the color developing solution is improved and the generation of stain is small.

Other objects of the present invention will be clarified by the following description of the present specification.

[Structure of the Invention] As a result of various studies, the inventors of the present invention have found that the object of the present invention is to perform at least a color development step after imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer. Further, in the processing method of a silver halide color photographic light-sensitive material, which is subjected to processing including a bleach-fixing step subsequent to the color developing step, the silver halide emulsion layer comprises silver halide grains composed of 80 mol% or more of silver chloride. A silver halide emulsion layer containing at least one sequestering agent having the function of sequestering iron ions and at least one sequestering agent of calcium used in the color developing step. A sequestering agent of the same type is not present at the same time,
The bleach-fixing solution used in the bleach-fixing step has a pH of from 4.5 to 10 and a sulfite concentration of 4 × 10 ^-3 mol or less per color developing solution.
The present invention has been completed by finding out that it can be achieved by a processing method of a silver halide color photographic light-sensitive material in the range of 6.8.

General formula [I] (In the formula, R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms.) [Specific Structure of the Invention] The color developer used in the present invention has been conventionally used as a preservative. In place of hydroxylamine present in the formula [I]
The compound represented by (hereinafter referred to as the compound of the present invention) is used.

In the general formula [I], R ¹ and R ² each have 1 to 1 carbon atoms.
The alkyl group having 1 to 3 carbon atoms represented by R ¹ and R ² may be the same or different, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and iso.
-Propyl group and the like.

R ¹ and R ² are preferably both ethyl groups.

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the present invention is not limited thereto.

These compounds of the present invention are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

The concentration of the compound of the present invention in the color developer is preferably the same level as that of hydroxylamine usually used as a preservative, for example, 0.2 g / l to 50 g / l is preferably used, and more preferably 1 g / l to 30 g. / l, more preferably 5g / l ~ 20g
/ l.

Among the compounds represented by the general formula [I] of the present invention, for example, N, N-diethylhydroxylamine can be used as a preservative for a black and white developing agent in a color developer containing a black and white developing agent. Are known.

Usually, black-and-white developing agents such as hydroquinone, hydroquinone monosulfonic acid, phenidone, and para-aminophenol are relatively stable when used as a black-and-white developing agent in a black-and-white developing solution, and sulfite should be used as a preservative. However, it is known that the storage stability thereof is extremely poor when it is added to the color developing solution to cause a cross-oxidation reaction with the color developing agent. To maintain the black and white developing agent added to the color developer,
Hydroxylamine has little effect.

As a preservative for black and white developing agents added to color developers
As an example of using N, N-diethylhydroxylamine, it is known to use with phenidone in a so-called external color development method of developing a color photographic light-sensitive material by a reversal method using a color developer containing a coupler. ing. The role of phenidone in this case is to increase the development speed of the external photosensitive material having poor developability and to increase the density of the dye image.

Further, in a magenta color developer containing no such phenidone, N, N-diethylhydroxylamine is
It is known that destruction of the coupler rather adversely affects the storage stability of the external color developer (see Japanese Patent Publication No. 45-22198).

As a preservative for black and white developing agents added to color developers
Other examples of using compounds of the present invention, such as N, N-diethylhydroxylamine, in internal color developers are:
A technique for preserving the phenidone derivative added to the color developing solution (see JP-A-53-32035), and a technique for preserving the phenidone derivative together with hydroquinones (JP-A-53-32035).
52-153437).

As described above, the compound of the present invention is conventionally known to be used as a preservative for a black and white developing agent added to a color developing solution, but a preservative for a color developing agent in a normal color developing solution is used. Is not known as.

As described above, some of the compounds of the present invention are already known as preservatives for black and white developing agents added to color developers, but in the present invention, the sulfite concentration described below is 4 Not more than × 10 ^-3 mol / l effectively acts as a preservative for a normal color developing solution, but it is also effective in improving the bleaching stain generated in the bleach-fixing solution described in detail below. It was amazing.

The color developer used in the present invention has a sulfite concentration of 4 × 10 ⁻³ mol or less, preferably 2 × 10 ^{−3 to} 0 mol, per 1 color developer.

In the conventional color developing solution, sulfite is usually used as one of the preservatives in an amount of about 8 × 10 ^-3 to 4 × 10 ^-2 mol per color developing solution. Application to the invention resulted in a decrease in color density which is believed to be due to the dissolution of silver chloride. The present invention solves the above problems by reducing the sulfite concentration to a specific range and further by using a bleach-fixing solution having a specific pH described above in combination.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

As the color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of the effect of the present invention.

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage of not contaminating the light-sensitive material and being less prone to skin rash, In the invention, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I].

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble group _{- (CH 2) n-CH} 2 OH, - ( CH ₂ ) m-NHSO _2- (CH ₂ ) n-CH ₃ ,-(CH ₂ ) mO- (C
H ₂ ) n-CH ₃ ,-(CH ₂ CH ₂ O) nCmH _2m-1 (m and n are 0 respectively
Represents the above integers. ), —COOH group, —SO ₃ H group and the like are preferred.

Specific examples of the color developing agent preferably used in the invention are shown below.

Illustrative coloring phenomenon Of the above-illustrated color developing agents, preferred for use in the present invention are Exemplified Nos. (A-1), (A-2), (A-3), and (A-
4), (A-6), (A-7) and (A-15), and (A-1) is particularly preferable.

The color developing agent is usually used in the form of salt such as hydrochloride, sulfate, p-toluenesulfonate.

The color developing agent having a water-soluble group used in the present invention is
Usually, it is preferably used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developer, but from the viewpoint of rapid processing, it is 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per color developer. Is more preferable.

The color developer used in the present invention may contain the following developer components in addition to the above components.

As the alkaline agent other than the carbonate, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination, The effect of the present invention, that is, the precipitation is not generated, and it can be used in combination within a range of maintaining the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate are used for the necessity of preparation or for the purpose of increasing ionic strength. can do.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary.
Development accelerators include U.S. Pat. Nos. 2,648,604 and 3,6.
71,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990, Second 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol and its derivatives described in 44-9504 publication, nonionic compounds such as polythioethers, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also US Patent No. 2,
Examples thereof include benzyl alcohol, phenethyl alcohol described in No. 304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

In the above, particularly for poorly soluble organic solvents typified by benzyl alcohol, by using the color developing solution for a long period of time, tar easily occurs particularly in running processing in a low replenishment system, and the generation of such tar is Adhesion to the processed paper sensitive material may even cause a serious failure that significantly impairs its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a stirring device is required for the preparation of the color developing solution itself, but the use of such a stirring device also causes Due to the badness, the effect of promoting development is limited.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as labor and cost,
It is preferable to reduce or eliminate the amount used.

Further, the color developing solution used in the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other Japanese Patent Publication No. 47-33378, 44-9509 each gazette The compounds mentioned can be used as organic solvents for increasing the solubility of developing agents.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor releasing type couplers (so-called DIR
It is also possible to add a coupler), or a development inhibitor releasing compound.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multi-layer effect accelerator can be used.

In the present invention, the effect of the object of the present invention is better exhibited when the triazyl stilbene-based optical brightening agent represented by the following general formula [XV] is used in the color developer according to the present invention.

General formula [XV] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (eg, phenoxy, p-sulfophenoxy etc.), alkyl group (eg methyl, ethyl etc.), aryl group (eg phenyl, methoxyphenyl etc.), amino group, alkylamino group (eg methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino). , Β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N
-(Β-sulfoethyl) -N'-methylamino, N-
(Β-hydroxyethyl-N′-methylamino, etc.), arylamino group (eg, anilino, o-, m-, p-sulfoanilino, o-, m-, p-chloroanilino, o
-, M-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned, but not limited to these.

[Exemplified compound] The triazyl stilbene-based whitening agent represented by the general formula [XV] is synthesized, for example, by the usual method described on page 8 of "Fluorescent whitening agent" edited by Chemical Industry Association (August 1976). be able to.

These triazyl stilbene whitening agents are preferably used in the range of 0.2 to 6 g, and particularly preferably 0.4 to 3 g, per 1 color developing solution used in the present invention.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. In this case, the component having a low solubility in water can be added by mixing with the organic solvent such as triethanolamine. More generally, a plurality of components, each of which can coexist stably, are prepared in a concentrated aqueous solution, or in a solid state in a small container prepared in advance by adding to water and stirring to prepare a color developing solution of the present invention. Obtainable.

In the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C. or higher,
The temperature is 50 ° C. or lower, and the higher the temperature, the quicker the processing can be performed, which is preferable. On the other hand, the image storage stability is preferably not so high, and the temperature is preferably 33 ° C. or higher and 45 ° C. or lower.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it can be set within 2 minutes.
It is also possible to perform in the range of 30 seconds to 1 minute 30 seconds.

In the processing method of a silver halide color photographic light-sensitive material of the present invention, the compound represented by the general formula [I] is contained, and further, the sulfite concentration is 4 × 10 per color developing solution.
^-3 mol or less, using a color developing solution, various other methods including one-bath treatment, for example, a spray method for atomizing the treatment liquid, or a web by contact with a carrier impregnated with the treatment liquid Although various processing methods such as a method or a developing method using a viscous processing solution can be used, the processing steps substantially include steps such as color development, bleach-fixing, washing with water or a stabilizing process in place thereof.

The bleach-fixing step of the present invention is a bleach-fixing bath in which bleaching and fixing are processed in a single bath, and the bleach-fixing solution has a pH of 4.5 to 6.8. Therefore, in the present invention, it is possible to effectively prevent the occurrence of stains that are likely to occur in the bleach-fixing solution.

The bleaching agent that can be preferably used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is an aminopolycarboxylic acid or an organic acid such as citric acid, iron,
Coordination of metal ions such as cobalt and copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine Citric acid (or tartaric acid) [9] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. 20-250g
/ l, more preferably 25-100 g / l. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. Bleach-fixing solution composed of a large amount of compounds added, and further iron (III) diaminetetraacetate (III)
It is also possible to use a special bleach-fixing solution having a composition comprising a combination of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 20 g to 120 g / l are used.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The processing temperature is 80 ° C. or lower and the temperature is 3 ° C. or higher, preferably 5 ° C. or lower than the temperature of the processing solution in the color developing tank.

The halide grains used in the silver halide color photographic light-sensitive material applied to the present invention are silver halide grains containing at least 80 mol% of silver chloride, more preferably 90 mol% or more, and further preferably It contains 95 mol% or more.

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. Silver bromide is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and when silver iodide is present, 1 mol% or less, preferably 0.5 mol% or less. Such a silver halide grain substantially consisting of silver chloride according to the present invention contains 80% by weight or more of all the silver halide grains in the silver halide emulsion layer in which the silver halide grain is contained. It is preferable that the content is 100%, more preferably 100%.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal or any other crystal, and any ratio of {100} plane to {111} plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-17).
No. 0070) can also be used.

The silver halide grains used in the present invention may be those obtained by any of the acid method, the neutral method and the ammonia method.

In addition, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiodioxide. Urea, polyamine and the like; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride and the like or ruthenium, palladium, platinum, etc. Sensitizers for water-soluble salts such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these are sensitizers or antifoggants depending on the amount) Acting as an agent, etc.) or in combination as appropriate (eg, gold sensitizer and sulfur sensitizer). Combination of agents, together like a gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−6 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
242,588, Japanese Patent Publication Nos. 44-14030, 52-24844 and the like can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, 2,739,149 and 2,9.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in 45,763 and British Patent 505,979. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patents 2,269,234, 2,270,378 and
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes as described in 2,442,710, 2,454,629, 2,776,280 and the like. Furthermore, U.S. Patents 2,213,995 and 2,493,748
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat. No. 2,519,001 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43-4936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 42884, No. 45-18433, No. 47-37443, No. 48
-28293, 49-6209, 53-12375, JP-A-52-2393
No. 1, No. 52-51932, No. 54-80118, No. 58-153926, No.
59-116646, 59-116647 and the like.

Further, as a combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-34535
No. 55-1569, JP-A No. 50-33220, No. 50-38526,
51-107127, 51-115820, 51-135528, 52-
No. 104916, No. 52-104917 and the like.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanine, for example, Japanese Patent Publication Nos. 44-32753 and 46-11627,
JP-A-57-1483 and merocyanine include, for example, JP-B-48-38408, JP-A-48-41204, and JP-A-50-40662.
No. 56-25728, No. 58-10753, No. 58-91445,
No. 59-116645, No. 50-33828 and the like.

Further, as a combination of thiacarbocyanine with other carbocyanine, for example, Japanese Patent Publication Nos. 43-4932 and 43-4932
No. 4933, No. 45-26470, No. 46-18107, No. 47-8741,
JP-A-59-114533, etc., and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in a hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used are British Patent 584,609.
No. 1,277,429, JP-A-48-85130, 49-99620
No. 49, No. 114420, No. 49-129537, No. 52-108115,
59-25845, 59-111640, 59-111641, US Patents 2,274,782, 2,533,472, 2,956,079, 3,1
25,448, 3,148,187, 3,177,078, 3,247,12
No. 7, No. 3,260,601, No. 3,540,887, No. 3,575,704,
3,653,905, 3,718,472, 4,071,312, 4,0
The thing described in 70,352 can be mentioned.

These AI dyes are generally 2x per mole of silver in the emulsion layer.
It is preferable to use 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol.

The photographic coupler used in the present invention is preferably a phenol-based compound or a naphthol-based compound as a cyan coupler, for example, U.S. Patents 2,369,929 and 2,434,2.
72, 2,474,293, 2,895,826, 3,253,924
Issue 3,034,892, Issue 3,311,476, Issue 3,386,301,
3,419,390, 3,458,315, 3,476,563, 3,5
It can be selected from those described in No. 31,383 and the like, and the synthetic method of these compounds is also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As a pyrazolone-based magenta coupler, US Pat.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
84,514, 3,888,680, JP-A-49-29639, 49-11
No. 1631, No. 49-129538, No. 50-13041, Japanese Patent Publication No. 53-4716
Nos. 7, 54-10491 and 55-30615; pyrazolotriazole-based magenta couplers include couplers described in US Pat. No. 1,247,493 and Belgium Patent 792,525, and have diffusion resistance As the colored magenta coupler of, a compound in which an arylazo substitution is generally used at the coupling position of a colorless magenta coupler is used, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608,
3,005,712, 3,684,514, British Patent 937,621,
Examples thereof include compounds described in JP-A-49-123625 and JP-A-49-31448.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391, in which a dye flows out into a processing solution upon reaction with an oxidized product of a developing agent, can also be used.

As the photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are U.S. Patents 2,875,057 and 3,265,506.
No., No. 3,664,841, No. 3,408,194, No. 3,277,155,
No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. 49-13576, JP-A No. 48-29432, No. 48-68834, No. 49-10736, No. 49-1
22335, 50-28834, 50-132926 and the like, together with the synthetic method.

The amount of the above diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mol per mol of silver in the photosensitive silver halide emulsion layer.
2.0 mol.

In the present invention, a DIR compound is preferably used in addition to the above diffusion resistant coupler.

Further, in addition to the DIR compound, a compound that releases a development inhibitor upon development is also included in the present invention.
297,445, 3,379,529, West German patent application (OLS) 2,41
7,914, JP-A Nos. 52-15271, 53-9116, and 59-12383.
No. 8, No. 59-127038, etc. are mentioned.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidant of a color developing agent, the mother nucleus of the coupler forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529
No. 54-13333, No. 55-161237 and the like, when a coupling reaction with an oxidant of a color developing agent, a development inhibitor is released but a compound which does not form a dye is also included. Be done.

Furthermore, JP-A Nos. 54-145135, 56-114946 and
When reacted with an oxidant of a color developing agent as described in 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction or an elimination reaction. The so-called timing DIR compounds, which are compounds that release development inhibitors by, are also included in the present invention.

Further, when reacting with an oxidized product of a color developing agent described in JP-A-58-160954 and JP-A-58-162949, a timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye. It also includes a bound timing DIR compound.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloid used for preparing the emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

As the support of the silver halide color photographic light-sensitive material used in the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, such as a glass plate, Examples thereof include polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and other usual transparent supports may be used. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
In these constituent layers, a hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder, and in the layer, the hydrophilic colloid can be contained in the emulsion layer as described above. Various photographic additives can be included.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, a color paper is a silver halide color photographic light-sensitive material as long as it is a light-sensitive material processed by a so-called internal development method containing a coupler in the light-sensitive material. , A color negative film, a color positive film, a slide color reversal film, a movie color reversal film, a TV color reversal film, a reversal color paper and the like can be applied to any silver halide color photographic light-sensitive material.

[Specific effects of the invention] As described in detail above, in the method for processing a silver halide color photographic light-sensitive material of the present invention, silver halide grains comprising 80 mol% or more of silver chloride are contained in the silver halide emulsion layer. Since it is contained, rapid development processing is possible.

Further, in the processing method of the present invention, the concentration of sulfite, which has been most frequently used as a preservative in the past, is set to the color developer 1.
Since the compound of the present invention represented by the general formula [I] is used instead of 4 × 10 ⁻³ mol or less, even in the high silver chloride-containing light-sensitive material according to the present invention, the dye concentration is lowered by the silver development reaction. Didn't get up. At the same time, the color developing solution was sufficiently stabilized by the compound of the present invention, and bleach fog did not occur in the bleach-fixing process.

Further, in the present invention, since the pH of the bleach-fixing solution used in the bleach-fixing step is in the range of 4.5 to 6.8, bleaching fog, that is, the generation of stains in the bleach-fixing solution is more completely suppressed.

Hereinafter, the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited thereby.

[Example 1] The following layers were sequentially coated on a polyethylene-laminated paper support from the support side to prepare a photosensitive material sample.

Layer 1 ... 1.2 g / m ² of gelatin, 0.42 g / m ² (in terms of silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion (95 mol% as AgCl), and
1.1 x 10 ^-3 dissolved in 0.50 g / m ² dioctyl phthalate
A layer containing the following yellow coupler (Y-1) in mol g / m ² .

Layer 2 ... Intermediate layer consisting of 0.6 g / m ² of gelatin.

Layer 3: 1.2 g / m ² of gelatin, 0.26 g / m ² of green-sensitive silver chlorobromide emulsion (98 mol% as AgCl), and 1.0 × 10 ⁻³ mol g dissolved in 0.28 g / m ² of dioctyl phthalate. / m ² layer containing the following magenta coupler (M-1).

Layer 4 ... an intermediate layer consisting of 1.3 g / m ² of gelatin.

Layer 5 ... 1.4 g / m ² gelatin, 0.27 g / m ² red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride) and 1.5 × 10 ^-3 mol dissolved in 0.22 g / m ² dibutyl phthalate. A layer containing the following comparative cyan coupler (C-1) at g / m ² .

Layer 6 A layer containing 0.25 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 1.0 g / m ² of gelatin and 0.22 g / m ² of dioctyl phthalate.

Layer 7 ... A layer containing 0.48 g / m ² of gelatin.

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2, 4 and 7 so that the amount was 0.015 g per 1 g of gelatin.

Next, these samples were subjected to wedge-shaped exposure by a conventional method, and then the development processing described below was performed.

Processing step Processing temperature Processing time [1] Color development 35 ℃ 45 seconds [2] Bleach fixing 35 ℃ 45 seconds [3] Wash with water 30 ℃ 90 seconds [4] Dry 60-80 ℃ 60 seconds However, the bleach-fixing solution 250 ml of the above color developing solution was mixed per 1 bleach-fixing solution, stored at 40 ° C. for 3 days, and then developed. Similarly, the color developer used after storage at 40 ° C. for 3 days was used.

Using the Sakura Photodensitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) for the sample after development processing, Dmin of the unexposed part (the minimum density of the magenta dye density, which causes a fast coupling speed and causes fog) ) And the maximum density part of the yellow density where the developing speed is slow and the color density is hard to appear.

The results are summarized in Table 1.

The color developing solution and bleach-fixing solution used had the following composition.

(Color developing solution) -Potassium chloride 1.0g-Potassium sulfite (described in Table 1) -Sodium polyphosphate 2.0g-Color developing agent (Exemplified compound A-1) 5.5g-Potassium carbonate 30g-Hydroxylamines (Table 1) Description) Add 10g water to make 1 and add pH 1 with potassium hydroxide and 50% sulfuric acid.
Adjust to 0.15.

[Bleaching fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Add water to bring the total volume to 1 and adjust the pH with potassium carbonate or glacial acetic acid as shown in Table 1. .

As is apparent from Table 1, the compound of the present invention represented by the above general formula [I] (wherein the sulfite concentration in the color developing solution is in the range of 4 × 10 ^-3 mol / l or less) Hydroxylamines) and the pH of the bleach-fix solution is 4.
It can be seen that in the range of 5 to 6.8, a sufficient yellow dye density can be obtained and the generation of magenta stain in the unexposed area is small even though the color development time is as short as 45 seconds. However, the sulfite concentration in the color developing solution, the presence or absence of the compound represented by the general formula [I] according to the present invention, or the pH of the bleach-fixing solution is not the same as the yellow dye concentration when it is outside the present invention. Problems such as sufficient amount and large amount of magenta stain occur, which lowers the commercial value.

Further, when the color developing solution after storage was observed, tar was generated when the compound of the present invention was not added.

[Example 2] Color developing agent (A-1) in the color developing solution used in Example 1
Was changed to (B-1) or (B-2) below, and a similar experiment was conducted. As a result, the magenta stain in the unexposed area deteriorated by 0.02. Similarly, the color developing agent (A-1) of Example 1 was replaced with the exemplified compounds (A-2), (A-4) and (A-1).
When the same experiment as in Example 1 was performed by changing each to 5), almost the same result was obtained.

[Example 3] The same as in Example 1 except that the silver halide composition of the blue sensitive layer in the silver halide color light-sensitive material used in Experiment No. 6 of Example 1 was changed as shown in Table 2 below. The same experiment was performed. The results are summarized in Table 2.

As is clear from Table 2, the yellow dye concentration is almost sufficient when the silver halide composition of the silver halide color photographic light-sensitive material is 80 mol% or more of silver chloride, but when the silver chloride content is lower than this. It can be seen that a sufficient dye concentration cannot be obtained in the above.

Further, it can be seen that when it is 90 mol% or more, a better dye concentration is obtained, and when it is 95 mol% or more, it is particularly good. With respect to this effect, when the silver halide compositions of the red-sensitive layer and the green-sensitive layer were changed in the same manner, the cyan dye concentration and the magenta dye concentration also showed similar results. Above all,
The silver chloride content of all silver halide emulsion layers is 80 mol% or more,
It has been found that especially above 90 mol%, especially above 95 mol%, all layers give preferred dye densities and give perfect black.

[Example 4] The exemplary compound (A'-) was added to the color developer used in Example 1.
2), (A'-4) and (A'-9) (all are triazyl stilbene optical brighteners) were added in an amount of 2 g / l, and the same experiment as in Example 1 was carried out except that magenta was used. The occurrence of stain was improved by 0.01 to 0.02.

[Example 5] The same experiment was performed by changing the addition amount of the exemplary compound (I-1) in the color developer used in Example 1 and Experiment No. 6 as shown in Table 3 below.

The results are summarized in Table 3.

The appearance in the above table shows the results of observing the degree of coloration after storage of the color developing solution, and the larger the number of +, the more the coloration.

From the above table, the compound represented by the general formula [I] is 0.2 to 50 g.
In the range of / l, it was found that the effects of the present invention (magenta stain, quickness, storability of liquid, etc.) were satisfactorily achieved, and 1 to 30 g / l was more favorable, and 5 ~ 20g
It turns out that when / l, it is particularly good.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer is subjected to imagewise exposure and then subjected to a treatment including at least a color developing step and a bleach-fixing step following the color developing step. In the method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer is a silver halide emulsion layer containing silver halide grains consisting of 80 mol% or more of silver chloride, and the color development step is performed. The color developer used is one in which at least one sequestering agent having the function of sequestering iron ions and at least one sequestering agent having the function of sequestering calcium are not present at the same time, and formula contains a compound represented by [I], and there is 4 × 10 ^-3 mol or less sulfite concentration per color developing solution 1, further wherein the bleaching constant construction Bleach-fixing solution used in the
A method of processing a silver halide color photographic light-sensitive material, which has a pH in the range of 4.5 to 6.8. General formula [I] (In the formula, R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms.)