JPH0690481B2 - 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, those skilled in the art have demanded a technique capable of rapid processing of 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 subjected to running processing 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-58-184142 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), etc., and regarding 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 of being forced to be used in a concentration range where the amount of sulfite 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, the bleach-fix solution tends to have a low replenishment rate or a high reproduction rate due to the recent demand for low pollution and cost reduction, and the amount of the color developing solution accumulated in the bleach-fix solution is large. 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, etc.). Under such circumstances, the deterioration of photographic characteristics such as further increase in bleaching fog is remarkable, and there is a conventionally known technique (for example, Japanese Patent Laid-Open No. 50-136031).
No. 1,131,335, U.S. Pat. No. 3,293,036, etc.) and the like cannot be compensated.

Another problem is that a high-silver-chloride-containing light-sensitive material, which is a very effective technique for speeding up, is a case where a fixing agent (for example, a thiosulfate commonly used in a bleach-fixing solution) is mixed in a color developing solution. However, it has been found that there is a drawback that physical development occurs and remarkable cyan fogging occurs. In particular, color developing solutions in recent years tend to be replenished at low levels due to demands for low pollution and cost reduction, and along with this, thiosulfuric acid mixed and accumulated in the color developing solution from an adjacent bleach-fixing solution tank. The amount of salt tends to increase, which is an increasingly difficult situation for a light-sensitive material containing high silver chloride.

OBJECT OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material which uses a high chloride silver halide to provide rapid developability and has improved fog in a bleach-fixing solution. It is in the provision of processing methods. 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 fog 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 of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which causes less fog even when the bleach-fixing solution is mixed in the color developing solution.

[Structure of the Invention] As a result of various studies by the present inventors, the above-mentioned object of the present invention was as follows.
A silver halide color photographic light-sensitive material which is subjected to imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer and then subjected to processing including at least a color development step and a bleach-fixing step subsequent to the color development step. In the processing method, at least one layer of 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 at least one layer of the silver halide emulsion layer. Contains a cyan coupler represented by the following general formula [C], has a sulfite concentration of 4 × 10 ⁻³ mol or less per color developing solution, and the bleach-fixing solution used in the bleach-fixing step has a pH of Is 4.5
It was found that the effect of the object of the present invention can be achieved in the range of 6.8 to 6.8, and the present invention has been completed.

General formula [C] [Wherein _one of R and R ₁ is a hydrogen atom and the other is at least a linear or branched alkyl group of 2 to 12, and X is a hydrogen atom or N-hydroxyalkyl-substituted-p-phenylenediamine-based color development. It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent, and R ₂ represents a ballast group. [Specific Structure of the Present Invention] In the processing method of the silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion layer is composed of 80 mol% or more of silver chloride in order to enable rapid development processing. It contained silver halide grains.

In the present invention, the decrease in dye concentration due to the silver development reaction, which tends to occur when such a high silver chloride-containing light-sensitive material is used, is adjusted to a sulfite concentration used as a preservative of 4 × 10 ⁻ per color developing solution. It was prevented by setting it to ³ mol or less.

Further, in the present invention, one of the problems caused by using a high silver chloride-containing light-sensitive material, that is, bleach fog, that is, stains generated in the bleach-fix solution, has a pH of 4.
The problem can be solved by controlling the ratio to 5 to 6.8, and by using a specific cyan coupler, another problem of the light-sensitive material having a high silver chloride content, that is, the resistance against incorporation of a bleach-fixing solution can be improved.

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 physical development of silver chloride. The present invention uses the above problems in combination by reducing the sulfite concentration to a specific range, using a specific cyan coupler in the light-sensitive material, and further using a bleach-fixing solution having the specific pH described above. It has been resolved.

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- (CH 2) n-CH 3, - (CH 2 CH 2 O) n Cm H 2m + 1 (m and and n each represents an integer of O or more.), —COOH group, —SO ₃ H group and the like.

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

Illustrative color developing agent Of the above-illustrated color developing agents, preferred examples for use in the invention are Nos. (A-1), (A-2), and (A-
3), (A-4), (A-6), (A-7) and (A
-15), particularly preferably (A-
1).

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.

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 (for example, methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
Aryl groups (eg phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, 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 of the present invention can be synthesized, for example, by the usual method described on page 8 of "Fluorescent Whitening Agent" edited by Chemical Industry Association (August 1976).

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 of the color developer of the present invention.

The color developer of the 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 above effects of the present invention, that is, precipitation can be prevented, and they 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 and borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary.
US Pat. Nos. 2,648,604 and 3,67 as development accelerators.
1,247, 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, 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 Depending on the proximity of the processed paper to the photosensitive material, it 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 also the use of such a stirring device results in poor solubility. Therefore, there is a limit to the effect of promoting development.

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 there are problems such as requiring labor and cost, it is preferable to reduce or eliminate the use amount as much as possible.

When the compound represented by the following general formula [I] is used in the color developing solution used in the present invention in place of hydroxylamine which has been conventionally used as a preservative, the effect of the object of the present invention is further improved. It is particularly preferably used in the present invention because it exhibits good performance, the storage stability of the color developer is improved, and silver development due to hydroxylamine does not occur when a high silver chloride-containing light-sensitive material is used.

General formula [I] (In the formula, R ¹ and R ² each represents an alkyl group having 1 to 3 carbon atoms.) 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 developing solution is similar to that of hydroxylamine usually used as a preservative, for example, 0.1 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.

The color developer used in the present invention has the following general formula [B-
I] and at least one compound selected from the compounds represented by the general formula [B-II] (hereinafter,
When it contains a compound of the present invention), the effect of the object of the present invention is better exhibited, and the organic acid iron complex salt (for example, in the bleach-fixing solution during handling of the rack of the automatic processor) (for example,
It is particularly preferably used because it has the effect of stabilizing the color developing solution of the present invention even when (ethylenediaminetetraacetic acid iron (III) complex salt) is mixed in the color developing solution.

General formula [BI] General formula [B-II] In the general formulas [BI] and [B-II], R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, or -OR. ₇ , -COOR ₈ , Alternatively, it represents a phenyl group. Also, R ₇ , R ₈ , R ₉ and R
₁₀ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₄ represents —OH or a hydrogen atom, R ₃ represents a halogen atom, a sulfonic acid group, or a carbon atom of 1
7-alkyl group, -OR _7, -COOR _8, Alternatively, it represents a phenyl group.

The alkyl group represented by R ₃ , R ₄ , R ₅ and R ₆ is
Examples thereof include methyl group, ethyl group, iso-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group and benzyl group, and R ₇ The alkyl groups represented by R ₈ , R _9, and R ₁₀ have the same meanings as described above, and further include an octyl group and the like.

Examples of the phenyl group represented by R ₃ , R ₄ , R ₅ and R ₆ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are shown below, but the chelating agent is not limited to these.

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-I-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1,2,3- Trihydroxybenzene-5-carboxylic acid (BI-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-5-carboxy -N
-Butyl ester (BI-6) 5-t-butyl-1,2,3 trihydroxybenzene (B-II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2 , 3,8-Trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropyl-naphthalene ( B-II-5) 2,3-Dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, as a compound particularly preferably used in the present invention, 1,2-dihydroxybenzene-3,5-disulfonic acid And it can also be used as an alkali metal salt such as sodium salt or potassium salt.

In the present invention, the compound of the present invention is the color developer 1
It can be used in the range of 5 mg to 20 g, preferably
Good results are obtained by adding 10 mg to 10 g, more preferably 20 mg to 3 g.

The compounds of the present invention may be used alone or in combination. Furthermore, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1,2,4
-Other chelating agents such as phosphonocarboxylic acid such as tricarboxylic acid and polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

When the color developing solution according to the present invention contains the compound represented by the following general formula [D], not only the effects of the present invention are more favorably exhibited, but also against the air oxidation of the color developing solution. It is more preferably used because it shows an improving effect.

General formula [D] (In the formula, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R _11
12 and R ₁₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) ethanolamine, (D-2) diethanolamine, (D-3) triethanolamine, (D-4) di-isopropanolamine, (D-5) 2-methylaminoethanol, (D-6). 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-9) 1-diethylamino-2-propanol, (D-10) 3-diethylamino-1. -Propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) isopropylaminoethanol, (D-13) 3-amino-1-propanol, (D-14) 2-amino-2- Methyl-1,3-propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyldiethanolamine, (D-17 2-amino-2- (hydroxymethyl) -1,
3-propanediol.

These compounds represented by the general formula [D] are preferably used in the range of 3 g to 100 g, and more preferably in the range of 6 g to 50 g per 1 color developing solution from the viewpoint of the effect of the object of the present invention.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication The compound can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sexulfate (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. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

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

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Also, more generally, a plurality of components each of which can coexist stably in a concentrated aqueous solution, or in a solid state prepared in advance in a small container is added to water and prepared by 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 used at pH 9.5 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the quicker the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

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.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred organic acid used to form such a metal acid 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
Use with / 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 containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. Use a bleach-fixing solution with a composition containing a large amount of added, and a special bleach-fixing solution with a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. You can 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 70 g to 250 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, dimethylsulfoamide, dimethylsulfoxide 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, but it is preferably 55 ° C. or lower to suppress evaporation and the like.

The bleach-fixing solution according to the present invention has a pH of 4.5 to 6.8. This is because if the pH is below 4.5, the bleach-fixing solution itself becomes unstable, and fluidization easily occurs, and if the pH of the bleach-fixing solution is above 6.8, it is impossible to prevent magenta stain. Is. Particularly, in the present invention, when the pH of bleach-fixing is in the range of 5.5 to 6.5, the effect of the object of the present invention is particularly preferable. Will be described.

The silver 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, preferably 90 mol% or more, more preferably 95 mol% or more. The content is at least mol%.

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. The silver bromide content 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 it is made to exist, and it is more preferable that it is 100%.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal, or another 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.

Further, 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 active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Methylbenzothiazolium chloride or the like or a sensitizer of a water-soluble group such as nithenium, palladium, platinum, rhodium or iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

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 ^{−3 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 No. 929,080 and US Pat.
1,658, 2,493,748, 2,503,776, 2,5
No. 19,001, No. 2,912,329, No. 3,656,959, No. 3,
672,897, 3,694,217, 4,025,349, and
4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030
No. 52-24844 and the like. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
72,908, No. 2,739,149, No. 2,945,763, cyanine dyes such as those described in British Patent No. 505,979,
Typical examples thereof include merocyanine dyes and complex cyanine dyes. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, U.S. Pat.Nos. 2,269,234, 2,270,378, and 2,442,71.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. 0, No. 2,454,629, No. 2,776,280 and the like. Furthermore, U.S. Pat.Nos. 2,213,995 and 2,493,748
No. 2,519,001, West German Patent No. 929,080, and the like, cyanine dyes, merocyanine dyes, or complex cyanine dyes can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

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

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, examples of the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine include, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47-2.
No. 5379, No. 48-38406, No. 48-38407, No. 54-34535,
55-1569, JP-A-50-33220, 50-38526, 51-
107127, 51-115820, 51-135528, 52-10491
No. 6, 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 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and a styryl dye can be advantageously used.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, dye solutions such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, and fluorinated alcohols described in Japanese Patent Publication No. 40659/50 are previously prepared. It is used by dissolving it in the 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 include British Patent 584,60.
No. 9, No. 1,277,429, JP-A No. 48-85130, No. 49-996.
No. 20, No. 49-114420, No. 49-129537, No. 52-108
No. 115, No. 59-25845, No. 59-111640, No. 59-111
641, U.S. Patent No. 2,274,782, No. 2,533,472, No. 2,956,079, No. 3,125,448, No. 3,148,187,
No. 3,177,078, No. 3,247,127, No. 3,260,601
No. 3, No. 3,540,887, No. 3,575,704, No. 3,653,90
No. 5, No. 3,718,472, No. 4,078,312, No. 4,070,3
Those described in No. 52 can be mentioned.

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

Next, the cyan coupler used in the present invention will be described.

The cyan coupler of the present invention can be represented by the above general formula [C], and the general formula [C] will be further described.

In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R ₁ and R in the above general formula [C] is, for example, an ethyl group, a propyl group or a butyl group.

In the general formula [C], the ballast group represented by R ₂ is
An organic group having a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing from the layer to which it is applied to other layers. As a typical ballast group, an alkyl group or an aryl group having a total carbon number of 8 to 32 can be mentioned, but a total carbon number of 13 to 28 is preferable. These alkyl group and aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxy group, an acyl group, an ester group and a hydroxy group. Group, cyano group, nitro group, carbamoyl group, carbonamido group, alkylthio group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group and halogen, and the substituent of the alkyl group may be the above-mentioned alkyl group except the alkyl group. The substituents mentioned for the aryl group can be mentioned.

The preferred ballast group is represented by the following general formula.

R ³ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. As the substituent, an alkyl group,
Examples thereof include a hydroxy group, a halogen atom, and an alkylsulfonamide group, and the most preferable one is a branched alkyl group such as t-butyl group.

The group capable of leaving upon coupling, which is defined by X in the above general formula [C], determines the number of equivalents of the coupler and influences the reactivity of the coupling, as is well known to those skilled in the art. Typical examples are chlorine, halogen represented by fluorine, aryloxy group, substituted or unsubstituted alkoxy group, acyloxy group, sulfonamide group, arylthio group, heteroylthio group, heteroyloxy group, sulfonyloxy group, carbamoyloxy group. Groups and the like. More specific examples include JP-A-50-10135,
50-120334, 50-130441, 54-48237, 51-146
828, 54-14736, 47-37425, 50-123341,
No. 58-95346, Japanese Patent Publication No. 48-36894, U.S. Pat.No. 3,476,56
No. 3, No. 3,737,316, and No. 3,227,551.

Next, exemplary compounds of the cyan coupler used in the present invention will be described. Examples of the exemplified compound include, but are not limited to, those in which R ₁ , X, R ₂ and R are respectively specified in the general formula [C] as described below.

The method for synthesizing the exemplary compound of the cyan coupler according to the present invention is shown below, but other exemplary compounds can be synthesized by the same method.

Synthesis Example of Exemplified Compound (1) [(1) -a] Synthesis of 2-nitro-4,6-dichloro-5-ethylphenol 2-nitro-5-ethylphenol 33 g, iodine 0.6 g and ferric chloride 1.5 g is dissolved in 150 ml glacial acetic acid. 40 ℃ to this
Then, 75 ml of sulfuryl chloride is added dropwise over 3 hours. The precipitate formed during the dropping is reacted and dissolved by heating under reflux after the completion of the addition of sulfuryl chloride. Heating under reflux takes about 2 hours. The reaction solution is poured into water and the produced crystals are purified by recrystallization with methanol. (1) -a was confirmed by nuclear magnetic resonance spectrum and elemental analysis.

[(1) -b] Synthesis of 2-amino-4,6-dichloro-5-ethylphenol 21.2 g of the compound of [(1) -a] was dissolved in 300 ml of alcohol, and a catalytic amount of Raney nickel was added thereto. Hydrogen was passed through at normal pressure until there was no hydrogen absorption. After the reaction, Raney nickel was removed and the alcohol was distilled off under reduced pressure. The residual [(1) -b] was subjected to the next acylation without purification.

Synthesis of [(1) -c] 2 [(2,4-di-tert-acylphenoxy) acetamido] -4,6-dichloro-5-ethylphenol Crude amino form obtained in [(1) -b] 18.5 g to 500 ml
Dissolved in a mixed solution of glacial acetic acid and 16.7 g of sodium acetate,
To this was added 2,4-di-tert-aminophenoxyacetic acid chloride 2
An acetic acid solution prepared by dissolving 8.0 g in 50 ml of acetic acid is added dropwise at room temperature. After dropping for 30 minutes and stirring for 30 minutes, the reaction solution is poured into ice water. The precipitate formed is collected by filtration, dried, and recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectrum.

C ₂₁ H ₃₅ NO ₃ Cl ₂ C HN Cl Calculated value (%) 66.00 7.34 2.92 13.76 Measured value (%) 64.91 7.36 2.99 14.50 The addition amount of the cyan coupler of the present invention is not limited,
2 × 10 ^{−3 to} 5 per mol of silver in the red-sensitive silver halide emulsion layer
X10 ^-1 mol is preferred, more preferably ^{1x10 -2 to} 5x
It is 10 ^-1 mol.

In the present invention, the cyan coupler of the present invention may be used in combination with other cyan couplers, and examples of cyan couplers that can be used in combination include phenol compounds and naphthol compounds, for example, U.S. Pat.Nos. 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,
It can be selected from those described in No. 3,419,390, No. 3,458,315, No. 3,591,383 and the like, and the synthetic methods of these compounds are 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, 55-30615; pyrazolotriazole-based magenta couplers include couplers described in U.S. Pat. No. 1,247,493 and Belgian Patent 792,525; As the colored magenta coupler of, a compound in which the coupling position of a colorless magenta coupler is substituted with an arylazo is generally used, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608.
No. 3,005,712, No. 3,684,514, British Patent 937,621
And the 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.

In addition to the DIR compound, compounds that release a development inhibitor upon development are also included in the present invention.
3,297,445, 3,379,529, West German patent application (OLS) 2,4
17,914, JP-A Nos. 52-15271, 53-9116, and 59-1238
38, 59-127038 and the like.

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 coupler active site, for example, British Patent No. 935,454. , USA Special Note 3,22
7,554, 4,095,984, and 4,149,886.

The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidized product of a color developing agent, the mother nucleus of the coupler forms a dye, while releasing a development inhibitor. In the present invention, U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,95
8,993, 3,961,959, 4,052,213, JP-A-5
3-110529, 54-13333, 55-161237, etc. release a development inhibitor when coupled with an oxidant of a color developing agent, but do not form a dye. Compounds are also included.

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, on the other hand, the detached 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, 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 contain various other photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure 17643. Agent,
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. Pat.No. 2,761,79
A simultaneous coating method of two or more layers by the method described in No. 1 and No. 2,941,898 can also be used.

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.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

In the method for 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, which can be applied to any silver halide color photographic light-sensitive material.

[Specific effects of the invention] As described above, according to the processing method of the present invention, the storage stability of the color developing solution is excellent, the stain and the photographic characteristics of the maximum color density due to bleach-fixing are excellent, and particularly rapid. A method of processing a silver halide color photographic light-sensitive material suitable for processing can be provided.

Specific Examples of the Invention Hereinafter, the present invention will be described in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

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

Layer 1 ... Dissolved in 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion (96 mol% as AgCl) and 0.60 g / m ² dioctyl phthalate A layer containing 1.10 × 10 ⁻³ mol g / m ² of the following yellow coupler (Y-1).

Layer 2 ... an intermediate layer consisting of 0.56 g / m ² of gelatin.

Layer 3 ... 1.25 g / m ² gelatin, 0.26 g / m ² green-sensitive silver chlorobromide emulsion (98 mol% as AgCl) and 1.14 × 10 ^-3 mol g dissolved in 0.3 g / m ² dioctyl phthalate / m ² A layer containing the following magenta coupler (M-1).

Layer 4 ... Intermediate layer consisting of 1.15 g / m ² of gelatin.

Layer 5 ... 1.23g / m ² of gelatin, 0.26 g / m ² of red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride) and 0.220 g / m ² of 1.3 × 10 ^-3 mol, dissolved in dibutyl phthalate A layer containing the following comparative cyan coupler (C'-1) at g / m ² .

Layer 6 A layer containing 1.10 g / m ² of gelatin and 0.34 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba-Geigy) dissolved in 0.220 g / m ² of dioctyl phthalate.

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

As a hardening agent, 2,4-dichloro-6-hydroxy-s-triazine sodium was added to layers 2, 4 and 7 so that the amount was 0.012 g per 1 g of gelatin.

A comparative color paper was prepared as described above. Similarly, the cyan coupler (C'-1) was changed to a cyan coupler as shown in Table 1 below to prepare and use experimental samples as samples of the present invention and comparative samples.

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

Processing step Processing temperature Processing time [1] Color development 35 ℃ 45 seconds [2] Bleach fixing 35 ℃ 45 seconds [3] Water washing 30 ℃ 100 seconds [4] Dry 60-80 ℃ 90 seconds The bleach-fix solution used had the following composition.

(Color developing solution) -Potassium chloride 2.0g-Potassium sulfite (described in Table 1) -Sodium polyphosphate 2.0g-Color developing agent (Exemplified compound A-1) 5.6g-Potassium carbonate 30g Add water to make 1 and water PH 1 with potassium oxide 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 1 to the total amount of carbonic acid. Adjust the pH with potassium or glacial acetic acid as described in Table 1.

However, 0.3 ml of the bleach-fixing solution and Cu ²⁺ (1 ppm) per color developing solution were added to the color developing solution, and 250 ml of the color developing solution was further mixed into the bleach-fixing solution. After storage for 3 days at 45 ° C., development processing was performed.

The sample after development was processed using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to determine the cyan density of the unexposed area, the magenta density of the unexposed area where the coupling speed was high and fog was a problem, and The yellow density of the highest density part where the developing speed is slow and the color density is hard to appear was measured.

The results are summarized in Table 1.

As is clear from Table 1, the concentration of the sulfite in the color developing solution is in the range of 4 × 10 ^-3 mol / l or less, and the content of the photographic material represented by the general formula [C] of the present invention. The cyan coupler of the invention is contained, and the pH of the bleach-fixing solution is 4.5 to 6.8.
When it is in the range of, a sufficient yellow dye density can be obtained despite the extremely short color development time of 45 seconds,
In addition, it can be seen that cyan fog and magenta stain in the unexposed area are less likely to occur. However, when the sulfite concentration in the color developing solution, the presence or absence of the cyan coupler represented by the general formula [C] according to the present invention in the light-sensitive material, or the pH of the bleach-fixing solution is outside the range of the present invention, it is yellow. It is understood that problems such as insufficient dye concentration, large amount of magenta stain, and cyan fog occur, and commercial value is reduced.

[Example 2] Color developing agent (A- in the color developing solution used in Example 1)
When 1) was changed to (B-1) or (B-2) below and the same experiment was conducted, the magenta stain in the unexposed area deteriorated by 0.02. Further, similarly, the color developing agent (A-1) of Example 1 was used as the exemplified compounds (A-2) and (A
-4) and (A-15), respectively, and the same experiment as in Example 1 was performed, and almost the same results were obtained.

[Example 3] 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, and otherwise the same as in Example 1. The same experiment. The results are summarized in Table 2.

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

Further, when it is 90 mol% or more, a better dye concentration is obtained,
Further, it is found that when the content is 95 mol% or more, it becomes 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. In particular, the silver chloride content of all silver halide emulsion layers is 80 mol% or more,
It has been found that 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. Occurrence of stain is 0.01 to 0.02, that is, 20 to 40%
There is also an improvement in that the stain also decreases by%.

[Example 5] The color developers used in Example 1 and Experiment No. 6 were each supplemented with 12 g / l of the exemplified compounds (I-1), (I-5) and (I-2).
When the amount of the color developing agent in the color developing solution after storage was measured, the decomposition rate was improved by 3 to 4%. The magenta density (stain) of the unexposed area was further reduced by about 0.01.

Example 6 In the color developer used in Example 1 and Experiment No. 6, 0.5 g / each of the exemplified compounds (B-I-2), (B-I-3) and (B-II-3) was added. After adding l and performing a similar experiment,
The density of magenta stain in the unexposed area was further improved by 0.01 to 0.02.

Example 7 12 g / l of the exemplified compounds (D-3) and (D-7) were added to the color developing solution used in Example 1 and Experiment No. 6, respectively, and similar experiment was conducted. The color of the developer was improved and the magenta stain was further reduced by 0.01.

[Example 8] Exemplified cyan couplers (C'-1) of the light-sensitive materials used in Example 1 and Experiment No. 6 were converted into (C-20), (C-23), (C-
27) and (C-12) were changed, and similar experiments were conducted, and almost the same results were obtained.

[Example 9] In the silver halide color light-sensitive material used in Experiment No. 8 of Example 1, the amounts of sulfite in the color developing solution were changed as shown in Table 3, and Experiment No. 30 to 35 development processes were performed. The sample after development was measured for cyan density, magenta density and yellow density of the highest density area in the same manner as in Example 1. The results are shown in Table-3.

In the table, for example, if the maximum yellow density is not at least 2.30, the black balance of the print will be poor, and there will be a problem.

Further, in Experiment No. 8 of Example 1, the cyan coupler C-1 of the present invention was used in place of the comparative cyan coupler C'-1, and the concentration of sulfite in the color developing solution is shown in Table 3. The same development process as in Example 1 was performed, and the cyan density, magenta density of the unexposed area and the yellow density of the highest density area were measured.

The results are shown in Table-3. From the results of Table-3, in Experiment Nos. 33 to 35 using the comparative cyan coupler C'-1 of the present invention,
It can be seen that even if the sulfite concentration in the color developing solution is within the range of the present invention, the magenta concentration and the cyan concentration in the unexposed area are high and the fog is large.

Furthermore, Experiment Nos. 36 to 40 using the cyan coupler of the present invention
However, if the sulfite concentration in the color developing solution is high, a sufficient yellow density cannot be obtained. On the other hand, the experiment N of the present invention
It can be seen that from o.41 to 44, the magenta density and cyan density of the unexposed area are low and a sufficient yellow density can be obtained.

Claims (1)

[Claims] 1. A halogenation process comprising image-wise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, and then performing a process including at least a color development process and a bleach-fixing process subsequent to the color development process. In the method for processing a silver color photographic light-sensitive material, at least one of the silver halide emulsion layers is a silver halide emulsion layer containing silver halide grains composed of 80 mol% or more of silver chloride,
Further, at least one of the silver halide emulsion layers contains a cyan coupler represented by the following general formula [C], and further, the sulfite concentration is 4 × 10 ^-3 mol or less per color developer, and the bleaching is further performed. A method for processing a silver halide color photographic light-sensitive material, wherein the bleach-fixing solution used in the fixing step has a pH in the range of 4.5 to 6.8. General formula [C] [Wherein _one of R and R ₁ is a hydrogen atom and the other is at least a linear or branched alkyl group of 2 to 12, and X is a hydrogen atom or N-hydroxyalkyl-substituted-p-phenylenediamine-based color development. It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent, and R ₂ represents a ballast group. ]