JP2607082B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material capable of continuously forming a stable color photographic image while extremely reducing the replenishing amount.

BACKGROUND OF THE INVENTION Generally, when processing a silver halide color photographic light-sensitive material (hereinafter referred to as photographic material), a constant amount of development per unit area of the photographic material is performed in order to keep the composition of a color developing solution constant and maintain photographic performance. Replenisher is replenished.

The composition of the developer changes due to photographic processing, and the photographic performance also changes.

For example, the concentration of the color developing agent is consumed and decreased by the reaction, and the concentration of the halide having an inhibitory action is eluted from the photographic material by the reaction and increases. Therefore, the activity of the developer changes and becomes inactive if nothing is done. As a method for preventing such inactivation, for example, German Patent Application Publication (DE-A) 2,007,459, 2,007,457 and 2,71
7,674, U.S. Patent (US-A) 3,647,461, 3,647,46
Nos. 2 and 4,186,007 and European Patent Application Publication (EP-A) No.
No. 00029722.

These methods are called a replenishment method, and are performed by replenishing a replenisher.

Substances consumed in the development process are maintained at the desired concentration by the addition of such replenishers, while at the same time preventing the accumulation of unwanted halides in the developer, the amount of liquid lost from the developing bath. A larger volume of replenisher is added.

In this case, the concentration of the halide in the replenisher is low, and it has recently been possible to reduce the replenishment volume with a replenisher containing no halide at all, but still results in a relatively large amount of overflow. Has brought. Alternatively, the replenishment amount may be reduced by removing the halide concentration from the developing solution by a specific means, or in some cases, the halide in the overflow solution may be removed to compensate for the lacking component and used again as a replenisher. As a result, a method of reducing the overflow liquid as a result is actively used.

The former has a disadvantage that the halide concentration is increased and development is suppressed, so that it is necessary to eliminate the inhibitory effect by performing a high activation treatment, and furthermore, the amount of drainage is relatively large.

In the latter case, the apparatus is an ion exchange tower or an electrodialysis tower, which is generally expensive. Further, there is a disadvantage that maintenance work becomes extremely complicated, such as the necessity of an analysis operation in order to always keep the developing composition constant.

Therefore, especially in a minilab or the like, a low replenishment system (LR system) that can easily reduce replenishment is generally adopted. The disadvantage of this method, however, is that the bromide accumulates at significantly higher concentrations. As a result, a high temperature treatment is performed to overcome the suppression effect as described above. In this case, the effects of evaporation cannot be ignored and toxic components are concentrated and increased, and the liquid is liable to be oxidized.

As a method for solving the drawbacks of these methods, JP-A-61-7
In the specification of Japanese Patent No. 0552, a photographic material having a very high silver chloride content containing silver halide is treated with a replenishment amount as low as not to overflow even when replenished, so that elution of bromide ions is reduced, and consequently bromide ions are reduced. There has been proposed a processing method which does not require high-temperature treatment because the concentration of the compound does not become high.

This method is well known in the past, since bromide has a much larger development inhibiting effect than chloride,
Although this is not new, chloride ions having a small inhibitory effect are more easily eluted into the developer, but low replenishment processing can be achieved without high-temperature processing.

However, according to the research of the present inventors, as the ratio of silver chloride in the photographic material increases, the performance of the conventional developer cannot be maintained, the color density becomes low, and the color developing solution is aged. The gradation changes remarkably with the passage of time, and the disadvantage that the photographic performance changes even if the concentration of the sulfite as a preservative is changed by air oxidation appears. It turned out that it was not practical for practical use.

The present inventors further studied using a photographic material having a high silver chloride content having the various advantages described above. As a result, when processed with a conventional color developing solution, the maximum density did not increase, resulting in a very short time. It turned out that processing could not be achieved.

Further, it was found that when silver chloride exceeded 90 mol%, not only the maximum density but also the intermediate density did not increase, and sufficient stable development could not be obtained.

The present inventors have conducted numerous studies and analyzed the cause, and found that the main cause was the presence of hydroxylamine sulfate, which was used without exception in conventional color developing solutions.

It was found that the presence of hydroxylamine sulfate caused a greater suppression of development as the proportion of silver chloride in the photographic material increased. As a result, it was found that the higher the ratio of silver chloride was, the easier the physical development was, and the photographic performance changed.

Therefore, even if the elution of bromide generated in the development reaction by silver chloride is suppressed, photographic performance cannot be stabilized if hydroxylamine is present in the developer. The performance changes due to the above factors. In addition, in the low replenishment process, the sulfite ion concentration in the developer tends to change with time,
It was also found that the photographic performance of silver-based photographic materials was sensitive to the sulfite concentration.

Based on these analyses, the present inventors have conducted intensive studies, and the photographic material uses silver halide grains of a specific concentration or more, using a specific compound instead of the conventional hydroxylamine during color development, By processing with a certain amount of chloride or more, all of the above-mentioned disadvantages were solved, continuous processing of a sufficiently high photographic density was possible, and it was found that a stable photographic density was always obtained. The present invention has been accomplished.

[Object of the Invention] Accordingly, an object of the present invention is to provide a processing method capable of eliminating these drawbacks and constantly obtaining photographic performance stably even when the replenishment amount is significantly reduced.

[Constitution of the Invention] The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support by imagewise exposing it to at least a p-phenylenediamine-based color developing agent. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide emulsion layer is continuously processed while replenishing a replenisher. The color developer contains silver halide particles containing silver chloride, and the color developer contains a compound represented by the following general formula [I] and a color developer 1
This was achieved by a method for processing a silver halide color photographic light-sensitive material containing at least 2 × 10 ^-2 mol of chloride per mol and a replenishment rate of a replenisher of a color developing solution of 100 ml / m ² or less.

General formula [I] In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

DETAILED DESCRIPTION OF THE INVENTION The method of the present invention comprises at least one of reducing exposed silver halide to silver, bleaching to oxidize the reduced silver, and fixing to remove silver salts from the recording material. Includes two development stages. Bleaching and fixing can be combined in some cases by a known method such as a bleach-fixing solution.

Color development is performed in an aqueous development bath. The temperature of the developer can be maintained at the commonly used normal levels of 25 ° C. to 50 ° C., and for photographic materials using silver halide grains in which silver chloride is greater than 70 mol%, the development time can be considerably shorter. Have the advantage of being processed.

In the present invention, a compound represented by the general formula [I] is used in the color developing solution instead of the conventional hydroxylamine sulfate.

Therefore, it is also important that the present invention does not contain hydroxylamine sulfate.

In the general formula [I], represents R ₁ and R ₂ are each an alkyl group or a hydrogen atom are not hydrogen atoms at the same time, R ₁
And the alkyl groups represented by R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. R ₁
And the alkyl group of R ₂ includes those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxyamine-based compound represented by the general formula [I] are described in US Pat. Nos. 3,287,125 and 3,293,095.
No. 34, No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention usually contain free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of phosphate, acetate, etc.

The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.2 g / l to 50 g / l, preferably 0.5 g / l.
To 30 g / l, more preferably 1 g / l to 15 g / l.

The compound represented by the general formula [I] of the present invention is used in a conventional color developing solution for a silver halide color photographic light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. However, among the compounds of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative for a black-and-white developing agent in a color developing solution to which a black-and-white developing agent is added. In a so-called external color developing method in which a color photographic light-sensitive material is developed by a reversal method using a color developing solution containing a coupler, there is a technique used together with phenidone. (Tokukosho 45
-22198).

In particular, it has been found that the compound of the present invention has a sufficiently high stability over time even when the sulfite ion concentration is reduced, so that the change in concentration over time can be reduced and the photographic performance can be stabilized as a result.

According to the invention, the developing bath is replenished with a replenisher. Preferably, overflow slightly occurs, and there is no need to supply a replenisher by another means to correct for evaporation.However, economically, replenishment is reduced to the extent that overflow does not occur at all, and the level of the liquid decreases. It is preferable that the replenisher is automatically supplied and corrected by a bird drinking method (birds fountain) or the like. In this case, the replenishing solution may be the color developing solution or the color developing solution having a low concentration. It may be water. In each case, it is necessary that the consumed components of the developer components be sufficiently supplemented, but in the present invention, elution of bromide having a large inhibitory effect among halides as inhibitory components is extremely small, while chlorides of chlorides are significantly reduced. Elution is significantly higher. However, this chloride has a large development promoting effect in a photographic material using a silver chlorobromide emulsion having a high ratio of silver bromide, as compared with the conventional silver halide photographic material of the present invention having a high silver chloride ratio. In the above, chloride has only a very weak inhibitory effect, so if chloride is added to the developer at a certain concentration or more in advance, the developing effect will be stabilized, for example, the replenishment amount will be large or small The change in photographic density can be extremely small,
Further, by using the compound represented by the general formula [I] in combination, various disadvantages of the photosensitive material having a high silver chloride content are also improved.

Based on the surprising findings described above, a low replenishment system in which the change in photographic density is extremely small has been completed, instead of the low replenishment system having the drawbacks as in the prior art. Therefore, the bromide ion in the developer of the present invention preferably contains only a very low concentration in the replenisher and the tank solution, but the concentration of the bromide ion in the replenisher and the tank solution is substantially the same, It is desirable to have a small amount of bromide ions in the replenisher.

The silver halide in the photographic material according to the present invention contains only a very low concentration of silver bromide, and the amount eluted during development is very small, but the bromide in the replenisher is changed so that the bromide ion concentration in the developer does not change. It is necessary to adjust the amount of ions, and in particular, the bromide ion concentration in the replenisher is kept low to prevent an increase in bromide ions concentrated by evaporation.

The chloride in the present invention may be any compound that releases chloride ions in a color developing solution, and specific compounds include potassium chloride, sodium chloride, lithium chloride, magnesium chloride and the like.

The silver halide grains used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention must contain 70 mol% or more of silver chloride.
It has been found that the effect is preferably close to 0%, but when the amount of silver chloride is 90 mol% or more, an effect substantially close to 100% of silver chloride can be obtained. In particular, when the silver chloride content is 95 mol% or more, the effect of the object of the present invention is particularly excellent. The developing agent is used in the range of 0.5 g to 100 g per developer, preferably in the range of 2 to 15 g. Color development is usually 20
The treatment is carried out at a temperature in the range of from 0 ° C to 80 ° C, preferably from 30 ° C to 50 ° C.

The pH at which development takes place is generally above 8 and preferably 9.5.
That is all.

Development is carried out in the presence of pH buffers, development inhibitors, antifoggants, complexing agents for softening, preservatives, development accelerators, competing couplers, fogging agents, auxiliary developer compounds and viscosity modifiers. Research Disclosure 17544, December 1978, Section XXI, Industrial Oppotunities Ltd., Homewell Havant,
Published by Hampshire, Grent Britain, and Ullman's Enchlopedy del Technischen Hemiy (Ullman
s Enzyklpudie der technisehen Chemie), 4th edition, 18
Vol., 1979, especially pages 451, 452 and 463-465. Suitable developer compositions include Grant Haist,
Modern Photographic Processing (Modern P
hotographie Processing), John Wiley and Sans, 1973, Vol. 1 and 2
Has been given to.

In the present invention, when a manganese salt or a cerium salt is used in combination with the color developing solution of the present invention, the antioxidant performance of the color developing solution is further improved, and the deterioration of the color developing property during storage over time is also improved. Since such an effect is also obtained, it is more preferably used in the present invention.

The manganese salt and cerium salt according to the present invention are compounds that release manganese ions or cerium ions when dissolved in a developer, and are preferably used below, but are not limited thereto. .

Manganese chloride Manganese sulfate Manganese sulphite Manganese manganese phosphate Manganese manganese permanganate Manganese manganese oxalate Manganese citrate Manganese citrate Ethylenediaminetetraacetate Manganese sulphate Cerium nitrate Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium oxalate These The manganese salt and the cerium salt are preferably used in the form of ions (manganese ion and cerium ion) in the range of 0.1 mg to 100 mg, more preferably 0.3 mg to 20 mg, per color developing solution,
In particular, from 0.5 mg to 10 mg in view of the effect of the object of the present invention,
It is preferably used.

Usually, sulfite is used as a preservative in the color developing solution, but in the color developing solution according to the present invention, when the sulfite concentration is 1.6 × 10 ^-2 mol or less per color developing solution, In addition, it is possible to suppress the drop in color density, which is considered to be caused by the physical phenomena of dissolution of high-silver chloride-containing photosensitive materials, and the reduction in preservation ability is extremely slight. In the present invention, the sulfite concentration in the color developing solution is preferably 1.6 × 10 ^-2 mol / l or less, because it is possible to provide a color developing solution which makes it possible or a processing method of a silver halide color photograph using the solution. Used. Furthermore, this effect is better exhibited by 1
× 10 ⁻² mol / l or less, more preferably 4 × 10 ⁻³ mol
/ l or less.

Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

As a color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it exhibits the desired effects of the present invention and generates little fog.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin damage than para-phenylenediamine-based compounds having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less susceptible to fogging, but in particular, the object of the present invention can be efficiently achieved by combining it with the compound represented by the general formula [I] in the present invention.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine-based compound, and specific water-soluble groups include-(CH ₂ ) _{n-
CH 2 OH, - (CH 2} ) m -NHSO 2 - (CH 2) n -CH 3, - (CH 2) m O- (C
_{H 2) n -CH 3, -} (CH 2 CH 2 On Cm H 2 m + 1 (m and n each represents an integer of 0 or more.), - COOH group, as -SO ₃ H group and the like No.

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

Illustrative color developing agents Among the color developing agents exemplified above, the ones which are preferably used in the present invention because of low occurrence of fog are exemplified by No. (A-
1), (A-2), (A-3), (A-4), (A-
6), compounds represented by (A-7) and (A-15), and particularly preferably (A-1).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is usually preferably used in an amount of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developing solution, but from the viewpoint of rapid processing, the color developing agent is preferably used. The range is more preferably 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liquid.

The color developing agents may be used alone or in combination of two or more, and if desired, used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. You may.

Further, instead of using the above color developing agent in the color developing solution, a color developing agent can be added to the light-sensitive material. In this case, the color developing agent used is, for example, a dye precursor. A typical dye precursor is disclosed in
58-65429, those described in paragraphs 58-24137 etc. are used,
Specifically, for example, 2 ', 4'-bismethanesulfonamido-4-diethylaminodiphenylamine, 2'-methanesulfonamido-4'-(2,4,6-triisopropyl) benzenesulfonamido-2-methyl- 4-N-
(2-methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4'-
(2,4,6-triisopropyl) benzenesulfonamido-4- (hydroxytrisethoxy) diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis ( (2,4,6-triisopropyl) benzenesulfonamidediphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'- (2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-methoxy-2'-methanesulfonamide-4 '
-(2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-dihexylamino-4'-
(2,4,6-triisopropylbenzenesulfonamide)
Diphenylamine, 4-n-hexyloxy-3'-methyl-4 '-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-diethylamino-4'-(2,4,6- Triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-dimethylamino-2-phenylsulfonyl-4 '-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine and the like.

The amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22 mg, more preferably ^{4 to 12} mg, per 100 cm ² of the photosensitive material.

When the color developing solution according to the present invention contains a compound represented by the following general formula [D], it not only exerts the effect of the present invention more favorably but also has an effect on air oxidation of the color developing solution. It is more preferably used to show an improvement effect.

General formula [D] (Wherein, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂₂ and R ₂₃ 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 ₁ represents an integer of ₁ to 6, and X ′ and Z ′ each represent 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- (H Rokishimechiru) 1,3
-Propanediol.

These compounds represented by the general formula [D] are preferably used in the range of 3 g to 100 g, more preferably in the range of 6 g to 50 g per color developing solution in terms of the effects of the present invention.

The color developer according to the present invention includes the following general formula [B-
When the compound represented by any one of [I] to [B-IV] is contained, the objective effects of the present invention are more favorably exhibited, and furthermore, a color developing solution and bleaching fog generated upon immediate bleaching or bleach-fixing treatment are also included. Since it has an improved effect, it is more preferably used in the present invention.

General formula [BI] General formula [B-II] In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom,
A halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR ₁₅ , -COOR ₁₆ , Or, it represents a phenyl group. Also, R ₁₅ , R ₁₆ , R ₁₇ and R
₁₈ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, respectively. However, when R ₁₂ represents —OH or a hydrogen atom, R ₁₁ is a halogen atom, a sulfonic acid group, a carbon atom 1
To 7 alkyl groups, -OR ₁₅ , -COOR ₁₆ , Or, it represents a phenyl group.

The alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ includes those having a substituent, for example, a methyl group, an ethyl group, is
o-propyl group, n-propyl group, t-butyl group, n-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Methyl carboxylic acid group, benzyl group, etc.
_15, as the R _16, an alkyl group represented by R ₁₇ and R ₁₈ are as defined above, can be further octyl group and the like exemplified.

Examples of the phenyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(BI-1) 4-isopropyl-1,2-dihydroxybenzene (BI-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (BI-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 (BI-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid (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 Compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can be used as an alkali metal salt such as a sodium salt and a potassium salt.

In the present invention, the above general formulas [BI] and [B-II]
Can be used in an amount of 5 mg to 20 g per color developing solution, and good results can be obtained by adding 10 mg to 10 g, more preferably 20 mg to 3 g per color developing solution.

General formula [B-III] General formula [B-IV] (In the general formulas [B-III] and [B-IV], L represents an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -O-
L ₈ -O-L ₈ - or -L ₉ -Z-L ₉ - represents a. Where Z
Is, N-L ₁₀ -R _40, −R ₄₂ or Represents

L _{1 to} L ₁₃ each represent an alkylene group. R ₃₃ to R ₄₃ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including salts thereof). Provided that at least two of R _{33 to} R ₃₆ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof)
And at least two of R _{37 to} R ₃₉ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). In the general formulas [B-III] and [B-IV], the alkylene group represented by L, the cycloalkylene group and the phenylene group, and the alkylene group represented by L _{1 to} L ₁₃ may have a substituent. Including. Next, preferred specific exemplary compounds of the compounds represented by the general formulas [B-III] and [B-IV] are shown below.

[Exemplary Compound] [B-III-1] Ethylenediaminetetraacetic acid [B-III-2] Diethylenetriaminepentaacetic acid [B-III-3] Ethylenediamine-N- (β-hydroxyethyl) -N,
N ', N'-Triacetic acid [B-III-4] Propylenediaminetetraacetic acid [B-III-5] Triethylenetetraminehexaacetic acid [B-III-6] Cyclohexanediaminetetraacetic acid [B-III-7] 1 1,2-Diaminopropanetetraacetic acid [B-III-8] 1,3-diaminopropan-2-ol-tetraacetic acid [B-III-9] Ethyl ether diamine tetraacetic acid [B-III-10] Glycol ether diamine tetraacetic acid [ B-III-11] Ethylenediaminetetrapropionic acid [B-III-12] Phenylenediaminetetraacetic acid [B-III-13] Ethylenediaminetetraacetic acid disodium salt [B-III-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [B-III-15] Ethylenediaminetetraacetic acid tetrasodium salt [B-III-16] Diethylenetriaminepentaacetic acid pentasodium salt [B-III-17] Ethylenediamine N-(beta-hydroxyethyl) -N,
N ', N'-triacetate sodium salt [B-III-18] Propylenediaminetetraacetate sodium salt [B-III-19] Ethylenediaminetetramethylenephosphonic acid [B-III-20] Cyclohexanediaminetetraacetate sodium salt [B -III-21] diethylenetriaminepentamethylenephosphonic acid [B-III-22] cyclohexanediaminetetramethylenephosphonic acid [B-IV-1] nitrilotriacetic acid [B-IV-2] iminodiacetic acid [B-IV-3] nitrilotripropion Acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] Iminodimethylenephosphonic acid [B-IV-6] Trisodium nitrilotriacetic acid [B-IV-7] Sodium hydroxyethyliminodiacetic acid Among the compounds represented by the general formula [B-III] or [B-IV], particularly preferred compounds used in the present invention include [B-III-1], [B-III-2], [B-III-5],
[B-III-8], [B-III-19], [B-IV-1], [B-IV-4]
And [B-IV-7]. Further, the compound represented by the general formula [B-III] or [B-IV] is preferably used in the range of 0.1 to 20 g per color developing solution, and particularly in the range of 0.3 to 5 g in view of the object of the present invention. Is particularly preferably used.

The compounds represented by the general formulas [BI] to [B-IV] may be used alone or in combination.
Furthermore, other chelating agents such as oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid are combined. May be used.

In the present invention, it is preferable to use a triazinylstilbene-based fluorescent whitening agent represented by the following general formula [III] in the color developing solution according to the present invention, because the occurrence of fog is further reduced.

General formula [III] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ each represent 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 groups (eg, methyl, ethyl, etc.), aryl groups (eg, phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (eg, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N
-(Β-sulfoethyl) -N′-methylamino, N-
(Β-hydroxyethyl-N′-methylamino and the like), arylamino groups (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.

Specific examples include the following compounds, but are not limited thereto.

[Exemplary compound] The triazylstilbene-based brightener represented by the general formula [III] is described in, for example, "Fluorescent Brightener" (edited by the Chemical Industry Association of Japan) (Showa
It can be synthesized by the usual method described on page 8).

These triazinylstilbene-based brighteners are preferably used in the range of 0.2 to 6 g, more preferably 0.4 to 3 g, per color developing solution used in the present invention.

The color developing solution of the present invention contains poly (alkyleneimine). Poly (alkyleneimines) are composed of substituted or unsubstituted repeating alkylene chain units linked together via a nitrogen atom. These are well-known commercially available substances. Representative poly (alkyleneimines) include compounds represented by the following general formula [I '].

General formula [I '] (In the formula, R ₁ 'represents an alkylene group having 1 to 6 carbon atoms, R _2' represents an alkyl group, n 'represents. An integer of 500 to 20,000) the R _1' atoms represented by The alkylene group having 1 to 6 atoms may be linear or branched, and preferably has 2 to 4 carbon atoms.
Alkylene group such as ethylene group, propylene group, butene group, isobutene group, dimethylethylene group, ethylethylene group and the like. The alkyl group represented by R ₂ 'is preferably an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group and the like, and further having a substituent (for example, a hydroxyl group). Including. n 'represents the number of repeating units in the polymer chain;
It represents an integer of 0 to 20,000, preferably an integer of 500 to 2,000. Poly (ethylene imine) wherein R ₁ 'is an ethylene group is most preferred for the purposes of the present invention.

Specific examples of the poly (alkyleneimine) used in the color developing solution of the invention are shown below, but the invention is not limited thereto.

Exemplary compound PAI-1 poly (ethyleneimine) PAI-2 poly (propyleneimine) PAI-3 poly (butenimine) PAI-4 poly (isobutenimine) PAI-5 poly (N-methylethyleneimine) PAI-6 poly (N -Β-hydroxyethylethyleneimine) PAI-7 poly (2,2-dimethylethyleneimine) PAI-8 poly (2-ethylethyleneimine) PAI-9 poly (2-methylethyleneimine) poly (alkyleneimine) In the color developing solution, it can be used in any amount that can achieve the object of the present invention, but generally 0.1 to 500 g per color developing solution is preferred,
More preferably, it is used in the range of 0.5 g to 300 g.

The use of the poly (alkyleneimine) of the present invention together with hydroxylamine in a color developing solution can improve the storage stability of the color developing solution and reduce the sulfite concentration. No., published in Japanese Unexamined Patent Publication No. However, in such a method, hydroxylamine is decomposed, particularly when heavy metals are mixed, and storage stability is reduced, so that not only is the technique of improving preservation unsatisfactory, but also the action as a preservative is excellent and heavy metals are mixed. When a hydroxylamine derivative such as diethylhydroxylamine or dimethylhydroxylamine, which the present inventors have found as a strong preservative, is used in a color developing solution, the coloring of the solution and the resulting photosensitive material and container etc. There is no description in the above-mentioned patent publication that the polyalkyleneimine effectively solves the contamination problem of the above. In other words, the problem of coloring of the liquid and the contamination of the photosensitive material and the container due to such a problem do not occur with hydroxylamine, but are a problem that occurs specifically when a hydroxylamine derivative such as diethylhydroxylamine or dimethylhydroxylamine is used. Thus, the existence of such a problem has not been known at all, and it is a surprising effect that polyalkyleneimine effectively solves this problem.

In the present invention, the processing time of the color development step may be any time, but is usually from 5 seconds to 5 minutes. Usually, a high silver chloride photosensitive material of the present invention uses a color development time of 15 seconds to 60 seconds.When color development is performed for a long time of 150 seconds or more, a large amount of processing and a small amount of processing are performed. Since the effect of reducing the difference in the photographic characteristics is reduced, the photographic processing characteristics of the large-scale lab and the mini-lab (small-scale lab) are brought close to each other, and the effect of uniformizing the photographic characteristics in the market is exhibited. In particular, this effect becomes remarkable when the color development step is 180 seconds or longer.

Replenishing amount to the largest effect of the photographic material per m ² present invention, it is treated with less than 100 ml.

In addition, volume loss due to evaporation sets the replenishment rate to a level slightly less than the rate at which developer is carried off the equipment, and the remaining volume loss is compensated for by adding replenisher from a simple automatic replenisher. It has been found that this can be easily and automatically compensated.

In a preferred embodiment, the concentrated and adjusted kit used for preparing the replenisher can be directly supplied to the developing bath, and the shortage of water can be supplied from the water replenisher while controlling the decrease in the liquid level.

In the preferred developer of the present invention, it is preferable that benzyl alcohol is not substantially contained. Here, “substantially not contained” means that benzyl alcohol is 2 ml / l or less, and it is most preferred that the present invention does not contain benzyl alcohol at all. Benzyl alcohol has a very low solubility and an extremely small replenishment rate. In the process of the present invention, the solution is easily concentrated, so that adhesion to photographic materials due to precipitation of oil and generation of tar due to oxidation of the color developing agent are extremely troublesome. Problems.

Further, since the solubility is extremely small, when the above-mentioned adjusted concentration kit is directly introduced into the developing tank, a mechanical mixing device is required, which is extremely complicated. Therefore, benzyl alcohol was found to be an undesirable additive in order to maximize the effects of the present invention.

In the present invention, after the color development processing, processing is performed with a processing liquid having a fixing ability. When the processing liquid having the fixing ability is a fixing liquid, a bleaching processing is performed before that. As a bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes metal silver produced by development to silver halide, It has the function of coloring the uncolored part of the color former, and its composition is aminopolycarboxylic acid or oxalic acid, organic acids such as citric acid, iron, cobalt,
Coordinated metal ions such as copper. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[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 ether diamine tetra acetic acid [10] Glycol ether diamine tetra acetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra (trimethyl ammonium) salt [15] ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt In addition to containing a metal complex salt as a bleaching agent, various additives can be included. As the additive, it is particularly desirable to include a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, or a chelating agent. Further, pH buffers such as borates, oxalates, acetates, carbonates, and phosphates, and alkylamines, polyethylene oxides, and the like which are known to be added to normal bleaching solutions can be appropriately added. .

Further, the fixing solution and the bleach-fixing solution include sulfites such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and the like, boric acid, borax, sodium hydroxide, potassium hydroxide. , Sodium carbonate, potassium carbonate,
A single or two or more pH buffers comprising various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained.

When processing is performed while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate or sulfite, or the bleach-fix. These salts may be added to the replenisher to replenish the treatment bath.

In the present invention, in order to increase the activity of the bleaching solution or bleach-fixing solution, air or oxygen is blown in the bleaching bath or the bleach-fixing bath and in the bleach replenisher or the bleach-fixing replenisher storage tank as required. Or an appropriate oxidizing agent, for example, hydrogen peroxide, bromate, persulfate or the like may be added as appropriate.

In the present invention, from the viewpoint of rapid processing, a bleach-fixing solution is preferably used, and when bleach-fixing is performed immediately after color development using a high silver chloride photosensitive material as in the present invention, a stain called bleach fog occurs. Cheap. Therefore, as a result of various studies, it was found that the use of the bleach-fixer having a pH in the range of 4.5 to 6.8 not only can solve this problem but also has the effect of reducing the silver bleaching speed.

In particular, this effect is good when the pH of the bleach-fix solution is 5 to 6.3.

In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution, as well as a washing solution or a stabilizing solution instead of a washing solution. For example, an electrolysis method (French Patent No. 2,299,667), a precipitation method (JP-A-5
2-73037, German Patent 2,331,220), ion exchange method (JP-A-51-17114, German Patent 2,548,237), metal replacement method (UK Patent 1,353,805) and the like can be effectively used.

In the processing method of the present invention, after bleaching and fixing (or bleach-fixing) processing after color development processing, stable processing may be performed without washing with water, or washing processing may be performed, and then stable processing may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. The following steps are included as typical specific examples of a preferable treatment method.

(1) Color development → bleach-fix → washing with water (2) Color development → bleach-fix → small amount of washing → washing with water (3) Color development → bleach-fix → washing → stable (4) Color development → bleach-fix → stable (5) Color developing → Bleaching and fixing → First stable → Second stable (6) Color development → Washing (or stable) → Bleaching and fixing → Washing (or stable) (7) Color developing → Stop → Bleaching and fixing → Washing (or stable) (8) (9) color development → bleaching → fixing → washing → stable (10) color developing → bleaching → small amount of washing → fixing → first stable → second stable (11) color developing → bleaching → small amount washing → fixing → small amount washing → water washing → stable (12) Color development → small amount washing → bleaching → small amount washing → fixing → small amount washing → water washing → stable (13) Color development → stop → bleach → small amount washing → fixing → Washing with small amount of water → Washing → Stable Among these processes, (4) or (5) Step is preferably used.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention flows into a bleaching solution or a bleach-fixing solution in the subsequent step. This is because, when a certain amount of the color developing solution according to the present invention is introduced into the bleaching solution or bleach-fixing solution, the generation of sludge in the bleaching solution or bleach-fixing solution is suppressed, and more surprisingly, This is because the recovery efficiency of silver is also improved.

Further, in addition to the above-mentioned method, when the part or all of the overflow of the stabilizer in the subsequent step is poured into the bleach-fixing solution or the fixing solution, the above-mentioned effect is particularly excellent.

Specific examples of these are, for example, those shown in FIG.

The silver chloride used in the present invention is at least 70 mol%
A silver halide emulsion layer containing silver halide grains comprising a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously incorporated in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer may contain, for example, a non-diffusible color coupler which produces a cyan partial color image, generally of the phenol or .alpha.-naphthol type. The green-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a magenta partial color image, usually a 5-pyrazolone based color coupler and a pyrazolotriazole. The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having a closed ketomethylene group. The color coupler can be, for example, a 6-, 4- or 2-equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Agfa's research report (Mitteilungln aus den Forschung
slaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.111 (196
1) "Color coupler" (Farbkuppler) by W.Pelz; K. Venkataraman (KV)
enkataraman), "The Chemirsry of Synthetic Dye"
s), Vol.4, 341-387, Academic Press (Academ
ic Press), (1971); T.H. James (T.
H. James), "The Theory of the Photographic Process"
Process, 4th edition, pages 353-362; and Research Disclosure No. 17643, section VII. According to one particularly preferred embodiment, it is well coupled without the normally added benzyl alcohol. A color coupler is used. Benzyl alcohol is commonly used as a phase transfer agent to allow the coupling between the oxidized color developer and the coupler to proceed at a desired rate to form an image dye. However, benzyl alcohol, in practical use, is always a source of complications as described above, especially a source of hindrance based on tar formation. Suitable couplers which can be used without benzyl alcohol are described in DE-A-3,209,710, 2,44.
1,779, 2,640,601 and EP-A-006768
It is shown in No. 9.

Preferred yellow couplers have a structure corresponding to the formula: The following magenta couplers are particularly preferred: The following cyan couplers are particularly preferred.

Among the yellow couplers, in particular, when using a high-speed reactive yellow coupler, the coloring property during short-time processing is improved, and the stain of the lowest density part is also improved.In the present invention, the high-speed reactive yellow coupler is used. It is preferably used.

The fast-reactive yellow coupler used in the blue-sensitive silver halide emulsion layer according to the present invention is a yellow coupler having a relative coupling reaction rate of 0.3 or more, preferably a yellow coupler having a relative coupling reaction rate of 0.5 or more. .

The coupling reaction rate of the coupler is determined by mixing two types of couplers M and N which give different dyes which can be clearly separated from each other, adding the resulting mixture to a silver halide emulsion, and performing color development. Can be determined as a relative value by measuring the amount of the dye.

Maximum density (DM) max of coupler M, density D in the middle stage
Assuming that the color development of M and the color development of coupler N represent (DN) max and the color development of DN, respectively, the reaction activity ratio RM / RN of both couplers is expressed by the following equation.

That is, a silver halide emulsion containing a mixed coupler is exposed to various stages, and several sets of DM and DN obtained by color development are subjected to two orthogonal axes. The value of the coupling activity ratio RM / RN can be determined from the slope of the straight line obtained by plotting as follows.

Here, when the value of RM / RN is determined for various couplers as described above using a fixed coupler N, a relative value of the coupling reaction rate, that is, a relative coupling reaction rate value is determined.

In the present invention, it refers to the RM / RN value when the following coupler is used as the above coupler N.

Although the addition amount of the high-speed reactive yellow coupler of the present invention is not limited, it is preferably 2 × 10 ^{-3 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol, per mol of silver of the blue-sensitive silver halide emulsion layer. X 10 ^{-2 to} 5 x 10 ^-1 mol.

Hereinafter, specific examples of the high-speed reactive yellow coupler of the present invention will be described, but the present invention is not limited thereto.

(Exemplary compound) In the present invention, as the magenta coupler, a pyrazolotriazole-based magenta coupler is more preferably used than the above-mentioned pyrazolone-based magenta coupler. This is because, when using a high silver chloride photosensitive material, bleaching is not performed immediately after color development, or when bleach-fixing is performed, stains tend to occur in unexposed areas, but pyrazolotriazole-based magenta couplers are used as magenta couplers. This is because not only is this disadvantage improved when used, but also the highest density magenta dye density in short-time processing is better. Among the pyrazolotriazole couplers, couplers represented by the following general formula [MI] are particularly preferably used.

General formula [MI] In the magenta coupler represented by, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group represented by R, a phenyl group is preferable.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group, or the like; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, or the like; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group Group, arylphosphonyl group, etc .; acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc. An acylcarbonyl group such as an alkylcarbonyloxy group or an arylcarbonyloxy group; a carbamoyloxy group such as an alkylcarbamoyloxy group or an arylcarbamoyloxy group; As an alkylureido group, an arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a heterocyclic group preferably having 5 to 7 members, and specifically, Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; The heterocyclic oxy group preferably has a 5- to 7-membered heterocyclic ring, for example, 3,4,5,6- As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolyl group. Ruthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group and the like; siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutyi group; Siloxy group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl and the like; bicyclo [2.2.1] as a bridged hydrocarbon compound residue
Heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decane-1-yl, 7,7-di-methyl-bicyclo [2.2.1] heptan-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described above for R. Is mentioned.

The compound represented by the general formula [MI] is more specifically represented by, for example, the following general formulas [M-II] to [M-VII].

In the general formulas [M-II] to [M-VII], R _{1 to} R ₈ and X have the same meanings as R and X.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

General formula [M-VIII] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], particularly preferred is a magenta coupler represented by the general formula [M-II].

Formula [M-I] is formed by Z in the ring and the formula [M-VIII] may be possessed by the ring formed by Z ₁ in the substituent, and the general formula [M-II] ~ [M -VI], R _{2 to} R ₈ are preferably those represented by the following general formula [M-IX].

Formula [M-IX] -R ¹ -SO ₂ -R ^{2 In the} formula, R ¹ represents an alkylene group, and R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6, and may be linear or branched.

The cycloalkyl group represented by R ² preferably have 5-6 membered.

Further, when used in positive image forming, and most preferred as substituents R and R ₁ on the heterocyclic ring represented by the following general formula [M-
X].

General formula [MX] In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

And two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may be combined to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle); Further on the ring
R ₁₁ may combine to form a bridged hydrocarbon compound residue.

Among the general formulas [MX], preferred are (i) R ₉
When at least two of R ₁₁ to R ₁₁ are an alkyl group, (i
i) one of R _{9 to} R ₁₁ , for example, R ₁₁ is a hydrogen atom,
When the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

When used for negative image formation, the substituents R and R ₁ on the heterocyclic ring are most preferably represented by the following general formula [M-XI]
Is represented by

General formula [M-XI] R ₁₂ —CH ₂ — wherein R ₁₂ has the same meaning as R described above.

Preferred as R ₁₂ is a hydrogen atom or an alkyl group.

 Hereinafter, typical specific examples of the compound according to the present invention will be shown.

In addition to the above specific examples of the compound according to the present invention, specific examples of the compound according to the present invention include compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791. And N
o.1-4,6,8-17,19-24,26-43,45-59,61-104,106-1
Compounds represented by 21,123 to 162,164 to 223 can be mentioned.

In addition, the coupler is used in the Journal of the Chemical Societe
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, JP-A-58-42045,
59-162548, 59-171956, 60-33552, 60-4
The compound can be synthesized with reference to 3659, 60-172982 and 60-190779 and the like.

The coupler of the present invention usually contains 1 × / mol of silver halide.
It can be used in an amount of 10 ⁻³ mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol.

The magenta coupler according to the present invention can be used in combination with other types of magenta couplers.

In the present invention, among the above-mentioned cyan couplers, a cyan coupler represented by the following general formula [CI] or [C-II] is preferably used. This is because when a bleaching or bleach-fixing process is carried out immediately after color development using a high silver chloride photosensitive material, stains are apt to occur in the rice exposed area, but as a cyan coupler, the following general formula [C-I]
Alternatively, when a specific cyan coupler represented by [C-II] is used, not only this disadvantage is improved but also the silver bleaching performance of the photosensitive material is more improved.

General formula [C-I] General formula [C-II] Wherein, R _1, R ₂ and R ₄ are each an optionally substituted aliphatic group, an aryl group or a heterocyclic group, R ₃
And R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group which may have a substituent, an aryl group or an acylamino group. However, R ₃ may form a ring with R ₂ . R ₅
Represents an alkyl group which may have a substituent, and Z ₁ and Z ₂
Each represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent. m represents 0 or 1.

Next, the general formula [CI] or [C-
II] will be described in detail.

R ₁ , R ₂ and R ₄ are an aliphatic group, preferably having 1 to 32 carbon atoms.
(For example, a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, an allyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.), or a heterocyclic ring (for example, a 2-pyridyl group, 2- Imidazolyl group, 2-
Furyl group, 6-quinolyl group, etc.)
Alkyl group, aryl group, heterocyclic group, alkoxy group (for example, methoxy group, eumethoxyethoxy group, etc.), aryloxy group (for example, 2,4-di-t-amylphenoxy group, 2-chlorophenoxy group, 4- A cyanophenoxy group or the like), an alkenyloxy group (such as a 2-propenyloxy group), an acyl group (such as an acetyl group or a benzoyl group), an ester group (such as a butoxycarbonyl group, a phenoxycarbonyl group, or an acetoxy group). Benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (eg, acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (for example, , Dipropylsulfamoylamino group Imide group (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureide group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.) Or an aliphatic or aromatic thio group (eg, an ethylthio group, a phenylthio group, etc.), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, or the like.

R ₃ and R ₆ represent an aliphatic group, an aryl group or an acylamino group, each of which may have a hydrogen atom and a halogen atom. However, R ₃ may form a ring together with R ₂ . Here, examples of the substituent of the group which may have a substituent include the groups described above for R ₁ , R ₂ and R ₄ .

In the general formula [CI], n represents 0 or 1.

In the general formula [C-II], R ₅ represents an alkyl group which may have a substituent, and preferably an alkyl group which may have a substituent having a total of 2 or more carbon atoms (for example, an ethyl group, Propyl, butyl, pentadecyl, t-butyl,
Cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group,
Butanamidomethyl group, methoxymethyl group).

In the general formulas [CI] and [C-II], Z ₁
And Z ₂ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. Examples of the detachable group include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (eg, an ethoxy group, a dodecyloxy group, a methoxyethylcarbamoylmethoxy group, a carboxypropyloxy group,
Methylsulfonylethoxy group, etc.), aryloxy group (eg, 4-chlorophenoxy group, α-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (eg, acetoxy group, tetradecanoyloxy) Group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino Group), an alkoxycarbonyloxy group (eg, an ethoxycarbonyloxy group, a benzoyloxycarbonyloxy group, etc.), an aryloxycarbonyloxy group (eg, a phenoxycarbonyloxy group, etc.), an aliphatic or aromatic thio group For example, ethylthio group, phenylthio group, etc. Chitorazoriruchio group), an imido group (e.g.,
A succinimide group, a hydantoinyl group, etc.) and an aromatic azo group (eg, a phenylazo group). These leaving groups may include photographically useful groups.

Also in formula [C-I], preferred R ₁ is an aryl group or a heterocyclic group, and is a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, or a sulfamoyl group. , A sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group.

When R ₃ and R ₂ do not form a ring in the general formula [C-I], R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula [C-II], R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula [C-II], preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula [C-II], R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to μ carbon atoms.

R ₆ in the general formula [C-II] is preferably a hydrogen atom or a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

Preferred in the general formulas [CI] and [C-II],
Z ₁ and Z ₂ are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula [C-II], Z ₂ is preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

When n = 0 in the general formula [CI], Z ₂ is more preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine group atom.

The cyan dye-forming coupler represented by the general formula [CI] or [C-II] is usually used in a silver halide emulsion layer (particularly for a red-sensitive emulsion). The addition amount is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, more preferably 1 × 10 ^{−2 to} 3 × 10 ⁻¹ mol, per mol of silver halide.

Also, the method for synthesizing the cyan couplers represented by the general formulas [CI] and [C-II] is described in U.S. Pat. Nos. 3,772,002 and 4,334,011.
No. 4,327,173, 4,427,767 and the like, and can be easily synthesized.

Specific compounds represented by the general formulas [C-I] and [C-II] are listed below, but the invention is not limited thereto.

The cyan coupler according to the present invention is usually silver halide 1
1 × 10 ^-3 to 1 mol per mole, can be preferably employed in the range of 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

In the present invention, when a high-silver chloride light-sensitive material of the present invention is used in combination with a nitrogen-containing heterocyclic mercapto compound, not only the effects of the present invention can be achieved well, but also a bleach-fix solution in a color developing solution. Another effect is that the effect on the photographic performance caused by the inclusion of phthalocyanine is extremely small, which is a more preferable embodiment in the present invention.

The nitrogen-containing heterocyclic mercapto compound according to the present invention has a nitrogen-containing heterocyclic ring, an imidaline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, and a thiazole ring. , Thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring , Pyrazine ring,
Selected from pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring (for example, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc.). It is desirable. Among them, particularly preferred nitrogen-containing heterocyclic mercapto compounds include an oxazole ring,
Oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, pyrimidine ring, triazine ring and polyazaindene rings.

Hereinafter, specific examples of the mercapto compound useful in the present invention will be described.

The compounds described above were obtained from Journal of Chemical Society (J. Chem. Soc.) 49, 1748, 1927, and Journal of Organic Chemistry (J. Org. Chem.) 39, 2
469, 1965, JP-A-50-89034, JP-A-55-79436, JP-A-51-10
2639, 55-59463, Annalen Hemy (Ann.Ch
im.), 44-3, 1954, Japanese Patent Publication No. 40-28496, Chemical Berichte (Chem. Ber.) 20, 231, 1887, USP. 3,259,976,
Chemical and Pharmaceutical Bulletin (Tokyo)
26, 314 (1978), Berichte der Deutschen
Hemischen Geusers draft (Berichte bar Deu)
tscben Chemischen Gesellsdraft) 82,121 (1948); U.S. Patent Nos. 2,843,491, 3,017,270; UK Patent No. 94
0,169, Journal of American Chemical
The compound can be synthesized with reference to the method described in Society, 44, 1502-1510 and the like.

The nitrogen-containing heterocyclic mercapto compound (hereinafter simply referred to as mercapto compound) is described in, for example, JP-A-51-107129,
Nos. 48-102621, 55-594463, and 59-124333.

In the present invention, the mercapto compound is preferably added to two or more photographic constituent layers.

The total amount of the mercapto compound used varies widely depending on the layer constitution of the silver halide photographic light-sensitive material, the type of the mercapto compound, the amount of silver halide, the processing conditions, etc., and is generally from 10 ^-8 mol to 10 mol / m ^{2. -4} mol, preferably 10 ^-7 mol
Although it is in the range of 10 ^-5 mol, it is not limited to the total amount itself in the present invention, but is determined by the degree of fogging prevention of each emulsion layer and the magnitude of the effect of the mercapto compound between the layers.

The silver halide grains used in the silver halide emulsion layer of the present invention contain at least 70 mol% of silver chloride, and the remainder may contain bromide or iodide, but is preferably substantially silver chloride. It is preferable that the iodide is extremely small. In special cases, the blue photosensitive layer contains 30 mol% bromide
It is also a preferred embodiment that the silver halide contains two other layers, for example, the green photosensitive layer and the red photosensitive layer have a chloride content of about 99%. Silver halide is preferably a core-shell grain and has a double layer structure.

In one embodiment, the grains are composed of at least two regions of differing halide composition, for example, one core and at least one shell, wherein at least one region B has at least 10 mol% of silver bromide, preferably at least 25 It contains mol% of silver bromide, but not more than 50 mol% of silver bromide.

Region B can be present as a core or as a shell around the core. The particles preferably comprise a core wrapped in at least one region B. In that case,
Region B can be present in the silver halide grains as a shell or on the surface of the crystal.

In another embodiment, the particles have at least one zone ZBr having a high content of bromide of at least 10 mol%,
The bromide-rich zone ZB
Does not have r.

The silver bromide rich zone ZBr in these grains can be present either as a core or as a layer within the silver halide grains.

Silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or accelerated feeding of the materials). Particularly preferred is the method of preparation by the double inflow method with adjustment of pAg; Research Disclosure No. 1764
3, see sections I and II.

Emulsions can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, such as tin compounds as described in Belgian Patent Nos. 493,464 and 568,687, and polyamines such as diethylene triamine or aminomethylsulfinic acid according to Belgian Patent No. 547,323. It is a derivative. Gold, platinum, palladium,
Noble metals and noble metal compounds such as iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is described in Zeitschrift Fair Bissenshaftriche Photography (Z.Wiss.Photo.) 46 , 65-72.
(1951) in the article by R. Koslovsky; see also Research Disclosure No. 17643, supra, section III.

Emulsions can be sensitized by optically known methods, for example using conventional polymethine dyes such as neuthocyanines, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like;・ FM Hamer's “Cyanine Dyes and Related Compounds” (19)
64) Ullmanns Enzyklpadie der technischen
Chemie), 4th Edition, Volume 18, p. 431 and following, and Research Disclosure No. 17643, Section IV above.

Conventional antifoggants and stabilizers may be used. Azaindene is a particularly suitable stabilizer, with tetra- and pentazaindene being preferred, especially those substituted with hydroxyl or amino groups.
Compounds of this type are described, for example, in Birr, Zeitschrift Fair Bissenshaftrich Photography (Z. Wiss. Photo.) 47, 1952, p. Disclosure No. 17643, section IV.

The components of the photographic material can be combined by conventional known methods; for example, US Pat. Nos. 2,322,027, 2,533,5
No. 14, No. 3,689,271, No. 3,764,336 and No. 3,765,89
See No. 7. The components of the photographic material, such as couplers and UV absorbers, can also be combined in the form of a charged latex; see DE-A-2,541,274 and EP-A-14,921. The components can also be fixed in the material as a polymer; for example, DE-A-2,044,992, U.S. Pat. Nos. 3,370,952 and 4,0802
See No. 11.

Conventional layer supports can be used for the material, for example cellulose ester supports such as cellulose acetate supports and polyester supports. Paper supports are also suitable, and they can be coated, for example, with polyolefins, in particular polyethylene or polypropylene; in this regard, see Research Disclosure No. 17643, supra, section XVII.

Conventional hydrophilic film formers can be used as protective colloids or binders for the layers of the recording material, such as proteins, especially gelatin, alginic acid or its esters, derivatives such as amides or salts, carboxymethylcellulose and Cellulose derivatives such as cellulose sulphate, starch or derivatives thereof or hydrophilic synthetic agents; see also the binders shown in Research Disclosure 17643, Section IX, supra.

The layers of the photographic material can be cured in the customary manner, for example using epoxides, heterocyclic ethyleneimines or acryloyl-type hardeners. Furthermore, the layers can be cured by a method according to DE-A-2,218,009 to produce color photographic materials suitable for high-temperature operation. The photographic layer or color photographic multilayer material can be cured with a diazine, triazine or 1,2-dihydroquinoline-based curing agent or a vinylsulfone-type curing agent. Other suitable curing agents are DE-A-2,439,551,
Nos. 2,225,230 and 2,317,672 and Research Disclosure 17643, Section XI.

[Specific effects of the present invention] As described above, in the present invention, additional means such as a regenerating process of a color developing solution are not required, the cost can be reduced economically, and the developing solution can be used without deterioration of photographic performance. A processing method for a silver halide color photographic light-sensitive material capable of always supplying a photographic performance of an obtained image stably even if the replenishing amount is significantly reduced was provided.

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

Example-1 An experiment was conducted using the following color paper, processing solution, and processing step.

[Color Paper] The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The average molecular weight of polystyrene coated paper
100,000, a mixture of 200 parts by weight of polyethylene having a density of 0.95 and 20 parts by weight of polyethylene having an average molecular weight of 2,000 and a density of 0.80 was added with 6.8% by weight of anatase titanium oxide,
A coating layer having a thickness of 0.035 mm was formed on the surface of high-quality paper having a weight of 170 g / m ² by the extrusion coating method, and a coating layer having a thickness of 0.04 mm was formed on the back surface using only polyethylene. After performing a pretreatment by corona discharge on the polyethylene-coated surface of the support, each layer was sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1, wherein the emulsion contains 350 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye 2,5-di-t-butylhydroquinone 200 sensitized using 2.5 × 10 ^-4 mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate
mg / m ² and 2 × 10 ⁻¹ mol per mol of silver halide of an exemplary yellow coupler Y-5 as a yellow coupler,
It is applied so that the silver amount is 300 mg / m ² .

Second layer: 300 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
A mixture of (2-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole 200 mg /
The gelatin layer containing m ² is coated so as to have a gelatin of 1900 mg / m ² .

Third layer: A green-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1, wherein the emulsion contains 450 g of gelatin per mol of silver halide and the following per mol of silver halide: Structure sensitizing dye Magenta coupler M-5 was sensitized using 2.5 × 10 ^-4 mol and dissolved and dissolved in a solvent in which dibutyl phthalate and tricrenylene phosphate were mixed at a ratio of 2: 1. It is coated so as to contain 10 ^-1 mol and to have a silver amount of 280 mg / m ² .
As an antioxidant, 0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained per 1 mol of the coupler.

Fourth layer: 30 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-tert-butylphenyl) -5 Mixture of chloro-benzotriazole (2: 1.
5: 1.5: 2) the gelatin amount in the gelatin layer containing 500 mg / m ² is applied so that the 1900 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver halide emulsion having the silver halide composition shown in Table 1, wherein the emulsion contains 500 g of gelatin per mol of silver halide and the following per mol of silver halide: Structure sensitizing dye 2,5-Di-t-butylhalodroquinone 150 mg / m ² sensitized using 2.5 × 10 ⁻⁵ mol and dissolved and dispersed in dibutyl phthalate, and a cyan coupler and an exemplary cyan coupler C′-2. It is coated so as to contain 3.5 × 10 ^-1 mol per mol of silver halide and to have a silver amount of 280 mg / m ² .

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 900 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized, and 4-hydroxy-6-methyl-
It contained 1,3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardening agent and saponin as a coating aid.

The above-mentioned light-sensitive material (silver halide composition was changed) was subjected to stepwise exposure, and was processed with the following processing steps and a processing solution (a preservative of a color developing solution was changed; The maximum concentration of the yellow dye was measured and the ratio of the comparative preservative to pear was calculated. The results are shown in Table 1.

Standard processing step [1] Color development 38 ° C for 1 minute [2] Bleaching and fixing 38 ° C for 1 minute [3] Rinse at 25-35 ° C for 1 minute [4] Drying 75-100 ° C for about 2 minutes Processing solution composition As is evident from Table 1, in the case of an emulsion containing 70 mol% or more of silver chloride, the use of the hydroxylamine derivative according to the present invention as a preservative of a color developing solution is very preferable because the maximum concentration does not decrease. You can see that.

Example 2 Each color developing solution to which the preservative described in Table 2 was added used in Example 1 was stored for 10 days, and the color developing solution of the preservative pear immediately after preparation was used as a comparison. After the development processing, the gamma value (density of 0.
8 to a concentration of 1.8), and the ratio was calculated using the preservative pear immediately after preparation as a comparison. Table 2 shows the results.

As is clear from Table 2, in the case of an emulsion containing 70% or more of silver chloride, the use of the hydroxylamine derivative according to the present invention as a preservative means that the gamma value does not change even when the color developer is stored. It turns out to be very favorable.

Example (3) Emulsion No. E used in Example (1) was used as a silver halide emulsion, and Y-5, M-5 and C'-2 used in Example were used as couplers in Table (3). The light-sensitive materials used in Example (1) were used except that the couplers were changed as shown.

The color developer is VEHA (exemplified compound (I-
Processing was performed according to the processing steps of Example (1) using the color developing solution using 1)).

After the treatment, the maximum reflection density and the minimum reflection density of the yellow, magenta and cyan dyes were measured with a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Kogyo Co., Ltd.). The results are summarized in Table (3).

As is clear from Table (3), the high-speed reactive yellow couplers (light-sensitive materials No. 2 to No. 6), the magenta coupler represented by the general formula [MI] (light-sensitive materials Nos. 7 to 13), and The use of cyan couplers represented by the general formulas [C-I] and / or [C-II] (light-sensitive materials Nos. 14 to 26) improves both the maximum color density and the minimum density. It can be seen that this is a preferable coupler.

In particular, fast-reacting yellow couplers of the general formula [M
-I] and a general formula [C-
It turns out that it is particularly preferable when the cyan coupler represented by I] or [C-II] is used in combination.

Example (4) As the silver halide emulsion, the emulsion No. E used in Example (1) and the organic inhibitors (1, 3, 5) shown in Table (4) were used.
) And the color developing solution is DEHA as a preservative.
Further, 0.5 ml of the bleach-fixing solution used in Example (1) was added per color developing solution, and development was carried out in the same manner as in Example (1). Of the bleach-fix solution was calculated as 100 and the ratio was calculated. The results are summarized in Table (4).

As is clear from Table (4), when the specific heterocyclic mercapto compound according to the present invention is used in the present invention, the relative gamma value does not change so much even when the bleach-fixing solution is mixed in the color developing solution, and the stability is stable. It can be seen that the obtained photographic characteristics are exhibited.

Example -5 In Example 1, the concentration of potassium sulfite in the color developing solution was changed as shown in Table 5, and 1 g / l of potassium sulfite was used as a preservative for comparison with the experiment of Example 1. Was subjected to a development treatment, the maximum density of the yellow dye was measured, and the ratio of the maximum density of 1 g / l of potassium sulfite with the preservative pear to 100 was calculated. The results are shown in Table-5.

From Table 5, it can be seen that in the present invention, potassium sulfite is particularly preferred to be 1.0 g / l or less in the color developing solution.

Example (6) Color developer Nos. 1 to 22 having the following compositions were prepared.

Next, the color developer described in Table (6) was applied with an opening ratio of 100 cm ² / l
The tar property of the color developing solution after 2 weeks was evaluated while being stored at 38 ° C. in a glass container having an air contact area of 100 cm ² with respect to the color developing solution (1).

 However, the appearance of the liquid was divided into the following four stages.

++ Large amount of tar generated ++ Tar adhered to wall surface (black) + Tar generated slightly on surface-No tar generated As is clear from Table (6), the preservative (I-1) of the present invention
Cerium sulfate and manganese sulfate are added as metal compounds to the polyhydroxy compound (color developing solutions Nos. 4 and 5) according to the present invention, and aminopolycarboxylic acid (color developing solution N
o.6 to 8), alkanolamines (Nos. 9 and 10), polyalkylimines (11) and the above compounds in combination (Nos. 12 to 1)
7) When added, the tar properties are improved, and it can be seen that there is a more remarkable improvement effect when used in combination.
This improvement effect is achieved by using the preservative according to the present invention (No. 18 to No. 2).
It can be seen that the improvement effect as described above can be obtained even in the case of 2).

Example (7) The color developing solution (No. 1 to 22) described in Example (6) was heated to 50 ° C.
After 5 days, it was sealed and stored in a glass bottle, and the same treatment and evaluation as in Example (4) were performed.

 The results are summarized in Table (7).

As is clear from Table (7), when the bleach-fixing solution was stored in a very small amount of contamination (model running state), the preservative (I-1) of the present invention contained cerous sulfate and sulfuric acid as metal compounds. Manganese may be added or the polyhydroxy compound according to the present invention (color developing solutions No. 4 ', 5')
Aminopolycarboxylic acid (color developing solutions No. 6 'to 8'), alkanolamines (No. 9 'and 10'), polyalkyl imine (11 ') and the above compounds (No. 12' to 17 ') )
When added, the fluctuation of the photographic characteristics after storage is improved, and it can be seen that there is a more remarkable improvement effect when used together. This improvement effect is achieved by using the preservative according to the present invention (N
o.18 'to 22'), it can be seen that the above-described improvement effect can be obtained.

Example 8 The color developing agent (A-) in the color developing solution used in Example 1 was used.
When the same experiment was conducted by changing 1) to the following (B-1) or (B-2), the magenta stain in the unexposed portions was deteriorated by 0.03 in all cases. Similarly, the color developing agent (A-1) of Example 1 was replaced with the exemplified compound (A-2),
Example 1 was changed to (A-4) and (A-15), respectively.
When the same experiment was performed, almost the same results were obtained.

Example (9) The fluorescent whitening agent (exemplified compound (A'-4)) in the color developing solution used in Example (1) was changed as shown in Table (8) below. The developing process was performed according to The unexposed part of the yellow stain after processing is converted to Sakura photoelectric densitometer PD
The measurement was performed using A-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.).

 The results are shown in Table (8).

Table (8) shows that the use of the triazylstilbene-based fluorescent whitening agent represented by the general formula [III] in combination with the treatment method of the present invention further improves yellow stain.

Example-10 The following layers were sequentially coated on a polyethylene-laminated paper support from the support side to prepare silver halide photosensitive materials (emulsions Nos. G, H, I and J).

Layer 1: 1.20 g / m ² of gelatin, 0.40 g / m ² (in terms of silver, the same applies hereinafter) of a blue-sensitive silver halide emulsion and 1.0 × 10 ⁻³ mol g / mol dissolved in 0.55 g / m ² of dioctyl phthalate layer containing m ² of yellow coupler (Y-5).

Layer 2: an intermediate layer made of 0.70 g / m ² of gelatin.

Layer 3 ... 1.20g / m ² of gelatin, 0.22 g / m ² green-sensitive silver halide emulsion and 0.30 g / m ² of dioctyl phthalate 1.0 × dissolved in 10 ^-3 mol g / m ² of magenta coupler (M -5) -containing layer.

Layer 4: an intermediate layer made of 0.70 g / m ² gelatin.

Layer 5 ... gelatin 1.20 g / m ^2, was dissolved in dibutyl phthalate red-sensitive silver halide emulsion and 0.25 g / m ² of 0.28 g / m ²
A layer containing 1.75 × 10 ⁻³ mol g / m ² of a cyan coupler (C′-2).

Layer 6: Layer containing 1.0 g / m ² of gelatin and 0.32 g / m ² of Tinuvin 328 (an ultraviolet absorber manufactured by Ciba Geigy) dissolved in 0.25 g / m ² of dioctyl phthalate.

Layer 7: 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 in gelatin 1 respectively.
It was added so as to be 0.017 g per g.

The average silver halide composition in the silver halide emulsion is shown in Table 9.

The color paper sample thus prepared was subjected to a printing process, followed by running processing by an automatic developing machine in accordance with the following processing steps.

Processing Steps (1) Color development 35 ° C for 45 seconds (2) Bleaching and fixing 35 ° C for 45 seconds (3) Rinsing alternative stability 30 ° C for 90 seconds (4) Drying 60 ° to 80 ° C for 1 minute 30 seconds Composition of processing solution used Is as follows.

The running process is performed by filling the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution in an automatic developing machine, and processing the color paper sample at intervals of 3 minutes. And a water-washing alternative stable replenisher were replenished through a metering pump.

The replenishing amount of the color developing tank has been described in Table 9, color paper 1 m ² per blix replenisher 220ml as replenishing amount to the bleach-fixing tank, rinsing alternative stabilizing replenishing solution 250ml replenisher as replenisher amount to the stabilizing tank did.

The stabilizing bath of the automatic developing machine is a stabilizing bath which becomes the first to third tanks in the direction of the flow of the photosensitive material. The replenishing is performed from the last tank, and the overflow solution is transferred from the last tank to the preceding tank. The overflow liquid was further allowed to flow into the preceding tank to form a multi-tank countercurrent system.

When the amount of the color developing replenisher replenished in the color developing tank becomes twice the capacity of the color developing tank, the maximum color density of the yellow dye is measured by passing through a wedge-exposed check sample and starting. The activity of the developer was evaluated by calculating a relative value with the maximum color density at the time being 100. Table 9 shows the results.
It was shown to.

From the above results, the silver halide composition was outside the range of the present invention (emulsion
In Comparative Example No. G) and Comparative Example in which the concentration of chloride in the tank solution was less than 2 × 10 ⁻² mol / l, even if the silver halide composition was within the present invention, the replenishment amount was reduced. Although the photographic density sharply decreases, if both the silver halide composition and the chloride concentration in the tank solution are within the present invention, even if the replenishment amount is reduced, the photographic density does not decrease and extremely good running performance is obtained. It can be seen that it can be obtained.

Example (11) Emulsion used in Example (10) as a silver halide emulsion
Except that No. J was used, the silver halide color light-sensitive material described in Example (10) was used, and the halide concentration (mol / l) of the color developing replenisher and the tank solution was KBr / KCl = 0.0059 / 0.
With 054 color developer replenisher amount is color developer was running at 100 ml / m ^2, and a bleach-fixing solution, using a stabilizing solution,
The pH of the bleach-fix solution was changed as shown in Table (10), and the same processing was performed as in Example (10), and the minimum reflection density and desilvering property of the yellow dye were evaluated.

The minimum reflection density is PDA-65 (Konishiroku Photo Industry Co., Ltd.)
Desilverability was measured by a fluorescent X-ray method.

 The results are shown in Table (10).

As is clear from Table (10), as the pH of the bleach-fixer increases, both the minimum reflection density and the desilvering property deteriorate, and when the pH is too low (bleach-fixer No. 1), the minimum reflection density increases.

When the pH of the bleach-fix solution is 4.5 to 6.8 (Nos. 2 to 6), the minimum reflection density and the desilvering property are both good, which can be said to be a preferable embodiment for the present invention.

Example (12) Emulsion NO of Example (1) was used as the silver halide composition.
Except that (F) was used, the color photographic material of Example (10) was used. The color developing solution had a halide concentration of replenisher and a KBr / KCl concentration of 0.0017 mol / 0.054 mol of the tank solution. Solution replenisher volume 200ml / m ² Color development temperature 38 ° C
When the color development processing time is shown in Table (11), a running process was performed in the same manner as in Example (10).

The running process was performed until the amount of the color developing replenisher replenished in the color developing tank solution became twice the amount of the tank solution.

 The running processing amount is shown in Table (11).

 The evaluation method was the same as in Example (10).

 The results are shown in Table (11).

As is clear from Table (11), when the processing time of color development is short, especially when the processing time is 45 seconds or less, the fluctuation in photographic density is large depending on the amount of running per day, whereas it is 2 minutes.
When the processing time is 30 seconds or more, especially 3 minutes or more, the photographic density is small and stable photographic characteristics are exhibited.

PA the 0.3NNaCl and 0.3NAgNO ₃ solution adjusting -K 2.6% gelatin solution of Example -13 Emulsion
While adjusting g, a silver chloride emulsion was prepared by a double jet method. While keeping pAg at 6.8 based on this emulsion, 2NNa
Its size by the addition of Cl and 2NAgNO ₃ solution was increased to 40 volumes.

A KBr / NaCl solution containing 40 mol% of bromide in the AgCl particles
AgNO ₃ solution was coated with AgBr / AgCl shell by a double jet method.

The grains obtained were monodisperse emulsions having an average of 0.58 μm, but had an AgCl content of 96 mol% and a AgBr content of 4 mol% based on the total silver halide.

Preparation of photographic materials Using Emulsion K, the photographic materials shown in the following table were prepared.

Table-12 Emulsion 1. Support Polyethylene coated paper 2. Blue photosensitive layer Coupler Y-5 (DBP dispersion) 3. Intermediate layer 4. Green photosensitive layer Coupler M-5 (DOP dispersion) 5. Intermediate layer 6. Red photosensitive layer Coupler C-7 (DOP dispersion) 7. Protective layer 8. UV agent-containing layer Hardener and UV absorber Treatment process Bath Temperature Time Developing bath 35 ° C 50 ° Bleaching and fixing bath 35 ° C 50 ° Stable 30 ° C 50 ° Developing bath Has the following composition: The developer bath was processed using the following replenisher solution at a rate of 80 ml / m ² : To make a bleach-fix bath replenisher, the solution in the tank was simply made 800 ml.

Comparison For comparison, the same photographic material was developed by a conventional developing method using a conventional developing solution.

The developer was replenished using the following replenisher solution at a rate of 80 ml / m ² : The bleach-fix bath is as described above.

Take the developed sample and photographic material for 30 days after adjusting the developer.
The maximum color density of the sample developed after processing 200 m ² was measured, but the photographic density of the sample processed with the developing solution of the present invention hardly changed in the developing solution immediately after preparation and in the developing solution after continuous processing. In addition, it was found that there was almost no overflow, and economic processing could be performed extremely stably. Of course, no tar was formed in the developing tank because benzyl alcohol was not contained. On the other hand, in the comparative experiment, immediately after the preparation of the developing solution, a marked decrease in the color-forming density was observed due to the presence of hydroxylamine, and the density subsequently changed remarkably, so that stable processing could not be carried out. Significant tar formation was also observed due to benzyl alcohol.

Example-14 As an additional experiment, a silver halide photographic light-sensitive material containing silver bromide in various ranges was treated with the color developing solution of the present invention. When only 10 mol% or less was contained, no elution of bromide was found in the developer even when the development reaction was carried out to the maximum. An attempt was made to determine the amount of bromide in the actual running solution, and this was proved.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a specific mode in which a part or all of a processing solution is allowed to flow into another tank in the processing of a silver halide color photographic light-sensitive material according to the present invention.

Claims (6)

(57) [Claims] An imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, followed by a color developing solution containing at least a p-phenylenediamine-based color developing agent. In the method for processing a silver halide color photographic light-sensitive material, wherein the silver halide emulsion layer is developed and continuously processed while replenishing the color developing solution with a replenisher, the silver halide emulsion layer contains at least 70 mol% of silver chloride. The color developing solution contains silver particles, contains the compound represented by the following general formula [I] and at least 2.0 × 10 ^-2 mol of chloride per color developing solution, and replenishes a replenisher of the color developing solution. A method for processing a silver halide color photographic light-sensitive material, wherein the amount is less than 100 ml / m ² . General formula [I] In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein said silver halide grains are silver halide grains containing at least 90 mol% of silver chloride. Processing method. 3. A halogen according to claim 1, wherein said color developing solution contains at least 3 × 10 ^-2 mol of chloride per color developing solution. Processing method of silver halide color photographic light-sensitive material. 4. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein said color developer contains substantially no benzyl alcohol. Method. 5. The color developing solution according to claim 1, wherein the color developing solution does not overflow even if it is continuously processed while replenishing a replenisher. A method for processing a silver halide color photographic light-sensitive material as described in the above item). 6. A method according to claim 1, wherein a replenisher is supplied so as to keep the liquid level of said developing bath constant. A method for processing a silver halide color photographic light-sensitive material as described in the above item).