JP2645259B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic 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 by extremely reducing the replenishing amount.

[0003]

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

[0004] The composition of the developing solution changes with 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) Nos. 2,007,459 and 2,0
07,457 and 2,717,674, U.S. Patent (US-A)
Nos. 3,647,461, 3,647,462 and 4,186,007 and EP-A-00029722.

[0006] These methods are called a replenishment method, and are performed by replenishing a replenisher.

The substances consumed in the development process are maintained at the desired concentration by the addition of such replenishers, while at the same time being lost from the development bath in order to prevent the accumulation of unwanted halides in the developer. A larger volume of replenisher is added than is required.

In this case, the concentration of the halide in the replenisher is low, and it has recently been possible to reduce the replenishment amount by a replenisher containing no halide, but still produces a relatively large amount of overflow. Has the consequences. 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.

In the former, since the halide concentration becomes high and development is suppressed, it is necessary to eliminate the inhibitory effect by performing a high activation treatment, and furthermore, there is a disadvantage that the amount of drainage is relatively large.

The latter 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, a low replenishment system (LR system), which can easily reduce replenishment, is particularly adopted in a minilab or the like. 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 disadvantages of these methods, Japanese Patent Application Laid-Open No. Sho 61-70552 discloses a replenishment method in which a silver halide has a remarkably high silver chloride content and a replenishment rate low enough not to overflow even when replenished. A treatment method has been proposed in which the treatment is carried out in a small amount, so that the elution of bromide ions is small, and as a result, the concentration of bromide ions does not become high.

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

However, according to the study 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 drawbacks are that the gradual change of the gradation with the lapse of time due to aging, and that the photographic performance changes even if the concentration of the sulfite as a preservative changes due to air oxidation. It turned out to be very practical.

The present inventors have 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 does not increase, and as a result, the maximum density is not so high. It has been found that short processing cannot 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 of this, and have found that the main cause is the presence of hydroxylamine sulfate, which has been used without exception in conventional color developing solutions.

It has been found that the greater the proportion of silver chloride in the photographic material, the greater the suppression of development in the presence of hydroxylamine sulphate. Due to the resulting ammonium ions, the higher the proportion of silver chloride,
It was found that physical development became easier and the photographic performance changed.

Therefore, even if the elution of bromide generated in the development reaction is suppressed by silver chloride, photographic performance cannot be stabilized if hydroxylamine is present in the developer. The performance changes due to factors other than the density of. In addition, in the low replenishment processing, the sulfite ion concentration in the developer tends to change with the passage of time, but it was also found that the photographic performance was sensitively changed by the sulfite concentration in the photographic material mainly containing silver chloride.

On the basis of these analyses, the present inventors have conducted intensive studies, and the photographic material uses silver chloride grains having a specific concentration or higher to convert silver chloride into a specific compound that can replace conventional hydroxylamine during color development. By using and further processing by containing a certain amount or more of chloride, it is possible to solve all of the above-mentioned drawbacks, perform continuous processing with sufficiently high photographic density, and always obtain stable photographic density. It has been discovered and led to the present invention.

[0021]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a processing method which eliminates these drawbacks and ensures that the photographic performance can always be stably obtained even if the replenishment amount is significantly reduced.

[0022]

The object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support after imagewise exposing the same to at least a p-phenylenediamine color developing agent. In a method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer is processed by a color developing solution containing at least 70%, and the color developing solution is continuously processed while replenishing a replenisher.
The color developer contains a compound represented by the following general formula [I] and at least 2.0 × 10 ^-2 mol of chloride per liter of the color developer. And a processing method using a color developing solution containing a manganese salt or a cerium salt.

[0023]

Embedded image 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.

The method of the present invention comprises at least one development step of reducing exposed silver halide to silver, bleaching to oxidize the reduced silver, and fixing to remove silver salts from the recording material. Contains. 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 kept at the commonly used levels of 25 ° C. to 50 ° C., and for photographic materials using silver halide grains in which the 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, in the present invention, it is also important that hydroxylamine sulfate is not contained.

In the general formula [I], R ₁ and R ₂ each independently represent an alkyl group or a hydrogen atom which is not a hydrogen atom, but the alkyl groups represented by R ₁ and R ₂ may be the same or different. And an alkyl group having 1 to 3 carbon atoms, respectively. The alkyl groups of R ₁ and R ₂ include those having a substituent, and R ₁ and R ₂ may combine to form a ring, and may form 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. No. 3,287,125,
No. 3,293,034, No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

[0030]

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[0031]

Embedded image These compounds of the present invention are usually free amine, hydrochloride,
It is used in the form of sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

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

The compound represented by the general formula [I] of the present invention can be used in place of hydroxylamine sulfate which has been widely used as a preservative in conventional color developing solutions for silver halide color photographic light-sensitive materials. 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. Yes,
For example, 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. (See Japanese Patent Publication No. 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 made extremely small, and the use of the compound represented by the above general formula [I] also improves various disadvantages of a photosensitive material having a high silver chloride content. .

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 keep bromide ions in the replenisher slightly low.

The silver halide in the photographic material of the present invention contains only a very low concentration of silver bromide, and the amount eluted during development is extremely small. However, a replenisher is used so that the bromide ion concentration does not change in the developer. It is necessary to adjust the amount of bromide ions therein, 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 capable of releasing chloride ions in a color developer, and specific compounds include potassium chloride, sodium chloride, and the like.
Examples thereof include lithium chloride and magnesium chloride.

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 silver chloride in an amount of 70 mol% or more, and should be close to 100%. However, it was found that when the amount of silver chloride was 90 mol% or more, an effect substantially close to 100% of silver chloride could 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 a range of 0.5 g to 100 g, preferably 2 to 15 g, per liter of the developing solution. The color development processing is usually performed at a temperature in the range of 20 ° C to 80 ° C, preferably in the range of 30 ° C to 50 ° C.

The pH at which development takes place is generally 8 or higher, preferably 9.5 or higher.

Development involves the presence of pH buffers, development inhibitors, antifoggants, complexing agents for softening, preservatives, development accelerators, competing couplers, fog agents, auxiliary developer compounds and viscosity modifiers. Can be done below;
Disclosure (Research Disclosure) 1754
4, December 1978, Section XXI, Industrial Oppotunities, Inc.
Ltd.), Homewell Havant, Hampshire, Grent Bri
Issued tain, and Ullman's Encyclopedia del
Technischen Hemiy (Ullmans Enzyklpudie der
technisehen Chemie), 4th edition, volume 18, especially in 1979
See pages 451, 452 and 463-465. Suitable developer compositions include Grant Haist, Modern
Photographic processing (Modern Photograp)
hie Processing), John Wiley and Sans, 1973, Vols.

The compound of the present invention represented by the general formula [I]
Color developers containing manganese or cerium salts are oxidized
Prevention performance is improved, and the color development during storage over time is also reduced.
Be improved.

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. Not something.

Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese permanganate Potassium manganese Manganese oxalate Manganese manganese citrate Ethylenediaminetetraacetate Manganese sulphate Cerium nitrate Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium acid These manganese salts and cerium salts are preferably used in the form of ions (manganese ions and cerium ions) in the range of 0.1 mg to 100 mg, more preferably 0.3 mg to 20 mg, per liter of the color developing solution. In particular, 0.5 mg to 10 mg is preferably used from the viewpoint of the effects of the present invention.

Usually, sulfite is used as a preservative in the color developing solution. In the color developing solution according to the present invention, the sulfite concentration is 1.6 × 10 ^-2 mol or less per liter of the color developing solution. When used, a high silver chloride-containing photosensitive material can be used because it is possible to suppress a decrease in color density, which is considered to be caused by physical dissolution development of the high silver chloride-containing photosensitive material, and the reduction in preservation ability is extremely small. The present invention can provide a color developing solution which enables rapid processing by using the solution or a method for processing a silver halide color photograph using the solution. In the present invention, the sulfite concentration in the color developing solution is 1.6 × 10 ^-2 mol / mol. Liter or less is preferably used. Further, the effect is more preferably exhibited at 1 × 10 ⁻² mol / l or less, more preferably at 4 × 10 ⁻³ mol / l or less.

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

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

The p-phenylenediamine compound having a water-soluble group has less contamination of the photosensitive material and has less skin contamination than a paraphenylenediamine compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage that the skin is less irritating,
In particular, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I] in the present invention.

The water-soluble group has at least one amino group on a p-phenylenediamine compound or a benzene nucleus.
One having. Examples of specific water-soluble _{group, - (CH 2) n -CH} 2 OH, - (CH 2) m -NHSO 2 - (CH 2) n -CH 3, - (CH 2 _{) m O- (CH 2) n} -CH 3, - (CH 2 CH 2 O) n -C m H 2m + 1 (m and n represent an integer of 0 or more, respectively), -. COOH group, -SO _Three
H groups and the like are preferred.

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

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

Embedded image Of the color developing agents exemplified above, fog is less likely to occur and is preferably used in the present invention.
1), (A-2), (A-3), (A-4), (A-
6), (A-7) and (A-15), particularly preferably (A-1).

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

The color developing agent having a water-soluble group used in the present invention is usually 1 × 10 4 per liter of color developing solution.
^{-2 to} 2 × 10 ^-1 mol is preferably used, but from the viewpoint of rapid processing, per liter of the color developing solution is preferably used.
The range of 1.5 × 10 ^{-2 to} 2 × 10 ^-1 mol is more preferable.

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

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 may be a dye precursor. Representative dye precursors include those described in JP-A-58-65429 and JP-A-58-24137, and specifically, for example, 2 ', 4'-bismethanesulfonamido-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4 '-(2,4,6
-Triisopropyl) benzenesulfonamido-2-methyl-4-N- (2-methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4 '-(2,4,6-triisopropyl) benzenesulfone Amido-4- (hydroxytrisethoxy)
Diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis (2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 2,4'-bismethane Sulfonamido-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamido-4 '-(2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-methoxy-
2'-methanesulfonamide-4 '-(2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido) 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 light-sensitive material is preferably 0.5 to 22 mg, more preferably ^{4 to 12} mg, per 100 cm ² of the light-sensitive 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 because it shows an improvement effect.

[0063]

Embedded image (Wherein, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₂₂ and R ₂₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 2 to 6 carbon atoms. In the above formula, n1 is an integer of 1 to 6, X 'and Z' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 to 2 carbon atoms.
6 represents a hydroxyalkyl group. )

Preferred specific examples of the compound represented by the formula [D] are as follows. (D-1) ethanolamine, (D-2) diethanolamine, (D-3) triethanolamine, (D-4)
Di-isopropanolamine, (D-5) 2-methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-
8) 2-diethylaminoethanol, (D-9) 1-diethylamino-2-propanol, (D-10) 3-diethylamino-1-propanol, (D-11) 3-dimethylamino-1-propanol, (D- 12) Isopropylaminoethanol, (D-13) 3-amino-1-propanol, (D-14) 2-amino-2-methyl-1,3-
Propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyldiethanolamine, (D-17) 2-amino-2- (hydroxymethyl) -1,3-propanediol.

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

When the color developing solution according to the present invention contains a compound represented by any one of the following general formulas [BI] to [B-IV], the objective effects of the present invention can be more favorably exhibited. It is more preferably used in the present invention because bleaching fog generated upon bleaching or bleach-fixing processing immediately after color development is also improved.

[0067]

Embedded image In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₁₅ , —COOR ₁₆ , 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 represents a halogen atom, a sulfonic acid group, Represents a phenyl group.

The alkyl groups represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include those having a substituent, for example, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, a t-propyl group.
-Butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and the alkyl group represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is as defined above. And an octyl group.

The phenyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ includes a phenyl group, a 2-hydroxyphenyl group, a 4-aminophenyl group and the like.

The 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-dihydroxy Naphthalene-6 Carboxylic acid (B-II-4) 2,3- dihydroxy-8-isopropyl - naphthalene (B-II-5) 2,3- dihydroxy-8-chloro --6
Sulfonic acid Among the above compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
5-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 compounds represented by the above-mentioned general formulas [BI] and [B-II] can be used in an amount of 5 mg to 20 g, preferably 10 mg to 10 g, per liter of color developing solution. More preferably, good results are obtained by adding 20 mg to 3 g.

[0072]

Embedded image (Formula [B-III] and [B-IV] in, L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -
_{O-L 8 -O-L 8} - or -L ₉ -Z-L ₉ - the Represents 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). However, 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). It is an acid group (including its salt) or a phosphonic acid group (including its salt). )

In the general formulas [B-III] and [B-IV], the alkylene group, cycloalkylene group and phenylene group represented by L, and the alkylene group represented by L _{1 to} L ₁₃ have a substituent. Including things.

Next, these general formulas [B-III] and [B
Preferred specific examples of the compound represented by -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] 1,2-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 Diaminetetraacetic acid [B-III-11] Ethylenediaminetetrapropionic acid [B-III-12] Phenylenediaminetetraacetic acid [B-III-13] Ethylenediaminetetraacetic acid disodium salt [B-III-14] Ethylenediaminetetraacetic acid ( Trimethylammonium) salt [B-III-15] tetrasodium ethylenediaminetetraacetate [B-III-16] diethylenetriaminepentaacetic acid pentasodium salt [B-III-17] ethylenediamine-N-(beta-hydroxyethyl) -
N, N ', N'-triacetic acid sodium salt [B-III-18] Propylenediaminetetraacetic acid sodium salt [B-III-19] Ethylenediaminetetramethylenephosphonic acid [B-III-20] Cyclohexanediaminetetraacetic acid 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] Nitrilotripropionic acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] Iminodimethylenephosphonic acid [B-IV-6] Nitrilotriacetic acid trisodium salt [B-IV-7] Hydroxyethyliminodiacetic acid Sodium salt represented by the general formula [B-III] or [B-IV] Among the compounds, particularly preferred compounds used in the present invention [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 an amount of 0.1 to 20 g per liter of the color developing solution, and in particular, from 0.3 to 5 g in view of the object of the present invention. A range is particularly preferably used.

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

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, since the occurrence of fog is further reduced.

[0078]

Embedded image 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 (for example, methoxy, ethoxy, methoxyethoxy and the like), and an aryloxy group (for example, 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, etc.), arylamino group (for example, 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 the present invention is not limited thereto.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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The triazylstilbene-based brightener represented by the general formula [III] can be prepared by the usual method described in, for example, “Fluorescent Whitening Agent” edited by the Chemical Industry Association of Japan (published in August 1976), page 8. Can be synthesized.

These triazinylstilbene-based brighteners are used in an amount of 0.2 to 6 per liter of the color developer used in the present invention.
g is used preferably, particularly preferably 0.4 to 3 g.
g range.

The color developing solution of the present invention contains a 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 '].

Formula [I '] (In the formula, R ₁ ′ represents an alkylene group having 1 to 6 carbon atoms, R ₂ ′ represents an alkyl group, and n ′ represents an integer of 500 to 20,000.)

The alkylene group having 1 to 6 carbon atoms represented by R ₁ 'may be linear or branched, and is preferably an alkylene group having 2 to 4 carbon atoms, for example, ethylene, propylene, butene, Examples thereof include an isobutene group, a dimethylethylene group, and an ethylethylene group. 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 (such as a hydroxyl group). Including. n 'represents the number of repeating units in the polymer chain, and represents an integer of 500 to 20,000, preferably
It is an integer between 500 and 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 present invention are shown below, but the present invention is not limited thereto.

Illustrative Compounds PAI-1 Poly (ethylene imine) PAI-2 Poly (propylene imine) 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) ) Can be used in the color developing solution in any amount that can achieve the object of the present invention, but is generally preferably from 0.1 to 500 g, more preferably from 0.5 g to 300 g per liter of the color developing solution. used.

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. 56-94349. 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 developing step may be any time, but is usually from 5 seconds to 5 minutes. In general, a high silver chloride photosensitive material as in the present invention uses a color development time of 15 seconds to 60 seconds.
When processing for a long time of 50 seconds or more, the difference in photographic characteristics between large-scale processing and small-volume processing is reduced, and the photographic processing characteristics of large-scale labs and mini-labs (small-sized labs) approach. It is more preferably used because the effect of making the photographic characteristics in the market uniform is exhibited. In particular, this effect becomes remarkable when the color development step is 180 seconds or longer.

The replenishing rate is in the range of 300 to 10 ml per m ² of the photographic material, but in order to maximize the effect of the present invention,
Processing in the range of 150ml to 30ml. Particularly preferred is in the range of 120 ml to 50 ml, most preferably 1 ml.
Processed in the range of 00ml to 80ml.

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

In a preferred embodiment, the concentrated and adjusted kit used to make the replenisher is directly charged into the developing bath, and the shortage of water can be supplied from the water replenishing device while controlling the lowering of the liquid level. .

The preferred developer of the present invention preferably contains substantially no benzyl alcohol. Here, “substantially not contained” means that benzyl alcohol is 2 ml / liter or less, and it is most preferred that the benzyl alcohol is not contained at all in the present invention. Benzyl alcohol has a very low solubility and an extremely small replenishment rate. In the processing as in the present invention, the solution is easily concentrated, so that the adhesion failure to the photographic material due to the precipitation of oil or the oxidation of the color developing agent causes the tar to be removed. Generate extremely troublesome problems such as generation.

Also, since the solubility is extremely small, when the above-mentioned concentrated kit is directly charged 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 color development processing,
Processing is performed with a processing solution having a fixing ability. When the processing solution having the fixing ability is a fixing solution, a bleaching process is performed before the processing. 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 effect of coloring the uncolored part of the color former, and its configuration is aminopolycarboxylic acid or oxalic acid, iron with an organic acid such as citric acid,
Coordinated metal ions such as cobalt and 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. [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 tetra propionic 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 The bleaching solution used is an organic acid as described above. And a variety of additives. 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. PH buffers such as borates, oxalates, acetates, carbonates, and phosphates, and those known to be added to normal bleaching solutions such as alkylamines and polyethylene oxides can be appropriately added. .

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

When processing is performed while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, or the like; These salts may be contained in the bleach-fix replenisher and replenished in the processing bath.

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

In the present invention, from the viewpoint of rapid processing,
A bleach-fixing solution is preferably used. When bleach-fix processing is performed immediately after color development using a high silver chloride photosensitive material as in the present invention, stains called bleach fog are likely to occur. Therefore, as a result of various studies, it was found that by using the pH of the bleach-fixing solution in the range of 4.5 to 6.8, not only this problem could be solved but also the effect of reducing the silver bleaching speed could be obtained.

This effect is particularly 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 such as a fixing solution or a bleach-fixing solution, as well as a washing solution or a stabilizing solution instead of a washing solution. For example, electrolysis method (French patent 2,299,667), precipitation method (JP-A-52-73037, German patent 2,331,220), ion exchange method (JP-A-51-17114, German patent 2,548,237)
And metal replacement method (UK Patent No. 1,353,805) can be used effectively.

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. Can be 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.

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

As a specific embodiment of these, for example, FIG.
And the like.

The silver halide emulsion layer containing silver halide grains containing at least 70 mol% of silver chloride used in the present invention has 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.

The red-sensitive layer can thus contain, for example, non-diffusible color couplers which form cyan partial color images, generally of the phenol or α-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 an open chain 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 work report (Mitteilunglnaus)
den Forschungslaboratorien der Agfa), Leverkusen / Munchen,
Vol. III. p. 111 (1961) "Color Coupler" by W. Pelz (Farbkuppl
er); K. Venkataraman
), "The Chemistry of Synthetic Dyes",
Vol. 4, 341-387, Academic Press
mic Press), (1971); TH James, "The Theory of the Photographic Process" (The Theory of the Photographic Process)
Photographic Process, 4th edition, pp. 353-362; and Research Disclosure (Research Disclosure)
osure) No. 17643, Section VII.

According to a particularly preferred embodiment, a color coupler which is sufficiently coupled without the benzyl alcohol usually added 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,
As described above, it is always a source of trouble, especially a source of trouble due to tar formation. Suitable couplers which can be used without benzyl alcohol are described in DE-A-3,209,710.
Nos. 2,441,779, 2,640,601 and EP-A-0067689.

Preferred yellow couplers have a structure corresponding to the formula:

[0117]

Embedded image

[0118]

Embedded image The following magenta couplers are particularly preferred. :

[0119]

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[0120]

Embedded image The following cyan couplers are particularly preferred. :

[0121]

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[0122]

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Among the above-mentioned yellow couplers, especially when a high-reactivity yellow coupler is used, the coloring property in short-time processing is improved and the stain in the lowest density part is also improved. Yellow couplers are preferably used.

The fast-reacting 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,
Preferred are yellow couplers having a relative coupling reaction rate of 0.5 or more.

The coupling kinetics of the couplers are different for the two couplers M which give different dyes which can be clearly separated from one another.
And N are mixed, added to a silver halide emulsion, and color-developed to determine the relative amount of each dye in a color image obtained by measurement.

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

[0127]

(Equation 1) In other words, a silver halide emulsion containing a mixed coupler,
Exposure of various stages is given, and several sets of DM and DN obtained by color development are converted into two orthogonal axes.

[0128]

(Equation 2) The value of the coupling activity ratio RM / RN can be determined from the slope of a straight line obtained by plotting as

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, the RM / RN value when the following coupler is used as the above coupler N is referred to.

[0131]

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

The following are specific examples of the high-speed reactive yellow coupler of the present invention, but the invention is not limited thereto.

[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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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.

[0154]

Embedded image 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, cycloalkyl and the like. A halogen 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, heterocyclicthio Each group, a spiro compound residue, a bridged hydrocarbon compound residue and the like are also included.

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.

As the sulfonamide group represented by R,
Examples thereof 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 carbon atoms.
~ 12, particularly preferably 5 ~ 7, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group or an arylsulfinyl group; a phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group or an aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; acyl group as alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group as alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group as alkylsulfamoyl group, arylsulfamoyl An acyloxy group such as an alkylcarbonyloxy group or an arylcarbonyloxy group; a carbamoyloxy group such as an alkylcarbamoyloxy group or an arylcarbamoyloxy group; The de group alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenoxy-1, 3,5
-Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutarimide A spiro compound residue such as spiro [3.3] heptane-1-yl; a bridged hydrocarbon compound residue such as bicyclo [2.2.1] heptane-1
-Yl, tricyclo [3.3.1.1 ^3,7 ] decane-1
-Yl, 7,7-dimethyl-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, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0166]

Embedded image (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. Those mentioned are mentioned.

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

[0169]

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

Preferred among the general formulas [MI] are those represented by the following general formula [M-VIII].

[0171]

Embedded image In the formula, R ₁ , X and Z ₁ represent R, R in the general formula [MI]
Synonymous with X and Z.

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

The substituents which the ring formed by Z in the general formula [MI] and the ring formed by Z ₁ in the general formula [M-VIII] may have, and the ring represented by the general formula [MI]
R _{2 to} R ₈ in [I] to [M-VI] are preferably those represented by the following general formula [M-IX].

In the formula [M-IX] -R ¹ -SO ₂ -R ² , 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 carbon atoms.
And may be linear or branched.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group.

When used for positive image formation, the most preferable substituents R and R ₁ on the heterocyclic ring are those represented by the following formula [MX].

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

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ are bonded to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle). R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

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

Further, among (i), preferred are R ₉ to
Two of R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

When used for forming a negative image, the most preferable substituents R and R ₁ on the heterocyclic ring are those represented by the following formula [M-XI].

Formula [M-XI] R ₁₂ -CH ₂ -In the formula, R ₁₂ has the same meaning as R described above.

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

The following are typical specific examples of the compounds according to the present invention.

[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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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 Japanese Patent Application No.
Among the compounds described on pages 66 to 122 of the specification of No. 1-9791, among the compounds described in Nos. 1-4, 6, 8-17, 19-24,
26-43, 45-59, 61-104, 106-121, 1
Compounds represented by 23 to 162 and 164 to 223 can be mentioned.

[0206] Also, the above-mentioned coupler is the Journal of the Chemical Society (Journal of the Chemical Society).
l Society), Perkin I (1977), 2047
~ 2052, U.S. Patent 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 60-3
No. 3552, No. 60-43659, No. 60-172982 and No. 60-1907
It can be synthesized with reference to No. 79 and the like.

The coupler of the present invention can be used in an amount of usually 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide.

The magenta coupler according to the present invention can be used in combination with another type of magenta coupler.

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 has the drawback that when bleaching or bleach-fixing is carried out immediately after color development using a high silver chloride photosensitive material, stains tend to occur in the unexposed areas, 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 defect is improved but also the silver bleaching performance of the photosensitive material is more improved.

[0210]

Embedded image In the formula, R ₁ , R ₂ and R ₄ each represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent, and R ₃ and R _{6 each} represent a hydrogen atom, a halogen atom, Represents an aliphatic group, an aryl group or an acylamino group which may have a group. However, R ₃ may form a ring with R ₂ . R ₅ represents an alkyl group which may have a substituent, and each of Z ₁ and Z ₂ 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 compound represented by the above general formula [C-I] according to the present invention
Alternatively, the cyan coupler represented by [C-II] will be described in detail.

R ₁ , R ₂ and R ₄ are an aliphatic group, preferably an aliphatic group having 1 to 32 carbon atoms (eg, a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, an allyl group), an aryl group ( For example, a phenyl group, a naphthyl group, or the like, or a heterocyclic ring (for example, a 2-pyridyl group, a 2-imidazolyl group, a 2-furyl group, a 6-quinolyl group, or the like) is represented by an alkyl group, an aryl group, or a heterocyclic group. Ring group,
An alkoxy group (for example, methoxy group, eumethoxyethoxy group, etc.), an aryloxy group (for example, 2,4-di-t-amylphenoxy group, 2-chlorophenoxy group,
4-cyanophenoxy group, etc.), alkenyloxy group (eg, 2-propenyloxy group), acyl group (eg, acetyl group, benzoyl group, etc.), ester group (eg, butoxycarbonyl group, phenoxycarbonyl group, 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,
(E.g., dipropylsulfamoylamino group),
Imide group (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group,
A dimethylureido group), an aliphatic or aromatic sulfonyl group (eg, a methanesulfonyl group, a phenylsulfonyl group, etc.), an aliphatic or aromatic thio group (eg, an ethylthio group, a phenylthio group, etc.), a hydroxy group, a cyano group, It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.

R ₃ and R ₆ each represent a hydrogen atom, a halogen atom, an aliphatic group, an aryl group or an acylamino group which may have a substituent. 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, Ethyl, propyl, butyl, pentadecyl, t-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenylthiomethyl, butanamidomethyl, methoxymethyl, etc.).

Formula [C-I] and Formula [C-II]
In the formula, 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,
Methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.),
Aryloxy group (for example, 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, etc.), alkoxycarbonyloxy group (Eg, ethoxycarbonyloxy group, benzoyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, titrazolylthio group Imide group (eg, succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.)
and so on. These leaving groups may include photographically useful groups.

In the general formula [C-I], preferred R _{1 is}
Is an aryl group, a heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, a cyano group. Further preferred is an aryl group substituted with a group.

When R ₃ and R ₂ do not form a ring in the general formula [CI], R ₂ is preferably a substituted or unsubstituted alkyl group or aryl group, and 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 is an alkyl group having 2 to 15 carbon atoms and a methyl group having a substituent having 1 or more carbon atoms, and the substituent is an arylthio group, an alkylthio group, an acylamino group. , An aryloxy group and an alkyloxy group are preferred.

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

In formula [C-II], preferred R ₆ is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

In the general formulas [CI] and [C-II], preferred 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, particularly preferably a chlorine atom or a fluorine atom.

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

The cyan dye-forming coupler represented by the general formula [CI] or [C-II] is usually used for 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, per mol of silver halide.
Used in moles.

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

The compounds represented by the following general formulas [CI] and [C-II]
Specific compounds represented by the following are listed, but the present invention is not limited thereto.

[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

Embedded image The cyan coupler according to the present invention is generally used in an amount of 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol per mol of silver halide.
It can be used in the range of 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 the color developing solution can be used. Since the effect on the photographic performance that occurs when the bleach-fixing solution is mixed is extremely small, there is another effect. Therefore, it is a more preferable embodiment in the present invention.

The nitrogen-containing heterocyclic mercapto compound according to the present invention is characterized in that the nitrogen-containing heterocycle is an imidaline ring, imidazole ring, imidazolone ring, pyrazoline ring, pyrazole ring, pyrazolone ring, oxazoline ring, oxazole ring, oxazolone ring, thiazoline ring. , 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, benz Selenazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring (for example, triazaindene ring, Zainden ring, is preferably selected from pentazaindenes ring) and the like. Of these, particularly preferred nitrogen-containing heterocyclic mercapto compounds include oxazole rings, oxadiazole rings, thiadiazole rings,
A triazole ring, a tetrazole ring, a benzimidazole ring, a benztriazole ring, a pyrimidine ring, a triazine ring, and a polyazaindene ring.

The following are specific examples of the mercapto compound useful in the present invention.

[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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[0250]

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[0251]

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[0252]

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[0253]

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[0254]

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[0255]

Embedded image The above compounds are described in Journal of Chemical Society (J. Chem. Soc.) 49, 1748, 1927;
Of Organic Chemistry (J. Org. Che)
m. 39, 2469, 1965, JP-A-50-89034, 55-79436
No. 51-102639, No. 55-59463, Annalen Chemie, 44-3, 1954, Japanese Patent Publication No. 40-28496
No., Chemical Berichte (Chem. Ber.) 20, 231, 188
7, USP. No. 3,259,976, Chemical and Pharmaceutical Beurethane
eutical Bulletin) (Tokyo) Vol. 26, 314 (1978), Berichte der Deutschen Hemischen Geisels draft (Berichte bar Deutscben Chemischen)
Gesellsdraft) 82, 121 (1948); U.S. Pat. No. 2,843,49
No. 1, No. 3,017,270, UK Patent No. 940,169, Journal of American Chemical Society, 44,
The compound can be synthesized with reference to the methods described in 1502 to 1510 and the like.

The nitrogen-containing heterocyclic mercapto compound (hereinafter, simply referred to as mercapto compound) is described in, for example, JP-A-51-1.
07129, 48-102621, 55-594463, and 59-12
It is described in each gazette of No. 4333.

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

The total amount of the mercapto compound used was as follows:
It varies widely depending on the layer constitution of the silver halide photographic light-sensitive material, the type of mercapto compound, the amount of silver halide, the processing conditions, etc., and is generally 10 ^-8 mol to 10 ^-4 mol, preferably 10 ^-7 mol per 1 m ^2. Although the range of 10 ^-5 mol, without being limited to the total addition amount itself in the present invention, the degree of fogging prevention of the emulsion layers, and is defined by the size 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 may contain at least 70 mol% of silver chloride, and the remainder may contain bromide or iodide. Preferably, the amount of bromide and iodide is very small. In a special case, it is also preferable that the blue photosensitive layer is silver halide containing 30 mol% of bromide and the other two layers, for example, the green photosensitive layer and the red photosensitive layer have about 99% chloride. It is. Silver halide is preferably a core-shell grain and has a double layer structure.

In one embodiment, the grains consist of at least two regions of differing halide composition, for example one core and at least one shell, at least one region B comprising at least 10 mol% of silver bromide, preferably Contains at least 25 mol% silver bromide, but not more than 50 mol% silver bromide.

Region B can exist as a core or as a shell around a 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 grains have at least one zone ZBr having a high content of at least 10 mol% bromide and no bromide rich zone ZBr on the surface of the silver halide grains.

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

The silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or accelerated feeding of the material). Particular preference is given to preparation by the double-flow method with controlled pAg; see Research Disclosure No. 17643, sections I and II.

The emulsion 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, for example, in Belgian Patent Nos. 493,464 and 568,687, and, for example, Belgian Patent No. 547,3
No. 23, such as polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives. Gold, platinum,
Noble metals and noble metal compounds such as palladium, iridium, ruthenium or rhodium are also suitable sensitizers.
This chemical sensitization method is described in Zeitschrift Fair Bissenshaftriche Photography (Z. Wiss. Pho
46 , 65-72 (1951) in R. Koslovsky's dissertation; also, Research Disclosure No. 17643, supra, section I.
See also II.

Emulsions are prepared in optically known manner, for example using conventional polymethine dyes such as neuthocyanins, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like.
Can be sensitized; FM Hammer (FM
Hamer) 's "Cyanine Soybeans and Related Compounds" (The Cyanine Dyes and relate)
d Commpounds (1964) Ullmanns Enzyklpa
die der technischen Chemie) 4th edition, Vol. 18, p. 431 and the following, and the above-mentioned Research Disclosure N
o. See 17643, section IV.

Conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer,
Tetra- and penta-azaindenes are preferred, particularly those substituted with a hydroxyl or amino group. Compounds of this type are described, for example, in Birr, Zeitschrift Fair Bissenshaftrich Photography (Z. Wiss. Photo.) 47, 195.
2, pages 2 to 58, and Research Disclosure No. 17643, supra, section IV.

The components of the photographic material can be combined by conventional techniques; for example, US Pat. No. 2,322,027.
No. 2,533,514, No. 3,689,271, No. 3,764,336
No. 3,765,897. The components of the photographic material, such as couplers and UV absorbers, can also be combined in the form of a charged latex;
See 41,274 and European Patent Application 14,921. The components can also be fixed in the material as a polymer; for example, DE-A-2,044,992, U.S. Pat.
See Nos. 952 and 4,080,211.

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

The usual hydrophilic film formers can be used as protective colloids or binders for the layers of the recording material, for example proteins, especially gelatin, alginic acid or derivatives such as esters, amides or salts thereof, carboxymethylcellulose. And cellulose derivatives such as cellulose sulfate, starch or derivatives thereof, or hydrophilic synthetic binders; see also the binders set forth in Research Disclosure 17643, Section IX, supra.

The layers of the photographic material can be hardened in the customary manner, for example using epoxides, heterocyclic ethyleneimines or acryloyl 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 described in German Patent Application
Nos. 2,439,551, 2,225,230 and 2,317,672, and Research Disclosure 17643, supra, Section XI.

[0272]

As described above, according to the present invention, no additional means such as a regenerating process of a color developing solution is 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.

[0273]

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

Reference 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.

[0276] Polystyrene-coated paper includes:
200 parts by weight of polyethylene with an average molecular weight of 100,000 and a density of 0.95 and polyethylene 2 with an average molecular weight of 2,000 and a density of 0.80
And 0 parts by weight of anatase titanium oxide
It was added 6.8 wt%, to form a coating layer having a thickness of 0.035mm on the fine paper surface of the weight 170 g / m ² by extrusion coating, the thickness only by polyethylene on the back 0.04mm
The one provided with the above-mentioned coating layer was used. 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 mole of silver halide.
Sensitizing dye having the following structure per mole of silver halide

[0278]

Embedded image 2,5-di-t-butylhydroquinone 20 sensitized with 2.5 × 10 ^-4 mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate
It is coated so as to contain 0 mg / m ² and 2 × 10 ^-1 mol per mol of silver halide of the exemplified yellow coupler Y-5 as a yellow coupler and to have a silver amount of 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 ′) as an ultraviolet absorber
-Di-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2- (2-hydroxy-3 ', 5'-
Di -t - butyl phenyl) -5-chloro - is applied so that the gelatin 1900 mg / m ² of gelatin layer containing a mixture 200 mg / m ² of the benzotriazole.

Third layer: A green-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1,
The emulsion contains 450 g of gelatin per mole of silver halide,
Sensitizing dye having the following structure per mole of silver halide

[0281]

Embedded image Magenta coupler M-5 was sensitized using 2.5 × 10 ^-4 mol, and was dissolved and dispersed 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, 2,2,4-trimethyl-
0.3 mol of 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,
2- (2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-3'-
t-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2- (2'-hydroxy-
3 ′, 5′-t-butylphenyl) -5-chloro-benzotriazole mixture (2: 1.5: 1.5: 2)
The gelatin layer containing g / m ² is coated so that the amount of gelatin becomes 1900 mg / m ² .

Fifth layer: a red-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1,
The emulsion contains 500 g of gelatin per mole of silver halide,
Sensitizing dye having the following structure per mole of silver halide

[0284]

Embedded image 2,5-Di-t-butylhydroquinone 150 mg / m ² sensitized with 2.5 × 10 ^-5 mol and dissolved in dibutyl phthalate and halogenated with the cyan coupler and the exemplified cyan coupler C′-2 It is coated so as to contain 3.5 × 10 ^-1 mol per mol of silver and to have a silver amount of 280 mg / m ² .

Sixth layer: gelatin layer with gelatin amount of 900 mg
/ M ² .

The silver halide emulsion used for each photosensitive emulsion layer (first, third and fifth layers) was prepared according to the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used. With 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer,
Bis (vinylsulfonylmethyl) ether was contained as a hardener and saponin was used as a coating aid.

The above-mentioned light-sensitive materials (changed silver halide composition)
To the following processing step and processing solution (change the preservative of the color developing solution, compare with the preservative pear), measure the maximum density of the yellow dye of the obtained sample, and compare The ratio of preservative to pear was calculated. Table 1 shows the results.

Standard processing step [1] Color development 38 ° C. for 1 minute [2] Bleaching and fixing 38 ° C. for 1 minute [3] Rinse with water 25 to 35 ° C. for 1 minute [4] Drying 75 to 100 ° C. about 2 minutes <Color developing tank solution> Ethylene glycol 15 ml Potassium sulfite 1.0 g Sodium chloride 3 × 10 ^-2 mol Potassium carbonate 30.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate Salt (Exemplified Compound A-1) 5.5 g Optical brightener (Exemplified Compound A'-4) 1.0 g Preservative described in Table 1 5.0 g Hydroxyethyliminodiacetic acid 5.0 g 1,2-dihydroxybenzene-3,5 - disulfonic acid - a is added to make 1 liter disodium salt 0.2 g water, with KOH and H ₂ SO ₄ and PH10.20.

<Bleaching and fixing tank solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml pH with potassium carbonate or glacial acetic acid Adjust to 7.1 and add water to make 1 liter.

[0290]

[Table 1] 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 without lowering the maximum concentration. I understand.

Reference Example 2 Each of the color developing solutions to which the preservatives described in Table 2 were added and used in Reference Example 1 were stored for 10 days, and the color developing solution of the preservative pear immediately after preparation was used for comparison. After the development processing, the gamma value (a value between the density of 0.8 and 1.8) of the yellow dye was determined in the same manner as in Reference Example-1, and the ratio was calculated using the preservative pear immediately after preparation as a comparison. . Table 2 shows the results.

[0292]

[Table 2] 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 developing solution is preserved. It turns out that it is preferable.

Reference Example 3 As a silver halide emulsion, the emulsion N used in Reference Example 1 was used.
o. E and couplers used in Reference Examples are Y-5 and M-5.
And ginseng except that the C'-2 was changed to the coupler shown in Table 3
The photosensitive material used in Example 1 was used.

[0294] color developer was used color developer with VEHA (Exemplified Compound (I-1)) as a preservative reference
It processed according to the processing process of Example-1 .

After the processing, the maximum reflection density and the minimum reflection density of the yellow, magenta and cyan dyes are measured by the Sakura photoelectric densitometer P.
It was measured with DA-65 (manufactured by Konica Corporation). The results are summarized in Table 3.

[0296]

[Table 3] As is apparent 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 general formula The use of cyan couplers represented by [CI] and / or [C-II] (light-sensitive materials Nos. 14 to 26) improves both the maximum color density and the minimum density, and is preferred in the present invention. It turns out that it is a coupler.

Particularly, fast-reacting yellow couplers,
It turns out that it is particularly preferable when the magenta coupler represented by the general formula [MI] and the cyan coupler represented by the general formula [C-I] or [C-II] are used in combination.

Reference Example 4 As the silver halide emulsion, emulsion No. 1 used in Reference Example 1 was used. E and the organic inhibitors shown in Table 4 (added to each layer of 1, 3, 5), and the color developing solution was DEHA as a preservative.
Further, 0.5 ml of the bleach-fixing solution used in Reference Example 1 was added per liter of the color developing solution, and development was carried out in the same manner as in Reference Example 1. Thereafter, the gamma value of the yellow dye (density: 0.
8 to a density of 1.8), and the ratio was calculated with the bleach-fix solution not added as 100. The results are summarized in Table 4.

[0299]

[Table 4] As is clear from Table 4, by using the specific heterocyclic mercapto compound according to the present invention in the present invention, even when the bleach-fixing solution was mixed in the color developing solution, the relative gamma value did not change much and a stable photograph was obtained. It turns out that it shows a characteristic.

Reference Example-5 In Reference Example-1 , the experiment of Reference Example-1 was carried out by changing the concentration of potassium sulfite in the color developing solution as shown in Table 5 and comparing 1 g / liter of potassium sulfite with the preservative pear. The development was carried out in the same manner as described above, and the maximum density of the yellow dye was measured, and the ratio of the maximum density of 1 g / liter of potassium sulfite with the preservative pear to 100 was calculated. Table 5 shows the results.

[0301]

[Table 5] From Table 5, it can be seen that in the present invention, potassium sulfite is particularly preferable in the color developing solution in an amount of 1.0 g / liter or less.

Example 1 A color developer No. 1 having the following composition: 1 to 16 were adjusted.

(Color developing solution) Potassium sulfite 5.0 × 10 ⁻³ mol Sodium chloride 3.0 × 10 ⁻² mol Potassium carbonate 30 g 3-Methyl-4-amino-N-ethyl- (β-methanesulfonamidoethyl )-Aniline sulfate 5.5 g Fluorescent whitening agent (4,4'-diaminostilbene) 2.0 g Preservative shown in Table 6 5.0 Compound shown in Table 6 Addition amount shown in Table 6 Bleaching-fixing solution (Described in Reference Example-1 ) 0.3 cc of water was added to make the total volume 1 liter, and KOH and H ₂ SO ₄ were added.
To make pH 10.20.

Next, the color developing solution shown in Table 6 was mixed with an opening ratio of 100
The tar property of the color developing solution after 2 weeks was evaluated while storing at 38 ° C. in a glass container of cm ² / liter (the air contact area was 100 cm ² with respect to 1 liter of the color developing solution).

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

[0306]

[Table 6] As is clear from Table 6, when the preservative (I-1) of the present invention and cerous sulfate or manganese sulfate are contained, or the polyhydroxy compound according to the present invention (color developing solution N
o. 4, 5) aminopolycarboxylic acid (color developer No. 4)
When 6) is used in combination, 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.
It can be seen that the improvement effect as described above can be obtained even in the case of 11).

Example 2 50 parts of the color developing solution (Nos. 1 to 16 ) described in Example 1 were used.
The solution was sealed and stored in a glass bottle at 5 ° C. for 5 days, and the same treatment and evaluation as in Reference Example-4 were performed. The results are summarized in Table 7.

[0308]

[Table 7] As is clear from Table 7, when the bleach-fix solution was stored in a very small amount of contamination (model running state),
When the preservative (I-1) of the present invention and cerous sulfate or manganese sulfate are contained, or the polyhydroxy compound according to the present invention (color developing solution No. 4 ', 5'), aminopolycarboxylic acid ( When the color developing solution No. 6 ') was used in combination, the fluctuation of the photographic characteristics after storage was improved, and it can be seen that the use of the color developing solution further improved the effect. This improvement effect is achieved by using the preservative according to the present invention (No.
-11 '), it can be seen that the above-described improvement effect can be obtained.

Reference Example-6 The color developing agent (A-) in the color developer used in Reference Example-1
When the same experiment was performed by changing 1) to the following (B-1) or (B-2), the magenta stain in the unexposed portion was deteriorated by 0.03 in all cases. Also, the reference example
-1 color developing agent (A-1) with the exemplified compound (A-
2), (A-4) and (A-15), respectively, and the same experiment as in Reference Example-1 was performed. As a result, almost the same results were obtained.

[0310]

Embedded image

[0311] changing the fluorescent whitening agent of a color developing solution used in Reference Example -7 Reference Example -1 (Compound (A'-4)) as shown in the following Table (8), Reference Example 1 Developing process was performed according to the following. The unexposed yellow stain after the treatment is applied to the Sakura photoelectric densitometer PDA
It measured using -65 (made by Konica Corporation). Table 8 summarizes the results.

[0312]

[Table 8]

[0313]

Embedded image Table 8 shows that the use of the triazylstilbene-based optical brightener represented by the general formula [III] in combination with the treatment method of the present invention further improves yellow stain.

Reference Example -8 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). Gelatin layers ^{1 ... 1.20mg / m 2, 0.40g} / m
² (in terms of silver, the same applies hereinafter) of a blue-sensitive silver halide emulsion and 1.0 × 10 ⁻³ mol g / m ² of a yellow coupler (Y) dissolved in 0.55 g / m ² of dioctyl phthalate.
-5) -containing layer. 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 1.0 × 10 ⁻³ mol g / mol dissolved in 0.30 g / m ² of dioctyl phthalate.
layer containing m ² of magenta coupler (M-5). Layer 4: an intermediate layer made of 0.70 g / m ² of gelatin. Layer 5: 1.20 g / m ² gelatin, 0.28 g / m ²
1.75 × 10 ⁻³ molg / dissolved in 0.25 g / m ² of dibutyl phthalate.
a layer containing m ² cyan coupler (C′-2). Layer 6: 1.0 g / m ² of gelatin and 0.25 g / m ²
Containing 0.32 g / m ² of Tinuvin 328 (an ultraviolet absorber manufactured by Ciba Geigy) dissolved in 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 so that the amount became 0.017 g per 1 g of gelatin.

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

After the color paper sample thus prepared was printed by printing, it was subjected to running processing by an automatic developing machine according to 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

The composition of the processing solution used is as follows. [Color developing tank liquid] Potassium bromide Table 9 amount Potassium chloride Table 9 amount Potassium sulfite (50% solution) 1.0 ml Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methane Sulfonamidoethyl) -aniline sulfate 5.0 g Diethylhydroxylamine (85%) 5.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Ethylenediaminetetraacetic acid sodium salt 2.0 g Finished to 1 liter with water, pH 10.15 with potassium hydroxide or sulfuric acid [Color developing replenisher] Potassium bromide Table 9 amount Potassium chloride Table 9 amount Potassium sulfite (50% solution) 2.0 ml Color developing agent (3-methyl-4-amino-N-ethyl-N-) (Β-methanesulfonamidoethyl) -aniline sulfate 8.0 g diethylhydroxylamine (85%) 7.0 g triethanolamine 10.0 g potassium carbonate 30 g Ethylenediaminetetraacetic acid sodium salt 2.0 g Finished to 1 liter with water and adjusted to pH 10.40 with potassium hydroxide or sulfuric acid [Bleaching and fixing tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 5.50 with ammonia water or glacial acetic acid, and add water to make the total volume 1 liter. Ferric ammonium tetraacetate dihydrate 70.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 120.0 ml Ammonium sulfite (40% solution) 35 ml Adjust the pH to 5.40 with aqueous ammonia or glacial acetic acid to bring the total volume to 1 liter. [Washing alternative stable tank solution and replenisher] 5-chloro-2- Methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g 2-octyl-4-isothiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1- in diphosphonic acid (60% aqueous _{solution) 3.0 g Bi Cl 3 (45} % aqueous _{solution) 0.65g Mg SO 4 · 7H 2} O 0.2 g of ammonia water (ammonium 25% aqueous hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5 g water Adjust to 1 liter and adjust the pH to 7.0 with aqueous ammonia and sulfuric acid.

In the running process, an automatic developing machine is filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and while the color paper sample is being processed, the above-mentioned color developing replenisher and bleaching solution are bleached every 3 minutes. The fixation replenisher and the washing-replacement stable replenisher were replenished through a metering pump.

[0320] color replenishing amount of the 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 replenisher as a replenishing amount of the stabilizing tank Was replenished with 250 ml.

The stabilizing bath of the automatic developing machine is a first to third stabilizing bath in the flow direction of the photosensitive material.
The replenishment was performed from the final tank, and the overflow liquid was again flown from the final tank into the preceding tank, and this overflow liquid was again flowed into the preceding tank by a multi-tank countercurrent system.

When the amount of the color developing replenisher replenished in the color developing tank became twice the capacity of the color developing tank, the maximum color density of the yellow dye was measured by passing through a wedge-exposed check sample. The maximum color density at the start
The activity of the developer was evaluated by determining a relative value with 100.
The results are shown in Table 9.

[0323]

[Table 9] From the above results, the silver halide composition was out of the range of the present invention (emulsion N
In the comparative example of o.G) and the comparative example in which the concentration of chloride in the tank solution is less than 2 × 10 ^-2 mol / l, even if the silver halide composition is within the present invention, the replenishing amount is 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.

Reference Example -9 As a silver halide emulsion, the emulsion N used in Reference Example-8 was used.
o. Except that J was used, the silver halide color photographic material described in Reference Example 8 was used. The halide concentration (mol / liter) of the color developing replenisher and the tank solution was KBr / KC, respectively.
Using l = 0.0059 / 0.054, a color developing solution running at a color developing replenishing solution amount of 100 ml / m ² , and a bleach-fixing solution and a stabilizing solution, the pH of the bleach-fixing solution was as shown in Table 10. With the above changes, processing was performed in the same processing steps as in Reference Example-8, and the minimum reflection density and desilvering property of the yellow dye were evaluated.

The minimum reflection density was measured using PDA-65 (manufactured by Konica Corporation), and the desilverability was measured by a fluorescent X-ray method. The results are shown in Table 10.

[0326]

[Table 10] As is clear from Table 10, when the pH of the bleach-fixing solution is increased, the minimum reflection density and the desilvering property are both deteriorated.

The pH of the bleach-fix solution was 4.5 to 6.8 (No.
In the case of 6), both the minimum reflection density and the desilvering property are good, which can be said to be a preferable embodiment for the present invention.

Reference Example 10 The emulsion NO (F) of Reference Example 1 was used as the silver halide composition.
The color developing solution was prepared using the color photographic material of Reference Example 8 except that the KBr / KCl concentration of the replenisher and the tank solution was set to 0.0017 mol / 0.054 mol except for using the color developing material. 200 ml / m ²
The color development temperature was set to 38 ° C.
, A running process was performed in the same manner as in Reference Example-8 .

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

Table 11 shows the amount of running processing.

The evaluation was performed in the same manner as in Reference Example-8 . Table 11 shows the results.

[0332]

[Table 11] As is clear from Table 11, when the processing time of color development is short, especially when the processing time is less than 45 seconds, the photographic density varies greatly depending on the amount of running per day, while 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.

Reference Example 11 Preparation of Emulsion-K 0.3N NaCl and 0.3N in 2.6% gelatin solution
While controlling the pAg of the AgNO ₃ solution, a silver chloride emulsion was prepared by a double jet method. Based on this emulsion, 2N NaCl and 2NAgNO ₃ were added while maintaining pAg at 6.8.
The size was increased to 40 times the volume by adding the solution.

[0334] was subjected to Ag Br / Ag Cl shell by the simultaneous mixing method KBr / Na Cl solution and AgNO ₃ solution containing bromide 40 mol% in the Ag Cl particles.

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 material Using Emulsion K, photographic materials shown in the following table were prepared. 1. Support Polyethylene coated paper 2. 2. Blue photosensitive layer coupler Y-5 (DBP dispersion) Middle layer 4. 4. Green photosensitive layer coupler M-5 (DOP dispersion) Middle layer 6. 6. Red photosensitive layer coupler C-7 (DOP dispersion) Protective layer 8. UV agent-containing layer Hardener and UV absorber

The developing bath has the following composition: [Tank solution] 800 ml water 5 g diethyl-hydroxylamine-sulphate 5 g diethylenetriaminepentaacetic acid pentasodium salt 1.5 g 4-amino-N-ethyl-N- (β-methane-sulphone Amide) -Ethyl-m-Toluidine-Sesquisulfate (monohydrate) 5.2 g Potassium sulfite 0.9 g Potassium chloride 3 g Potassium carbonate 25 g Potassium hydroxide 1.5 g Make up to 1 liter with water, pH = 10.2

The developing bath was treated with the following replenisher solution at a rate of 80 ml / m ² : Replenisher solution 800 ml water 6 g diethyl-hydroxylamine-sulphate 6 g diethylenetriaminepentaacetic acid pentasodium salt 2 g 4-amino -N-ethyl-N- (β-methane-sulfonamide) -ethyl-m-toluidine-sesquisulfate (monohydrate) 12 g potassium sulfite 1.2 g potassium chloride 3 g potassium carbonate 25 g potassium hydroxide 13 g with water 1 liter, pH = 12.3

The bleach-fix bath had the following composition: [Tank solution] Water 700 ml Sodium sulfite 20 g Ammonium thiosulfate 100 g Sodium-iron salt of ethylenediamine-tetraacetic acid 45 g Potassium carbonate 9 g Make up to 1 liter with water PH = 7.0 To make up the bleach-fix bath replenisher, the solution in the tank was simply made 800 ml.

[Stabilizing solution] 0.3 g of o-phenylphenol 0.5 g of 1-hydroxyethylidene 1,1-diphosphonic acid 3 g of ammonia water 3 g The pH was adjusted to 7.8 with water. The same stable solution and stable replenisher were used.

[0341] For comparison comparison, the same photographic material by development processing method conventional using conventional developer and developing.

[Developer Solution, Tank Solution] Water 800 ml Bensil alcohol 14 ml Ethylene glycol 7 ml Hydroxylamine sulfate 1.5 g Diethylenetriaminepentaacetic acid potassium salt 1.5 g 4-Amino-N-ethyl-N- (β-methane-sulfonamido) tyl -M-Toluidine-sesquisulfate 5.2 g Potassium sulfite 2.5 g Sodium chloride 2.5 g Potassium carbonate 33 g Potassium hydroxide 0.8 g Make up to 1 liter with water, pH = 10.2

The developer was replenished using the following replenisher solution at a rate of 80 ml / m ² : [Replenisher solution] Water 800 ml Bensil alcohol 18 ml Ethylene glycol 9 ml Hydroxylamine sulfate 4 g Potassium diethylenetriaminopentaacetate 2 g 4-amino-N-ethyl-N- (β-methane-sulfonamide) -ethyl-m-toluidine-sesquisulfate 6.5 g potassium sulfite 5.0 g sodium chloride 2.5 g potassium carbonate 33 g potassium hydroxide 1.8 g with water 1 liter, pH = 10.5 The bleach-fix bath is as described above.

The maximum color density of the sample developed after adjusting the developing solution and the sample developed after processing the photographic material after 2,000 m ² processing for 30 days were measured. There was almost no change in each of the developers after the 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.

Reference Example -12 As an additional experiment, as a result of processing a silver halide photographic light-sensitive material containing silver bromide in various ranges with the color developing solution of the present invention, it is particularly surprising that the silver halide When only 10 mol% or less of bromide was contained, no elution of bromide into the developer was observed 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 when a part or all of a processing solution is allowed to flow into another tank in processing a silver halide color photographic light-sensitive material according to the present invention.

Claims (4)

(57) [Claims] 1. A method for imagewise exposing a silver halide color photographic material having at least one silver halide emulsion layer on a support, followed by a color developing solution containing at least a p-phenylenediamine 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. It contains silver particles, and the color developer contains a compound represented by the following general formula [I] and at least 2.0 × 10 ⁻² mol of chloride per liter of the color developer, and contains a manganese salt or a cerium salt. A method for processing a silver halide color photographic light-sensitive material, characterized by processing with a color developing solution contained therein. 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. A method for processing a silver halide color photographic material according to claim 1, wherein said color developer contains a p-phenylenediamine-based color developing agent. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein said color developing solution contains substantially no benzyl alcohol. 4. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed to a color developing solution containing at least a p-phenylenediamine 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. It contains silver particles, and the color developer contains a compound represented by the following general formula [I] and at least 2.0 × 10 ⁻² mol of chloride per liter of the color developer, and contains a manganese salt or a cerium salt. And processing with a color developing solution containing at least one of the compounds represented by the following general formulas [BI] to [B-IV]. Processing method of over photographic light-sensitive material. 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. (Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, a halogen atom, a sulfonic acid group, a carbon atom number of 1 to
7, an alkyl group of —OR ₁₅ , —COOR ₁₆ , 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 represents a halogen atom, a sulfonic acid group, Or, it represents a phenyl group. (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 - the Represents R _{33 to} R ₃₄ each represent a hydrogen atom, a hydroxyl group,
Represents a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). _However, at least two of R 33 _{to R 36} is a carboxylic acid group (including its salt) or a phosphonic acid group (including a salt thereof), also _R 37 to R
_At least two of the ₃₉ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). )