JPH0922100A - Method for processing silver halide color sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce fluctuation of characteristics of a color developing solution, such as preservability and resistances to lowering of pH and precipitation, and to prevent fluctuation of photographic performance, such as rise of fog in a dye image and rise of contrast by using a specified compound as the preservative of a color developing solution. SOLUTION: The silver halide color photographic sensitive material having silver halide emulsion layers containing dyeforming couplers on a transparent support is imagewise exposed and then subjected to processing including at least a color development process, and at that time, the color developing solution to be used for the color development process contains as a color developing agent a p-phenylenediaminde derivative and it contains at least one of the compounds represented by the formula in which each of R1 and R2 is a 1-3C alkyl group, such as methyl or ethyl, and such a hydroxyalkyl group, such as methoxy or ethoxy or each may combine with each other to form a ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide color photographic light-sensitive material, and more specifically, preserving property, pH.
Excellent liquid characteristics of color developer such as deterioration and precipitation.
There is no change in photographic performance such as increase in fog in dye images and high contrast, and the reaction efficiency of color development reaction is high and sufficient color density can be obtained, and silver halide color suitable for low replenishment and rapid processing. The present invention relates to a method for processing a photographic light-sensitive material.

[0002]

Processing of silver halide color photographic light-sensitive materials basically comprises two steps of color development and desilvering, and desilvering consists of a bleaching and fixing step or a bleach-fixing step. In addition, rinsing processing, stabilizing processing, and the like are added as additional processing steps.

In color development, the exposed silver halide is reduced to silver, and at the same time, an oxidized aromatic primary amine color developing agent represented by a p-phenylenediamine developing agent reacts with a coupler. Form a pigment. In this process, halogen ions generated by reduction of silver halide are eluted and accumulated in the developer. Separately, components such as an inhibitor contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver generated by development is bleached by an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts by a fixing agent. A one-bath bleach-fixing method in which the bleaching step and the fixing step are collectively processed simultaneously is also known.

In the color developing solution, the development inhibitor is accumulated by developing the silver halide color photographic light-sensitive material as described above, while the color-developing agent, benzyl alcohol, etc. are consumed or accumulated in the photographic light-sensitive material. Then, the concentration of those components decreases. Therefore, in a development processing method in which a large amount of silver halide color photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept in a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. We need a way to keep it. As such means, a method is usually employed in which a replenisher for replenishing deficient components and diluting unnecessary increased components is replenished. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method is a serious problem in terms of economy and pollution. Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a concentrated low replenishment method, or a method of adding a regenerant to the overflow solution and using it again as a replenisher. Etc. have been proposed.
Of these, the concentrated low replenishment method is extremely suitable for small-scale laboratories such as mini-labs because it requires no new equipment and is easy to manage.

In addition, in recent years, quick services have become popular as a part of improving services to users, and some services are also provided to process exposed films on the spot and to deliver prints to customers. .
Against the background of the demand of the era of shortening the delivery time, short-time processing, that is, speeding up of the processing is also strongly demanded together with low replenishment.

On the other hand, in an ordinary color developing solution, p-
Aromatic No. 1 represented by phenylenediamine type developing agents
To prevent the oxidation of the primary amine color developing agent, sulfite or a water-soluble salt of sulfite and hydroxylamine is added as a preservative.

If these sulfites are added alone to the developing solution, the storage stability is not always sufficient. Therefore, it has already been found that the addition of hydroxylamine as a water-soluble salt provides effective homeostasis. Are known.

However, the hydroxylamine salt is
A small amount of coexisting metal ions, particularly iron ions, decomposes it by catalyzing it, which not only reduces the preservative effect but also generates ammonia by decomposition, which causes fog and contamination on the color photographic light-sensitive material. It is known that abnormalities in photographic characteristics, especially the shoulders become harder.

The mixing of metal ions, particularly iron ions, in the color developing solution is carried out by a splash, a transport leader, a belt or a hanger for suspending a film, and the like. It is caused by so-called back contamination in which a bleaching solution containing salt or a bleach-fixing solution is brought in.

The hydroxylamine salt causes a decrease in pH with time of the color developing solution, and it is expected that the protons liberated when ammonia gas is generated cause the decrease in pH.

In order to prevent these unfavorable effects of metal ions, techniques for incorporating various metal chelating agents have been proposed and put into practical use. For example, US Pat. No. 3,83
A technique of using a hydroxyalkylidene-diphosphonic acid sequestrant described in 9,045 in combination with a lithium salt, a polyhydroxy compound described in US Pat. No. 3,746,544 and an aminopolycarboxylic acid. Technology of using acid sequestering agent in combination, US Pat. No. 4,26
Examples of the technique include the combined use of the polyhydroxy compound and the aminopolyphosphonic acid sequestering agent described in US Pat. No. 4,716, but these techniques have not been able to solve the above problems. is the current situation.

It has further been found by the present inventors that hydroxylamine salts reduce the solubility of color developing agents. The decrease in solubility of the color developing agent is used not only to precipitate the color developing agent at low temperature but also to circulate the processing solution in the developing tank or replenish the replenishing solution when performing continuous processing with an automatic developing machine. The color developing agent is deposited on the soft vinyl chloride pipe.

The various problems associated with these hydroxylamine salts are exacerbated at low supplementation treatments. That is, in the low replenishment process, not only the accumulated metal ions increase, but also the renewal rate of the developer decreases, so that the stagnation time of the developer in the processing tank significantly increases. For this reason, the above-mentioned problems such as the generation of fog due to the decomposition of the hydroxylamine salt, the high contrast of the shoulder portion, and the decrease in pH become more remarkable. Under these circumstances, it was also found that the conventional multi-supplementation treatment had little effect, for example, the decomposition of hydroxylamine salts was accelerated by trace metals, particularly copper ions, contained in the reagent. It has been found that it is difficult to detoxify this copper ion by using a conventional chelating agent.

In the low replenishment process, the concentration of the developer component in the replenisher is increased in order to reduce the amount of the replenisher,
Since it is necessary to raise the pH, the problem of precipitation of the color developing agent and lowering of the pH caused by the addition of the hydroxylamine salt becomes serious in the low replenishing process.

The various problems associated with hydroxylamine salts are also amplified by accelerating the development process. That is, for example, when the pH of the color developing solution is raised or the processing temperature is raised for speeding up, decomposition of the hydroxylamine salt is promoted, the preservative effect is significantly reduced, fog is generated, the shoulder has a high contrast and the pH is high. Is significantly reduced. Further, if the amount of the buffer is increased to maintain a high pH, the salt concentration in the color developing solution becomes high and the color developing agent is easily deposited. Further, for example, even if the concentration of the color developing agent is increased for speeding up, the precipitation of the color developing agent becomes remarkable similarly.

The inventors of the present invention continued to search for a technique for solving the instability of the treatment caused by the hydroxylamine salt and achieving good homeostasis, but in the course of the research, the hydroxylamine salt was colored. During development, we have found a significant fact that we are developing a considerable amount of silver halide. The progress of silver development with hydroxylamine salts reduces the amount of silver halide to be developed by the color developing agent,
Since the color density appears to decrease, the effective use of silver halide is significantly hindered. Further, the decrease in color density due to the progress of silver development due to such hydroxylamine salt is caused by increasing the pH, the concentration of the color developing agent and the processing temperature for speeding up, and decreasing the concentration of bromide ion in the color developing solution. It has become clear that this is particularly noticeable.

The present inventors treat a silver halide photographic light-sensitive material having a coupler for solving the above-mentioned various problems with a color developing solution containing a specific compound as a preservative and a specific color developing agent. The inventors of the present invention have found that they can be achieved by a method of processing a silver halide color photographic light-sensitive material, and have completed the present invention.

[0018]

Accordingly, the first aspect of the present invention is as follows.
The purpose of is a stable silver halide color in which there are few fluctuations in the liquid properties of the color developing solution such as preservability, pH drop and occurrence of precipitation, and there is no fluctuation in photographic performance such as increased fog in dye images and increased contrast. Another object of the present invention is to provide a method of processing a photographic light-sensitive material. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which has a high reaction efficiency of color development reaction and can obtain a sufficient color density. A third object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which has good processing stability even when the amount of replenisher is reduced and which is suitable for low replenishment. A fourth object of the present invention is suitable for rapid processing in which the processing stability is high and a sufficient color density can be obtained even if the temperature, pH and color developing agent concentration are increased or the bromide ion concentration is decreased. Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material.

[0019]

The above object of the present invention is to provide an image-wise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on a transparent support. In the method for processing a silver halide color photographic light-sensitive material, which is subjected to a treatment including at least a color developing step, the color developing solution used in the color developing step is a p-phenylenediamine-based compound having a water-soluble group as a color developing agent. The compound contains a compound, and the color developer contains at least one compound represented by the following general formula [I].

General formula [I] (In the formula, R ₁ and R ₂ are each a carbon atom number of 1 to 3.
Represents an alkyl group or an alkoxy group. Where R ₁
And R ₂ may combine to form a ring. ) It is achieved by a method of processing a silver halide color photographic light-sensitive material.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The color developing solution used in the processing method of the present invention contains a compound represented by the general formula [I] (hereinafter,
The compound of the present invention) is used as a preservative.

In the general formula [I], R ₁ and R ₂ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and the alkyl group having 1 to 3 carbon atoms represented by R ₁ and R _2. The group also includes those having a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (for example, a chlorine atom, a fluorine atom, a bromine atom, etc.),
An alkenyl group (eg, an allyl group etc.) can be mentioned. R ₁
Specific examples of the alkyl group for R ₂ include a methyl group, an ethyl group, a hydroxyethyl group, an i-propyl group, and an n-propyl group. Examples of the alkoxy group represented by R ₁ and R ₂ include a methoxy group,
Examples thereof include an ethoxy group. However, R ₁ and R ₂ may combine to form a ring.

Both R ₁ and R ₂ are preferably alkyl groups having 1 to 3 carbon atoms, and more preferably R ₁ and R _2.
1 and R ₂ are both ethyl groups.

Specific examples of the compound of the present invention used in the present invention are shown below, but the present invention is not limited thereto.

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

The concentration of the compound of the present invention in the color developer is
A concentration similar to that of hydroxylamine usually used as a preservative, for example, 0.1 g / l to 50 g / l is preferably used, and more preferably 0.5 g / l to 20 g / l.
It is.

Of the compounds represented by the general formula [I] of the present invention, for example, N, N-diethylhydroxylamine is used as a preservative for a black and white developing agent in a color developer containing a black and white developing agent. Is known to do.

Hydroquinone, which is usually a black and white developing agent,
Hydroquinone monosulfonic acid, phenidone, para-aminophenol, etc. are relatively stable when used as a black-and-white developing agent in a black-and-white developer, and are sufficiently preserved by using sulfite as a preservative. It is known that when added to a color developing solution, a cross-oxidation reaction with a color developing agent occurs and the storage stability thereof is extremely poor. Hydroxylamine has almost no effect on the preservation of the black and white developing agent added to the color developing solution.

As an example of using N, N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developing solution, a color developing solution containing a coupler is used and a color photographic light-sensitive material is prepared by a reversal method. Is known to be used with phenidone in the so-called external color development method. The role of phenidone in this case is
This is to increase the developing speed of an external photosensitive material having poor developability and to increase the density of a dye image.

Further, in magenta color developing solutions which do not contain such phenidone, for example, N, N-diethylhydroxylamine is known to have a bad influence on the storability of the external color developing solution, that is, destroying the coupler. (See Japanese Patent Publication No. 45-22198).

Another example of using the compound of the present invention as N, N-diethylhydroxylamine or the like as a preservative of a black-and-white developing agent added to a color developing solution is a color developing solution in an internal color developing solution. A technique for preserving the phenidone derivative added to the liquid (see JP-A-53-32035) and a technique for retaining the phenidone derivative with hydroquinones (see JP-A-52-153437) are also listed. be able to.

As mentioned above, the conventional compounds of the present invention are
It is known to be used as a preservative for black and white developing agents added to color developing solutions, and it is widely known to use hydroxylamine as a preservative for color developing agents in ordinary color developing solutions. There is.

That is, in the past, the present inventors have found out that a silver halide emulsion having a poor developability and a low activity of a color developing solution have conventionally been used for slow development at a relatively low temperature. Almost no silver amine development with hydroxylamine occurred, but in addition to improving the developability of the light-sensitive material, the recent development process in which an active developer is used to develop in a short time causes silver development with hydroxylamine to occur. It is thought that it came to be.

However, since hydroxylamine has hitherto been known as a preservative of a general color developing agent, the phenomenon of silver development by hydroxylamine has been almost overlooked.

As described above, the compound of the present invention is already known as a preservative for a black and white developing agent added to a color developing solution, but it not only acts effectively as a preservative for a color developing agent. Since it is strong against decomposition reaction using heavy metal ion as a catalyst, there is almost no change in processing characteristics and liquid characteristics such as increase in fog, contrast increase and pH decrease, and since exposed silver halide is not directly developed, good color density is obtained. The fact that is obtained is a completely unknown and unexpected and surprising effect.

The above-mentioned compound of the present invention may be used in combination with other preservatives. Examples of preservatives that can be used in combination include sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like. Examples thereof include bisulfite adducts of aldehydes and ketones, such as formaldehyde bisulfite adducts and glutaraldehyde bisulfite adducts.

The color developing agent used in the color developing solution of the present invention is a p-phenylenediamine compound having a water-soluble group.

The p-phenylenediamine compound having a water-soluble group has less contamination of the light-sensitive material and does not cause skin contamination than the para-phenylenediamine compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only does it have the advantage that the skin does not rash easily,
In particular, in the present invention, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I].

The water-soluble group has at least one amino group on the p-phenylenediamine compound or on the benzene nucleus.
And a specific water-soluble group is-
_{(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 each represent an integer of 0 or more),
A —COOH group, a —SO ₃ H group, and the like are preferred.

Specific examples of the color developing agent having a water-soluble group used in the present invention are shown below, but the present invention is not limited thereto.

Of the above-illustrated color developing agents, those which are preferred for use in the present invention are exemplified by No. The compounds are (1), (3) and (4).

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

The color developing agent having a water-soluble group used in the present invention is usually 1 g to 100 g per liter of color developing solution.
However, from the viewpoint of rapid processing and solubility of the main agent, 3 g to 50 g per liter of color developing solution can be used.
g is preferable, more preferably 4.5 g to 50 g, and particularly preferably 6.0 g to 50 g.

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

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. are used alone. Can be used together or in combination. Further, for the purpose of preparation, or for the purpose of increasing the ionic strength, disodium hydrogen phosphate, hydrogen phosphate 2
Various salts such as potassium, sodium bicarbonate, potassium bicarbonate and borate can be used.

If necessary, inorganic and organic antifoggants can be added. Examples of these antifoggants include sodium bromide, potassium bromide, sodium iodide and potassium iodide. Inorganic halide compounds and 6 of US Pat. No. 2,496,940
-Nitrobenzimidazole, No. 2,497,917
And 5-nitrobenzimidazoles described in JP-A No. 2,656,271, and in addition to o-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, or JP-B-46-41675. Examples thereof include the heterocyclic compounds described in JP-A No.

In addition to these various components, Japanese Patent Publication No. 46-1
The development inhibitor compounds disclosed in JP-A Nos. 9039 and 45-6149 and U.S. Pat. No. 3,295,976 can be used.

Among the above antifoggants, the bromide ion supplied from sodium bromide, potassium bromide or the like is preferably 1.3 × 10 ^-2 mol / l or less, more preferably from the viewpoint of rapid treatment. Is 8.4 × 10 ⁻³ mol / l or less.

If necessary, a development accelerator can also be used. US Pat. No. 2,64 as a development accelerator
No. 8,604, No. 3,671,247, Japanese Patent Publication No. 44
No. 9503, various pyridinium compounds, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2 , 531,83
No. 2, No. 2,950,970, No. 2,577,1
No. 27, and nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in JP-B-44-9504, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine described in JP-B-44-9509. Triethanolamine and the like are included. Further, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers,
Pyridine, ammonia, hydrazine, amines, etc. can be mentioned.

Further, in the color developing solution of the present invention, in addition to polyphosphoric acid such as sodium tetrapolyphosphate, tetrasodium pyrophosphate, condensed phosphate and the like, various chelating agents are used as a water softener and a heavy metal sequestering agent. Can be included.

Further, in the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos.
The compounds described in JP-A-4-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenolhexalphate (methol), phenidone, N, N'-diethyl-p-.
Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 g to 1.0 g /
l is preferred. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds, and the like can be added, if necessary.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

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

In the present invention, the above color developing solution is adjusted to pH.
Although it can be used in any pH range between 9.5 and 14, generally at low pH, the color developing reaction is not sufficient, and at high pH, various side reactions of the color developing agent occur, so that the pH is 9.8 to 1.
It is preferable to use between 3.

The processing method of the present invention results from the decomposition of hydroxylamine by using the compound represented by the above-mentioned general formula [I] in the color developing solution in place of hydroxylamine which has been conventionally used as a preservative. Improves aging stability of color developing solution such as pH decrease, and increase of fog in dye image, high gradation of gradation, and deterioration of photographic properties such as decrease of maximum color density which is considered to be caused by silver development by hydroxylamine. This is possible, and the effect is recognized even at around pH 10 where the color developing solution is usually used, but from the viewpoint of further speeding up, the pH is raised to pH 1
It is effective for improving the stability of the color developing solution with time and deterioration of various photographic characteristics in a system of 0.3 or more, and is particularly remarkable at pH 10.7 or more.

The color development processing temperature in the processing method of the present invention can improve the stability of the color developing solution with time and the deterioration of various photographic characteristics even if the processing is carried out at any temperature in the range of 30 ° C. to 70 ° C. Effective, but 3 from the perspective of rapid processing
0 ° C to 60 ° C is preferable, and 34 ° C to 55 is more preferable.
C., and the improving effect of the present invention is particularly remarkable in the temperature range suitable for this rapid processing.

The present invention can be applied to any system as long as it uses a color developing solution containing the compound of the present invention. For example, one-bath treatment and other various methods such as spraying treatment liquid can be applied. Spraying method, or a web method by contact with a carrier impregnated with a treatment liquid,
Alternatively, various processing methods such as a developing method using a viscous processing liquid can be used, but the processing step is substantially color development,
It consists of steps such as bleach-fixing, washing with water, or an alternative stabilizing treatment.

In the bleach-fixing step, the bleaching step and the fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are processed in one bath.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is
A metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these are as follows.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are 5 to 450 g / l, Preferably 2
Used at 0-250 g / l. To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. A bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide are also used. be able to.
As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used. it can.

The above-mentioned silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or thiosulfate. Typical examples are sodium, thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g / l or more, which can be dissolved, but generally 70 g
Used at ~ 250 g / l.

The bleach-fixing solution contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. Can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. Preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds; organic chelating agents such as aminopolycarboxylic acids; and stabilizers such as nitro alcohols and nitrates; organic compounds such as methanol, dimethylsulfamide and dimethylsulfoxide. A solvent or the like can be appropriately contained.

The bleach-fixing solution used in the present invention is described in JP-A-4
6-280, Japanese Patent Publication Nos. 45-8506 and 46-55.
6, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-
8836, 53-9854, JP-A-54-716.
Various bleaching accelerators described in No. 34 and No. 49-42349 can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used at pH 5.0 or higher and pH 9.5 or lower, preferably pH 6.0 or higher and pH 8.5 or lower. The preferred pH is 6.5 or higher and 8.5.
It is processed as follows. The processing temperature is 80 ° C. or lower and the temperature is 3 ° C. or higher, preferably 5 ° C. or lower than the temperature of the processing solution in the color developing tank, but it is preferably 55 ° C. or lower to suppress evaporation and the like.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, a color development step using a color developing solution containing the compound of the present invention, the bleach-fixing step, followed by washing with water or a stabilizing treatment as an alternative thereto. Is given.

Hereinafter, the stabilizing treatment which can be applied to the present invention in place of washing with water will be described.

PH of a substitute solution for washing with water applicable to the present invention
Is preferably in the range of 5.5 to 10.0, more preferably in the range of pH 6.3 to 9.5, and particularly preferably in the range of pH 7.0 to 9.0. As the pH adjusting agent which can be contained in the stabilizing solution for washing with water applicable to the present invention, any one of generally known alkali agents or acid agents can be used.

The treatment temperature of the stabilizing treatment is 15 ° C. to 60 ° C.
C., preferably in the range of 20.degree. C. to 45.degree. Also, the treatment time is preferably shorter from the viewpoint of rapid treatment, but is usually 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes. However, it is preferable that the treatment time is longer in the latter-stage tank. In particular, it is desirable to sequentially perform the treatment with a treatment time that is 20% to 50% longer than that in the previous tank. No water washing treatment is required after the stabilization treatment applicable to the present invention, but rinsing by small amount of water washing and surface washing in an extremely short time can be arbitrarily performed as necessary. In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow from a pre-bath, when a stabilizing treatment step applicable to the present invention is supplied in a stabilizing treatment step using a multi-tank countercurrent method. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to a stabilization tank as a concentrated solution, or the above-mentioned compound and other additives are added to a stabilization tank to be replaced with a water washing alternative stabilizing solution. Although there are various methods such as a method of supplying the liquid, the liquid may be added by any method.

As described above, in the present invention, the treatment with the stabilizing solution refers to the treatment for stabilizing treatment in which the stabilizing treatment is carried out immediately after the treatment with the bleach-fixing solution and the washing treatment is not substantially carried out. The treatment liquid used for the treatment is called a water washing substitute stabilizer, and the treatment tank is called a stabilizing bath or a stabilizing tank.

The effect of the present invention is great when the number of stabilizing tanks in the stabilizing treatment applicable to the present invention is 1 to 5, and it is particularly preferably 1 to 3, and at most 9 or less. .

In the present invention, the above color developer is applied to a silver halide color photographic light-sensitive material containing at least one silver halide emulsion layer containing a dye-forming coupler. In the photographic light-sensitive material, a dye-forming coupler is contained in a color developing solution, and a dye is dyed or deposited in a gelatin layer during development, that is, a so-called external developing method (US Pat. No. 2,252,718, No. 2,592,243,
In contrast to JP-A-2,590,970), since the dye-forming coupler is not contained in the color developing solution but contained in the light-sensitive material, such a developing system is called an internal developing system. The photographic light-sensitive material is a so-called Agfa-type photographic light-sensitive material which uses a coupler containing a water-soluble group and a long-chain alkyl group as a diffusion preventing group in the same molecule (UK Patent No. 455, 5).
No. 56 and No. 465,823), or a so-called oil protect type photographic light-sensitive material in which a coupler having an oil-soluble ballast group is dispersed in gelatin together with a high boiling point solvent (US Pat. 2,322,027
No. specification).

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

The photographic coupler used in the present invention is preferably a phenol compound or a naphthol compound as a cyan coupler, for example, US Pat.
9,929, 2,434,272, 2,47
4,293, 2,895,826, 3,25
No. 3,924, No. 3,034,892, No. 3,31
1,476, 3,386,301, 3,41
9,390, 3,458,315, 3,47
It can be selected from those described in 6,563, 3,591,383 and the like, and the synthesis method of these compounds is also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds. Examples of pyrazolone-based magenta couplers include U.S. Pat. Nos. 2,600,788, 3,062,653, 3,127,269, 3,311,476, 3,419,391 and 3. 5,519,429, 3,558,318, 3,684,514, 3,888,680, JP-A-49-29639, 49-111631, 49-129538, Same 5
0-13041, JP-B-53-47167, 54
Nos. 10491 and 55-30615; pyrazolotriazole-based magenta couplers include couplers described in U.S. Pat. Nos. 1,247,493 and Belgium 792,525, which are diffusion resistant. As the colored magenta coupler having a positive polarity, a compound in which the coupling position of a colorless magenta coupler is substituted with an arylazo is generally used. For example, US Pat.
1,171, 2,983,608, 3,000
5,712, 3,684,514, British Patent 93
7,621, JP-A-49-123625, and JP-A-49-123625.
The compound described in No. 31448 is mentioned.

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

As the photographic yellow coupler, an open chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction are also advantageously used. Examples of these are US Pat. No. 2,875,05
No. 7, No. 3,265,506, No. 3,664,841
No. 3, ibid. 3,408,194, ibid. 3,277,155
Issue 3, Issue 3,447,928, Issue 3,415,652
Japanese Patent Publication No. Sho 49-13576, Japanese Patent Laid-Open No. Sho 48-2943
No. 2, No. 48-68834, No. 49-10736,
49-122335, 50-28834, 5
0-132926 and the like together with the synthetic method.

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

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

Further, in addition to the DIR compound, compounds which release a development inhibitor upon development are also included in the present invention. For example, US Pat. Nos. 3,297,445 and 3,379,5.
No. 29, West German Patent Application (OLS) 2,417,914
JP-A-52-15271, JP-A-53-9116,
Examples thereof include those described in Nos. 59-123838 and 59-127038.

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

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler. Patent 935,4
No. 54, U.S. Pat. No. 3,227,554, U.S. Pat.
Nos. 5,984 and 4,149,886.

The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidized product of a color developing agent, the mother nucleus of the coupler forms a dye, while releasing a development inhibitor.
Further, in the present invention, US Pat.
928, 041, 3,958, 993, 3,9
61,959, 4,052,213, JP-A-53.
-110529, 54-13333, 55-1
A compound which releases a development inhibitor but does not form a dye when subjected to a coupling reaction with an oxidized product of a color developing agent as described in No. 61237 etc. is also included.

Furthermore, JP-A-54-145135
No. 56-114946 and No. 57-154234.
When reacted with an oxidant of a color developing agent as described in No. 1, the mother nucleus forms a dye or a colorless compound, while the released timing group suppresses development by an intramolecular nucleophilic substitution reaction or elimination reaction. So-called timing DIR compounds, which are compounds that release agents, are also included in the present invention.

Further, JP-A-58-160954 and JP-A-58-160954.
162949 also includes a timing DIR compound having a timing group as described above bonded to a coupler mother nucleus which forms a completely diffusible dye when reacted with an oxidized form of a color developing agent described in JP-A-162949. .

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

The silver halide contained in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide and chloroiodide. Any of silver, silver iodobromide, silver chloroiodobromide, a mixture thereof and the like can be used, and they are appropriately selected depending on the purpose and application of the silver halide color photographic light-sensitive material.

In the present invention, in particular, when the silver halide used in at least one silver halide emulsion layer is substantially silver chlorobromide having a silver chloride content of 20 mol% or more, the conventional preserving agent is used. The problem of maximum color density reduction, which is a problem when using the agent hydroxylamine, is particularly effectively solved by using the compound of the present invention as a preservative.

It is expected that this is because the development of silver with hydroxylamine, which is a conventional preservative, is likely to proceed, especially in the case of silver chloride. In the present invention, even in such a system, A good maximum color density can be obtained.

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of {100} plane to {111} plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

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

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

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

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and dioxide. Thiourea, polyamine, etc .;
Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or water-soluble solutions of ruthenium, palladium, platinum, rhodium, iridium, etc. Sensitizers of acid salts, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these act as sensitizers or antifoggants depending on the amount). ) And the like, alone or in combination (e.g., a gold sensitizer and a sulfur sensitizer are combined, a gold sensitizer and a selenium sensitizer are combined, etc.) to be chemically sensitized.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before this chemical ripening,
At least one kind of a nitrogen-containing heterocyclic compound having at least one kind of hydroxytetrazaindene and a mercapto group may be contained during the aging or after the aging.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × with respect to 1 mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range.
Optical sensitization may be carried out by adding 10 ^-3 mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080.
Nos. 2,231,658 and 2,493,7
No. 48, 2,503,776, 2,519,00
No. 1, No. 2,912,329, No. 3,656,959
Nos. 3,672,897, 3,694,217
Nos. 4,025,349 and 4,046,572
No., British Patent 1,242,588, JP-B-44-14
Examples thereof include those described in No. 030 and No. 52-24844. Sensitizing dyes used in green-sensitive silver halide emulsions include, for example, US Pat.
9,201, 2,072,908, 2,73
9,149 and 2,945,763, British Patent 50
Typical examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in US Pat. No. 5,979. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, US Pat. Nos. 2,269,234 and 2,270,378,
Representative examples thereof include cyanine dyes, merocyanine dyes or complex cyanine dyes as described in Nos. 2,442,710, 2,454,629 and 2,776,280. . Further, U.S. Pat. Nos. 2,213,995 and 2,493,748,
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in US Pat. it can.

These sensitizing dyes may be used alone,
Also, these may be used in combination.

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

Representative examples of particularly preferable spectral sensitization methods include, for example, Japanese Patent Publication Nos. 43-4936, 43-22884, and 45-1 relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 8433, No. 47-37443, No. 48-2829.
3, No. 49-6209, No. 53-12375, JP-A No. 52-23931, No. 52-51932, No. 5
4-80118, 58-153926, 59-
116646, 59-116647, etc. are mentioned.

The combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine is described in, for example, Japanese Patent Publication No. 45-25831.
Nos. 47-11114, 47-25379, 48-38406, 48-38407, 54-
No. 34535, No. 55-1569, JP-A-50-33
No. 220, No. 50-38526, No. 51-10712
No. 7, No. 51-115820, No. 51-135528
Nos. 52-104916 and 52-104917.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) and other carbocyanine, for example, Japanese Examined Patent Publication No. 44-327.
53, 46-11627, and JP-A-57-1483.
And merocyanine, for example, Japanese Patent Publication No. 4
8-38408, 48-41204, 50-4
0662, JP-A-56-25728, and JP-A-58-10.
753, 58-91445, 59-11664.
No. 5, No. 50-33828 and the like.

The combination of thiacarbocyanine with other carbocyanine is described in, for example, Japanese Patent Publication No.
-4932, 43-4933, 45-2647
No. 0, No. 46-18107, No. 47-8741, JP-A No. 59-114533 and the like, and JP-B-49-62 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes.
The method described in No. 07 can be advantageously used.

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

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

A dye (AI dye) which is water-soluble or can be decolorized by a color developing solution can be added to the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention. As the AI dye, an oxonol dye, Hemioxonol dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include:
British Patents 584,609 and 1,277,429,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-49-129537, and JP-A-48-85130
2-108115, 59-25845, 59-
111640, 59-111641, US Pat. Nos. 2,274,782, 2,533,472, 2,956,079, 3,125,448, 3,148,187, 3,177,078, 3,247,127, 3,260,601, 3,540,887, 3,575,704, 3,653,905, 3 , 718,472, 4,071,312, and 4,070,352.

Generally, these AI dyes are preferably used in an amount of 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol, per mol of silver in the emulsion layer. To use.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants and stabilizers described in Research Disclosure No. 17643,
An ultraviolet absorber, a color stain inhibitor, a fluorescent brightener, a color image fading inhibitor, an antistatic agent, a hardener, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloid used for preparing an emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, albumin,
Proteins such as casein, cellulose derivatives such as hydroxyethylcellulose derivatives, carboxymethylcellulose and the like, starch derivatives, polyvinyl alcohols, polyvinylimidazoles, polyacrylamides and other mono- or copolymer synthetic hydrophilic polymers are included. .

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

Various coating methods such as dipping coating, air doctor coating, curtain coating and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. Further, a simultaneous coating method of two or more layers by the method described in US Pat. Nos. 2,761,791 and 2,941,898 can be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, an arrangement of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side is preferred. . Each of these photosensitive silver halide emulsion layers may be composed of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, a curl preventing layer, a protective layer and an antihalation layer are constituted. The layers can be appropriately combined and used. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

[0114]

As described above, according to the present invention,
It is excellent in the liquid properties of the color developer, that is, preservability, pH drop and occurrence of precipitation, there is no fluctuation of photographic performance such as increase of fog in dye image, high contrast, and high reaction efficiency of color development reaction. It was possible to obtain a sufficient color density and to provide a processing method of a silver halide color photographic light-sensitive material suitable for low replenishment and rapid processing.

[0115]

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

Example 1 (Experiment A) A light-sensitive material for color negative (Sample 1) comprising layers having the following constitution was prepared on a cellulose triacetate film support.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Gelatin layer containing 0.8 g / m ² gelatin Third layer: First red-sensitive emulsion layer Silver iodobromide (iodination Silver; 5.0 mol%, average particle size 0.6μ
m) ... Silver coating amount 1.8 g / m ² Sensitizing dye I (below) ... 5 × 10 ⁻⁵ mol per 1 mol of silver Sensitizing dye II (below)… 1.5 × per 1 mol of silver 10 ^-5
Molar cyan coupler (below): 0.050 per mol of silver
Molar fourth layer: second red-sensitive emulsion layer Silver iodobromide (silver iodide; 6.0 mol%, average grain size 1.0 μm)
m) ... Silver coating amount 2.0 g / m ² Sensitizing dye I (below) ... 3.5 × 10 ^{-5 with} respect to 1 mol of silver
Molar sensitizing dye II (below): 1.0 × 10 ^-5 per mol of silver
Molar cyan coupler (below) ... 0.020 per mol of silver
Molar fifth layer: an intermediate layer consisting of 0.8 g / m ² of gelatin Sixth layer: first green-sensitive emulsion layer Silver iodobromide (silver iodide; 5.0 mol%, average grain size 0.6 μm)
m) ... Silver coating amount 1.8 g / m ² Sensitizing dye III (below) ... 4.0 × 10 ^{-5 with} respect to 1 mol of silver
Molar sensitizing dye IV (below) ... 1.1 × 10 ^-5 per mol of silver
Mol Magenta coupler (below) ... 10 g per mol of silver 7th layer: second green-sensitive emulsion layer Silver iodobromide (silver iodide; 7.0 mol%, average particle size 1.2 μm)
m) ... Silver coating amount 1.8 g / m ² Sensitizing dye III (below): 2.60 × 10 per 1 mol of silver
^-5 mol Sensitizing dye IV (below) ... 0.90 × 10 per mol silver
^-5 mole magenta coupler (below) ... 0.02 for 1 mole silver
Mol 8th layer: yellow filter layer gelatin layer containing yellow colloidal silver in gelatin aqueous solution 9th layer: 1st blue-sensitive emulsion layer silver iodobromide (silver iodide; 6.0 mol%, average grain size 0.5 μm)
m) ... Silver coating amount 1.5 g / m ² yellow coupler (below) ... 0.25 per mol of silver
Mol 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide; 7.0 mol%, average grain size 1.20 μm)
m) ... Silver coating amount 1.21 g / m ² yellow coupler (below) ... 0.06 per 1 mol of silver
Mol 11th layer: 1st protective layer Gelatin layer containing emulsified dispersion of UV absorber 12th layer: 2nd protective layer Gelatin layer containing trimethylmethacrylate particles (diameter 1.5 μm) Other than the above composition in each layer , Gelatin hardening agents and surfactants were added.

Sensitizing dye I: Anhydro-5,5'-dichloro-3,3 '-(γ-sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: Anhydro-9- Ethyl-3,3'-di-
(Γ-sulfopropyl) -4,5,4 ′, 5′-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5′-dichloro-3,3′-di -(Γ-Sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: anhydro-5,6,5 ', 6'-tetradichloro-1,1'-diethyl-3,3'-di- {β-
[Β- (γ-Sulfopropoxy) ethoxy]} ethyl imidazolocarbocyanine hydroxide sodium salt The color negative photosensitive material prepared as described above is added with KS-
After performing white stepwise exposure using a 7 type sensitometer (manufactured by Konishi Rokusha Kogyo KK), color development processing was performed according to the following processing steps.

[0119] The composition of the treatment liquid used is as follows.

[Color developer] Potassium carbonate 28 g Sodium carbonate hydroxide 2.5 g Potassium sulfite 5.0 g Sodium bromide 1.3 g Potassium iodide 2 mg Preservative listed in Table 1 Sodium chloride 0.6 g Tetrachloride Sodium polyphosphate 2.5 g Sulfate salt of the exemplified color developing agent (3) 4.8 g Potassium hydroxide 1.2 g Water is added to make 1 liter.

The pH is adjusted as in Table 1 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach] Ethylenediamineironammonium iron acetate 100.0 g Ethylenediaminetetraacetic acid disodium 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water is added to make 1 liter.

The pH is adjusted to 5.8 with aqueous ammonia or glacial acetic acid.

[Fixer] Ammonium thiosulfate 150.0 g Anhydrous sodium bisulfite 12.0 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium carbonate 10.0 g Water is added to make 1 liter.

The pH is adjusted to 6.0 with aqueous ammonia or glacial acetic acid.

[First Stabilizing Solution] 2-Methyl-4-isothiazolin-3-one 0.01 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.5 g Make up to 1 liter with water.

The pH was adjusted to 7.1 with potassium hydroxide.

[Second Stabilizing Solution] Formalin (37% aqueous solution) 2 ml Conidax (manufactured by Konishi Rokusha Kogyo KK) 5 ml Water is added to make 1 liter.

The maximum dye concentration of the processed sample was measured using an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.). The results are shown in Table 1.

(Experiment B) Next, after using the same sample and similarly exposing it, after processing with the same processing steps and the same processing solution as in Experiment A except that the color developing agent was removed from the color developing solution. The maximum silver concentration of the treated sample was evaluated by measuring the transmission gray density using PDA-65, and the results are also shown in Table 1.

As is clear from the results shown in Table 1, in the control experiments 7 to 12 in which the conventional preservative hydroxylamine was not used, silver was not developed in any pH range and the maximum color development was observed. The concentration increased as the pH increased, but in Comparative Experiments 1 to 6 using hydroxylamine, silver was developed at a low pH, albeit slightly, and the tendency increased as the pH increased. Is large. Regarding the maximum color density, what should increase with increasing pH is shown in Experiment 7-
The concentration is lower than 12 and more surprisingly p
The maximum color density is lowered in a high H area. From the above, it is confirmed that the silver development and the decrease in the maximum color density are due to hydroxylamine.

Further, Experiments 31 to 3 using comparative preservatives
In No. 6, the result was similar to that of hydroxylamine.

On the other hand, in Experiments 13 to 30 of the present invention in which the compound of the present invention was used as a preservative, it was found that the method was an excellent method with almost no silver development and almost no decrease in maximum color density. More specifically, among the compounds of the present invention, the exemplified compounds (1), (3) and (5) are preferable to the exemplified compound (8), and the exemplified compound (3) is particularly excellent. .

Example 2 (Experiment A) The following color paper (Sample 2) was self-made and color-developed.

After a pretreatment by corona discharge was applied to a paper support whose surface was coated with a polyethylene layer containing anatase-type titanium oxide as a white pigment, the following layers were sequentially coated to give a color photographic paper. Had made.

First layer: A silver chlorobromide photographic emulsion containing 90 mol% of silver bromide was added to anhydro-5-methyl-5'-methoxy-3,3'-di (3-sulfopropyl) selenacyanine hydro. It was optically sensitized by oxide, and was added with 2,5-di-t-butylhydroquinone and α- [4- (1-benzyl-2-phenyl-3,5-
Dioxo-1,2,4-triazolydyl)]-α-pivalyl-2-chloro-5- [γ- (2,4-di-t-amylphenoxy) butylamido] acetanilide protected dispersion was added, It was coated so as to have a silver content of 0.35 g / m ² .

Second layer: di-t-octylhydroquinone and 2- (2'-hydroxy-) as a UV absorber.
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-
A gelatin solution containing a protect dispersion containing a mixture of 3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole was applied as an intermediate layer.

Third layer: A silver chlorobromide photographic emulsion containing 70 mol% of silver bromide was mixed with anhydro-9-ethyl-5,5'-diphenyl-3,3'-di (3-sulfopropyl) oxa. Optically sensitized with carbocyanine hydroxide, and then added with 2,5-di-t-butylhydroquinone, 2,2,4
-Trimethyl-6-lauryloxy-7-t-octyl coumarone and 1- (2,4,6 as magenta coupler)
-Trichlorophenyl) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone protected dispersion was added to silver 0.4 g / m ²
It was painted so that

Fourth layer: The same liquid as the second layer was applied as an intermediate layer.

Fifth layer: A silver chlorobromide photographic emulsion containing 70 mol% of silver bromide was mixed with anhydro-2- [3-ethyl-5-.
(1-Ethyl-4 (1H) -quinolilidene) ethylidene-4-oxo-thiazolidine-2-ylidene] methyl-
Optically sensitized with 3- (3-sulfopropyl) benzoxazolium hydroxide, to which 2,5-di-t
-Butyl hydroquinone and 4- as cyan coupler
Chloro-2- (pentafluorobenzamide) -5-
{Α- (2,4-di-t-pentylphenoxy) -is
o-valeroamido} phenol is dispersed in dibutyl phthalate, and 2- (4-butanesulfonylphenylureido) -5- {α- (2,4-di-t-pentylphenoxy) -butanamide} phenol is further dispersed in dibutyl phthalate. And added together, silver 0.27 g / m ²
It was painted so that

Sixth layer: A gelatin solution was applied as a protective layer.

The silver halide photographic emulsion used in each of the above light-sensitive layers was prepared by the method described in JP-B-46-7772, chemically sensitized with sodium thiosulfate, and 4-hydroxy as a stabilizer. -6-methyl-1,
3,3a, 7-Tetrazaindene was added. In addition, saponin as a coating aid and bis (vinylsulfonylmethyl) ether as a hardener were added to the coating solutions for all layers. The color photographic paper produced as described above was subjected to white step exposure using a KS-7 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.), and then color development processing was performed according to the following steps.

Processing step Temperature (° C.) Time (minute) Color development 35 1.5 Bleach fixing 33 1.5 Water wash 30 3.0 Dry 75-85 The composition of the processing liquid used is as follows.

[Color developer] Benzyl alcohol 10.0 ml Triethanolamine 10.0 ml Preservative in Table 1 Amount in Table 1 Exemplified color developing agent (1) sulfate 5.0 g Potassium sulfite (55% aqueous solution) 8.0 ml Potassium carbonate 28.0 g Potassium bromide 0.9 g Potassium hydroxide 1.0 g Condensed polyphosphoric acid 2.0 g Water is added to make 1 liter.

The pH is adjusted as in Table 1 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleaching Fixing Solution] Ethylenediaminetetraacetic acid iron (III) ammonium salt 65 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Water was added to make 1 l, and ammonia was added. Adjust the pH to 7.0 with water or dilute sulfuric acid.

[Stabilizer] 5-chloro-2-methyl-4-isothiazolin-3-one 3.03 g orthophenylphenol 0.01 g 2-methyl-4-isothiazolin-3-one 0.03 g 1-hydroxyethylidene- 1,1'-Diphosphonic acid 0.5 g Magnesium nitrate 0.04 g Zinc sulfate 0.5 g Ammonia water (38% aqueous solution) 2 g Water is added to make 1 liter.

The pH is adjusted to 7.8 with 20% potassium hydroxide or 10% dilute sulfuric acid.

The maximum reflection dye density of the processed sample was measured using an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.). The results are shown in Table 2.

(Experiment B) Next, using the same processing solution as in Experiment A except that the color developing agent was removed from the color developing solution after the same sample was exposed to light in the same manner. Then, the silver density of the processed sample was evaluated by measuring the reflection gray density using PDA-65, and the results are also shown in Table 2.

As is clear from the results in Table 2, even in the processing of silver halide color photographic light-sensitive materials for paper,
The same results as in the processing of the silver halide color photographic light-sensitive material for film of Example 1 were obtained, and the effect of the present invention was confirmed on paper.

Example 3 (Experiment A) Color negative sample used in Example 1 (Sample 1)
Was treated according to the same treatment step as in Experiment A of Example 1 and was treated with the same treatment liquid. However, here, the color development processing time was set to 90 seconds, and the color development temperature was changed as shown in Table 3. Further, the pH of the color developing solution was set to 11.0, and the kind and the addition amount of the preservative were as shown in Table 3. Example 1
The maximum dye concentration was measured in the same manner as in Experiment A of Table 1 and the results are shown in Table 3.

(Experiment B) The color paper sample (Sample 2) used in Example 2 was used and treated with the same treatment liquid according to the same treatment steps as in Experiment A of Example 2. However, here, the color developing temperature was changed as shown in Table 3. The pH of the color developing solution was set to 11.5, benzyl alcohol was removed from the color developing solution, and the type and amount of preservative added were as shown in Table 3. The maximum reflective dye concentration was measured in the same manner as in Experiment A of Example 2, and the results are shown in Table 3.

As is apparent from the results in Table 3, control experiments 78 to 8 in which a color negative sample is treated with a color developer which does not use the conventional preservative hydroxylamine.
In No. 2, the maximum color density also increased as the processing temperature was increased, but in Comparative Experiments 73 to 77 using hydroxylamine, the maximum color density did not increase so much even when the temperature was increased, and further processing was performed. The maximum color density decreased at high temperature. This is the same tendency as in Example 1, and is considered to be an adverse effect due to the development of silver with hydroxylamine. On the other hand, in Experiments 83-87 using the compound of the present invention in place of hydroxylamine, the above Experiments 78-8
It can be seen that the maximum color density of about 2 is obtained.

Also, the same experiment was conducted using the color paper sample, and the same result as when the color negative sample was treated was obtained.

Example 4 (Experiment A) Color negative sample used in Example 1 (Sample 1)
Was treated according to the same treatment step as in Experiment A of Example 1 and was treated with the same treatment liquid. However, here, the color developing treatment time was set to 90 seconds, and the color developing agent concentration was changed as shown in Table 4. The pH of the color developing solution was set to 11.0, and the types of preservatives and the addition amounts thereof were as shown in Table 4. The maximum dye concentration was measured in the same manner as in Experiment A of Example 1, and the results are shown in Table 4.

(Experiment B) Using the color paper sample (Sample 2) used in Example 2, the same treatment process as in Experiment A of Example 2 was followed, and treatment was performed with the same treatment liquid. However, here, the concentration of the color developing agent was changed as shown in Table 4. The pH of the color developing solution was set to 11.5, benzyl alcohol was removed from the color developing solution, and the type and amount of preservative added were as shown in Table 4. The maximum reflective dye concentration was measured in the same manner as in Experiment A of Example 2, and the results are shown in Table 4.

From the results in Table 4, in the system in which the concentration of the color developing agent was changed, Experiments 103 to 107 in which the color negative sample was treated with the color developing solution using hydroxylamine as the conventional preservative were The maximum color density was not sufficient as compared with Experiments 108 to 112 which were processed with the color developing solution using no compound, whereas the maximum color density was increased in Experiments 113 to 117 which were processed with the color developing solution using the compound of the present invention. It is about the same as 112 and is sufficiently large.

Further, the same results were obtained for the color paper samples as for the color negative samples, and it can be seen that the processing method of the present invention is excellent in all cases.

Example 5 (Experiment A) Color negative sample used in Example 1 (Sample 1)
Was treated according to the same treatment step as in Experiment A of Example 1 and was treated with the same treatment liquid. However, here, the color developing treatment time was set to 90 seconds, and the concentration of sodium bromide in the color developing solution was changed as shown in Table 5. The pH of the color developing solution was set to 11.0, and the types of preservatives and the addition amounts thereof were as shown in Table 5. The maximum dye concentration was measured in the same manner as in Experiment A of Example 1, and the results are shown in Table 5.

(Experiment B) The color paper sample (Sample 2) used in Example 2 was used and treated with the same treatment liquid according to the same treatment steps as in Experiment A of Example 2. However, here, the concentration of potassium bromide in the color developing solution was changed as shown in Table 5. The pH of the color developing solution was set to 11.5, benzyl alcohol was removed from the color developing solution, and the type and amount of preservative added were as shown in Table 5. The maximum reflective dye concentration was measured in the same manner as in Experiment A of Example 2, and the results are shown in Table 5.
It was shown to.

As is clear from Table 5, in the system in which the bromide ion concentration was changed, the same tendency as in Examples 1 to 3 was exhibited by decreasing the bromide ion concentration. That is, in both the color negative sample and the color paper sample, a control experiment 138 to treat with a color developing solution which does not use the conventional preservative hydroxylamine.
In Examples 142 and 153-157, the maximum color density was increased as the concentration of bromide ion, which is a development inhibitor, was decreased. However, even if the concentration of bromide ion was decreased, comparative experiments 133-137 and 148-15 using hydroxylamine were performed.
In No. 2, the maximum color density did not increase so much, and in the place where the bromide ion concentration was low, the maximum color density decreased. This is considered to be an adverse effect of silver development by hydroxylamine as in Example 1. On the other hand, Experiments 143-1 using the compound of the present invention in place of hydroxylamine
In Examples 47 and 158 to 162, the maximum color densities similar to those in Experiments 138 to 142 and 153-157 were obtained, which shows that this is an excellent method.

As can be seen from the above Examples 1 to 5, p
In any condition suitable for rapid processing such as increasing H, increasing processing temperature, increasing color developing agent concentration, decreasing bromide ion concentration, etc., by using the compound of the present invention in place of conventional hydroxylamine, Surprising results were obtained without the adverse effect of reducing the maximum color density, indicating that the method of the present invention is an excellent processing method suitable for rapid processing.

Example 6 Using the color negative sample (Sample 1) used in Example 1, the same treatment solution as in Experiment A of Example 1 was used and the same treatment liquid was used. However, here the color development temperature is 35 ° C.
And the color development time was 90 seconds. The types and addition amounts of color developing agents and the types and addition amounts of preservatives are as shown in Table 6. The pH of the color developing solution was set to 11.0. The processed sample was measured for the transmission density of the yellow dye using an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to prepare a sensitometric curve. Next, from the density point 0.15 higher than the lowest density to 1.0 higher than the lowest density
The slope (gamma value) to the high density point was calculated.

Iron ion 3 mg / l was added to the color developer after processing.
(FeCl ₃ equivalent amount) was added, and copper ion was further added at 3 mg / l.
(CuCl ₂ equivalent amount) was added and the mixture was stored at 35 ° C. for 1 week. After storage, the same process was repeated to calculate the gamma value.

The difference in the minimum density of the yellow dye before and after storage and the difference in the yellow gamma value were determined and are listed in Table 6.
Table 6 also shows the difference in pH before and after storage.

Example 7 Using the color paper sample (Sample 2) used in Example 1, the same processing steps as in Experiment A of Example 2 were followed and the same processing liquid was used. However, in this case, the type and addition amount of the color developing agent and the type and addition amount of the preservative were changed as shown in Table 7. The pH of the color developing solution was set to 12.0, and benzyl alcohol was removed from the color developing solution. Using the optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.), the sample after the treatment was used to measure the reflection density of the cyan dye, to create a sensitometric curve and to measure the minimum reflection density of the magenta dye. . Next, the reflection density of the cyan dye is 0.8
The gradient (gamma value) from the density point of 1 to the density point of the reflection density of 1.8 was calculated.

Iron ion 3 mg / l was added to the color developer after processing.
(FeCl ₃ equivalent amount) was added, and further copper ion 3 mg / l
(CuCl ₂ equivalent amount) was added and the mixture was stored at 35 ° C. for 1 week. After the storage, the same processing was repeated, the minimum reflection density of the magenta dye was measured, and the cyan gamma value was calculated.

The difference in the minimum reflection density of the magenta dye and the difference in the cyan gamma value before and after storage were determined and are shown in Table 7. Table 7 also shows the difference in pH before and after storage.

As is apparent from Table 6, in Comparative Experiments 163 and 164 where color negative samples were processed with a comparative color developing agent having no water soluble groups, iron and copper ions were incorporated into the color developing solution. When the compound of the present invention is used as a preservative in place of hydroxylamine, it is possible to prevent the pH of the color developer from decreasing, but the effect of reducing the yellow fog in the dye image and the gradation Although the improving effect is not sufficient, Experiments 166, 168, 170 and 172 using the compound of the present invention in place of hydroxylamine for the color negative sample using the color developing agent having a water-soluble group which is a constitution of the present invention Then, experiments 165, 167, 16 using hydroxylamine respectively
Compared with Nos. 9 and 171, the pH of the color developing solution was not lowered, the increase of fog in yellow was suppressed to a low level, and the gradation was also improved, showing that this is an excellent processing method. A more detailed examination of the present invention shows that Examples (1), (3) and (4) are particularly effective in terms of the type of color developing agent.

In the experiment obtained by using the color paper in Table 7, the same tendency as that of the color negative sample was obtained,
It can be seen that the processing method of the present invention has the same effect not only on the color negative but also on the color paper processing method.

The residual amount of the color developing agent in the color developing solution after storage was analyzed by the cerium sulfate method. In any of the color developing solutions using the preservative of the present invention, hydroxylamine sulfuric acid was used as the preservative. It was found that there was a residual amount almost equal to that of the color developing solution using a salt, and that it showed good preservability of the color developing agent.

Example 8 A color developing replenisher for color negative and a color developing replenisher for color paper having the following compositions were prepared.

[Color Development Replenisher for Color Negative] Potassium carbonate 28 g Sodium hydrogencarbonate 3.0 g Potassium sulfite 7.0 g Preservative shown in Table 8 Table 8 Content sodium tetrapolyphosphate 3.2 g Color developing agent shown in Table 8 Amount described in Table 8 Potassium hydroxide 6.0 g Water is added to make 1 liter.

The pH is adjusted to 11.5 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Color development replenisher for color paper] Triethanolamine 15.0 ml Preservative in Table 8 Amount in Table 8 Color developing agent in Table 8 Amount in Table 8 Potassium sulfite (55% aqueous solution) 12.0 ml Potassium carbonate 28 g Condensed polyphosphoric acid 3.5 g Water is added to make 1 liter.

The pH is adjusted to 12.0 with 20% potassium hydroxide or 10% dilute sulfuric acid.

These color developing replenishers were stored at room temperature for 1 week and the state of deposition of the color developing agent was visually evaluated. The results are shown in Table 8.

The deposition state of the color developing agent in Table 8 is as follows:
No precipitation is indicated by ◯, a large amount of the color developing agent is precipitated on the bottom by xx, and the interval is divided into three equal parts, and the ones with less precipitation are evaluated by Δ, ×, xx and evaluated in 5 steps. .

As is apparent from Table 8, the deposition state of the main agent in the system of the color developing solution in which the concentration of the color developing agent was variously changed was such that when the color developing agent having no water-soluble group for comparison was used, Precipitation was large in a color developing solution using an amine, which was improved by using the compound of the present invention, but was not sufficient. On the other hand, in the system of the present invention using the color developing agent having a water-soluble group, it is found that the use of the compound of the present invention in place of hydroxylamine can favorably prevent the precipitation of the main agent. Particularly, good results are shown in combination with the color developing agent (1).

From the above results, it can be seen that the present invention is suitable for a system using a low replenishing concentrated solution.

Example 9 The content of silver bromide in the green-sensitive layer of the third layer and the content of silver bromide in the red-sensitive layer of the fifth layer of the color paper sample used in Example 2 were changed as shown in Table 9. The sample thus prepared was treated with the same treatment liquid as in Example 2 according to the same treatment steps as in Example 2.

However, here, the color development time was variously changed as described below. Except for benzyl alcohol in the color developing solution, the amount of potassium bromide added was 0.6 g /
1 and the pH was adjusted to 11.5.

The maximum color development reflection density of the yellow dye when color-developed at 35 ° C. for 10 minutes was measured by using an optical densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.), and the maximum color development of the yellow dye at this time was performed. When the reflection density was set to 100, the processing time required for the maximum color development reflection density of this yellow dye to be 80 (referred to as the development convergence time) was determined and shown in Table 9. Since the development convergence time is the development time of the blue-sensitive emulsion layer having the lowest development speed, it indicates the development completion time of the photosensitive material. Table 9 also shows the maximum color reflection densities of the yellow dye, magenta dye, and cyan dye when the development processing was performed for the convergence time.

As is clear from Table 9, when the silver halide color photographic light-sensitive material for color paper has a silver halide emulsion layer composed of silver chlorobromide, the silver chloride content in the silver halide emulsion layer is Increase (decrease in silver bromide content)
Accordingly, when the treatment is performed with a color developing solution containing hydroxylamine, which is a conventional preservative, the development convergence time can be shortened, but the maximum color density of the layer having an increased silver chloride content is lowered. On the other hand, in the experiment in which the color developer containing the compound of the present invention was used in place of hydroxylamine, it was found that the maximum color density was not decreased and the rapid processing was possible.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Kurematsu 1st Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Yoko Matsushima 1st Sakura-cho, Hino-shi, Tokyo Konica stock company

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on a transparent support is imagewise exposed, and then subjected to a treatment including at least a color development step. In the method for processing a silver halide color photographic light-sensitive material, the color developing solution used in the color developing step contains a p-phenylenediamine compound having a water-soluble group as a color developing agent. Contains at least one compound represented by the following general formula [I]. General formula [I] (In the formula, R ₁ and R ₂ are each a carbon atom number of 1 to 3.
Represents an alkyl group or an alkoxy group. Where R ₁
And R ₂ may combine to form a ring. ) A method of processing a silver halide color photographic light-sensitive material, comprising: