JP2654702B2 - Color image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method using the same, and in particular, to a high quality excellent in ultra-rapid processing. Color print,
The present invention relates to a novel color image forming method for forming.

(Prior Art) In recent years, there has been an increasing demand for higher efficiency and higher productivity for processing color photographic light-sensitive materials. This tendency is particularly remarkable in the production of color prints, and there is a strong demand for shortening the print processing time due to demands for finishing in a short delivery period.

The process of finishing a color print comprises exposure and color development as is well known. Use of a photosensitive material having high sensitivity leads to a reduction in exposure time.
On the other hand, in order to shorten the color development processing time, it is essential to realize a system in which a photosensitive material capable of accelerating the development and a processing solution or a processing method are combined.

As a technique for achieving such a problem, a color containing a silver chloride emulsion instead of a silver chlorobromide emulsion having a high silver bromide content, which has been widely used in color photographic materials (hereinafter referred to as color photographic paper). Methods for processing photographic light-sensitive materials are known. For example, International Patent Publication WO 87-04534
JP-A No. 11-139,055 discloses a method for rapidly processing a color photographic light-sensitive material comprising a silver chloride emulsion with a color developer substantially free of sulfite ions and benzyl alcohol.

In addition to the above patents, JP-A-61-70552 uses a high silver chloride color photographic light-sensitive material and reduces the amount of developing solution by adding a replenishing amount that does not cause overflow to the developing bath during development. A method for replenishment is described.
No. 6655 discloses a method of processing a high silver chloride color photographic light-sensitive material with a color developing solution containing a hydroxylamine-based compound and a certain concentration or more of chloride ion for the purpose of stabilizing the processing.

Thus, by using a high silver chloride emulsion and devising a developing solution, the conventional chlorobromide emulsion system can be developed for 3 minutes and 30 seconds (for example, color processing CP-20 manufactured by Fuji Photo Film Co., Ltd.).
To 45 seconds development (for example, total processing time of 4 minutes such as color processing CP-40FAS manufactured by Fuji Photo Film Co., Ltd.), but other color system (for example, electrostatic transfer system, thermal transfer system, inkjet system) total Compared to the processing time, it is still not a satisfactory level.

Therefore, silver halide color for ultra-rapid processing with a total processing time drastically reduced by using a silver halide color development method that can obtain high-quality color prints at low cost and developing color development within 20 seconds The development of photosensitive materials was desired.

On the other hand, rapid processing approaches other than emulsion technology are being studied. In particular, JP-A-63-38937 discloses a technique capable of reducing the development time to 180 seconds or less in a silver chlorobromide emulsion system.
No. 63-40144, No. 63-146039, No. 61-286855, No. 6
JP-A-289350 and JP-A-61-286854 propose a method for controlling the swelling thickness of a light-sensitive material and the amount of gelatin applied by a processing solution and a new developing agent.

However, based on these conventional findings, a satisfactory high quality color photograph could not be obtained with a color development time of 20 seconds or less.

Further, for a color photographic light-sensitive material capable of ultra-rapid processing, shortening the time from the start of processing to the end of processing (in a dry state) is, of course, important as a commercial value. In this case, the developer component and the bleach-fix component remain in the photosensitive material more frequently than in conventional processing for the purpose of simplification and speed.

It has been known that residual developer components and bleach-fix components on photosensitive materials affect print storability. The residual color developing agent reacts with the unreacted coupler over time to generate undesired stain. If the bleaching component remains, the light-sensitive material becomes an oxidizing atmosphere, so that it works with couplers, hydroquinone, binder gelatin and the like in the light-sensitive material particularly at high humidity and high temperature to generate yellow stain. These stains tend to be improved if the pH is kept low, but the discoloration of cyan and yellow under high humidity and high temperature becomes worse. In the specifications of JP-A-58-14834, JP-A-61-20864, JP-A-60-263939, JP-A-61-170742, JP-A-58-132743 and JP-A-61-151538, washing with water is sufficient. A technique is disclosed in which the coloring component is not brought into the photographic material when the photographic material is not used, or the color is rendered colorless. However, in even ultra-rapid processing cases, the effect is insufficient since such water washing time and rinsing weight bring a large amount of developer components or the bleach-fixing solution components than just the conventional washing to become very small, particularly continuous processing In some cases, more coloring components from the bleach-fix bath are brought in, and the coloring components remain in the photosensitive material.If the resulting print is stored at high temperature or high humidity, stains may occur in the white area. However, the commercial value has been reduced, for example, the image portion has faded.

(Problems to be Solved by the Invention) As is apparent from the above description, it is an object of the present invention to provide a high-quality and ultra-rapid process, and to preserve the print under high temperature and high humidity. It is to provide a method for forming a color image excellent in the above.

(Means for Solving the Problems) As a result of intensive studies, the present invention has found that the photosensitive material "alkaline consumption" is reduced to 2.6 mmol / m ² or less, and the "pH buffer capacity" of the washing bath is reduced to 12 cc / 100 ml. Over 90 and silver chloride 90
The present inventors have found that the above objects can be achieved by adjusting the content to mol% or more, and reached the present invention. The present invention is the following color image forming method.

(1) A non-diffusion-resistant dye that forms a dye on at least one side of a support by coupling a silver halide emulsion composed of 95 mol% or more of silver chloride with an oxidized form of an aromatic primary amine color developing agent. In a method of forming a color image by developing a color light-sensitive material having at least two layers having different photosensitivity in accordance with the composition containing the oil-soluble coupler, the "alkali consumption" of the color light-sensitive material is 2.6 mmol. / m ² or less and the color development time is substantially within 20 seconds, the time from color development to drying is within 100 seconds in total, and the `` pH buffer capacity '' of the final bath is 12 cc / 100 ml that's all,
A color image forming method characterized by being at most 36 cc / 100 ml.

(2) The pH of the final treatment bath according to claim (1).
Is a color image forming method of 5 to 6.5.

(3) In claim (1), the final treatment is 2 to 5
A countercurrent system bath contain a chelating agent to the final bath, and the replenishing amount of the bath, a color image forming method characterized by per color light-sensitive material 1 m ^2, is treated with 150ml or less.

 Hereinafter, the present invention will be described in more detail.

In the present invention, since the total processing time (including the drying process) is set to 100 seconds or less, the bleach-fixing process, which is the next process of the development, requires about 10 to 40 seconds. The same is expected for the subsequent washing process. It is known that the residual color developing agent and the residual bleach-fixing agent significantly deteriorate the storage stability of prints. Haruhiko Iwano, Takatoshi Ishikawa and Motoichi Furuzawa et al. Described the 5th International Symposium on Photofinishing Technology (1988).
Chicago), The Chemistry of Washing “The Way Two Enough Photo Processing Quality at Minilab”
Washing `` The way to ensure Photoprocessing Qualit
y at Minilabs ”), washing time, washing temperature and agitation speed are effective in removing the developing agent.
The removal of ferric ethylenediaminetetraacetate, which is frequently used as a bleaching agent, is effective with washing water and multi-stage countercurrent, and there is a finding that this difference depends on the magnitude of interaction with the binder. . Especially in the ultra-rapid processing of the present invention,
When the temperature of the final bath, for example, water washing and stabilization, or the final bath is a countercurrent system of 2 to 5 tanks, the effect of increasing the initial washing speed is large, which is preferable. Further, in order to shorten the time of the final step accompanying the ultra-rapid operation, it is preferable to add a chelating agent to the final bath from the viewpoint of making the coloring substance colorless. Immediately after this print was processed, it was found that the pH of the photosensitive material surface was lowered by exposure to high temperature and high humidity even though the pH of the film surface was near neutrality. It has been known that polycarboxylic acid, which is one of chelating agents, has a pH buffering ability. The first column on page 3 of JP-A-49-83441 discloses that it acts as a pH buffer in a stabilizing bath for photographic processing.
From this, it can be considered that the stabilizing bath containing the chelating agent has a pH buffering ability. Also, JP-A-62-958,
In 959, the pH buffering action of the stabilizing bath is disclosed, but the magnitude of the pH buffering capacity is not described, and it is considered that the control of the pH of the membrane was not considered. In the present invention, by adding a larger amount of the pH buffer, the pH of the film surface of the initial photosensitive material does not change as compared with the case where the buffer is small. Has been found to be improved. I.e. big for washing bath
Providing the pH buffering ability is a major improvement factor, and it has been found that even when it is actually implemented, it has a great effect.

In particular, when ultra-rapid processing is performed, the amount of the bleach-fix solution brought into the final washing bath increases. This component contains a component that lowers the pH under high humidity and high temperature, and the pH is greatly lowered as compared with ordinary washing with water. Therefore, fading of cyan and yellow deteriorates.

Further, the storage stability (fading and increase in stain) of the print of the color light-sensitive material of the present invention is influenced by the pH of the light-sensitive material. The optimum pH value varies depending on the dye formed in the light-sensitive material. Generally, the higher the pH, the worse the stain (stain on a white background). In the case of fading under high temperature and high humidity, some pigments are decomposed by acid,
It is not preferable that the pH is too low (pH 5 or less). The pH of the light-sensitive material can be improved by appropriately selecting the pH of the final processing bath of the present invention and its pH buffering capacity.

Further, as described above, the removal of the coloring substance is advantageous when the temperature is higher because the diffusion rate may be faster. Conventionally, when the amount of the replenisher is large, it is possible to sufficiently wash with a large amount of washing water. However, for the purpose of quick processing and simplification, a higher temperature is preferable.

Furthermore, the present invention reduces the "alkaline consumption" of the light-sensitive material so as to be suitable for ultra-rapid processing, that is, reduces the pH buffering capacity, thereby causing a rapid development and color development reaction,
Conversely, in the final bath, a large pH buffer capacity was added to the film to ensure the preservation of prints, and it was particularly important for processing photographic materials for ultra-rapid processing with low "alkali consumption". It is.

Next, a method for determining the “pH buffer capacity” used in the present invention will be described.

Prepare 100 ml of the washing bath used in the present invention and adjust the pH to 6.5 with 1N sulfuric acid or 1N sodium hydroxide.
Next, 1N sulfuric acid was added until the pH reached 5.0, and the required amount was reduced to `` p
Defined as "H buffer capacity", and the unit is cc / 100ml. Naturally, this value represents the ability to maintain the pH of the liquid brought into the light-sensitive material, so it is an important physical property value for the storage stability of the print as shown above . In the present invention, it is preferably 12 to 36 ml / 100 ml.

In the present invention, “alkaline consumption” is measured and calculated by the following measurement method.

As a means for calculating the “alkaline consumption”, first, a fixed area (specifically, 1 m ² ) of the light-sensitive material of the present invention is sampled, and the light-sensitive material is separated between the support and the coating amount. A typical support is a laminate of polyethylene on paper and can be peeled between the layers. Next, crush the coating layer side finely, and divide it into a certain amount of water (specifically, 100 ml).
Disperse in. Next, this solution is titrated with an aqueous alkali solution (specifically, 0.11N potassium hydroxide solution), and the pH is adjusted from pH 6.0 to pH 6.0.
The amount of potassium hydroxide required to reach 10.0 is defined as "alkaline consumption" in millimoles.

When the support contains an acid component and cannot be peeled off as described above, it can be evaluated by reducing the measured value of only the support.

This alkali consumption is to evaluate the acid component contained in the photosensitive material, and its pH buffering capacity,
Specifically, it is affected by gelatin and other organic compounds which are hydrophilic binders in the photosensitive material.

In the present invention, if the alkali consumption is large, the high alkalinity during the initial development cannot be maintained, so that the initial development is delayed and the object of the present invention cannot be achieved. Therefore, when ultra-rapid processing is intended, the alkali consumption of the photographic material is a very important parameter in terms of accelerating the initial development.

The following method is preferable for reducing the “alkaline consumption” which is a feature of the present invention.

First, the hydrophilic colloid having an acidic group in the light-sensitive material layer is reduced.

As a hydrophilic colloid of a color photographic light-sensitive material using a silver halide emulsion as a light sensor, gelatin is most preferably used. However, due to its functional groups, gelatin has a pH buffering capacity against the penetration of alkaline solutions.

It is important to reduce the buffer capacity to accelerate the initial development in rapid processing, and a method of reducing the amount of gelatin is preferable.

Second, membrane physical properties may be degraded only by weight loss of gelatin, and therefore, it is used in combination with a hydrophilic polymer having no acidic functional group.

As the hydrophilic polymer that can be used in the present invention, those exemplified in the present specification can be used. In particular, polyacrylamide, polydextran, and polyvinyl alcohol are preferably used. When such a means is used in combination with a hardener, a photosensitive material having a high initial swelling rate can be formed.

Third, the type of gelatin used as the hydrophilic colloid is changed.

Specifically, the alkali consumption can be reduced by changing the number of functional groups and changing the isoelectric point by using a different processing method at the time of producing gelatin or using esterified gelatin or amidated gelatin in which the acid groups of gelatin have been reduced. Can be suppressed.

Fourth, the amount of materials of organic compounds other than gelatin (specifically, couplers, hydroquinone and phenolic compounds, etc.) is reduced.

Fifth, alkali consumption can be reduced by adjusting the pKa value of the organic compound described in the fourth.

As described above, it is important to suppress the "alkaline consumption" of the photosensitive material, which is a solution of the present invention. The alkali consumption is 2.6 mmol / m ² or less, but 1.82 mmol / m ²
The following is preferred.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline D-7 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline D- 8 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-9 N, N-dimethyl-p-phenylenediamine D-10 4-Amino-3-methyl-N-ethyl-N-methoxy Luaniline D-11 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline D-12 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline Above p-phenylenediamine Particularly preferred among the derivatives are Exemplified Compounds D-4 and D-6.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 to about 10 g, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

The developer used in the present invention more preferably contains an organic preservative in place of the sulfite ion of hydroxylamine.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metal salts described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and for details, see Japanese Patent Application No. 62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
The content is preferably from × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /
It is. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are lowered, and
If the amount is less than ^10-5 mol / m, fogging cannot be sufficiently prevented.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When the color developer is directly added, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbon salts, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantage of being inexpensive. It is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylene, triaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic acid 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '-Bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429 and the like, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As antifoggants, alkali metal halides such as alkali metal halides such as sodium chloride, potassium bromide and potassium iodide can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer applicable to the present invention is 20 to
50 ° C, preferably 30 to 45 ° C. The processing time is preferably within 20 seconds, preferably within 15 seconds. The replenishment amount is preferably small, but is suitably 20 to 600 ml, preferably 30 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 40 to 200 ml,
Most preferably, it is 60 ml to 150 ml.

Next, the desilvering step applicable to the present invention will be described. In the desilvering step, generally, any steps such as a bleaching step, a fixing step, a fixing step, a bleach-fixing step, a bleaching step, a bleach-fixing step, and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution to which the present invention can be applied will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.
An iron ion complex salt may be formed. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Of the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount of addition is 0.1 to 1.0 mol /, preferably 0.1 mol / mol.
05 to 0.50 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Compounds having a mercapto group or a disulfide bond described in 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), JP-B-45-8506, JP-A-52-50 -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary; Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. . Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / mol, more preferably 0.04 to 0.40 mol /.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering processing such as fixing or bleach-fixing, it is general to carry out final processing, that is, washing and / or stabilizing processing.

One feature of the washing bath of the present invention is that it contains a chelating agent.

Usable chelating agents can be selected from aminopolycarboxylic acid, aminopolyphosphonic acid phosphonocarboxylic acid, alkylidene diphosphonic acid, metaphosphoric acid, pyrophosphoric acid and polyphosphoric acid. Specific examples of the chelating agent are described below, but the present invention is not limited thereto.

Among these, alkylidene diphosphonic acid is particularly effective. The amount of the chelating agent used is preferably 1 to 100 g, more preferably 5 to 50 g per washing bath.

The carboxylic acid and phosphonic acid groups of these chelating agents are
Salts may be formed with metal ions such as magnesium, calcium, bismuth, lithium, sodium, potassium, ammonium and zinc.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment type such as countercurrent and forward flow, and various other conditions. Can be set. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal
of the Society of Motion Picture and Televi-sion
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, can be the light-sensitive material 1 m ² per 0.02 or less, the effect of the present invention is remarkable, deposited by the residence time increase of water in the tank, bacteria proliferate, the generated suspended solid photosensitive material Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-12
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A No. 145, benzotriazole described in JP-A-61-26761, copper ions and others, written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2).

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various fungicides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

A so-called rinsing liquid is similarly used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The pH buffering agent that can be used in the washing bath of the present invention is, specifically, borate, metaborate, borax, phosphate, monocarboxylate, dicarboxylate, polycarboxylate, oxycarboxylic acid Examples include salts, amino acids, aminocarboxylates, sodium hydroxide, potassium hydroxide and the like.

The preferred pH of the washing step or the stabilizing step is 5 to 6.5. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 15 to 55 ° C, preferably 35 to 45 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably 10 seconds to 45 seconds, more preferably 15 seconds
Seconds to 30 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferred replenishment amount is 0.5 to 50 times, preferably 2 to 1 times the photosensitive material and the amount brought in from the previous bath per unit area.
5 times. Alternatively, the amount is 300 ml or less, preferably 150 ml or less, per 1 m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

In the case of performing the water-washing treatment in a plurality of baths, the continuous bath is a treatment of the same time, but it is preferable that the treatment is performed in a short time in the pre-bath and the post-bath time is long. In the short rinsing time of the present invention, the ratio of the total rinsing time may be short or the ratio of the transition time from the bath to the bath may be large.
Since the total washing time is short, the total bathing time is insufficient and the developing solution or the bleaching and fixing components cannot be washed out. To perform efficient washing in a short time, the post-bath time is 0.1 times or more and 1.3 times or less of the total bath, preferably 1.
It is preferable that the treatment is carried out within a range of 0 to 1.15.

 The drying step that can be used in the present invention will be described.

In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired.

As a means of shortening the drying time, as an improvement on the light-sensitive material side, the light-sensitive material of the present invention with low alkali consumption, that is, one of the improvements is a decrease in the amount of gelatin. That is, it is preferable that the hydrophilic colloid (eg, gelatin) as the binder is 2.0 to 8.0 g / m ² . By reducing the amount of gelatin, the drying time can be shortened to reduce the amount of washing water brought in. or,
From the viewpoint of reducing the amount brought in, it is possible to stop drying by sucking water from the sample taken out of the washing bath using a squeeze roller or cloth. In the improvement from the dryer, of course, it is possible to stop the drying by increasing the temperature and wind,
Drying can be accelerated depending on the irradiation angle of the drying air onto the sample and the method of removing the exhaust air.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order.

The image forming system including the light-sensitive material and processing which can be used in the present invention can be used for rapid processing of commonly used color prints, but can also be used for intelligent color hard copy applications where speeding is more desired. is there.

In particular, as an aspect of the intelligent color hard copy, an aspect in which scanning exposure is performed using high-density light such as a laser (for example, a semiconductor laser) or a light-emitting diode is preferable.

Many semiconductor lasers have photosensitivity in the infrared region, and a light-sensitive material used therefor can use an infrared-sensitive silver halide emulsion layer instead of at least one of the above emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

Further, depending on the required image quality and quality, the color coupler may be of two colors. In this case, the corresponding silver halide emulsion layers may be two layers. In this case, a full-color image is not obtained, but an image can be formed more quickly.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core (core). Shell) [single layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface (the edge of the particle when on the particle surface,
A structure in which different composition parts are joined on corners or surfaces)
And the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the number average of the grain sizes is similar to the diameter of a circle equivalent to the projected area of the grains) is from 0.1 μm to 0.1 μm. 2μ is preferred.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called dispersion of 15% or less is preferable.
At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle in terms of circle / thickness) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chemi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), GFDuffin, Pho-tographic Emulsion Chemi
stry (Focal Press, 1966), VLZelikman et a
lMaking and Coating Photographic Emulsion (Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any one method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called control double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs the spectrum in the wavelength region corresponding to the target spectral sensitivity-a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocylic com by FM Harmer.
pounds-Cyanine dyes and related compounds (John W
iley & Sons [New York, London], 1964). As specific examples of the compounds and the spectral sensitization method, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention prevents fogging during the production process, storage or photographic processing of the light-sensitive material. Alternatively, various compounds or precursors thereof can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

When the present invention is applied to a color light-sensitive material, a yellow coupler, a magenta coupler, and a cyan coupler, which are coupled to an oxidized form of an aromatic amine-based color developing agent to form yellow, magenta, and cyan, respectively, are applied to the color light-sensitive material. Is usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following general formulas (C-1), (C-II), (MI), and (M-II)
And (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) General formula (Y) In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadigital group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymesyl group and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ 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,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

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

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

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) 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 (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), imidazo [1,2-b] described in U.S. Pat. No. 4,500,630 in terms of low yellow side absorption and light fastness of a color forming dye. Pyrazoles are preferred, U.S. Pat.
Pyrazolo [1,5-b] [1,2,4] triazole described in JP 50,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents However representative of R ₁₃ and R ₁₄ are each an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂ and R
₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom; Atomic desorption type is particularly preferred.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.
No. 2,418,613, No. 2,700,453, No. 2,701,197, No. 2,728,659, No. 2,732,300, No. 2,735,765,
No. 3,982,994, No. 4,430,425, UK Patent No. 1,363,
No. 921, U.S. Pat.Nos. 2,710,801, 2,816,028, and 6-hydroxychromans, 5-hydroxyclamans, and spirochromans are U.S. Pat.Nos. 3,432,300, 3,573,050, 3,574,627, and 3,698,909. issue,
No. 3,764,337, JP-A-52-152225, spiroindanes in U.S. Pat.No. 4,360,589, p-alkoxyphenols in U.S. Pat.
No. 2,066,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are described in U.S. Pat.
No. 5, JP-A-52-72224, U.S. Pat.No. 4,228,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. In Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, the metal complexes are U.S. Pat. 4,241,1
55 and British Patent 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
Nos. 3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R _1- (A) _n -X General formula (FII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes addition of an aromatic amine-based developing agent to the compound of the general formula (FII). Represents a group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by the general formulas (FI) and (FII) are described in specifications such as JP-A-63-158545, JP-A-62-283338, EP-A-298321, and 277589. Are preferred.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearson,
et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
No. 229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a binder or protective colloid which can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used in the present invention include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, proteins such as casein; hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, Cellulose derivatives such as cellulose sulfates; sugar derivatives such as sodium alginate, pyrodextran, and starch derivatives; polyvinyl alcohol, poly (N-vinylpyrrolidone) modified with polyvinyl alcohol, polyvinyl alcohol partial acetal, anionic compounds and cationic compounds , Polyacrylic acid and its neutralized product, polymethacrylic acid and its neutralized product, polyacrylamide, polyvinylimidazole, homopolymer such as polyvinylpyrazole Synthetic hydrophilic polymeric substances consisting of each of the copolymers and the like.

A hydrophilic polymer containing gelatin can be used by appropriately crosslinking to increase the initial swelling.

The total hydrophilic colloid used in the light-sensitive material is 2.0 to 8.0 g / m ²
And more preferably 3.5 to 6.5 g / m ² .
If the amount of the hydrophilic colloid is large, development, especially the initial development is delayed, and if it is small, the physical properties of the film when wet are affected, which is not preferable.

For this purpose, any of the conventionally known hardeners are
They can be used alone or in combination.

That is, for example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethyloxyurea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Active vinyl compound (1,3,5-triacryloyl-hexahydro-2-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compound (2,4-dicrol-6-hydroxy-3) -Triazine, etc.), mucohalogenic acids (mucochloric acid, mucophenoxycyclolic acid, etc.) and the like can be used.

Hardening agents preferably used are aldehyde compounds such as formaldehyde, glyoxal, S-triazine compounds such as 2-hydroxy-4,6-dichlorotriazine sodium salt and vinyl sulfone compounds.

The amount of the hardening agent used is affected by the presence of a hardening accelerator or a hardening inhibitor, but is preferably 1 × 10 ⁻⁶ mol / g · gelatin to 1 × 10 ⁻² mol / g · gelatin. Used in range. More preferably, it is used at 5 × 10 ⁻⁵ mol / g · gelatin to 5 × 10 ⁻³ mol / g · gelatin.

Typical hardener HCHO CH ₃ CHO _{OHCCH 2 3 CHO ClCH 2 CONHCOCH 2} Cl ClCH 2 COOCH 2 CH 2 OOCCH 2 Cl CH ₃ COCl CH ₃ COCH ₂ Cl CH ₂ = CHSO ₂ (CH ₂ ) ₃ SO ₂ CH = CH ₃ C (CH ₂ SO ₂ CH = CH ₂ ) _{4 CH 2 = CHCOOCOCH = CH 2 CH} 2 = CH-O-CH = CH 2 (CH ₂ = CHSO ₂ · CH ₂ CONHCH _{2 2 A} hardening aid may be used when hardening a hydrophilic colloid using these hardening agents. Examples of the hardening aid include:
Examples thereof include a hydrogen bond breaking agent such as thiourea and urea, and an aromatic hydrocarbon having a hydroxyl group such as hydroquinone.

Further, only the carbonized layer may be hardened by polymerizing the hardener.

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include polyamide films, polycarbonate films, polystyrene films, and vinyl chloride resins.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal foil layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be sought.

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

Example 1 A multilayer color printing paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × 10 ^-4 mol for small size emulsion)
Mol) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.27 Gelatin 1.17 Yellow coupler (ExY 0.68 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.29 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.38 Color mixture inhibitor (Cpd-5) 0.11 Solvent ( Solv-1) 0.27 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion has AgBr0.
0.12 gelatin 1.25 magenta coupler (ExM) 0.26 color image stabilizer (Cpd-2) 0.06 color image stabilizer (Cpd-3) 0.08 color image stabilizer (Cpd-4) 0.03 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.52 Fourth layer (ultraviolet absorbing layer) Gelatin 0.47 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv- 5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm average grain size and 0.45 µm grain size (Ag mole ratio). Variation coefficient of grain size distribution) Are 0.09 and 0.11, AgBr0 for each emulsion.
0.20 Gelatin 0.89 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.19 Color image stabilizer (Cpd-7) 0.31 Color image stabilizer (6 mol% is partially contained in a part of the particle surface) Cpd-8) 0.04 Solvent (Solv-6) 0.34 Sixth layer (ultraviolet absorbing layer) Gelatin 0.24 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.25 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.05 Liquid paraffin 0.02 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ Thus, Sample 101 was prepared. The blue-sensitive emulsion layer and the green-sensitive emulsion layer of this sample had 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene is contained in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide.

A sensitometer (Fuji Photo Film Co., Ltd., FWH
Using a mold and a color temperature of a light source of 3200 ° K), a gradation exposure of a three-color separation filter for sensitometry was given. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step.

The composition of each processing solution is as follows.

Bleaching / fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water 1000ml pH (25 ℃) 6.0 Rinse solution (same as tank solution and replenisher) Deionized water (3ppm for calcium and magnesium each)
In the case where the washing bath is a multi-tank, a so-called multi-stage countercurrent method was adopted in which the last tank was refilled and overflowed to the previous tank sequentially.

Instead of the above-mentioned washing liquid containing only ion-exchanged water, a sample was prepared by using the washing bath formulations A to M in the following table and treating the washing process under the conditions in the following table. (NO and K are the washing bath formulas described above.) The washing bath formulation was prepared by the following method.

NOA: K-1430g + 2NNaOH 150ml + Solution I 561ml + 0.2NNaOH 258m
l NOB: K-1430g + 2N NaOH 150ml + II solution 820ml NOC: Change I solution to 538ml and 0.2NNaOH 282ml for NOA NOD: Change to K-14 10g for NOA NOF: Change to 529ml I solution + 0.2NNaOH 291ml for NOA NOG : change in I solution 594ml + 0.2NNaOH226ml against NOA Noj: change in K-15 30 g against _{NOA NOK: 11.8gH 3 PO 4,} 85% of 8.13ml orthophosphoric acid + 7.2 g acetic acid, 7.
08 ml 96% glacial acetic acid + 7.41 g H ₃ BO ₃ is adjusted to ₁ with ion-exchanged water (calcium and magnesium are each 3 ppm or less).

NOL: only ion-exchanged water NOM: 30 g of K-14 + 150 ml of 2NNaOH is adjusted to 1 with ion-exchanged water, and further adjusted to pH 6.5 with 1NNaOH.

NO, E, H and I used the same liquid as the NOA liquid.

 Here, the following solutions were used as the solution I and the solution II.

Solution I: 3.92 g H ₃ PO ₄ , 2.71 ml 85% orthophosphoric acid + 2.40 g acetic acid, 2.
36 ml 96% glacial acetic acid + 2.47 g H ₃ BO ₃ was made 1 with H ₂ O.

Solution II: 50 ml 0.2 M potassium dihydrogen phosphate + 15.1 ml 0.2 N NaOH
After performing +129 ml H ₂ O color development, the color densities of yellow, magenta and cyan were measured with a densitometer to obtain a so-called characteristic curve.

Next, Sample 10A (Comparative Example) was prepared by changing only the following portions of Sample 101.

This light-sensitive material was also processed by changing the processes of washing Nos. A to M.

Further, the obtained sample was allowed to stand at 80 ° C. and 70% RH for one week, and the increase in the density (stain) of the unexposed portion was evaluated.

In all of the treatments A to K using the photosensitive material sample 101 (each of the washing bath formulations A to K), the image was completed by 15 ″ development, and the purpose of the ultra-rapid processing of the present invention was achieved. Then, the image was not completed by 15 seconds development.

The “alkaline consumption” was 2.6 mmol / m ^{2 for} sample 101 and 10 A for 10 A.
3.1 mmol / m ² .

Next, the increase in the yellow density (stain) caused by leaving it at 80 ° C. and 70% RH is shown.

Furthermore, the samples treated with the washing baths L and M are the film surfaces of the photosensitive material
This was probably due to a decrease in pH, but it was also found that the cyan image and the yellow image were significantly faded at 80 ° C. and 70% RH for 1 week.

As described above, it can be seen that good preservability can be obtained by using the light-sensitive material of the present invention and the washing bath of the present invention.

The following table shows the fading of the sample at 80 ° C. and 70% for one week at the end of the continuous treatment. The residual rate is a value obtained by multiplying the initial density (2.0) by 100 times the density when the part having the dye density of 2.0 before entering the condition of 80 ° C. and 70% was left at 80 ° C. and 70% for one week.

As is clear from the table, the samples treated with the washing baths L and M seem to be mainly caused by a decrease in the pH of the film surface of the light-sensitive material. Large fading of yellow image.

As described above, it can be seen that good preservability can be obtained by combining the light-sensitive material of the present invention and the washing bath of the present invention.

Example-2 Sample 201 obtained by changing only the following parts in Sample 101
It was created.

The alkali consumption of this sample was 1.75 mmol / m ² .

The same treatment (washing bath No. A and K) as in Example 1 was performed on this sample.

The result of the stain which performed the test by the same method as Example-1 is shown.

It can be seen that the stain using the photosensitive material 201 is very good.

Claims (3)

(57) [Claims] 1. The method according to claim 1, wherein at least one side of the support has 95 mol%
The light-sensitivity of the silver halide emulsion comprising the silver halide emulsion comprising silver chloride and an oxidized form of an aromatic primary amine color developing agent containing a diffusion-resistant oil-soluble coupler which forms a dye by coupling is different. In the method of developing a color light-sensitive material having at least two layers to form a color image, the "alkali consumption" of the color light-sensitive material is 2.6 m
mol / m ² or less, the color development time is substantially within 20 seconds, the time from color development to drying is 100 seconds or less in total, and the pH buffer capacity of the final bath is 12 cc / 100
A color image forming method characterized by being at least 36 ml / 100 ml. 2. A color image forming method according to claim 1, wherein said final treatment bath has a pH of 5 to 6.5. 3. The method according to claim 1, wherein the final processing comprises:
A countercurrent system of from 2 to 5 tanks, contain a chelating agent to the final bath, and the replenishing amount of the bath, a color image forming method characterized by per color light-sensitive material 1 m ^2, is treated with 150ml or less .